CN103007989A - Cracking assistant for improving low-carbon olefin concentration - Google Patents

Abstract

The invention discloses a cracking assistant for improving a low-carbon olefin concentration. The cracking assistant comprises a modified MFI molecular sieve, a first clay-containing phosphor-aluminum inorganic binder, other inorganic binders and a group VIII metal additive and second clay or no second clay. The first clay-containing phosphor-aluminum inorganic binder comprises an aluminum component, a phosphor component and first clay. The modified MFI molecular sieve contains phosphor and one or more of transition metals such as Fe, Co, Ni, Cu, Mn, Zn, Sn and Bi. There is not an absorption peak at the wavelength of 1633cm<-1> in a modified MFI molecular sieve infrared spectra obtained by trimethylpyridine as a probe molecule. Phosphorus distribution D is in a range of 0-0.8 and is a TEM-EDX-characterized ratio of phosphorus content of a part of a molecular sieve crystal grain to phosphorus content of the center of the molecular sieve crystal grain, wherein a distance between the part of the molecular sieve crystal grain and the edge of the molecular sieve crystal grain is 1/5 of a distance between the edge of the molecular sieve crystal grain and the center of the molecular sieve crystal grain. The cracking assistant is used for catalytic cracking, can improve a catalytic cracking liquefied gas yield, can improve yields of low-carbon olefins such as ethylene, propylene and isobutene, can improve a low-carbon olefin concentration of catalytic cracking liquefied gas, can improve a heavy oil conversion capacity of a catalyst composition, and can improve the selectivity of dry gas and coke.

Description

A kind of cracking additive that improves low-carbon alkene concentration

Technical field

The present invention relates to a kind of cracking additive that improves catalytic cracking liquefied gas low-carbon alkene concentration, relate to furtherly a kind of cracking additive that improves density of propylene in the catalytic cracking liquefied gas.

Background technology

Propylene is important Organic Chemicals.Along with the growth of the acryloyl derivative demands such as polypropylene, the whole world increases year by year to the demand of propylene.Fluid catalytic cracking is the important method of producing the low-carbon alkenes such as propylene, in order to increase the productive rate of propylene, adopts in catalytic cracking process that to contain catalyst or auxiliary agent with MFI structural zeolite be effective technological approaches.

USP3,758,403 early are disclosed in the method for adding ZSM-5 zeolite in the catalytic cracking catalyst can improve the octane number of gasoline and increase C ₃～C ₄The productive rate of alkene.For example, add in containing the conventional catalyst of 10%REY behind 1.5,2.5,5 to 10% ZSM-5 zeolite, octane number improves, and the productive rate of low-carbon alkene increases; Use also has same effect when containing the auxiliary agent of ZSM-5 zeolite.

USP 5,318, proposed the hydrocarbon conversion process process of the catalyst that forms less than 30 the zeolite with MFI structure based on a kind of large pore zeolite and silica alumina ratio in 696.This technique is produced high-knock rating gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly propylene.

USP 5,997, disclose a large amount of methods of using the shape slective cracking auxiliary agents in the heavy charge catalytic cracking process in 728.Said auxiliary agent is comprised of the ZSM-5 zeolite that adds 12～40% in the [amorphous, and system's reserve at least 10% is so that the ratio of ZSM-5 in catalyst surpasses 3%.The method can when increasing substantially low-carbon alkene, additionally not increase aromatic production and loss gasoline yield.

After ZSM-5 zeolite carried out modification with phosphorus-containing compound, its cracking activity stability can improve, and reduced the consumption of zeolite.

The zeolite that discloses a kind of phosphorous and rare earth among the CN 1049406C and had the MFI structure, it is aRE without hydrochemical compositions ₂O ₃BNa ₂OAl ₂O ₃CP ₂O ₅DSiO ₂, a=0.01～0.25 wherein, b=0.005～0.02, c=0.2～1.0, d=35～120.This zeolite has excellent hydrothermal activity stability and good selectivity of light olefin when being used for the hydro carbons pyrolytic conversion.

