CN107971018A - 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
CN107971018A
CN107971018A CN201610921781.7A CN201610921781A CN107971018A CN 107971018 A CN107971018 A CN 107971018A CN 201610921781 A CN201610921781 A CN 201610921781A CN 107971018 A CN107971018 A CN 107971018A
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molecular sieve
acid
weight
catalytic cracking
microballoon
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CN107971018B (en
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王丽霞
袁帅
刘宇键
田辉平
刘俊
周翔
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • 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
    • 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

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 first molecular sieve is 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.The catalyst is used for heavy oil catalytic cracking, and activity is not high, and productivity of low carbon olefin hydrocarbon is not high.
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.The catalyst can increase substantially propene yield and selectivity in catalytic cracking liquefied gas.
But the existing catalyst for cracking Propylene Selectivity containing Y type molecular sieve and shape-selective molecular sieve is 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 Excellent hydrothermal stability and the Propylene Selectivity of higher, the second object of the present invention are to provide the preparation method of the catalyst And methods for using them.
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 ~65% 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；The catalytic cracking catalyst intermediary hole Bronsted acid amount accounts for total acid content Ratio is, for example, 25%~65% for 20%~70%.Total specific surface area of the catalyst is 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 is, for example, for 0.14-0.35ml/g 0.16~0.32ml/g such as 0.25~0.45ml/g or 0.15~0.30ml/g or 0.25~0.40ml/g.It is described mesoporous to be The hole of a diameter of 2~100nm of finger-hole.
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, and mesoporous Bronsted acid amount accounts for total acid content Ratio for 20%~70% be, for example, 25%~65%, 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.
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.The MFI structure molecular sieve such as ZSM-5, ZSP, One or more in ZRP molecular sieves, the ZSM-5 molecular sieve can be NaZSM-5 or be passed through by NaZSM-5 molecular sieves Modified obtained molecular sieve, such as HZSM-5, ammonium type ZSM-5, phosphorous and/or transition metal ZSM-5 are crossed, wherein the 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.The IMF structure molecular screens such as IM-5, can be Na types IM-5 or pass through modification by NaIM-5 Obtained modification IM-5 molecular sieves, such as one or more in Hydrogen IM-5, ammonium type IM-5 and phosphorus and/or transition metal change The IM-5 molecular sieves of property, one kind or more in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga Kind.The BEA structure molecular screens can be the BEA structure molecular screens of sodium form or be changed by sodium form BEA structure molecular screens The modification BEA structure molecular screens that property obtains, such as Hydrogen BEA structure molecular screens, ammonium type BEA structure molecular screens, phosphorous and/or mistake The BEA structure molecular screens of metal are crossed, wherein in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga One or more described in BEA structure molecular screens be, for example, beta-molecular sieve, can be sodium form beta-molecular sieve or by sodium form Beta-molecular sieve is by modified obtained modified beta molecular sieve, such as H β, NH4One kind in beta-molecular sieve, phosphorus and/or transition metal or The beta-molecular sieve of a variety of modifications, one kind in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga or It is a variety of.The ferrierite such as Fer molecular sieves, can be sodium form Fer molecular sieves or by sodium form Fer molecular sieves By modified obtained MODIFIED Fe r molecular sieves, such as HFer, NH4One kind or more in Fer molecular sieves, phosphorus and/or transition metal Kind of modified Fer molecular sieves, one kind in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga or It is a variety of.
Preferably, 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.
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, 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 described in step a includes alkalization Compound, it is preferred that the alkali compounds is strong basicity inorganic compound, for example, the alkali compounds is sodium hydroxide, hydrogen One or more in potassium oxide, lithium hydroxide, ammonium hydroxide, high alkali deflection aluminium acid sodium.Alkalescence used in described step a Solution is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide are molten, in Ammonia, high alkali deflection aluminium acid sodium solution At least one.The alkaline solution is the aqueous solution of alkali compounds.
The catalytic cracking catalyst preparation method provided according to the present invention, a kind of embodiment, alkalescence used in step a Solution preferably includes high alkali deflection aluminium acid sodium, is preferably high alkali deflection aluminium acid sodium solution.Preferably, the high alkali deflection aluminium acid sodium solution In, Na2O content is 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 DEG C to 100 DEG C are preferably 40~75 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 it is small when 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, for example, I 0.2~10 it is small when or 0.5~6 it is small when, filtering, 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, 30~75 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.Preferably, organic acid described in step b is oxalic acid, the inorganic acid For 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 is micro- with first chamber The weight ratio of ball is preferably (0.02~0.3)：1 or (0.015~0.15)：1 or (0.02~0.2)：1；Inorganic acid and first group The weight ratio of compound 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 sodium for exchanging to get off in catalyst and the ammonium salt not exchanged.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.
