US20080308455A1 - Catalyst and a Method for Cracking Hydrocarbons - Google Patents

Catalyst and a Method for Cracking Hydrocarbons Download PDF

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Publication number
US20080308455A1
US20080308455A1 US11/813,056 US81305605A US2008308455A1 US 20080308455 A1 US20080308455 A1 US 20080308455A1 US 81305605 A US81305605 A US 81305605A US 2008308455 A1 US2008308455 A1 US 2008308455A1
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Prior art keywords
catalyst
zeolite
additive
calculated
slurry
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Inventor
Jun Long
Wenbin Jiang
Mingde Xu
Huiping Tian
Yibin Luo
Xingtian Shu
Jiushun Zhang
Beiyan Chen
Haitao Song
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority claimed from CNB2004101028104A external-priority patent/CN100497530C/zh
Priority claimed from CNB2004101028138A external-priority patent/CN100389174C/zh
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Assigned to RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC, CHINA PETROLEUM & CHEMICAL CORPORATION reassignment RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHEN, BEIYAN, JIANG, WENBIN, LONG, JUN, LUO, YIBIN, SHU, XINGTIAN, SONG, HAITAO, TIAN, HUIPING, XU, MINGDE, ZHANG, JISHUN
Assigned to RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC, CHINA PETROLEUM & CHEMICAL CORPORATION reassignment RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC RE-RECORD TO CORRECT THE ASSIGNEE'S ADDRESS ON A DOCUMENT PREVIOUSLY RECORDED AT REEL 020008, FRAME 0632. (ASSIGNMENT OF ASSIGNOR'S INTEREST) Assignors: CHEN, BEIYAN, JIANG, WENBIN, LONG, JUN, LUO, YIBIN, SHU, XINGTIAN, SONG, HAITAO, TIAN, HUIPING, XU, MINGDE, ZHANG, JISHUN
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • 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
    • 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
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • 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
    • 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
    • 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
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a catalyst and a method for cracking hydrocarbons. More particularly, the present invention relates to a catalyst and a method for cracking hydrocarbons used to increase the concentration of propylene in FCC liquefied petroleum gas (LPG).
  • LPG liquefied petroleum gas
  • Propylene is an important organic chemical raw material. With the rapid increase of the demand for the derivatives such as polypropylene, the requirement for propylene in the whole world is increased rapidly year by year. Fluid catalytic cracking is one of the most important technologies to produce light olefins and propylene. As for most of the FCC apparatus, using the catalyst or the addition agent containing zeolite with MFI structure is an effective technology in order to increase light olefins and propylene.
  • U.S. Pat. No. 5,318,696 disclosed a hydrocarbon conversion technology based on a catalyst which is consisted of a marcoporous zeolite and a zeolite with MFI structure and a Si/Al ratio of lower than 30. This technology is used to produce gasoline with high octane number by employing improved FCC process and increase low-carbon olefins, especially propylene.
  • U.S. Pat. No. 5,997,728 disclosed a method in which a shape-selective cracking addition agent is used in large amount in the FCC process of heavy feedstock.
  • the addition agent comprises the amorphous matrix by adding 12 ⁇ 40% ZSM-5 zeolite, and its inventory in the system is at least 10%, which makes the content of ZSM-5 zeolite in the catalyst higher than 3%.
  • This method increases low-carbon olefins in a large scale, at the same time it doesn't increase the yield of aromatic extraly and lose the yield of gasoline.
  • the cracking activity and hydrothermal stability of ZSM-5 zeolite is increased and the use level of zeolite can be reduced after the modification of ZSM-5 zeolite by phosphorous compounds.
  • CN1049406C disclosed a zeolite with MFI structure which containing P and rare earth.
  • This zeolite displays excellent hydrothermal stability and good selectivity of low-carbon olefins when used in the conversion of hydrocarbons at high temperature.
  • CN1034223C disclosed a cracking catalyst used to produce low-carbon olefins, which is consisted of 0 ⁇ 70% clay (based on weight of catalyst), 5 ⁇ 99% inorganic oxide and 1 ⁇ 50% zeolite.
  • the zeolite is the mixture of 0 ⁇ 25 wt % REY or high silica Y zeolite and 75 ⁇ 100 wt % five membered ring high silica zeolite containing P and rare earth.
  • U.S. Pat. No. 5,110,776 disclosed the preparation of ZSM-5 zeolite catalyst modified with P, in which the modification procedure with P is proceeded by dispersing the zeolite into a solution of P compounds at a pH value of 2 ⁇ 6, mixing with matrix and spray-drying.
  • the obtained catalyst increases the octane number of gasoline, and at the same time it doesn't increase the yield of dry gas and coke.
  • U.S. Pat. No. 6,566,293 disclosed a cracking catalyst comprising P modified ZSM-5 zeolite.
  • the preparation of P modified ZSM-5 zeolite is proceeded by dispersing the zeolite into a solution of P compounds at a pH value of higher than 4.5, in which the loading content of P (calculated by P 2 O 5 ) is at lease 10 wt %, then mixing with matrix and other zeolite components and spray-drying.
  • the obtained catalyst has high yield of low-carbon olefins.
  • U.S. Pat. No. 5,171,921 disclosed a ZSM-5 zeolite modified by P.
  • the Si/Al ratio of the zeolite is 20 ⁇ 60.
  • the zeolite displays higher activity than the zeolite without P modification when used in the conversion of C 3 ⁇ C 20 hydrocarbons to C 2 ⁇ C 5 olefins.
  • U.S. Pat. No. 6,080,303 disclosed a method used to increase the catalytic activity of microporous and mesoporous zeolites, in which microporous and mesoporous zeolites are treated with P compounds firstly and then combined with AlPO 4 gel. This method may improve the activity and hydrothermal stability of microporous and mesoporous zeolites.
  • U.S. Pat. No. 5,472,594 disclosed a hydrocarbon conversion technology based on a catalyst which comprises a marcoporous zeolite and a P modified mesoporous zeolite with MFI structure. This technology is used to produce gasoline with high octane number by employing improved FCC process and increase low-carbon olefins, especially C 4 /C 5 .
  • USP2002/0003103A1 disclosed a FCC technology employed to increase the yield of propylene, in which at least part of the gasoline products are piped into the second riser reactor and cracked again.
  • the catalyst composition used comprises mesoporous zeolite such as ZSM-5 and inorganic binder possessing cracking activity.
  • the inorganic binder component contains P and the P/Al ratio is 0.1 ⁇ 10. This technology may increase low-carbon olefins in a large scale, especially the yield of propylene.
  • USP2002/0049133A1 disclosed a catalyst with high zeolite content and high attrition strength.
  • the catalyst comprises 30 ⁇ 85 wt % ZSM-5 zeolite, 6 ⁇ 24 wt % P (calculated by P 2 O 5 ), ⁇ 10 wt % Al 2 O 3 and the remainder clay, in which P exists in matrix.
  • the catalyst can increase light olefins, especially the yield of propylene.
  • U.S. Pat. No. 5,236,880 disclosed a catalyst containing the zeolites with MFI or MEL structures, in which the zeolite is modified by the metal of Group VIII, preferred by Ni. After the introduction of Ni, the zeolite is treated at a controlled temperature under thermal or hydrothermal conditions, which leads to the enrichment of the metal of Group VIII and Al on the surface. When used in the conversion of hydrocarbons, the catalyst may increase the octane number of gasoline and the yield of C 3 ⁇ C 4 olefins.
  • CN1057408A disclosed a cracking catalyst containing high Si zeolite and high cracking activity, in which the high Si zeolite is ZSM-5 zeolite, ⁇ zeolite or MOR zeolite containing 0.01 ⁇ 3.0 wt % P, 0.01 ⁇ 1.0 wt % Fe or 0.01 ⁇ 10 wt % Al.
  • the high Si zeolite is obtained by heating H— or K-ZSM-5 zeolite, ⁇ zeolite or MOR zeolite with a Si/Al ratio of higher than 15 to 350 ⁇ 820° C. and passing it into an aqueous solution of Al halide, Fe halide or ammonium phosphate at a volume hourly space velocity of 0.1 ⁇ 10 h ⁇ 1 .