Disclose a kind of catalyst for cracking for the production of low-carbon alkene among the CN 1034223C, formed by the clay of 0～70% (take catalyst weight as benchmark), 5～99% inorganic oxide and 1～50% zeolite.Zeolite wherein is the mixture of five-membered ring silica-rich zeolite of the phosphorous and rare earth of the REY of 0～25 % by weight or Y-type high-Si zeolite and 75～100 % by weight.This catalyst has hydrothermal activity stability, conversion ratio and the C that the catalyst take ZSM-5 zeolite as active component is higher ₂ ⁼～C ₄ ⁼Productive rate.

USP5 discloses the preparation method with the ZSM-5 zeolite catalyst of phosphorus modification in 110,776.Described phosphorus modifying process is that zeolite is dispersed in the phosphorus-containing compound aqueous solution of pH value 2～6, then with matrix making beating, spray drying forming.The gained catalyst does not increase dry gas and coke yield when improving octane number.

USP6 discloses a kind of Cracking catalyst of phosphorous modified ZSM-5 zeolite in 566,293.The preparation of described phosphorous modified ZSM-5 is that zeolite is dispersed in the phosphorus-containing compound aqueous solution of pH value more than 4.5, makes the phosphorus of zeolite-loaded at least 10 % by weight (with P ₂O ₅Meter), then pull an oar spray drying forming with matrix and other zeolite component.The gained catalyst has higher productivity of low carbon olefin hydrocarbon.

USP 5,171, disclose a kind of ZSM-5 zeolite with the phosphorus modification in 921.This zeolite has 20～60 silica alumina ratio, by after 500～700 ℃ of steam treatment, is used for C with the phosphorus-containing compound dipping ₃～C ₂₀Hydrocarbon changes into C ₂～C ₅During the reaction of alkene, the ZSM-5 that relatively processes without phosphorus has higher activity.

USP6 discloses a kind of method that improves aperture and mesopore zeolite catalytic activity in 080,303.The method is to process aperture and mesopore zeolite with phosphorus compound, zeolite and the AlPO that then will process through phosphorus ₄The gel combination.The method can be improved activity and the hydrothermal stability of aperture and mesopore zeolite.

USP 5,472, disclose the hydrocarbon conversion process process of the catalyst that forms based on a kind of large pore zeolite and phosphorous MFI structure mesopore zeolite in 594.This technique is produced high-knock rating gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly C ₄/ C ₅

Also report and in matrix, introduce phosphorus compound the phosphorus modification except ZSM-5 zeolite is carried out, can improve selective to low-carbon alkene of catalyst or auxiliary agent.

A kind of catalytic cracking process process that increases productivity of propylene is disclosed among the USP 2002/0003103A1.This technical process re-starts the cracking reaction except at least part of gasoline product is entered in second riser, in the carbon monoxide-olefin polymeric that adopts except containing macropore USY zeolite, the inorganic binder component that also contains the mesopore zeolites such as ZSM-5 and have cracking performance.Phosphorous in the inorganic binder component wherein, its P/Al ratio is 0.1～10.This technical process is increased low carbon olefine output significantly, particularly increases productivity of propylene.

The catalyst of a kind of high zeolite content, high abrasion resistance strength is disclosed among the USP 2002/0049133A1.This catalyst contains the ZSM-5 zeolite of 30～85 % by weight, and the phosphorus of 6～24 % by weight is (with P ₂O ₅Count), and the Al that is lower than 10 % by weight ₂O ₃With other components such as clay of surplus, phosphorus wherein is present in the matrix.This catalyst is used for catalytic cracking process, can increase light olefin, especially productivity of propylene.