Catalytic cracking catalyst preparation method according to the present invention, the condition of calcination process includes described in step c：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 c 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 The step of method of production low-carbon alkene includes contacting hydrocarbon ils with catalytic cracking catalyst provided by the invention.The condition of reaction Refer to the condition of existing producing low-carbon alkene by catalytic pyrolysis.The hydrocarbon ils is petroleum hydrocarbon, can be part cut petroleum hydrocarbon, It can also be full cut petroleum hydrocarbon, be particularly suitable for heavy oil pyrolysis production low-carbon alkene.The heavy oil such as decompression residuum, often Press residual oil, catalytic cracking light cycle oil, heavy catalytic cycle oil, solvent-deasphalted oils, lube oil finishing oily and above-mentioned oil Product pass through the one or more in the hydrotreating oil that hydrotreating obtains.
Catalytic cracking catalyst provided by the invention, has abundant meso-hole structure, and suitable mesoporous acidity, have compared with High hydrothermal stability, reacts for heavy oil catalytic pyrolysis, and conversion ratio is higher, and heavy oil yield is low, and yield of liquefied gas is high, coke production Rate is low, the high income of propylene, and the selectivity of BTX high incomes, especially propylene is good.Catalytic pyrolysis provided by the invention produces low-carbon Olefins process, than existing methods with higher cracking hydrocarbon oil activity, there is more high conversion, have higher productivity of propylene with BTX yields.Catalytic cracking catalyst preparation method provided by the invention, is less than using Y type molecular sieve and apertureMolecule Sieve, or two or more apertures are less than 6.9 angstroms of molecular sieve, are first made after catalyst again by the method pair of alkali, sour coupling processing The pore passage structure of molecular sieve has carried out the stability and low-carbon alkene and BTX selectivity that further modulation improves catalyst Rate.
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 State the dissolved colloidal state material that adhesive oxides come from its corresponding oxide precursor such as oxide, such as Ludox, aluminium One or more in colloidal sol, peptization boehmite, silicon-aluminum sol and phosphorated aluminiferous collosol.On the basis of catalyst total amount, In terms of weight percent oxide, the contents of adhesive oxides is preferably 15 weight %~55 for the weight % of 10 weight %~60 Weight % is, for example, the weight of the weight % or 20~50 weight % or 25~50 weight % or 12 weight % of 10 weight %~30~28 Measure %.
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.It is described The content of first molecular sieve is preferably that 25~65 weight % are, for example, 30~55 weight % or 30~65 weight % or for 30~55 Weight % 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.One or more in MFI structure molecular sieve such as ZSM-5, ZRP and ZSP molecular sieve, the ZSM-5 molecular sieve can To be NaZSM-5 or be by modified obtained molecular sieve by NaZSM-5 molecular sieves, such as HZSM-5, phosphorous and transition are golden The ZSM-5 of category, wherein the one or more in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga. The IMF structure molecular screens can be sodium form IMF structure molecular screens or IMF structure molecular screens pass through various modifications The modification IMF structure molecular screens that method is modified, for example, it is ammonium type IMF structure molecular screens, Hydrogen IMF structure molecular screens, phosphorous And/or one or more IMF structure molecular screens in transition metal, the transition metal such as RE, Fe, Ni, Co, Cu, One or more in Mn, Zn, Sn, Bi and Ga.The IMF structure molecular screens such as IM-5, can be Na type IM-5, also may be used To be by modified obtained modification IM-5 molecular sieves, such as Hydrogen IM-5 by NaIM-5.The BEA structure molecular screens are for example For beta-molecular sieve, it can be sodium form beta-molecular sieve or modified obtained modified beta molecular sieve, example are passed through by sodium form beta-molecular sieve Such as H β.The ferrierite such as Fer molecular sieves, can be sodium form Fer molecular sieves or by sodium form Fer molecular sieves By modified obtained MODIFIED Fe r molecular sieves, such as HFer, NH4One kind or more in Fer molecular sieves, phosphorus and/or transition metal Kind of modified Fer molecular sieves, one kind in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga or It is a variety of.The 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 voluntarily be prepared, for example, The preparation process of the sodium form IMF structure molecular screens includes：To use has IMF structure molecular screens slurries obtained by amine method crystallization to carry out After filtering and washing, washing molecular sieve is obtained；Wherein, counted and using total butt weight of the washing molecular sieve as base using sodium oxide molybdena Standard, the sodium content washed in molecular sieve are less than 3.0 weight %；The washing molecular sieve is dried and air roasting Afterwards, 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 State other molecular sieves outside the first molecular sieve, these molecular sieves often with catalytic cracking catalyst active component.Described second point The content of son sieve 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, apertureThe microspheroidal combination of molecular sieve (also referred to as molecular sieve of the aperture less than 0.69nm), natural mineral matter, adhesive oxides 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 Y type molecular sieve, aperture are less thanMolecular sieve, natural minerals Matter, adhesive oxides component precursor, the second optional molecular sieve, optional adjuvant component and water mashing, spray drying, The method optionally roasted is prepared, and the microspheroidal composition present invention is known as first chamber microballoon.The spray drying Be roasted to the prior art, the present invention does not have particular/special requirement.Such as the temperature of roasting can be 300~650 DEG C or 350~500 DEG C, when roasting time can be 0.5~10 small.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.The dosage of each component makes Contain in final catalyst, on the basis of total catalyst weight, the natural mineral matter of the weight % of 5 weight %~65,10 weight % The first molecular sieve of the weight % of the oxide of~60 weight % and 24 weight %~75.The dosage of more preferably each component makes finally The composition of catalyst is to include：It is, for example, 8~45 weights to count natural mineral matter content as the weight % of 5 weight %~50 using butt % is measured, it is, for example, 30~55 weight % to count the content of first molecular sieve as the weight % of 30 weight %~65 using butt, with oxygen The content of compound meter adhesive oxides is 15~55 weight % such as 25~50 weight % or 15~45 weight % or 20~35 The weight % of 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 15 weight %~65, the weight of preferably 20 weight %~55 Measure %.
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 % of the weight % or 15 weight % of 10 weight %~30~35, the weight % of preferably 12 weight %~28.
The preparation method of the catalytic cracking catalyst provided by the invention, dosage (the i.e. Y type molecular sieve of the first molecular sieve It is less than with apertureMolecular sieve dosage or two or more apertures be less thanMolecular sieve dosage) make In catalytic cracking catalyst, the content of the first molecular sieve counted using butt is preferably 30~70 as the weight % of 24 weight %~75 Weight % or 25~65 weight % is, for example, 30~55 weight %.Wherein Y type molecular sieve aperture is less thanMolecular sieve Than for 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 molecules Sieve such as DASY molecular sieves, for the DASY molecular sieves containing rare earth, USY molecular sieve, the USY molecular sieve containing rare earth, REY molecular sieves, The one or more of REHY molecular sieves, 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 One or more in structure molecular sieve such as ZSM-5, ZRP and ZSP molecular sieve, the ZSM-5 molecular sieve can be NaZSM-5, Either by NaZSM-5 molecular sieves by modified obtained molecular sieve, such as HZSM-5, phosphorous and/or transition metal ZSM- 5, wherein the one or more in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.Described IMF structure molecular screens can be sodium form IMF structure molecular screens or IMF structure molecular screens change by various method of modifying The modification IMF structure molecular screens that property obtains, such as ammonium type IMF structure molecular screens, Hydrogen IMF structure molecular screens, phosphorous and/or mistake Cross one or more IMF structure molecular screens in metal, the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, One or more in Sn, Bi and Ga.Such as IM-5, it can be Na types IM-5 or be obtained by NaIM-5 by modification Modification IM-5 molecular sieves, such as one or more in Hydrogen IM-5, ammonium type IM-5 and phosphorus and/or transition metal are modified IM-5 molecular sieves, the one or more in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga..Institute The BEA structure molecular screens stated are, for example, beta-molecular sieve, can be sodium form beta-molecular sieve or be changed by sodium form beta-molecular sieve process The modified beta molecular sieve that property obtains, such as H β, NH4The β that one or more in beta-molecular sieve, phosphorus and/or transition metal are modified divides Son sieves, the one or more in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.The magnesium Alkali zeolite 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 molecules that one or more in Fer molecular sieves, phosphorus and/or transition metal are modified Sieve, the one or more in the transition metal such as RE, Fe, Ni, Co, Cu, Mn, Zn, Sn, Bi and Ga.The aperture It is less thanMolecular sieve be preferably that sodium form, Hydrogen or ammonium type aperture are less thanMolecular sieve.
Method for preparing catalyst provided by the invention, it is preferred that on the basis of the weight of the first chamber microballoon, institute State in first chamber microballoon (also referred to as the first microsphere composition) in terms of butt natural mineral matter, the in terms of butt first molecular sieve, The weight ratio of adhesive oxides is counted as 5~65 using oxide：24~75：10~60, it is preferably 8~55：30~65：15~55 More preferably 8~45：30~55：20~50.Preferably, the first chamber microballoon contains in terms of butt 5%~65% Natural mineral matter, in terms of oxide 10%~60% adhesive oxides and in terms of butt 24%~75% the first molecule Sieve, it is preferred that on the basis of the weight of the first chamber microballoon, first microsphere composition contains 8 weight in terms of butt Measure the adhesive oxides of the weight % of the natural mineral matter of the weight % of %~55, in terms of oxide 15 weight %~55 and with butt Count the first molecular sieve of the weight % of 25 weight %~55.It is furthermore preferred that the first chamber microballoon contains in terms of butt 8~45 The oxidation of weight the % such as natural mineral matter of 20~45 weight %, in terms of oxide 20~50 weight % such as 10%~30% First molecular sieve of thing binding agent and in terms of butt 30~55 weight % such as 35~50 weight %.
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, first chamber slurries also contain adjuvant component and the second molecular sieve, and adjuvant component and the second molecular sieve are being sprayed It is incorporated into dry pervious any step in first chamber 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, 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 obtained catalytic cracking catalyst account for The ratio of total pore volume is, for example, 40%~60% or 45%~58% or 35~45% for 35%~60%.The catalytic pyrolysis The mesopore volume of catalyst is, for example, 0.15~0.30ml/g or 0.16~0.32ml/g for 0.14~0.35ml/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 handle, fixed fluidized bed micro- To be evaluated on anti-ACE, feedstock oil is hydrotreating oil (composition and physical property are shown in Table 3), and appreciation condition is 530 DEG C of reaction temperature, 620 DEG C of regeneration temperature, oil ratio are 5 (weight ratios).
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 method for the present invention adsorbs infrared acid process measure using 2,6 di tert butyl pyridine.Specifically Method is：Catalyst is pressed into 10mg/cm2Thin slice, be put into band CaF2In the infrared pond of window.First vacuumized 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.Room temperature collection spectrogram is dropped to, and calculates matter Sub- acid amount.Referring to Applied Catalysis A:General, 294,2005：92.
The Na of the present invention2O content 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), (zunyi, guizhou three closes white ore deposit, solid content 75 to galapectite Weight %), rectorite (Zhongxiang Hubei rectorite ore deposit, 75 weight % of solid content), montmorillonite (the red stone bentonite in Chaoyang City, Liaoning Province Company, 75 weight % of solid content), (Shandong Aluminium Industrial Corp, 65 weight % of solid content, when use, first use concentration 31 to boehmite 0.20) weight % hydrochloric acid peptizations, the hydrochloric acid and the molar ratio of boehmite counted using aluminium oxide is, Aluminum sol (Shandong Catalyst branch company, alumina content are 22.5 weight %), Ludox (Qingdao Marine Chemical Co., Ltd., silica content 25.5 weight %, pH value 3.0), phosphorated aluminiferous collosol (16 weight % of P content, 8 weight % of Al content, pH value 2.0), IM-5 points (Chang Ling branch company of Sinopec catalyst Co., Ltd produces son sieve, is synthesized by amine method, sodium form, silica alumina ratio (SiO2/Al2O3Rub That ratio, similarly hereinafter) for 30), (asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd, NaZSM-5, silica alumina ratio are ZSM-5 molecular sieve 44), beta-molecular sieve (catalyst branch company of Sinopec catalyst Co., Ltd produces, H β, silica alumina ratio 30), REY molecular sieves (asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd, content of rare earth are 10 mass %), (Sinopec is catalyzed DASY molecular sieves Asphalt in Shenli Refinery of