  • CN1465527A disclosed a MFI zeolite with P and transition metal.
  • the anhydrous chemical expression of the zeolite, calculated by mass of oxide, is (0 ⁇ 0.3) Na 2 O.(0.5 ⁇ 5) Al 2 O 3 — (1.3 ⁇ 10) P 2 O 5 .(0.7 ⁇ 15) M 2 O 3 .(70 ⁇ 97) SiO 2 , in which M is selected from one of the transition metals Fe, Co and Ni.
  • the zeolite may increase the yield and selectivity for C 2 ⁇ C 4 olefins and result in higher yield of LPG.
  • the object of the invention is to provide a new catalyst on the basis of the prior art and a method for cracking hydrocarbons by using this catalyst.
  • the catalyst prepared by using the modified MFI zeolite containing P and transition metal as disclosed in CN1465527A as active component, and introducing a proper content of transition metal additive and P additive further, could increase not only the yield of LPG in FCC effectively and the octane number of FCC gasoline, but also increase the concentration of propylene in LPG of FCC dramatically when used in the method for cracking hydrocarbons.
  • the catalyst supplied by this invention is characterized by that the catalyst comprises, calculated by dry basis, 10 ⁇ 65 wt % ZSM-5 zeolite, 0 ⁇ 60 wt % clay, 15 ⁇ 60 wt % inorganic oxide binder, 0.5 ⁇ 15 wt % one or more metal additives selected from the metals of Group VIIIB and 2 ⁇ 25 wt % P additive, in which the metal additive and the P additive are both calculated by oxide.
  • the catalyst supplied by this invention is preferably consisted of, calculated by dry basis, 20 ⁇ 50 wt % ZSM-5 zeolite, 10 ⁇ 45 wt % clay, 25 ⁇ 50 wt % inorganic oxide binder, 1.0 ⁇ 10 wt % one or more metal additives selected from the metals of Group VIIIB and 5 ⁇ 15 wt % P additive.
  • the ZSM-5 zeolite is preferably a ZSM-5 zeolite modified by P and one of the metals selected from Fe, Co and Ni.
  • the anhydrous chemical expression, calculated by oxide, is (0 ⁇ 0.3) Na 2 O.(0.5 ⁇ 5)Al 2 O 3 .(1.3 ⁇ 10)P 2 O 5 .(0.7 ⁇ 15)M x O y .(70 ⁇ 97)SiO 2 , in which x is the atom number of M and y is a number needed to satisfy the oxidation state of M.
  • the modified ZSM-5 zeolite is modified by P and Fe, and the anhydrous chemical expression, calculated by oxide, is (0 ⁇ 0.2) Na 2 O.(0.9 ⁇ 3.5) Al 2 O 3 .(1.5 ⁇ 7) P 2 O 5 .(0.9 ⁇ 10) M x O y .(82 ⁇ 92)SiO 2 .
  • the contents of metal additive of Group VIIIB and P additive do not include the contents of transition metal and P in the modified ZSM-5 zeolite.
  • the metal of Group VIIIB is selected from one or more of Fe, Co and Ni, more preferably Fe.
  • the clay is well known for the technicians in the art and there is no special limitation to it in this invention. It could be selected from one or mixture of more than one of kaolin, met a kaolin, sepiolite, attapulgite clay, montmorillonite, rectorite, diatomite, halloysite, steatite, bentonite, hydrotalcites, preferably from one or mixture of more than one of kaolin, metakaolinm, diatomite, sepiolite, attapulgite clay, montmorillonite and rectorite.
  • the inorganic oxide binder is selected from one or more of the inorganic oxides used as matrix and binder component of catalyst, which are well known for the technicians in the art and there is no special limitation to it in this invention. It is selected from one or mixture of more than one of pseudoboehmite, alumina sol, silica-alumina sol, water glass and phosphorus-alumina sol, preferably from one or mixture of more than one of pseudoboehmite, alumina sol and phosphorus-alumina sol.
  • the addition agent has phosphorus-alumina sol, the content of P in the phosphorus-alumina sol, calculated by P 2 O 5 , is added into the content of P additive.