Zeolite has following relevant report with metal-modified method and application thereof.For example USP 5,236, disclose the catalyst that contains MFI or MEL structural zeolite in 880.Wherein used zeolite is through VIII family metal, preferably with the Ni modification, and after this zeolite was introduced Ni, heat or hydrothermal treatment consists under the control temperature of experience harshness were so that VIII family metal and aluminium are at surface enrichment.Said catalyst is used for can improving octane number when alkane transforms, and increases C ₃～C ₄The productive rate of alkene.

A kind of catalyst for cracking that contains silica-rich zeolite is disclosed among the CN 1057408A, it is active to have higher catalytic pyrolysis, wherein said silica-rich zeolite is ZSM-5, β zeolite or the modenite that contains 0.01～3.0 % by weight phosphorus, 0.01～1.0 % by weight iron or 0.01～10 % by weight aluminium, that silica alumina ratio is heated to 350～820 ℃ greater than 15 Hydrogen or potassium type ZSM-5 zeolite, β zeolite or modenite, with 0.1～10 hour ^-1Volume space velocity obtain after passing into the halide solution of halide solution, iron of aluminium or saline solution of ammonium phosphate.

Disclose a kind of MFI structural zeolite of phosphorous and transition metal among the CN 1465527A, the anhydrous chemical expression of this zeolite is counted (0～0.3) Na with the quality of oxide ₂O (0.5～5) Al ₂O ₃(1.3～10) P ₂O ₅(0.7～15) M ₂O ₃(70～97) SiO ₂, wherein, M is selected from a kind of among transition-metal Fe, Co and the Ni.When this zeolite is applied to the catalytic cracking process of petroleum hydrocarbon, can improve C ₂～C ₄The productive rate of alkene and selective have higher liquefied gas yield, but density of propylene is not high in its liquefied gas, and dry gas and coke selectivity are relatively poor.

CN 1611299A discloses a kind of MFI molecular sieve of phosphorous and metal component, and its anhydrous chemical expression is counted with the weight of oxide: (0～0.3) Na2O (0.5～5.5) Al ₂O ₃(1.3～10) P ₂O ₅(0.7～15) M1 _xO _y(0.01～5) M2 _mO _n(70～97) SiO2, wherein M1 is selected from a kind of among transition-metal Fe, Co and the Ni, and M2 is selected from any among Metal Zn, Mn, Ga and the Sn.

At present, for the overwhelming majority's catalytic cracking unit, under the prerequisite of identical liquefied gas yield, the density of propylene that improves in the liquefied gas is the important channel of improving the catalytic cracking unit economic benefit, but existing catalyst aid is used for catalytic cracking process, Propylene Selectivity is not high, and density of propylene is not high in the liquefied gas; When promoter addition is larger, can weaken heavy oil conversion performance, existing phosphorus and transition metal modified MFI molecular sieve are for the production of propylene, and its dry gas and coke yield are higher.

Summary of the invention

The technical problem to be solved in the present invention provides a kind of cracking additive that improves catalytic cracking liquefied gas low-carbon alkene concentration, and this auxiliary agent is used for catalytic cracking, can improve density of propylene in the catalytic cracking liquefied gas, improves heavy oil conversion performance.

The invention provides a kind of assistant for calalytic cracking, take the butt weight of described auxiliary agent as benchmark, contain modification MFI molecular sieve in butt 10～75 % by weight, with the al composition in the phosphorus aluminium inorganic binder that contains the first clay (with Al ₂O ₃Meter), phosphorus component is (with P ₂O ₅Meter) and the phosphorus aluminium inorganic binder that contains the first clay of the first clay butt weight sum meter 3～30 % by weight, in other inorganic binders of oxide 3～30 % by weight, in oxide 0.5～15 % by weight be selected from the VIII family metal one or more metallic addition and in the second clay of butt 0～60 % by weight; Wherein, take the described phosphorus aluminium inorganic binder butt weight that contains the first clay as benchmark, the described phosphorus aluminium inorganic binder that contains the first clay comprises with Al ