CN107971013A - A kind of catalytic cracking catalyst and preparation method thereof - Google Patents

A kind of catalytic cracking catalyst and preparation method thereof Download PDF

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Publication number
CN107971013A
CN107971013A CN201610919769.2A CN201610919769A CN107971013A CN 107971013 A CN107971013 A CN 107971013A CN 201610919769 A CN201610919769 A CN 201610919769A CN 107971013 A CN107971013 A CN 107971013A
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molecular sieve
catalytic cracking
cracking catalyst
acid
weight
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CN107971013B (en
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王丽霞
周翔
田辉平
袁帅
刘宇键
刘俊
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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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    • 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
    • B01J29/08—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
    • B01J29/40—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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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

Abstract

A kind of catalytic cracking catalyst and preparation method thereof, the catalyst include 5~65% natural mineral matter, 10~60% adhesive oxides, 24~75% the first molecular sieve and 0.1%~15% phosphorus additive, and first molecular sieve is less than for apertureMolecular sieve and Y type molecular sieve or be less than for aperture

Description

A kind of catalytic cracking catalyst and preparation method thereof
Technical field
The present invention relates to a kind of catalytic cracking catalyst and preparation method thereof and quote.
Background technology
The low-carbon alkenes such as ethene, propylene, butylene are essential industrial chemicals, can be used to synthetic resin, fiber and rubber Glue etc..Wherein propylene is to be only second to a kind of of ethene to be used to manufacture the important source materials of petroleum chemicals, mainly for the production of polypropylene, The chemical products such as acrylonitrile, propylene oxide.Propylene is mainly derived from the accessory substance that thermal cracking produces ethene, propylene both at home and abroad at present Second largest source be FCC apparatus, there is provided about 30% amount of demand, in the U.S., FCC apparatus then provide petrochemical industry production Half of the product to propylene demand.
In recent years, the demand rapid development of propylene, is predicted according to HIS, by 2016, the growth rate of global propylene consumption By average out to 5% or so, more than the growth rate 3.4% of ethene.But the propylene/ethylene of steam cracking ratio cannot be adjusted flexibly It is whole.And its reaction temperature is up to 840-860 DEG C, energy expenditure accounts for the 40% of petrochemical industry energy consumption.Therefore by FCC come big Amount propylene enhancing is the effective and efficient approach increased for meet demand amount.
Beta molecular sieves are a kind of high silicon large pore molecular sieves, are synthesized first in 1967 by Mobil companies.1988 Year, Newsman and Kiggins determine beta by modern technologies such as electronic diffraction, high resolution electron microscope and computers The crystal structure of molecular sieve.Structural research shows that Beta molecular sieves have three cross one another 12 membered ring channels, parallel to (001) the twelve-ring aperture of the one-dimensional channels of crystal face is 0.57~0.75nm, another the two-dimentional holes parallel with (100) crystal face The twelve-ring aperture in road is 0.56~0.65nm.Due to the pore passage structure of Beta molecular sieves uniqueness, peracidity and good water Heat endurance, the prospect of its commercial Application is extensive, has been applied successfully to the stones such as the alkylation of isomerization, catalytic cracking and aromatic hydrocarbons Oily chemical field.
Y molecular sieve shows to be catalyzed well after 1964 are successfully synthesized out in alkane catalytic conversion reaction Effect.Y molecular sieve has a three-dimensional twelve-ring pore passage structure, aperture 0.74nm, and there are the super of diameter 1.3nm in molecular sieve Cage.Since Y molecular sieve has a structure in which feature, it was widely used in catalytic cracking reaction later, had excellent Performance.With the demand to products such as low-carbon alkenes, Y molecular sieve starts to be compounded with other molecular sieves, such as ZSM-5, energy Enough distributions for more neatly adjusting product.
CN103785460A proposes a kind of catalyst for producing low-carbon alkene and preparation method thereof, using MFI structure point The catalyst system that the beta-molecular sieve of son sieve and P Modification compounds, has the low-carbon of higher for naphtha catalytic cracking propylene Olefins yield.
CN101837301A proposes a kind of catalytic cracking propylene catalyst with yield increase and preparation method thereof, by shape-selective molecular sieve (ZSM-5 or beta-molecular sieve) and Y type molecular sieve mix homogenizing with matrix and form slurries, and spray drying, is then handled through acid solution Obtain catalytic cracking catalyst.
But existing catalyst for cracking is used for heavy oil conversion productivity of propylene and BTX yields are not high.
The content of the invention
One of the technical problem to be solved in the present invention is to provide a kind of fluid catalytic cracking catalyst, which has The catalyst has the propene yield of excellent hydrothermal stability and higher.The second object of the present invention is to provide the catalyst Preparation method and application method.
The present invention provides a kind of catalytic cracking catalyst, on the basis of the weight of catalyst, including (a) 5% in terms of butt ~64% natural mineral matter；(b) 10%~60% oxide；With the first molecular sieve of (c) 24%~75% in terms of butt, First molecular sieve is less than for Y type molecular sieve and apertureMolecular sieve, or first molecular sieve for aperture it is small InMolecular sieve in two or more；And D) with P2O5The phosphorus additive of meter 0.1%~15%；The catalysis is split The ratio that mesoporous Bronsted acid amount in solution catalyst accounts for total acid content is 20%~70% for example, 25%~65%.The catalyst Total specific surface area be preferably greater than 240m2/g。
Preferably, the mesopore volume of the catalytic cracking catalyst accounts for the ratio of total pore volume and is, for example, for 35%~60% 40%~60% or 45%~58% or 35~45%.The mesopore volume of the catalyst for 0.25~0.4ml/g or 0.25~ 0.45ml/g or 0.35~0.42ml/g.The mesoporous hole for referring to that bore dia is 2~100nm.
Preferably, the ratio that the mesopore volume of the catalytic cracking catalyst accounts for total pore volume is 35%~60%.It is described The mesopore volume of catalyst is, for example, 0.14~0.30ml/g or 0.25~0.35ml/g such as 0.15 for 0.14~0.35ml/g ~0.32ml/g.The mesoporous hole for referring to that bore dia is 2~100nm.
Preferably, total specific surface area (also referred to as specific surface area) of the catalytic cracking catalyst is 240~350m2/ g, example Such as it is 250~320m2/g。
Catalytic cracking catalyst provided by the invention, has more mesoporous Bronsted acid, it is preferred that mesoporous Bronsted acid amount accounts for The ratio of total acid content is, for example, 25%~65% for 20%~70%, it is preferred that for example can be 25%~50% or 30~ 55%.
Mesoporous pore volume, the total pore volume of the catalytic cracking catalyst are carried out using N2 adsorption BET specific surface area method Measurement；Total specific surface area of the catalyst is measured using N2 adsorption BET specific surface area method；The catalyst it is mesoporous Bronsted acid refers to that kinetic diameter isThe Bronsted acid that can touch of 2,6 di tert butyl pyridine molecule.Mesoporous proton Acid amount is adsorbed infrared acid process using 2,6 di tert butyl pyridine and is measured；Total acid content uses NH3- TPD methods are surveyed Amount.
Preferably, the phosphorus additive content in the catalytic cracking catalyst is with P2O50.1-15 weight % are calculated as, are, for example, 1 ~13 weight % are 1.5~8 weight % or 0.5-6.5 weight % or 2~5 weight %.