  • the catalyst supplied by this invention could be prepared from zeolite, clay and inorganic oxide binder through any methods disclosed in the existing preparation technologies of cracking catalyst such as spray-drying process, and there is no special limitation in this invention.
  • transition metal additives of Group VIIIB exist in the form of their oxide, phosphate, phosphite, basic phosphate, acid phosphate.
  • One or more of the inorganic compounds and organic compounds of the transition metal could be easy to dissolve in water, or hard to dissolve or insoluble in water.
  • the examples of the transition metal compounds include their oxide, hydroxide, chloride, nitrate, sulphate, phosphate and their organic compounds, etc.
  • the preferred transition metal compounds are selected from one or more of their chloride, nitrate, sulphate and phosphate.
  • the transition metal additive of Group VIIIB is preferably introduced by adding transition metal compounds to the slurry in any step before spray-drying in the preparation process of the catalyst. It also can be introduced after spray-drying through immersion or chemical adsorption of transition metal compounds and calcination process, including to immerse the catalyst with a aqueous solution of transition metal compounds or to treat it by chemical adsorption method, then to separate the solid and the liquid (if needed), and to dry and calcine.
  • the drying temperature is from room temperature to 400° C., preferred 100 ⁇ 300° C.
  • the calcination temperature is 400 ⁇ 700° C., preferred 450 ⁇ 650° C.
  • the calcination time is 0.5 ⁇ 100 h, preferred 0.5 ⁇ 10 h.
  • the transition metal additive may exist in any possible positions of the catalyst, such as the internal channel of the zeolite, the surface of the zeolite, the matrix, or exist in the internal channel of the zeolite, the surface of the zeolite and the matrix simultaneously, preferred in the matrix.
  • the P additive exists in the form of phosphorous compounds (such as the oxide of phosphorus, phosphate, phosphite, basic phosphate and acid phosphate).
  • the P additive can be introduced into the catalyst by one of the following methods or the combination of the following methods, but not limited to these methods:
  • the inorganic oxide binder Introduced into the catalyst by the inorganic oxide binder.
  • the inorganic oxide binder containing phosphorus-alumina sol after the catalyst is calcined, P is introduced into the catalyst.
  • the phosphorus-alumina sol could also be used as matrix and binder, so this part of P also belongs to the P additive supplied by this invention.
  • the drying temperature is from room temperature to 400° C., preferred 100 ⁇ 300° C.
  • the calcination temperature is 400 ⁇ 700° C., preferred 450 ⁇ 650° C.
  • the calcination time is 0.5 ⁇ 100 h, preferred 0.5 ⁇ 10 h.
  • the P additive may exist in any possible positions of the catalyst, such as the internal channel of the zeolite, the surface of the zeolite, in the matrix, or exist in the internal channel of the zeolite, the surface of the zeolite and the matrix simultaneously.
  • the phosphorous compounds are selected from one or more of the inorganic compounds and organic compounds of phosphorus.
  • the phosphorous compounds could be easy to dissolve in water, or hard to dissolve or insoluble in water.
  • the examples of the phosphorous compounds include the oxide of phosphorus, phosphoric acid, phosphate, phosphite, hypophosphite and organic compounds of phosphorus.
  • the preferred phosphorous compounds are selected from one or more of H 3 PO 4 , (NH 4 ) 3 PO 4 , (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 , AlPO 4 and phosphorus-alumina sol.
  • a method for cracking hydrocarbons using above catalysts is also supplied in this invention, in which hydrocarbons are contacted with a mixture of catalysts mentioned above under cracking condition, and then the cracked products are collected.
  • the contact of the hydrocarbons and the mixture of catalysts could be proceeded in all kinds of reactors.
  • the reactor could be a riser reactor, a fixed-bed reactor, a fluidized-bed reactor or a moving-bed reactor, preferably the reactor is the riser reactor.
  • the contact conditions include a contact temperature of 400 ⁇ 650° C., preferred 420 ⁇ 600° C., and a catalyst-to-oil ratio (the weight ratio of catalyst to hydrocarbon) of 1 ⁇ 25, preferred 3 ⁇ 20.