agent Co., Ltd, content of rare earth is (with RE2O3Meter) be 1.5 weight %).USY molecular sieve (Sinopec catalyst Asphalt in Shenli Refinery of limited company, content of rare earth is (with RE2O3Meter) it is 1.5 weight %, silica alumina ratio SiO2/Al2O3Molar ratio is 5.8).ZRP-1 molecular sieves, asphalt in Shenli Refinery of Sinopec Catalytica Inc. product, silica alumina ratio (SiO2/Al2O3Rub That 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 168g kaolin, and it is 31 weight % to be configured to solid content with decationized Y sieve water Slurries, stirring 0.5 it is small when after add the molecular sieve pulp containing 24gUSY, 45g beta-molecular sieve and 45g ferrierites, formation group Compound slurries (solid content is 35 weight %), stir evenly, and composition microballoon is made in spray drying, then by said composition microballoon When 500 DEG C of roastings 1 are small, 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 11.4g 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 5.3g oxalic acid, then 51g hydrochloric acid (HCl mass fractions 10%) and 33.4g silicate fluoride solutions (the 3 weight % of concentration of fluosilicic acid) are added, is warming up to 50 DEG C Constant temperature stirs 1h, filtering, washing, drying, up to catalytic cracking catalyst A provided by the invention.The materialization of catalyst sample A Matter is listed in table 1, after 800 DEG C, 17h, 100% vapor aging, carries out feedstock oil ACE evaluations, and the results are shown in table 2, evaluation Table 3 is listed in the property of feedstock oil.
Embodiment 2
411.8g Ludox is mixed with 80g montmorillonites, and it is 30 weights to be configured to solid content with decationized Y sieve water Measure the slurries of %, when stirring 2 is small after add the slurries that are formed by 75gREY types molecular sieve and 60gZSM-5 molecular sieves and water, stir Mix uniformly, form first chamber slurries (solid content is 35% weight), composition microballoon is made in spray drying, then will combination Thing microballoon obtains first chamber microballoon B1 when 350 DEG C of roastings 2 are small.
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 16gNaOH (purity 96%), are warming up to 70 DEG C of constant temperature stirring 0.3h, filtering, wash into Property；By filter cake plus water be beaten solid content be 10 weight % slurries, in stirring add 16g oxalic acid, then add 38g hydrochloric acid (HCl mass fractions 10%) and 35g silicate fluoride solutions (3 weight % of concentration), are warming up to 80 DEG C of constant temperature stirring 0.8h, filter, wash Wash, be dried to obtain catalytic cracking catalyst B provided by the invention.The physico-chemical property of catalyst sample B is listed in Table 1 below, by 800 DEG C, after 100% vapor aging 17h, carry out feedstock oil ACE evaluations with the feedstock oil shown in table 3, the results are shown in table 2.
Embodiment 3
400g Aluminum sols are mixed with 80g montmorillonites, and it is 30 weight % to be configured to solid content with decationized Y sieve water Slurries, when stirring 1 is small, adding includes the slurries of 30g ZRP-1 types molecular sieve, 60gIM-5 molecular sieves and 60g beta-molecular sieves, stirs Mix, form first chamber slurries (solid content is 35% weight), microsphere composition is made in spray drying.Then microballoon is combined Thing obtains first chamber microballoon C1 when 350 DEG C of roastings 2 are small.
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 19gKOH (purity 96%), are warming up to 60 DEG C of constant temperature stirring 1h, filtering, is washed to neutrality；Will Filter cake add water be beaten solid content be 10 weight % slurries, in stirring add 26g oxalic acid, then with the speed of 30-80ml/min Degree adds 250g sulfuric acid solutions (H2SO4Mass fraction 10%) and 95g silicate fluoride solutions (3 weight % of fluosilicic acid concentration), it is warming up to 70 DEG C of constant temperature stir 2h, and filtering, washs, is dried to obtain catalyst C provided by the invention.The physico-chemical property of catalyst sample C；Through Cross 800 DEG C, 17h, after 100% vapor aging, feedstock oil ACE evaluations, conversion ratio, gas are carried out with the feedstock oil shown in table 3 The evaluation results such as yield, amount of coke are listed in table 2.