In catalytic cracking catalyst provided by the invention, containing natural mineral matter, the natural mineral matter is, for example, height Ridge soil, halloysite, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite In one or more；The adhesive oxides are silica, aluminium oxide, zirconium oxide, titanium oxide, amorphous silica-alumina bond One or more in agent；The Y type molecular sieve be DASY molecular sieves, for the DASY molecular sieves containing rare earth, USY molecular sieve, One or more in USY molecular sieve containing rare earth, REY molecular sieves, REHY molecular sieves, HY molecular sieves, the aperture are less thanMolecular sieve be MFI structure molecular sieve, IMF structure molecular screens, BEA structure molecular screens, at least one in ferrierite Kind.The aperture is less thanMolecular sieve in it is two or more for MFI structure molecular sieve, IMF structure molecular screens, BEA knot Two or more in structure molecular sieve, ferrierite.The MFI structure molecular sieve can be the MFI structure molecular sieve of sodium form, Can also be by the molecular sieve modified obtained modification MFI structure molecular sieve of sodium form MFI structure, such as Hydrogen MFI structure molecular sieve, Ammonium type MFI structure molecular sieve, phosphorous and/or transition metal MFI structure molecular sieve, wherein the transition metal such as RE, One or more in Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.MFI structure the molecular sieve such as ZSM-5, Ke Yishi NaZSM-5 or be by NaZSM-5 molecular sieves by modified obtained molecular sieve, it is such as HZSM-5, ammonium type ZSM-5, phosphorous And/or the ZSM-5 of transition metal, wherein in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga It is one or more.The IMF structure molecular screens can be sodium form IMF structure molecular screens or IMF structure molecular screens pass through Cross the modification IMF structure molecular screens that various method of modifying are modified, such as ammonium type IMF structure molecular screens, Hydrogen IMF structures point One or more IMF structure molecular screens in son sieve, phosphorous and/or transition metal, the transition metal such as RE, Fe, One or more in Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.The IMF structure molecular screens such as IM-5, can be Na types IM-5 or the modification IM-5 molecular sieves obtained by NaIM-5 process modifications, such as Hydrogen IM-5, ammonium type IM-5 and phosphorus And/or the IM-5 molecular sieves that one or more in transition metal are modified, the transition metal such as RE, Fe, Ni, Co, Cu, One or more in Mn, Zn, Sn, Bi and Ga.The BEA structure molecular screens can be the BEA structure molecular screens of sodium form, Can be the modification BEA structure molecular screens being modified by sodium form BEA structure molecular screens, such as Hydrogen BEA structure molecular screens, ammonium Type BEA structure molecular screens, phosphorous and/or transition metal BEA structure molecular screens, wherein the transition metal such as RE, Fe, BEA structure molecular screens described in one or more in Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga are, for example, beta-molecular sieve, Ke Yishi Sodium form beta-molecular sieve or the modified beta molecular sieve obtained by the process modification of sodium form beta-molecular sieve, such as H β, NH4Beta-molecular sieve, The modified beta-molecular sieves of one or more in phosphorus and/or transition metal, the transition metal such as RE, Fe, Ni, Co, Cu, One or more in Mn, Zn, Sn, Bi and Ga.The ferrierite such as Fer molecular sieves, can be sodium form Fer molecules Sieve or by sodium form Fer molecular sieves by modified obtained MODIFIED Fe r molecular sieves, such as HFer, NH4Fer molecular sieves, The modified Fer molecular sieves of one or more in phosphorus and/or transition metal, the transition metal such as RE, Fe, Ni, Co, One or more in Cu, Mn, Zn, Sn, Bi and Ga.
Preferably, in the catalytic cracking catalyst, the Y type molecular sieve and aperture are less thanMolecular sieve Weight ratio be 1:8~4:0.1 or 0.3:1~20:1 or 0.15:1~1:1 or 1:4~4:0.1 or 0.3:1~20:1 or 1： 6.5~1：2.
The present invention also provides a kind of preparation method of the catalytic cracking catalyst, including preparation to include Y type molecular sieve, hole Footpath is less thanMolecular sieve, natural mineral matter, the microspheroidal composition of adhesive oxides, the present invention be known as first combination Thing microballoon, by the microsphere modified processing of the first chamber；The microsphere modified processing of the first chamber is included the following steps：
A, first chamber microballoon is put into alkaline solution and is handled, filtered and wash, obtain first group of alkali process Compound microballoon；
B, the alkali process first chamber microballoon obtained by step a is answered what is be made of fluosilicic acid, organic acid and inorganic acid Closing and handled in acid solution, filter and wash, optional ammonium, which exchanges, washes sodium processing, optionally filtering and optionally washing, optionally drying, Obtain being rich in mesoporous composition microballoon.
C, phosphorus additive is introduced in rich in mesoporous composition microballoon；
D, when calcination process at least 0.5 is small at 400~800 DEG C.
In catalytic cracking catalyst preparation method provided by the invention, the alkaline solution includes alkali compounds, Preferably, the alkali compounds is strong basicity inorganic compound, for example, the alkali compounds is sodium hydroxide, hydroxide One or more in potassium, lithium hydroxide, ammonium hydroxide, high alkali deflection aluminium acid sodium.Alkaline solution selects used in described step a From sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide be molten, in Ammonia, high alkali deflection aluminium acid sodium solution at least It is a kind of.The alkaline solution is preferably the aqueous solution of alkali compounds.
The catalytic cracking catalyst preparation method provided according to the present invention, alkaline solution preferably includes used in step a High alkali deflection aluminium acid sodium, is preferably high alkali deflection aluminium acid sodium solution.Preferably, in the high alkali deflection aluminium acid sodium solution, Na2O content For 270~310g/L, Al2O3Content is 30~50g/L, and solution density is 1.25~1.45g/mL.
The catalytic cracking catalyst preparation method provided according to the present invention, is handled described in step a：Including first is combined Thing microballoon is contacted with alkaline solution, wherein the alkaline solution includes alkali compounds, with the first combination of dry basis Thing microballoon with (ammonium hydroxide is with NH in terms of alkali metal oxide3Meter) alkali compounds weight ratio be 1:(0.01~ 0.35).Preferably, by the first chamber microballoon of dry basis and in terms of alkali metal oxide, (ammonium hydroxide is with NH3Meter) Alkali compounds weight ratio be 1：(0.05~0.25) or it is 1：(0.01~0.15).
Catalytic cracking catalyst preparation method provided by the invention, in being handled described in step a：With the of dry basis The weight ratio of one composition microballoon and water is 1：(5-20).
Catalytic cracking catalyst preparation method provided by the invention, in being handled described in step a：The temperature of the processing is 25 to 100 DEG C are preferably 30~80 DEG C or 45~65 DEG C, and processing time is when for example, 0.2-6 is small within more than 10 minutes or 0.2-4 Hour or 0.3~3 it is small when.
In catalytic cracking catalyst preparation method provided by the invention, in step b, by the alkali process the of gained in step a One composition microballoon is handled in the solution for the Compound-acid being made of fluosilicic acid, organic acid and inorganic acid, and the processing is The alkali process first chamber microballoon is contacted with the compound aqueous acid formed containing fluosilicic acid, organic acid and inorganic acid, Time of contact is, for example, more than 10 minutes, when being, for example, 0.2~10 small or when 0.5~6 is small, filtering, and optionally washing.It is obtained by filtration Filter cake or washing after filter cake, can also be contacted with ammonium salt solution, carry out ammonium exchange washes sodium processing so that obtained catalysis Sodium oxide molybdena is preferably more than 0.15 weight % no more than 0.2 weight % in agent.The ammonium salt can be common ammonium salt, example Such as, selected from least one of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate and ammonium nitrate.
In step b, the temperature of the processing is 25~100 DEG C, is, for example, 30~80 DEG C or 45~65 DEG C.
Catalytic cracking catalyst preparation method according to the present invention, wherein, organic acid may be selected from ethylenediamine described in step b At least one of tetraacethyl, oxalic acid, acetic acid, citric acid and sulfosalicylic acid are preferably oxalic acid, and the inorganic acid may be selected from salt At least one of acid, sulfuric acid and nitric acid are preferably hydrochloric acid.
In catalytic cracking catalyst preparation method provided by the invention, the condition handled described in step b is：With dry basis The first chamber microballoon of gauge, fluosilicic acid, the weight ratio of inorganic acid and organic acid are 1:(0.003~0.3):(0.01~ 0.45):(0.01~0.55).
Preferably, in catalytic cracking catalyst preparation method provided by the invention, the condition handled described in step b is： Using the weight ratio of the first chamber microballoon of dry basis, fluosilicic acid, organic acid and inorganic acid as 1:(0.005~0.3): (0.02~0.3):(0.02~0.3) or 1:(0.005~0.17):(0.015~0.15):(0.02~0.15) or 1:(0.005 ~0.1):(0.02~0.2):(0.02~0.15).The weight ratio of fluosilicic acid and first chamber microballoon is preferably, (0.005~ 0.3)：1 or (0.005~02)：1 or (0.005~0.17)：1 or (0.005~0.1)：1；Organic acid and first chamber microballoon Weight ratio be preferably (0.02~0.3)：1 or (0.015~0.15)：1 or (0.02~0.2)：1；Inorganic acid is combined with first The weight ratio of thing microballoon is preferably (0.01~0.2)：1 (or 0.02~0.3)：1 or (0.02~0.15)：1 or (0.02~ 0.15)：1.
In catalytic cracking catalyst preparation method provided by the invention, in step b, water and described first in terms of butt The weight ratio of composition microballoon is 3~20：1 is, for example, 4~15：1 or 5~10：1.
Catalytic cracking catalyst preparation method according to the present invention, wherein, sodium exchange process is washed in ammonium exchange described in step b makes Being contacted with ammonium salt solution with the composition obtained by compound acid treatment, the ammonium salt can be common ammonium salt, For example, selected from least one of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, sodium acetate and ammonium nitrate.Ammonium salt is exchanged and washed Filtered after sodium processing, optionally washing, to wash away the ammonium salt for exchanging sodium and do not exchange in catalyst.Such as ammonium exchanges and washes sodium In, the weight ratio of ammonium salt solution and the composition obtained by compound acid treatment is 5~20：1, the concentration of ammonium salt solution For 1~10 weight %, Contact Temperature is 30~80 DEG C, when time of contact is 0.5~2 small.
In catalytic cracking catalyst preparation method provided by the invention, the washing described in step b is conventional method, such as It is 1 according to first chamber microballoon and water weight ratio：5~10 weight ratio is eluted with water.The usual washing, makes washing Cleaning solution afterwards is neutrality, such as pH value is 6~8.
Phosphorus additive is introduced in catalytic cracking catalyst preparation method provided by the invention, described in step c to be included will be enriched in Mesoporous composition microballoon is contacted with phosphorus-containing compound.By carrying out the contact, to be impregnated and/or ion exchange is being urged Phosphorus additive is introduced in agent.Phosphorus additive can by it is one or many contact with composition it is described rich in mesoporous to be incorporated into In composition microballoon.The composition introduced after additive carries out introducing addition in addition once again after can drying and/or roasting Agent contact process, dry and roasting method is existing method, for example, can be roasted at 350~650 DEG C 0.5~8 it is small when.
In catalytic cracking catalyst preparation method provided by the invention, the method for phosphorus additive is introduced described in step c to be included With phosphorus-containing compound to being impregnated rich in mesoporous composition microballoon and/or ion exchange.The phosphorus-containing compound may be selected from One or more in phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.
Catalytic cracking catalyst preparation method according to the present invention, the condition of calcination process includes described in step d：At roasting The atmosphere of reason is air atmosphere, nitrogen atmosphere or steam atmosphere or the mixture atmosphere of above-mentioned atmosphere；Calcination temperature is 400- 800 DEG C, when roasting time is 0.5-8 small.Preferably, when calcination process 0.5~8 is small at 500~600 DEG C.
The method according to the invention, the calcination process process described in step d can be wet roastings, described wet roasting be 1~ Under 100 volume % water vapours (the vapor % i.e. containing 1~100 volume in atmosphere), more preferably 100% steam atmosphere into OK.
Catalytic cracking catalyst provided by the invention can be used for hydrocarbon oil catalytic cracking production low-carbon alkene, hydrocarbon oil catalytic cracking Produce the step of method of low-carbon alkene is included hydrocarbon ils and catalytic cracking catalyst haptoreaction provided by the invention.Reaction Condition refers to the condition of existing producing low-carbon alkene by catalytic pyrolysis.The hydrocarbon ils can be petroleum hydrocarbon, can be that part evaporates Divide petroleum hydrocarbon or full cut petroleum hydrocarbon.The hydrocarbon ils such as reduced crude, decompression residuum, catalytic cracking gently circulate Oil, heavy catalytic cycle oil, solvent-deasphalted oils, lube oil finishing be oily and above-mentioned hydrocarbon ils is obtained by hydrotreating plus One or more in hydrogen processing oil.
Catalytic cracking catalyst provided by the invention, has abundant meso-hole structure, has higher stability；For weight Matter petroleum hydrocarbon catalytic pyrolysis reacts, and conversion ratio is higher, the high income of propylene, BTX high incomes.Catalytic pyrolysis provided by the invention is urged Agent is used for heavy oil catalytic cracking, and more existing catalyst for cracking has the cracking hydrocarbon oil cracking activity of higher, has higher propylene Yield and BTX yields, have the Propylene Selectivity of higher.Catalytic cracking catalyst preparation method provided by the invention, using hole The molecular sieve and adhesive oxides of molecular sieve of the footpath less than 6.9 angstroms and Y type molecular sieve or two or more apertures less than 6.9 angstroms And natural mineral matter, be first made microsphere composition, then by alkali, sour coupling processing method to the pore passage structure and acid of catalyst Property carry out further modulation, make catalyst that there is the specific surface area of bigger and the mesopore volume of higher, appropriate mesoporous acidity, P Modification is carried out again after making carbon monoxide-olefin polymeric, can improve the performance of whole catalyst, improves the stability of catalyst And propylene and BTX selectivity, moreover it is possible to improve efficiency of the phosphorus to catalyst modification.
Embodiment
In catalytic cracking catalyst provided by the invention, containing natural mineral matter, wherein the natural mineral matter is for example Kaolin, halloysite, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and tired support One or more mixtures in soil etc..On the basis of catalyst total amount, percentage by weight meter, catalyst provided by the invention Middle natural mineral matter is preferably that 8~60 weight % are, for example, the weight of 15 weight %~60 using the content that butt is counted as 5~65 weight % Measure the weight % of % or 8~45 weight % or 20 weight %~55.
In catalytic cracking catalyst provided by the invention, containing adhesive oxides component, the oxide is oxidation Mixture more than one or both of silicon, aluminium oxide, zirconium oxide, titanium oxide, amorphous silica-alumina and aluminum phosphate material, institute It is molten certainly in the dissolved colloidal state material of its corresponding oxide precursor such as oxide, such as Ludox, aluminium to state adhesive oxides One or more in glue, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.On the basis of catalyst total amount, with Weight percent oxide meter, the contents of adhesive oxides are preferably the weight of 15 weight %~55 for the weight % of 10 weight %~60 Amount % is, for example, the weight % of the weight % or 20~50 weight % or 25~50 weight % or 12 weight % of 10 weight %~30~28.
In catalytic cracking catalyst provided by the invention, containing the first molecular sieve, first molecular sieve is Y type molecules Sieve and aperture are less thanMolecular sieve, the Y type molecular sieve is molecular sieve for catalytic cracking catalyst, the Y Type molecular sieve is, for example, DASY molecular sieves, the DASY molecular sieves containing rare earth, USY molecular sieve, the USY molecular sieve containing rare earth, REY point Sub- sieve, REHY molecular sieves, at least one of HY molecular sieves.Under preferable case, Y type molecular sieve and aperture are less thanMolecule The weight ratio of sieve is 1:8~4:0.1 or 0.3:1~20:1 or 0.15:1~1:1 or 1:4~4:0.1 or 1：3~15：1.State The content of one molecular sieve is preferably that 25~65 weight % are, for example, 30~55 weight % or 30~65 weight % or are 30~55 weights Measure % or 35~50 weight %.