  • the contact condition also includes the weight hourly space velocity of 10 ⁇ 120 h ⁇ 1 , preferred 15 ⁇ 80 h ⁇ 1 . But for a riser reactor the contact condition further includes the reaction time of 0.5 ⁇ 15 s, preferably 0.5 ⁇ 10 s.
  • the mixture of catalysts containing the catalysts mentioned above are consisted mainly of a main cracking catalyst and the catalyst mentioned above and the content of them is well known for the technicians in the art.
  • the content of the main cracking catalyst is 70 ⁇ 99 wt %, preferred 80 ⁇ 95 wt %, and the content of the catalyst supplied by this invention is 1 ⁇ 30 wt %, preferably 3 ⁇ 20 wt %.
  • the type and the composition of the main cracking catalyst is well known for the technicians in this area, which may be all kinds of cracking catalysts, such as all kinds of cracking catalyst containing zeolite.
  • the hydrocarbons are selected from one or more of all kinds of petroleum cuts, such as crude oil, atmospheric residuum, vacuumed residuum, atmospheric gas oil, vacuumed gas oil, straight run gas oil, propane deasphalted oil, coking gas oil and liquefied products of coal.
  • the hydrocarbons may have heavy metal impurities such as Ni and V, and impurities of S and N, in which the content of S can reach 3.0 wt %, the content of N can be up to 2.0 wt %, the content of metal impurities such as V and Ni can be as high as 3000 ppm.
  • the mixture of catalysts could be used onetime, but in a preferred situation the mixture of catalysts are regenerated and used cyclically.
  • the regeneration of the catalyst mixture is a process that the coke in the catalyst mixture is calcined under oxygen atmosphere which in general is air, as is well known for the technicians in the art.
  • oxygen atmosphere which in general is air, as is well known for the technicians in the art.
  • the regeneration temperature is 600 ⁇ 770, preferred 650 ⁇ 730° C.
  • the catalyst supplied by this invention by adding a proper content of the transition metal additive of Group VIIIB and the P additive, especially the samples using modified ZSM-5 zeolite as active component simultaneously, may increase the selectivity for propylene in FCC process, and consequently increase the concentration of propylene in LPG of FCC dramatically.
  • the content of propylene in the products is increased by 0.76 ⁇ 4.05% (Tables 3, 4, 5), the concentration of propylene in LPG is increased to higher than 35.70 wt %.
  • FIGS. 1 ⁇ FIG . 5 are the XRD patterns for the catalysts and the comparative catalysts prepared by the examples and the comparative examples.
  • the eight modified ZSM-5 samples A 1 ⁇ A 8 are prepared according to the method disclosed in CN1465527A.
  • the anhydrous chemical expressions are obtained on the basis of the chemical composition of the zeolite measured by X-ray fluoroscopy.
  • Sample A 1 0.04Na 2 O.3.57Al 2 O 3 .4.0P 2 O 5 .2.4Fe 2 O 3 .90.49SiO 2 .
  • Sample A 2 0.1Na 2 O.5.0Al 2 O 3 .2.0P 2 O 5 .0.9Fe 2 O 3 .92SiO 2 .
  • Sample A 3 0.1Na 2 O.5.3Al 2 O 3 .1.5P 2 O 5 1.1Fe 2 O 3 .92SiO 2 .
  • Sample A 4 0.03Na 2 O.2.2Al 2 O 3 .4.9P 2 O 5 ⁇ 2.1Fe 2 O 3 .90.8SiO 2 .
  • Sample A 5 0.1Na 2 O.0.94Al 2 O 3 .5.1P 2 O 5 .10.1Fe 2 O 3 .84SiO 2 .
  • Sample A 6 0.03Na 2 O.5.1Al 2 O 3 .4.8P 2 O 5 .3.6Co 2 O 3 .86.5SiO 2 .
  • Sample A 7 0.1Na 2 O.4.6Al 2 O 3 .6.9P 2 O 5 ⁇ 6.4Ni 2 O 3 .82SiO 2 .
  • Sample A 8 0.1Na 2 O.5.2Al 2 O 3 .4.5P 2 O 5 .2.0Ni 2 O 3 .88.2SiO 2 .