Embodiment 4
Catalyst C1 (butt quality) 200g made above is taken, adds water to be configured to the slurries of 10 weight % of solid content, adds Enter 30gNaOH (purity 96%), be warming up to 90 DEG C of constant temperature stirring 2h, filtering, wash to neutrality；Filter cake plus water are beaten to consolidate and contained Measure as the slurries of 10 weight %, 33g oxalic acid added in stirring, then add 70g hydrochloric acid (10 weight % of HCl mass fractions) and 667g silicate fluoride solutions (3 weight % of concentration), are warming up to 30 DEG C of constant temperature stirring 5.5h, and what filtering, washing, dry invention provided urges Change catalyst for cracking D.The physico-chemical property of catalyst sample D；After 800 DEG C, 100% vapor aging 17h, 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 %, stir evenly, stand 1 it is small when after add the types of the 45gDASY in terms of butt molecular sieves, 60g ferrierites and 45g IM-5, stirs evenly, and forms composition slurries (solid content is 35% weight), and microspheroidal composition is made in spray drying, then By microspheroidal composition when 350 DEG C of roastings 2 are small, first chamber microballoon D1 is obtained.
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 22gNaOH (purity 96%), be warming up to 30 DEG C of constant temperature stirring 3h, filtering, is washed into Property；By filter cake plus water be beaten solid content be 10 weight % alkali process composition slurries, in stirring add 5g citric acids, then 120g hydrochloric acid (10 weight % of HCl mass fractions) and 55g silicate fluoride solutions (3 weight % of fluosilicic acid concentration) are added, is warming up to 60 DEG C constant temperature stirring 2.5h, is filtered, washing, is dried to obtain catalytic cracking catalyst E provided by the invention.The thing of catalyst sample E Change property and be shown in Table 1, after 800 DEG C, 17h, 100% vapor aging, feedstock oil ACE evaluations, evaluation result such as conversion ratio, Gas recovery ratio, amount of coke etc. are listed in table 2.
Embodiment 6
First chamber D1 (butt quality) 200g made above is taken, adds water to be configured to the slurry of 10 weight % of solid content Liquid, adds 25gKOH (purity 96%), is warming up to 50 DEG C of constant temperature stirring 0.5h, filtration washing to neutrality；Filter cake plus water are beaten The slurries that solid content is 10 weight % are obtained, 35g oxalic acid is added in stirring, are then slowly added into 50g salpeter solutions (nitric acid quality point Number 10%) and 90g silicate fluoride solutions (3 weight % of concentration), 50 DEG C of constant temperature stirring 1h are warming up to, filtration washing is dried to obtain catalysis Agent sample F, the physico-chemical property of catalyst sample F, after 800 DEG C, 17h, 100% vapor aging, feedstock oil ACE evaluations, The results are shown in table 2.
Comparative example 1
Basic process, difference lies in without alkali and acid treatment modification, is used according to the method for embodiment 1 in this comparative example Ammonium sulfate, which exchanges, washes sodium, and gained sample is contrast sample Ι.Its physico-chemical property, feedstock oil ACE evaluation results are listed in table 2 and (comment Valency method is with embodiment 1, and following comparative example evaluation method 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
Basic process, difference lies in without compound acid treatment, uses ammonium nitrate according to the method for embodiment 1 in this comparative example Solution exchanges washing to reduce sodium content, and gained sample is contrast sample III.Its physico-chemical property, feedstock oil ACE evaluation results row In table 2.
Comparative example 4
Method according to embodiment 1 prepares catalytic cracking catalyst, unlike do not have to compound acid treatment, with fluosilicic acid with Oxalic acid is handled, and hydrochloric acid therein is replaced with the oxalic acid of equimolar amounts, obtains catalyst sample IV.Its physico-chemical property is listed in table 1, feedstock oil ACE evaluations are carried out according to the method for embodiment 1, the results are shown 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 Manage and handled with hydrochloric acid.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 be used for hydrocarbon ils cracking high conversion rate, propylene and BTX (benzene,toluene,xylene) yield higher, liquefied gas selectively raise, and slurry oil selectivity is obvious to be reduced.

Claims (20)

  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%~75% 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；
    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 total specific surface area of catalyst for 240~ 350m2/ g, the ratio that mesoporous Bronsted acid amount accounts for total acid content are 25%~50%.
  3. 3. 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, 0.15~0.30ml/g, and the ratio of mesopore volume and total pore volume is 35%~60%.
  4. 4. catalyst according to claim 1, it is characterised in that it is high that the natural mineral matter includes kaolin, more water Ridge soil, montmorillonite, diatomite, convex-concave rod stone, sepiolite, galapectite, hydrotalcite, bentonite and one kind or more in rectorite Kind；The oxide is silica, the one or more in aluminium oxide, zirconium oxide, titanium oxide, amorphous silica-alumina；The Y Type molecular sieve is DASY molecular sieves, is the DASY molecular sieves containing rare earth, USY molecular sieve, the USY molecular sieve containing rare earth, REY molecules Sieve, REHY molecular sieves, at least one of HY molecular sieves, the aperture is less thanMolecular sieve for MFI structure molecular sieve, At least one of IMF structure molecular screens, BEA structure molecular screens, ferrierite.
  5. 5. the catalyst according to claim 1, it is characterised in that first molecular sieve is Y type molecular sieve and aperture It is less thanMolecular sieve, 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.
  6. 6. a kind of preparation method of 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；First molecular sieve is less than for Y type molecular sieve and apertureMolecular sieve or described The first molecular sieve be less than for apertureMolecular sieve in it is two or more, it is described that the first chamber is microsphere modified Processing includes the following steps：
    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, obtain being rich in mesoporous composition microballoon；Alternatively, by step a gained alkali at Reason first chamber microballoon is handled in the Compound-acid solution being made of fluosilicic acid, organic acid and inorganic acid, is filtered, optionally Washing, ammonium, which exchanges, washes sodium processing, filtering and optionally washing, obtains being rich in mesoporous composition microballoon；
    C, when calcination process at least 0.5 is small at 400~800 DEG C.
  7. 7. preparation method according to claim 6, it is characterised in that the catalytic cracking catalyst optionally contains second point Son sieve, optionally contains adjuvant component, and the formation includes first molecular sieve, natural mineral matter, adhesive oxides The preparation process of first chamber microballoon 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.
  8. 8. preparation method according to claim 6, it is characterised in that the alkaline solution described in step a includes alkalescence Compound, the alkali compounds are one in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, high alkali deflection aluminium acid sodium Kind is a variety of；Preferably, the alkaline solution is selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, hydroxide At least one of ammonium salt solution, high alkali deflection aluminium acid sodium solution.
  9. 9. preparation method according to claim 6, it is characterised in that handled described in step a：Including by first chamber Microballoon is contacted with alkaline solution, wherein the alkaline solution includes alkali compounds, with the first chamber of dry basis Microballoon with (ammonium hydroxide is with NH in terms of alkali metal oxide3Meter) alkali compounds weight ratio be 1:(0.01~ 0.35)。
  10. 10. preparation method according to claim 6, it is characterised in that in being handled described in step a：With dry basis First chamber microballoon and water weight ratio be 1：(5-20), the temperature of the processing are room temperature to 100 DEG C, time 0.2- 4 it is small when.
  11. 11. method according to claim 6, the condition handled described in step a are：It is micro- with the first chamber of dry basis (ammonium hydroxide is with NH with alkali metal oxide in alkali compounds for ball3Meter) weight ratio be 1：(0.05~0.25) or 1： (0.01~0.15).
  12. 12. method according to claim 6, organic acid described in step b is ethylenediamine tetra-acetic acid, oxalic acid, acetic acid, citric acid and At least one of sulfosalicylic acid, the inorganic acid are at least one of hydrochloric acid, sulfuric acid and nitric acid.
  13. 13. method according to claim 6, it is characterised in that the condition handled described in step b is：With dry basis First chamber microballoon, fluosilicic acid, the weight ratio of organic acid and inorganic acid are 1:(0.003~0.3):(0.01~0.55): (0.01~0.45).
  14. 14. method according to claim 6, it is characterised in that the condition handled described in step b is：The of dry basis One composition microballoon, 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).
  15. 15. method according to claim 6, it is characterised in that the temperature handled described in step b is 25-100 DEG C, and the time is When 0.5-6 is small.
  16. 16. method according to claim 6, it is characterised in that ammonium described in step b, which exchanges, washes sodium processing procedure including ammonium salt is molten The step of first chamber micro-sphere contacts after liquid and acid treatment, the ammonium salt prepares for catalytic cracking catalyst and exchanges washing Common ammonium salt, may be selected from least one of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate and ammonium nitrate；Institute Stating ammonium and exchanging to wash sodium and handle makes the sodium oxide content in obtained catalytic cracking catalyst be preferably more than 0.2 weight %.
  17. 17. method according to claim 6, it is characterised in that the condition of calcination process includes described in step c：Calcination process Atmosphere 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.