The aperture is less thanMolecular sieve for MFI structure molecular sieve, IMF structure molecular screens, BEA structural molecules At least one of sieve, ferrierite.The MFI structure molecular sieve can be sodium form MFI structure molecular sieve or have Sodium form MFI structure molecular sieve passes through the MFI structure molecular sieve that various method of modifying obtain, such as the ammonium type exchanged by ammonium One or more modification MFI structures in MFI structure molecular sieve, Hydrogen MFI structure molecular sieve, phosphorous and/or transition metal Molecular sieve；MFI structure molecular sieve such as ZSM-5 can be NaZSM-5 or be to be obtained by NaZSM-5 molecular sieves by modification Molecular sieve, such as HZSM-5, NH4ZSM-5, phosphorous and/or transition metal ZSM-5；The wherein described transition metal is for example One or more in RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.The IMF structure molecular screens can be sodium form IMF Structure molecular screen or IMF structure molecular screens pass through the modification IMF structure molecular screens that various method of modifying are modified, Such as one or more IMF in ammonium type IMF structure molecular screens, Hydrogen IMF structure molecular screens, phosphorous and/or transition metal Structure molecular screen, the one or more in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.Institute The IMF structure molecular screens such as IM-5 stated, can be Na types IM-5 or pass through modified obtained modification by NaIM-5 IM-5 molecular sieves, such as Hydrogen IM-5, NH4IM-5, phosphorous and/or transition metal IM-5, the transition metal such as RE, One or more in Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.The BEA structure molecular screens are, for example, beta-molecular sieve, can To be sodium form beta-molecular sieve or pass through modified obtained modified beta molecular sieve, such as H β by sodium form beta-molecular sieve.Described Ferrierite such as Fer molecular sieves, can be sodium form Fer molecular sieves or be obtained by sodium form Fer molecular sieves by modification MODIFIED Fe r molecular sieves, such as HFer, NH4The Fer that one or more in Fer molecular sieves, phosphorus and/or transition metal are modified Molecular sieve, the one or more in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.Described Aperture is less thanMolecular sieve be preferably that sodium form, Hydrogen or ammonium type aperture are less thanMolecular sieve.
Sodium form IMF structure molecular screens are well-known to those skilled in the art, commercially available can also can voluntarily be prepared, example Such as, the preparation process of the sodium form IMF structure molecular screens includes：To use has IMF structure molecular screen slurries obtained by amine method crystallization After being filtered and being washed, washing molecular sieve is obtained；Wherein, in terms of sodium oxide molybdena and with total butt weight of the washing molecular sieve On the basis of, the sodium content in the washing molecular sieve is less than 3.0 weight %；The washing molecular sieve is dried and is roasted with air After burning, the sodium form IMF structure molecular screens are obtained.The IMF structure molecular screens, preferably there is the molecule that amine method crystallization obtains Sieve, it is described to there is amine method crystallization to refer to that carrying out hydrothermal crystallizing using template prepares molecular sieve, by taking the preparation of IMF molecular sieves as an example, Specific document may be referred to Chinese patent CN102452667A, CN103708491A, CN102452666A and CN103723740A. The air roasting is used to remove the template in washing molecular sieve, and the temperature of the air roasting can be 400-700 DEG C, when Between can be 0.5-10 it is small when.
Adjuvant component can also be contained in Cracking catalyst provided by the invention.In terms of butt, the content of adjuvant component does not surpass 30 weight % are crossed, are, for example, 0~30 weight % or 0.5~25 weight %.The adjuvant component such as desulfurizing assistant agent component, take off At least one of nitre adjuvant component, combustion adjuvant component.
The second molecular sieve can also be contained in Cracking catalyst provided by the invention, second molecular sieve is except institute Other molecular sieves outside the first molecular sieve are stated, these molecular sieves are usually used as catalytic cracking catalyst active component.Described The content of two molecular sieves is 0~20 weight %.Other molecular sieves such as SAPO molecular sieve, MCM molecular sieves.
In catalytic cracking catalyst preparation method provided by the invention, first prepare and be less than including Y type molecular sieve, apertureMolecular sieve (also referred to as aperture be less than 0.69nm molecular sieve), natural mineral matter, adhesive oxides microspheroidal combination Thing, is then modified processing.Preparation includes Y type molecular sieve, aperture is less thanMolecular sieve, natural mineral matter, oxide The microspheroidal composition of binding agent can pass through：The first molecular sieve such as Y type molecular sieve, aperture is less thanPoint It is prepared by sub- sieve, natural mineral matter, adhesive oxides component precursor and water mashing, spray drying, the method optionally roasted Obtain, the microspheroidal composition present invention is known as first chamber microballoon.The spray drying and the prior art is roasted to, this Invent no particular/special requirement.Such as the temperature of roasting can be 300~650 DEG C or 350~500 DEG C, roasting time can be 0.5 ~10 it is small when.It can be roasted under air atmosphere, nitrogen atmosphere, steam-laden atmosphere.
The preparation method of the catalytic cracking catalyst provided by the invention, including by natural mineral matter, the first molecular sieve It is mixed with beating with the colloidal sol of adhesive oxides such as oxide and/or the gel and water of oxide.It is catalyzed with catalytic pyrolysis On the basis of agent gross weight, the dosage of each component makes to contain in finally obtained catalytic cracking catalyst, the weight of 5 weight %~65 Measure the natural mineral matter of %, the first molecule of the weight % of the oxide of the weight % of 10 weight %~60 and 24 weight %~75 Sieve.The dosage of more preferably each component makes the composition of final catalyst be to include：Natural mineral matter content is counted as 5 weight % using butt ~50 weight % are, for example, 8~45 weight %, and the content of first molecular sieve is counted as the weight % of 30 weight %~65 using butt For example, 30~55 weight %, the content of adhesive oxides is counted as 15~55 weight % such as 20~50 weight % using oxide Or the weight % of 25~45 weight % or 20~35 weight % or 12 weight %~28.
The preparation method of the catalytic cracking catalyst provided by the invention, the natural mineral matter include kaolin, In halloysite, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite etc. One or more mixtures.In the catalytic cracking catalyst that the dosage of natural mineral matter makes, using catalyst total amount as base Standard, by weight percentage, the content of natural mineral matter is the weight % of 5 weight %~65, the weight % of such as 20 weight %~55 Or the weight of 8~45 weight % or 8~60 weight % or 15 weight %~60.
The preparation method of the catalytic cracking catalyst provided by the invention, the adhesive oxides precursor are selected from One or both of silica, aluminium oxide, zirconium oxide, titanium oxide, amorphous silica-alumina and aluminum phosphate material colloidal sol or gel Mixture above, the adhesive oxides precursor such as Ludox, Aluminum sol, peptization boehmite, silicon-aluminum sol And the one or more in phosphorated aluminiferous collosol.The dosage of adhesive oxides precursor, so as to get catalytic cracking catalyst In, on the basis of catalyst total amount, in terms of weight percent oxide, the contents of adhesive oxides is the weight of 10 weight %~60 Amount % is, for example, the weight % or 20~50 weight % of the weight % or 15 weight % of 15 weight %~55~35 or 12 weight %~28 Weight %.
The preparation method of the catalytic cracking catalyst provided by the invention, the first molecular sieve dosage (Y type molecular sieve and Aperture is less thanMolecular sieve dosage or two or more apertures be less thanMolecular sieve dosage) urging of making Change in catalyst for cracking, the content of the first molecular sieve counted using butt is the weight % of 24 weight %~75, preferably 30~70 weight It is, for example, 30~55 weight % or 30-55 weight % to measure % or 25~65 weight %.Wherein Y type molecular sieve aperture is less than Molecular sieve ratio be 1:8~4:0.1 or 0.3:1~20:1 or 0.15:1~1:1 or 1:4~4:0.1 or 1：3~15：1. The Y type molecular sieve such as DASY molecular sieves, be the DASY molecular sieves containing rare earth, USY molecular sieve, the USY molecules containing rare earth Sieve, REY molecular sieves, REHY molecular sieves, the one or more of HY molecular sieves.