  • Pseudoboehmite is an industry product of Shandong Alumina Company with a solid content of 60 wt %.
  • Alumina sol is an industry product of Qilu Catalyst Factory with an Al 2 O 3 content of 21.5 wt %.
  • Water glass is an industry product of Qilu Catalyst Factory with a SiO 2 content of 28.9 wt % and a Na 2 O content of 8.9 wt %.
  • kaolin is a kind of special kaolin for cracking catalyst manufactured by Suzhou kaolin Company with a solid content of 78 wt %.
  • ZRP-5 zeolite is an industry product with conventional MFI structure manufactured by Qilu Catalyst Factory with a P 2 O 5 content of 2.5 wt % and a crystallinity of 85 wt % as well as a Si/Al ratio of 50.
  • the characterization method of the XRD patterns for the catalyst samples is:
  • the XRD patterns were characterized on a D/MAX-IIIA X-Ray Diffractometer (from Rigaku) at 40 kV and 40 mA using Cu K ⁇ radiation and Ni filter.
  • the sample scans were collected at scan step of 0.02°, step time of 1 s and diffraction slit of 2 mm/2 mm/0.2 mm.
  • Examples 1 ⁇ 19 are used to explain the preparation of catalyst employed in the method supplied by this invention.
  • the catalyst ZJ 1 with 35 wt % A 1 , 28 wt % kaolin, 27.5 wt % Al 2 O 3 , 2.0 wt % Fe additive (calculated by Fe 2 O 3 ) and 7.5 wt % P additive (calculated by P 2 O 5 ) was obtained after the calcination of the microspheres at 500° C. for 1 h.
  • microspheres with 36.8 wt % A 1 , 26.6 wt % kaolin, 31.6 wt % Al 2 O 3 and 5.0 wt % Fe additive (calculated by Fe 2 O 3 ) were obtained after calcination at 500° C. for 1 h.
  • microspheres with 38.8 wt % A 1 , 50.2 wt % Al 2 O 3 and 11 wt % Fe additive (calculated by Fe 2 O 3 ) were obtained after calcination at 500° C. for 1 h.
  • the preparation method is as same as Example 1, but the difference is that the weight of kaolin is 1.25 kg (dry basis) and FeCl 3 .6H 2 O solution is replaced by 1 L Co(NO 3 ) 2 .6H 2 O solution (having 250 g CoO).
  • the catalyst ZJ 4 was obtained with 35 wt % A 1 , 25 wt % kaolin, 27.5 wt % Al 2 O 3 , 5 wt % Co additive (calculated by CoO) and 7.5 wt % P additive (calculated by P 2 O 5 ).
  • the preparation method is as same as Example 1, but the difference is that the weight of kaolin is 1.25 kg (dry basis) and FeCL 3 .6H 2 O solution is replaced by 1 L Ni(NO 3 ) 2 .6H 2 O solution (having 250 g NiO).
  • the catalyst ZJ 5 was obtained with 35 wt % A 1 , 25 wt % kaolin, 27.5 wt % Al 2 O 3 , 5 wt % Ni additive (calculated by NiO) and 7.5 wt % P additive (calculated by P 2 O 5 ) that doesn't include the P component of the modified MFI zeolite.
  • the catalyst ZJ 7 was obtained with 35 wt % A 1 , 20 wt % kaolin, 2.5 wt % Al 2 O 3 , 20 wt % SiO 2 , 15 wt % Fe additive (calculated by Fe 2 O 3 ) and 7.5 wt % P additive (calculated by P 2 O 5 ).
  • the catalyst was prepared according to the method of Example 1, but the difference is that the weight of A 1 is 2.25 kg (dry basis) and the weight of kaolin is 0.9 kg (dry basis).
  • the catalyst ZJ 8 was obtained with 45 wt % A 1 , 18 wt % kaolin, 27.5 wt % Al 2 O 3 , 2 wt % Fe additive (calculated by Fe 2 O 3 ) and 7.5 wt % P additive (calculated by P 2 O 5 ).
  • the catalyst was prepared according to the method of Example 9, but the difference is that A 1 is replaced by A 2 with same weight.