  18. 18. according to the catalytic cracking catalyst preparation method described in claim 8, it is characterised in that the oxide binder Agent precursor colloidal sol is Ludox, Aluminum sol, peptization boehmite, silicon-aluminum sol and one kind or more in phosphorated aluminiferous collosol Kind.
  19. 19. according to the catalytic cracking catalyst preparation method described in claim 6, 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 14%~65% natural mineral matter, with oxidation The adhesive oxides of thing meter 10%~60% and the first molecular sieve of butt meter 24%~75%.
  20. 20. a kind of method of hydrocarbon producing low-carbon alkene by catalytic pyrolysis, including by hydrocarbon ils and Claims 1 to 5 any one of them The step of Cracking catalyst haptoreaction.
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CN112473731A (en) * 2019-09-12 2021-03-12 中国石油化工股份有限公司 Catalytic cracking catalyst containing molecular sieve with Y and BEA structures and preparation method and application method thereof
CN112473732A (en) * 2019-09-12 2021-03-12 中国石油化工股份有限公司 Catalytic cracking catalyst for producing propylene and preparation method and application method thereof
CN112570017A (en) * 2019-09-29 2021-03-30 中国石油化工股份有限公司 Five-membered ring zeolite catalytic cracking catalyst
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CN112642475A (en) * 2019-10-11 2021-04-13 中国石油化工股份有限公司 Catalytic cracking catalyst for producing low-carbon olefin by hydrocarbon oil conversion
CN114425429A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Wear-resistant high-yield low-carbon olefin catalyst and preparation method thereof
CN114433189A (en) * 2020-10-19 2022-05-06 中国石油化工股份有限公司 Aromatization catalyst and preparation method and application thereof
CN114762830A (en) * 2021-01-11 2022-07-19 中国石油化工股份有限公司 Preparation method and preparation system of catalytic cracking catalyst

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CN110876926A (en) * 2018-09-05 2020-03-13 中国石油化工股份有限公司 Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst
CN111744528B (en) * 2019-03-27 2023-04-07 中国石油化工股份有限公司 Preparation method of multi-metal modified composite material
CN111744528A (en) * 2019-03-27 2020-10-09 中国石油化工股份有限公司 Preparation method of multi-metal modified composite material
CN112473731A (en) * 2019-09-12 2021-03-12 中国石油化工股份有限公司 Catalytic cracking catalyst containing molecular sieve with Y and BEA structures and preparation method and application method thereof
CN112473732A (en) * 2019-09-12 2021-03-12 中国石油化工股份有限公司 Catalytic cracking catalyst for producing propylene and preparation method and application method thereof
CN112473731B (en) * 2019-09-12 2023-05-05 中国石油化工股份有限公司 Catalytic cracking catalyst containing Y and BEA structure molecular sieves, and preparation method and application method thereof
CN112473732B (en) * 2019-09-12 2023-05-05 中国石油化工股份有限公司 Catalytic cracking catalyst for producing propylene and preparation method and application method thereof
CN112570017A (en) * 2019-09-29 2021-03-30 中国石油化工股份有限公司 Five-membered ring zeolite catalytic cracking catalyst
CN112569918A (en) * 2019-09-29 2021-03-30 中国石油化工股份有限公司 Improved zirconium-aluminum composite sol and preparation method and application thereof
CN112570017B (en) * 2019-09-29 2023-06-09 中国石油化工股份有限公司 Five-membered ring zeolite catalytic cracking catalyst
CN112642475A (en) * 2019-10-11 2021-04-13 中国石油化工股份有限公司 Catalytic cracking catalyst for producing low-carbon olefin by hydrocarbon oil conversion
CN112642475B (en) * 2019-10-11 2023-06-09 中国石油化工股份有限公司 Catalytic cracking catalyst for producing low-carbon olefin by hydrocarbon oil conversion
CN114425429A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Wear-resistant high-yield low-carbon olefin catalyst and preparation method thereof
CN114433189A (en) * 2020-10-19 2022-05-06 中国石油化工股份有限公司 Aromatization catalyst and preparation method and application thereof
CN114762830A (en) * 2021-01-11 2022-07-19 中国石油化工股份有限公司 Preparation method and preparation system of catalytic cracking catalyst
CN114762830B (en) * 2021-01-11 2023-06-09 中国石油化工股份有限公司 Preparation method and preparation system of catalytic cracking catalyst

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