The preparation method of the catalytic cracking catalyst provided by the invention, the aperture are less thanMolecular sieve For at least one of MFI structure molecular sieve, IMF structure molecular screens, BEA structure molecular screens, ferrierite.The MFI knots Structure molecular sieve can be sodium form MFI structure molecular sieve or be obtained by sodium form MFI structure molecular sieve by various method of modifying The MFI structure molecular sieve arrived, for example, exchanged by ammonium ammonium type MFI structure molecular sieve, Hydrogen MFI structure molecular sieve, contain One or more modification MFI structure molecular sieves in phosphorus and/or transition metal；The MFI structure molecular sieve such as ZSM- 5th, the one or more in ZSP, ZRP molecular sieve, ZSM-5 molecular sieve can be NaZSM-5 or be to have NaZSM-5 molecular sieves By modified obtained molecular sieve, such as HZSM-5, NH4ZSM-5 is phosphorous and/or the ZSM-5 of transition metal；The wherein described mistake Cross the one or more in metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.The IMF structure molecular screens can To be modification IMF that sodium form IMF structure molecular screens or IMF structure molecular screens pass through that various method of modifying are modified One kind in structure molecular screen, such as ammonium type IMF structure molecular screens, Hydrogen IMF structure molecular screens, phosphorous and/or transition metal Or a variety of IMF structure molecular screens, one in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga Kind is a variety of.Such as IM-5, it can be Na types IM-5 or modified obtained modification IM-5 molecules are passed through by NaIM-5 Sieve, such as Hydrogen IM-5, NH4IM-5, phosphorous and/or transition metal IM-5, the transition metal such as RE, Fe, Ni, One or more in Co, Cu, Mn, Zn, Sn, Bi and Ga.The BEA structure molecular screens are, for example, beta-molecular sieve, can be sodium Type beta-molecular sieve or the modified beta molecular sieve obtained by the process modification of sodium form beta-molecular sieve, such as H β, NH4Beta-molecular sieve, phosphorus And/or the beta-molecular sieves that one or more in transition metal are modified, the transition metal such as RE, Fe, Ni, Co, Cu, Mn, One or more in Zn, Sn, Bi and Ga.The ferrierite such as Fer molecular sieves, can be sodium form Fer molecular sieves, Can be by modified obtained MODIFIED Fe r molecular sieves such as HFer, NH by sodium form Fer molecular sieves4Fer molecular sieves, phosphorus and/or The modified Fer molecular sieves of one or more in transition metal, the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, One or more in Sn, Bi and Ga.The aperture is less thanMolecular sieve be preferably sodium form, Hydrogen or ammonium type aperture It is less thanMolecular sieve.
Method for preparing catalyst provided by the invention, it is preferred that in the first chamber microballoon in terms of butt natural ore deposit Material, the in terms of butt first molecular sieve, in terms of oxide adhesive oxides weight ratio 5~65：24~75：10~60, it is excellent Elect 8~55 as：30~65：15~55 more preferably 8~45：30~55：20~50.Preferably, the first chamber microballoon Natural mineral matter containing in terms of butt 5%~65%, in terms of oxide 10%~60% adhesive oxides and with butt First molecular sieve of meter 24%~75%, it is preferred that on the basis of the weight of the first chamber microballoon, first combination Thing microballoon contains the weight % of the natural mineral matter of the weight % of in terms of butt 8 weight %~55, in terms of oxide 15 weight %~55 Adhesive oxides and the weight % of in terms of butt 25 weight %~55 the first molecular sieve.It is furthermore preferred that first combination Thing microballoon contains natural mineral matter, 20~50 weight in terms of oxide of in terms of butt 8~45 weight % such as 20~45 weight % The adhesive oxides of amount % such as 10%~30% and the first of in terms of butt 30~55 weight % such as 35~50 weight % Molecular sieve.
Method for preparing catalyst provided by the invention, a kind of embodiment, by the precursor of inorganic oxide binder, example Such as the mixture of boehmite, Aluminum sol, Ludox, silicon-aluminum sol, silica-alumina gel or wherein two or more, with natural ore deposit Material such as kaolin and water (such as decationized Y sieve water and/or deionized water) mix, and are configured to solid content as 10~50 The slurries of weight %, stir evenly, slurries pH optionally are adjusted to 1~4 for example with inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid 2-3, stirs evenly, optionally at 20~80 DEG C stand 0~2 it is small when after such as 0.3~2 it is small when then add the first molecular sieve, First molecular sieve is less than for apertureMolecular sieve and Y type molecular sieve or be less than for apertureMolecular sieve in It is two or more, stir evenly, formed first chamber slurries, first chamber slurry solid content is, for example, 20~45 weight, Microspheroidal composition is made in spray drying.Then by the roasting of microspheroidal composition for example in 300~650 preferably 350~550 DEG C roastings When burning 0.5~6 is small, first chamber microballoon is obtained.If the catalytic cracking catalyst includes adjuvant component and/or Two molecular sieves, also contain adjuvant component and the second molecular sieve, adjuvant component and the second molecule in the first chamber slurries Sieve can be before spray drying any step be incorporated into slurries.
Washing of the present invention is well-known to those skilled in the art, and no specified otherwise, refers generally to wash, for example, can To be eluted using the water of 5-10 times of molecular sieve to molecular sieve.
Catalytic cracking catalyst preparation method provided by the invention, is rich in mesoporous combination in step c what step b was obtained Phosphorus additive is introduced in thing microballoon.Preferably, it is described to be introduced into the phosphorus additive content made in obtained catalytic cracking catalyst With P2O50.1-15 weight % are calculated as, are, for example, 1~13 weight % or be 1.5~8 weight % or 0.5-6.5 weight % or 2~5 Weight %.
Catalytic cracking catalyst preparation method provided by the invention, prepared catalytic cracking catalyst, has more Mesoporous Bronsted acid, the ratio that mesoporous Bronsted acid amount accounts for total acid content are 20%~70% for example, 25%~65%, it is preferred that for example Can be 25%~50% or 30~55%.
Catalytic cracking catalyst preparation method provided by the invention, prepared catalytic cracking catalyst, total specific surface area More than 240m2/ g, such as total specific surface area (also referred to as specific surface area) is 240~350m2/ g is, for example, 250~320m2/g。
Catalytic cracking catalyst preparation method provided by the invention, the mesopore volume of the catalytic cracking catalyst account for total hole The ratio of volume is, for example, 40%~60% or 45%~58% or 35~45% for 35%~60%.The catalyst it is mesoporous Volume is 0.14~0.35ml/g such as 0.15~0.30ml/g or 0.25~0.35ml/g or 0.15~0.32ml/g.
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.Used by the embodiment of the present invention instrument and Reagent, is the common instrument of those skilled in the art institute and reagent unless otherwise instructed.
Influence of the catalytic cracking catalyst in petroleum hydrocarbon catalytic pyrolysis to productivity of propylene and BTX yields uses feedstock oil ACE is evaluated.Method is as follows：By catalyst carry out 800 DEG C, 100% steam aging 15 it is small when in fixed fluidized bed micro- anti-ACE On evaluated, feedstock oil is hydrotreating oil (composition and physical property be shown in Table 3), and appreciation condition be 530 DEG C of reaction temperature, and regeneration is warm 620 DEG C of degree, oil ratio is 5 (weight ratios).
The specific surface area of the present invention is measured using GBT5816-1995 standard methods.
The pore volume of the present invention is measured using GB/T5816-1995 standard methods.
The total acid content of the present invention uses NH3- TPD methods are measured, referring to the research method of solid catalyst, oil Work, 30 (12), 2001：952.
The mesoporous Bronsted acid of the present invention adsorbs infrared acid process measure using 2,6 di tert butyl pyridine.Specific method For：Catalyst is pressed into 10mg/cm2Thin slice, be put into band CaF2In the infrared pond of window.First vacuumize at 400 DEG C, then drop to 150 DEG C of absorption 2,6- di-tert-butyl pyridines 15 minutes, then vacuumize 1 it is small when.Drop to room temperature collection spectrogram.And calculate Bronsted acid Amount.Referring to Applied Catalysis A:General, 294,2005：92.
The Na of the present invention2O、P2O5Content is measured using GB/T 30905-2014 standard methods.
RIPP standard methods of the present invention for details, reference can be made to《Petrochemical Engineering Analysis method》, Yang Cui surely compile by grade, and 1990 Year version.
The following examples illustrate catalyst provided by the invention and preparation method thereof, the wherein property of raw materials such as Under：Kaolin (Suzhou China Kaolin Co., Ltd, 75 weight % of solid content), montmorillonite (red stone swelling God in charge of the Earth in Chaoyang City, Liaoning Province Department, 75 weight % of solid content), (asphalt in Shenli Refinery of Sinopec Catalytica Inc., alumina content are Aluminum sol 22.5 weight %), Ludox (Qingdao Marine Chemical Co., Ltd., 25.5 weight % of silica content, pH value 3.0), IM-5 points (Chang Ling branch company of Sinopec Catalytica Inc. produces son sieve, there is the synthesis of amine method, sodium form (2.5 weight of sodium oxide content Measure %, silica alumina ratio 30), ZSM-5 molecular sieve (asphalt in Shenli Refinery of Sinopec Catalytica Inc., NaZSM-5, sial Than for 45), Beta molecular sieves (catalyst asphalt in Shenli Refinery produces, H β, silica alumina ratio 30), (Sinopec is catalyzed REY molecular sieves Asphalt in Shenli Refinery of agent limited company, content of rare earth are 10 mass %, silica alumina ratio 4.9), USY molecular sieve (urge by Sinopec Asphalt in Shenli Refinery of agent limited company, content of rare earth is (with RE2O3Meter) it is 1.5 weight %, silica alumina ratio SiO2/Al2O3Mole Than for 5.8).ZRP-1 molecular sieves, asphalt in Shenli Refinery of Sinopec Catalytica Inc. product, (present invention refers to silica alumina ratio SiO2/Al2O3Molar ratio) it is 40.
Solid content is the solid product amount that material is obtained when 800 DEG C of roastings 1 are small and the weight ratio of material.
Embodiment 1
267g Aluminum sols are mixed with 180g kaolin, and it is 30 weight % to be configured to solid content with decationized Y sieve water Slurries, when stirring 2 is small after add 15gUSY, 45g beta-molecular sieve and 45gZRP-1 molecular sieves, form composition slurries (solid content For 35 weight %), stir evenly, composition microballoon is made in spray drying, then that said composition microballoon is small in 500 DEG C of roastings 2 When, first chamber microballoon A1 is made.
Take first chamber microballoon A1 (butt quality, similarly hereinafter) 200g made above, add water be beaten solid content be 10 The slurries of weight %, add 15.1g high alkali deflection aluminium acid sodium solution (Na2O is 290g/L, Al2O3For 40g/L, solution density is 1.353g/mL), 50 DEG C of constant temperature stirring 0.5h are warming up to, filtering, washing to neutrality (wash to neutrality the cleaning solution referred to after washing For neutrality, pH6~8)；By filter cake plus water be beaten solid content be 10 weight % slurries, in stirring add 6.2g oxalic acid, then 54g hydrochloric acid (HCl mass fractions 10%) and 33.4g silicate fluoride solutions (3 weight % of concentration) are added, is warming up to 50 DEG C of constant temperature stirrings 1h, filtering, washing to neutrality obtain filter cake；By filter cake plus water be beaten solid content is that 40 weight % are rich in mesoporous composition Microballoon slurries, by 14.6gH3PO4(85 weight % of concentration) is dissolved in 60g water, is mixed with rich in mesoporous composition microballoon slurries Dipping, drying；Gained sample is when 550 DEG C of calcination process 2 are small, up to catalytic cracking catalyst A provided by the invention.Catalyst The physico-chemical property of sample A is listed in table 1, after 800 DEG C, 15h, 100% vapor aging, carries out feedstock oil ACE evaluations, as a result Table 2 is listed in, evaluation is listed in table 3 with the property of feedstock oil.
Embodiment 2
333.3g Aluminum sols are mixed with 100g montmorillonites, and it is 21.5 weights to be configured to solid content with decationized Y sieve water Measure the slurries of %, when stirring 0.5 is small after add 20gREY types molecular sieve and 130gZSM-5 molecular sieves, stir evenly, form first Composition microballoon is made in composition slurries (solid content is 35% weight), spray drying, then by composition microballoon in 350 DEG C of roastings Burn 2 it is small when, obtain first chamber microballoon B1.
First chamber microballoon B1 (butt quality) 200g made above is taken, adds water to be configured to 10 weight %'s of solid content First chamber microballoon slurries, add 20.5gNaOH (purity 96%), are warming up to 70 DEG C of constant temperature stirring 0.3h, filtering, washing are extremely It is neutral；By filter cake plus water be beaten solid content be 10 weight % slurries, in stirring add 25.1g oxalic acid, then add 38g salt Sour (HCl mass fractions 10%) and 55g silicate fluoride solutions (3 weight % of fluosilicic acid concentration), are warming up to 80 DEG C of constant temperature stirring 0.8h, Filtering, washing obtain filter cake；Filter cake plus water are beaten, obtain the slurries JY2 that solid content is 40 weight %；In 11.37g H3PO4It is (dense Spend 85 weight %) in add 90g water, with slurries JY2 be mixed with dipping drying, through 550 DEG C of calcination process 2 it is small when；I.e. the present invention carries The catalytic cracking catalyst B of confession.The physico-chemical property of catalyst sample B is listed in Table 1 below, by 800 DEG C, 15h, 100% vapor After aging, feedstock oil ACE evaluations are carried out with the feedstock oil shown in table 3, the results are shown in table 2.
Embodiment 3
353g Ludox is mixed with 80g montmorillonites, and solid content is configured to as 30 weight %'s with decationized Y sieve water Slurries, add 30g ZRP-1 types molecular sieve, 75gIM-5 molecular sieves and 45g beta-molecular sieves, stir evenly, and form first chamber Microsphere composition is made in slurries (solid content is 35% weight), spray drying.Then microsphere composition is roasted into 1-2 at 350 DEG C Hour, obtain first chamber microballoon C1.
First chamber microballoon C1 (butt quality) 200g made above is taken, adds water to be configured to the of 10 weight % of solid content One composition microballoon slurries, add 33.1gKOH (purity 96%), are warming up to 60 DEG C of constant temperature stirring 1h, filtering, is washed to neutrality； By filter cake plus water be beaten solid content be 20 weight % slurries, in stirring add 34.2g oxalic acid, 120g salt is then slowly added dropwise Sour (HCl mass fractions 10%) and 667g silicate fluoride solutions (3 weight % of concentration), are warming up to 70 DEG C of constant temperature stirring 2h, filtering, is washed Wash, be dry, add water be beaten solid content be 40 weight % slurries JY3；By 4.65g (NH4)2HPO4It is dissolved in 180g water, with Slurries JY3 is mixed with dipping, drying；Gained sample is when 550 DEG C of calcination process 2 are small, i.e., catalyst C provided by the invention.Catalysis The physico-chemical property of agent sample C；After 800 DEG C, 15h, 100% vapor aging, feedstock oil is carried out with the feedstock oil shown in table 3 ACE is evaluated, and the evaluation result such as conversion ratio, gas recovery ratio, amount of coke is listed in table 2.
Embodiment 4
Catalyst B1 (butt quality) 200g made above is taken, adds water to be configured to the slurries of 10 weight % of solid content, adds Enter 21.2gNaOH (purity 96%), be warming up to 90 DEG C of constant temperature stirring 2h, filtering, wash to neutrality；Filter cake plus water, which are beaten, to be consolidated Content is the slurries of 10 weight %, and 5.6g citric acids are added in stirring, then adds 188g hydrochloric acid (10 weights of HCl mass fractions Measure %) and 90g silicate fluoride solutions (3 weight % of fluosilicic acid concentration), 5.5h is stirred in 30 DEG C of constant temperature, filters, wash, be dried to obtain Rich in mesoporous composition DJ4；By 21.13gH3PO4(concentration 85%) is added in 160g water, and rich in mesoporous composition DJ4 It is mixed with dipping, drying；Gained sample is when calcination process 2 is small under 550 DEG C, 100% water vapour atmosphere, i.e., provided by the invention to urge Change catalyst for cracking D.The physico-chemical property of catalyst sample D；After 800 DEG C, 100% vapor aging 15h, feedstock oil ACE The evaluation results such as evaluation, conversion ratio, gas recovery ratio, amount of coke are listed in table 2.
Embodiment 5
353g Ludox is mixed with 80g montmorillonites, and it is 10~50 weights to be configured to solid content with decationized Y sieve water Measure the slurries of %, when stirring 1 is small after add 45gUSY types molecular sieves, 75g ferrierites and 30g ZSM-5 molecular sieves, stirring is equal It is even, composition slurries (solid content is 35% weight) are formed, spray drying is made microspheroidal composition, then combines microspheroidal Thing obtains first chamber microballoon D1 when 350 DEG C of roastings 2 are small.
Take it is made above urge first chamber microballoon D1 (butt quality) 200g, add water to be configured to 10 weight % of solid content First chamber microballoon slurries, add 38.1gNaOH (purity 96%), 30 DEG C of constant temperature stir 3h, and filtering, is washed to neutrality； By filter cake plus water be beaten solid content be 20 weight % alkali process composition slurries, in stirring add 7.1g citric acids, then 70g hydrochloric acid (10 weight % of HCl mass fractions) and 35g fluosilicic acid (3 weight % of concentration) are added, is warming up to 50 DEG C of constant temperature stirrings 1h, is filtered, washing, be dried to obtain it is dry after filter cake, add water be beaten solid content be 40 weight % slurries JY5；By 1.49g (NH4)2HPO4It is dissolved in 90g water, is mixed with dipping with the slurries JY5, drying；At 550 DEG C, 100 volume % water steam gained sample When calcination process 2 is small under vapour atmosphere, i.e., catalytic cracking catalyst E provided by the invention.The physico-chemical property of catalyst sample E is shown in Table 1, after 800 DEG C, 15h, 100% vapor aging, feedstock oil ACE evaluation, evaluation result for example conversion ratio, gas recovery ratio, Amount of coke etc. is listed in table 2.
Comparative example 1
In this comparative example basic process according to embodiment 1 method, difference lies in without reaming (i.e. without alkali and acid at Reason) and P Modification processing, exchanged with ammonium sulfate and wash sodium, gained sample is contrast sample Ι.Its physico-chemical property is shown in Table 1, raw material Oily ACE evaluation results are listed in table 2, appreciation condition of the appreciation condition with embodiment (following comparative example appreciation condition is herewith).
Comparative example 2
Method according to embodiment 1 prepares catalyst, unlike, without alkali process, when acid treatment, only make With organic acid and inorganic acid, fluosilicic acid is replaced with the hydrochloric acid of equimolar amounts.
Comparative example 3
In this comparative example basic process according to embodiment 1 method, difference lies in before P Modification without Compound-acid Dealumination treatment, is exchanged with ammonium nitrate solution and washes sodium, and gained sample is contrast sample III.Its physico-chemical property, feedstock oil ACE evaluations Conversion ratio, gas recovery ratio, amount of coke are listed in table 2.
Comparative example 4
In this comparative example basic process according to embodiment 1 method, difference lies in before P Modification without Compound-acid Dealumination treatment, carries out dealumination treatment, the molal quantity of fluosilicic acid is equal to the molal quantity of Compound-acid described in embodiment 1, institute with fluosilicic acid Sample is obtained as contrast sample IV, its physico-chemical property, formula are shown in Table 1, and feedstock oil ACE evaluation results are listed in table 2.
Comparative example 5
Method according to embodiment 1 prepares catalytic cracking catalyst, the difference is that the difference is that without at Compound-acid Reason is handled with hydrochloric acid.The mole of hydrochloric acid (HCl) is equal to the mole dosage of Compound-acid, and gained sample is contrast sample V. Its physico-chemical property, feedstock oil ACE evaluation results are listed in table 2.
Table 1
VIt is mesoporous/VTotal holeIt is the ratio between mesopore volume and total pore volume.
Table 2
Table 3
Project Feedstock oil
Density (20 DEG C), g/cm3 0.9334
Refractive power (70 DEG C) 1.5061
Four components, m%
Saturated hydrocarbons 55.6
Aromatic hydrocarbons 30
Colloid 14.4
Asphalitine <0.1
Solidification point, DEG C 34
Tenor, ppm
Ca 3.9
Fe 1.1
Mg <0.1
Na 0.9
Ni 3.1
Pb <0.1
V 0.5
C m% 86.88
H m% 11.94
S m% 0.7
Carbon residue m% 1.77
By table 2 as it can be seen that compared with contrast medium, catalyst provided by the invention is used for hydrocarbon ils cracking high conversion rate, and propylene is received Rate and BTX yield highers.As it can be seen that catalytic cracking catalyst provided by the invention has the conversion ratio of higher, have the third of higher Alkene yield and BTX (benzene,toluene,xylene) yield.

Claims (24)

  1. A kind of 1. catalytic cracking catalyst, by weight percentage comprising following components：
    A) in terms of butt 5%~65% natural mineral matter；
    B) in terms of oxide 10%~60% adhesive oxides；
    C) in terms of butt 24%~74% the first molecular sieve, first molecular sieve are less than for Y type molecular sieve and aperture Molecular sieve, or first molecular sieve is less than for apertureMolecular sieve in it is two or more；With
    D) with P2O5The phosphorus additive of meter 0.1%~15%；
    The ratio that the mesoporous Bronsted acid amount of the catalytic cracking catalyst accounts for total acid content is 20%~70%.
  2. 2. catalytic cracking catalyst according to claim 1, it is characterised in that the phosphorus additive content is 0.5~6.5 Weight % preferably 2~5 weight %.
  3. 3. catalytic cracking catalyst according to claim 1, it is characterised in that the catalytic cracking catalyst always than table Area is 240~350m2/ g, the ratio that mesoporous Bronsted acid amount accounts for total acid content are 25%~50%.
  4. 4. catalytic cracking catalyst according to claim 1, it is characterised in that the mesopore volume of the catalyst is 0.14 ~0.35ml/g is, for example, 0.14~0.30ml/g, and the ratio of mesopore volume and total pore volume is 35%~60%.
  5. 5. catalytic cracking catalyst according to claim 1, it is characterised in that the natural mineral matter includes kaolinite In soil, halloysite, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and rectorite One or more；The oxide is silica, aluminium oxide, zirconium oxide, titanium oxide, one kind in amorphous silica-alumina or more Kind；The Y type molecular sieve is DASY molecular sieves, is the DASY molecular sieves containing rare earth, USY molecular sieve, the USY molecules containing rare earth Sieve, REY molecular sieves, REHY molecular sieves, at least one of HY molecular sieves, the aperture is less thanMolecular sieve be MFI knot At least one of structure molecular sieve, IMF structure molecular screens, BEA structure molecular screens, ferrierite.
  6. 6. the catalytic cracking catalyst according to claim 1, it is characterised in that the Y type molecular sieve and aperture is small InMolecular sieve weight ratio be 1:8~4:0.1 or 0.3:1~20:1 or 0.15:1~1:1 or 1：6.5~1：2.