  • the catalyst ZJ 10 was obtained with 20 wt % A 2 , 37 wt % kaolin, 30 wt % Al 2 O 3 , 8 wt % Fe additive (calculated by Fe 2 O 3 ) and 5 wt % P additive (calculated by P 2 O 5 ).
  • the catalyst ZJ 12 with 40 wt % A 4 , 15 wt % kaolin, 35 wt % Al 2 O 3 , 5 wt % Fe additive (calculated by Fe 2 O 3 ) and 5 wt % P additive (calculated by P 2 O 5 ) was obtained after the calcination of the microspheres at 500° C. for 1 h.
  • microspheres with 57.89 wt % A 8 , 40 wt % Al 2 O 3 and 2.11 wt % Fe additive (calculated by Fe 2 O 3 ) were obtained after calcination at 500° C. for 1 h.
  • the catalyst ZJ 14 with 30 wt % A 6 , 30 wt % kaolin, 30 wt % Al 2 O 3 , 2.5 wt % Fe additive (calculated by Fe 2 O 3 ) and 7.5 wt % P additive (calculated by P 2 O 5 ) was Obtained after the calcination of the microspheres at 500° C. for 1 h.
  • the catalyst ZJ 15 with 25 wt % A 7 , 20 wt % kaolin, 45 wt % Al 2 O 3 , 5 wt % Fe additive (calculated by Fe 2 O 3 ) and 5 wt % P additive (calculated by P 2 O 5 ) was obtained after the calcination of the microspheres at 500° C. for 1 h.
  • microspheres with 50 wt % A 8 , 44.6 wt % Al 2 O 3 and 5.4 wt % Fe additive (calculated by Fe 2 O 3 ) were obtained after calcination at 500° C. for 1 h.
  • the catalyst was prepared according to the method of Example 1, but the difference is that A 1 is replaced by A 3 with same weight.
  • the catalyst ZJ 17 was obtained with 35 wt % A 3 , 28 wt % kaolin, 27.5 wt % Al 2 O 3 , 2.0 wt % Fe additive (calculated by Fe 2 O 3 ) and 7.5 wt % P additive (calculated by P 2 O 5 ).
  • the catalyst was prepared according to the method of Example 1, but the difference is that A 1 is replaced by A 6 with same weight.
  • the catalyst ZJ 18 was obtained with 35 wt % A 6 , 28 wt % kaolin, 27.5 wt % Al 2 O 3 , 2.0 wt % Fe additive (calculated by Fe 2 O 3 ) and 7.5 wt % P additive (calculated by P 2 O 5 ).
  • the catalyst was prepared according to the method of Example 1, but the difference is that A 1 is replaced by A 8 with same weight.
  • the catalyst ZJ 19 was obtained with 35 wt % A 8 , 28 wt % kaolin, 27.5 wt % Al 2 O 3 , 2.0 wt % Fe additive (calculated by Fe 2 O 3 ) and 7.5 wt % P additive (calculated by P 2 O 5 ).
  • Comparative examples 1 ⁇ 5 are used to explain the preparation of comparative catalysts.
  • This comparative example is used to explain the preparation of comparative catalyst containing modified ZSM-5 zeolite (sample A 1 ) and P additive, but without metal additive of Group VIIIB.
  • the comparative catalyst CB 1 with 35 wt % A 1 , 30 wt % kaolin, 27.5 wt % Al 2 O 3 and 7.5 wt % P additive (calculated by P 2 O 5 ) was obtained after the calcination of the microspheres at 500° C. for 1 h.
  • This comparative example is used to explain the preparation of comparative catalyst containing modified ZSM-5 zeolite (sample A 1 ), but without metal additive of Group VIIIB and P additive.
  • the XRD pattern of this catalyst is shown in FIG. 1 as line d.
  • This comparative example is used to explain the preparation of comparative catalyst containing conventional ZRP-5 zeolite.
  • the catalyst was prepared according to the method of Comparative Example 2, but the difference is that A 1 is replaced by ZRP-5 zeolite with same weight.
  • the comparative catalyst CB 3 was obtained with 35 wt % ZRP-5 zeolite, 30 wt % kaolin and 35 wt % Al 2 O 3 .
  • This comparative example is used to explain the preparation of comparative catalyst containing conventional ZRP-5 zeolite and P additive.
  • the catalyst was prepared according to the method of Example 1, but the difference is that A 1 is replaced by ZRP-5 zeolite with same weight.
  • the comparative catalyst CB 4 was obtained with 35 wt % ZRP-5 zeolite, 30 wt % kaolin, 35 wt % Al 2 O 3 and 5 wt % P additive not including the P of ZRP-5 zeolite.
  • This comparative example is used to explain the preparation of comparative catalyst containing modified ZSM-5 zeolite (sample A 1 ) and metal additive of Group VIIIB, but without P additive.
  • the comparative catalyst CBS with 35 wt % A 1 , 30 wt % kaolin, 30 wt % Al 2 O 3 and 5 wt % Fe additive was obtained after the calcination of the microspheres at 500° C. for 1 h.
  • Examples 20 ⁇ 38 are used to explain the method supplied by this invention employed on the fixed fluidized-bed reactor.
  • Catalysts ZJ 1 -ZJ 19 were subjected to aging treatment respectively at 800° C. for 8 h under a 100% steam atmosphere. Then the catalysts ZJ 1 -ZJ 19 after aging treatment were mixed in different content with the commercial FCC ECAT (industry trademark is MLC-500, and its main properties are listed in Table 1). The catalyst mixture was put into the reactor of a small-scaled fixed fluidized-bed reaction apparatus to proceed the catalytic cracking of the feedstock shown in Table 2 (the properties of the feedstock are shown in Table 2).
  • Comparative Examples 6 ⁇ 11 are used to explain the comparative method employed on the fixed fluidized-bed reactor.
  • the catalytic cracking of the same feedstock is proceeded according to the method of Example 20, but the difference is that the catalyst is 100% commercial FCC ECAT or the mixture of CB 1 —CB 5 and commercial FCC ECAT respectively.
  • Example No. 30 31 32 33 34 35 36 37 38 Catalyst 12% ZJ 11 + 10% ZJ 12 + 6% ZJ 13 + 10% ZJ 14 + 12% ZJ15 + 4% ZJ 16 + 8% ZJ 17 + 8% ZJ 18 + 6% ZJ19 + 88% ECAT 90% ECAT 94% ECAT 90% ECAT 88% ECAT 96% ECAT 92% ECAT 92% ECAT 92% ECAT Reaction 500 500 510 500 490 520 490 500 520 temperature, ° C.
  • Examples 39 ⁇ 47 are used to explain the method supplied by this invention employed on the riser reactor.
  • Catalysts ZJ 1 -ZJ 5 , ZJ 10 , ZJ 11 , ZJ 14 and ZJ 16 were subjected to aging treatment respectively at 800° C. for 8 h under a 100% steam atmosphere. Then the catalysts ZJ 1 -ZJ 5 , ZJ 10 , ZJ 11 , ZJ 14 and ZJ 16 after aging treatment were mixed in different contents with MLC-500 commercial ECAT. The catalyst mixture was passed into a small-scaled FCC riser reactor continually, at the same time the feedstock shown in Table 2 or the feedstock shown in Table 2 with steam was also passed into continually, which results in the contact of the VGO and the catalyst mixture. Then the catalyst and the reaction product were separated. The separated catalyst was passed into the regenerator to be regenerated, and then the regenerated catalyst was passed back to the riser reactor. The composition of catalyst mixtures (wt %), reaction condition and reaction results are listed in Table 6 and Table 7.
  • Comparative Examples 12 ⁇ 16 are used to explain the comparative method employed on the riser reactor by using comparative catalyst.
  • the catalytic cracking of the same feedstock is proceeded according to the method of Example 39, but the difference is that the catalyst mixture is replaced by 100% commercial FCC ECAT, mixture of CB 1 and industry FCC ECAT, mixture of CB 2 and industry FCC ECAT, mixture of CB 3 and commercial FCC ECAT and mixture of CB 4 and commercial FCC ECAT respectively.
  • the composition of catalyst mixtures used in comparative method, reaction condition and reaction results are listed in Table 6.

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