  7. 7. a kind of preparation method of any one of claim 1~6 catalytic cracking catalyst, including：
    Formation includes first molecular sieve, natural mineral matter, the first chamber microballoon of adhesive oxides, by described the The microsphere modified processing of one composition；It is described to include the following steps the microsphere modified processing of the first chamber：
    A, first chamber microballoon is put into alkaline solution and is handled, filtered and wash, obtain alkali process first chamber Microballoon；
    B, by step a gained alkali process first chamber microballoon be made of fluosilicic acid, organic acid and inorganic acid it is compound Handled in acid solution, filter and wash, optionally drying, obtains being rich in mesoporous composition microballoon；Alternatively, by step a The alkali process first chamber microballoon of gained is located in the Compound-acid solution being made of fluosilicic acid, organic acid and inorganic acid Reason, filtering, optionally washing, ammonium, which exchanges, washes sodium processing, filtering and optionally washing, optionally drying, obtains being rich in mesoporous composition Microballoon；
    C, phosphorus additive is introduced in rich in mesoporous composition microballoon；
    D, when calcination process at least 0.5 is small at 400~800 DEG C.
  8. 8. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that the catalytic cracking catalyst Optionally contain the second molecular sieve, optionally contain adjuvant component, the formation include first molecular sieve, natural mineral matter, The preparation process of the first chamber microballoon of adhesive oxides includes：
    By the first molecular sieve, natural mineral matter, the precursor colloidal sol of oxide, the second optional molecular sieve, optional auxiliary agent group Divide and be mixed with beating with water, is spray-dried, optionally roasting.
  9. 9. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that the alkalescence described in step a Solution includes alkali compounds, and the alkali compounds is sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, high-alkali One or more in sodium metaaluminate；Preferably, the alkaline solution is selected from sodium hydroxide solution, potassium hydroxide solution, hydrogen-oxygen Change at least one of lithium solution, Ammonia, high alkali deflection aluminium acid sodium solution.
  10. 10. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that handled described in step a： Including first chamber microballoon is contacted with alkaline solution, wherein the alkaline solution includes alkali compounds, with dry basis The first chamber microballoon of gauge with (ammonium hydroxide is with NH in terms of alkali metal oxide3Meter) alkali compounds weight ratio For 1:(0.01~0.35).
  11. 11. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that handled described in step a In：Using the weight ratio of the first chamber microballoon of dry basis and water as 1：(5-20), the temperature of the processing for room temperature extremely 100 DEG C, when the time is 0.2-4 small.
  12. 12. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that handled described in step a Condition is：Using the weight ratio of alkali metal oxide in the first chamber microballoon of dry basis and alkali compounds as 1： (0.05~0.25) or 1：(0.01~0.15).
  13. 13. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that organic acid described in step b For at least one of ethylenediamine tetra-acetic acid, oxalic acid, acetic acid, citric acid and sulfosalicylic acid, the inorganic acid is hydrochloric acid, sulfuric acid At least one of with nitric acid.
  14. 14. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that handled described in step b Condition is：Using the weight ratio of the first chamber microballoon of dry basis, fluosilicic acid, organic acid and inorganic acid as 1:(0.003 ~0.3):(0.01~0.55):(0.01~0.45).
  15. 15. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that handled described in step b Condition is：The first chamber microballoon of dry basis, fluosilicic acid, the weight ratio of organic acid and inorganic acid are 1:(0.005~ 0.3):(0.02~0.3):(0.02~0.3) or 1:(0.005~0.17):(0.015~0.15):(0.02~0.15) or 1: (0.005~0.1):(0.02~0.2):(0.02~0.15).
  16. 16. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that handled described in step b Temperature is 25-100 DEG C, when the time is 0.5-6 small.
  17. 17. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that ammonium described in step b is exchanged and washed The step of sodium processing procedure is included first chamber micro-sphere contacts after ammonium salt solution and acid treatment, the ammonium salt can be Catalytic cracking catalyst, which prepares to exchange, washs common ammonium salt, may be selected from ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, acetic acid At least one of ammonium and ammonium nitrate；The ammonium, which exchanges to wash sodium and handle, contains the sodium oxide molybdena in obtained catalytic cracking catalyst Amount is preferably more than 0.2 weight %, preferably more than 0.15 weight %.
  18. 18. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that phosphorus is introduced described in step C and is added Add agent to include will be enriched in mesoporous composition microballoon to contact with phosphorus-containing compound to be impregnated and/or the step of ion exchange.
  19. 19. catalytic cracking catalyst preparation method according to claim 18, wherein, the phosphorus-containing compound is selected from phosphorus At least one of acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.
  20. 20. catalytic cracking catalyst preparation method according to claim 7, it is characterised in that calcination process described in step d Condition include：The atmosphere of calcination process is air atmosphere, nitrogen atmosphere or steam atmosphere or the mixture gas of above-mentioned atmosphere Atmosphere；Calcination temperature is 400-800 DEG C, when roasting time is 0.5-8 small.
  21. 21. according to the catalytic cracking catalyst preparation method described in claim 7, it is characterised in that being formed includes described the One molecular sieve, natural mineral matter, the first chamber microballoon of adhesive oxides include：By the first molecular sieve, natural mineral matter, Adhesive oxides precursor, adhesive oxides precursor and water mashing, optionally spray drying, roasting；The oxidation One kind in thing binding agent precursor such as Ludox, Aluminum sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol It is or a variety of.
  22. 22. according to the catalytic cracking catalyst preparation method described in claim 7, it is characterised in that with the first chamber On the basis of the weight of microballoon, the first chamber microballoon includes：In terms of butt 5%~65% natural mineral matter, with oxidation The adhesive oxides of thing meter 10%~60% and the first molecular sieve of butt meter 24%~75%.
  23. 23. according to the catalytic cracking catalyst preparation method described in claim 7 or 22, it is characterised in that urged with catalytic pyrolysis On the basis of the weight of agent, the catalytic cracking catalyst contains with P2O5The phosphorus additive of meter 0.1%~15%, preferably comprises 0.5~6.5 weight % preferably phosphorus additives of 2~5 weight %.
  24. 24. a kind of method of hydrocarbon producing low-carbon alkene by catalytic pyrolysis, including by hydrocarbon ils and claim 1~6 any one of them The step of Cracking catalyst haptoreaction.
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CN111482199A (en) * 2020-04-26 2020-08-04 中国石油大学(北京) Olefin cracking catalyst, preparation method thereof and olefin cracking method
CN111482198A (en) * 2020-04-26 2020-08-04 中国石油大学(北京) Olefin cracking catalyst, preparation method thereof and olefin cracking method
CN113181960A (en) * 2021-04-19 2021-07-30 中科合成油技术有限公司 IM-5 molecular sieve containing heteroatom boron and modification method and application thereof
CN113731477A (en) * 2020-05-27 2021-12-03 中国石油化工股份有限公司 Catalyst for preparing propylene and preparation method and application thereof

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CN103007986A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration
CN104307560A (en) * 2014-10-20 2015-01-28 丁泳 Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst

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CN101837301A (en) * 2009-03-18 2010-09-22 中国石油天然气股份有限公司 Catalytic cracking propylene catalyst with yield increase and preparation method
CN103007986A (en) * 2011-09-22 2013-04-03 中国石油化工股份有限公司 Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration
CN104307560A (en) * 2014-10-20 2015-01-28 丁泳 Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111482199A (en) * 2020-04-26 2020-08-04 中国石油大学(北京) Olefin cracking catalyst, preparation method thereof and olefin cracking method
CN111482198A (en) * 2020-04-26 2020-08-04 中国石油大学(北京) Olefin cracking catalyst, preparation method thereof and olefin cracking method
CN111482199B (en) * 2020-04-26 2023-12-15 中国石油大学(北京) Olefin cracking catalyst, preparation method thereof and olefin cracking method
CN113731477A (en) * 2020-05-27 2021-12-03 中国石油化工股份有限公司 Catalyst for preparing propylene and preparation method and application thereof
CN113731477B (en) * 2020-05-27 2023-08-15 中国石油化工股份有限公司 Catalyst for preparing propylene and preparation method and application thereof
CN113181960A (en) * 2021-04-19 2021-07-30 中科合成油技术有限公司 IM-5 molecular sieve containing heteroatom boron and modification method and application thereof
CN113181960B (en) * 2021-04-19 2023-09-12 中科合成油技术股份有限公司 IM-5 molecular sieve containing heteroatom boron and modification method and application thereof

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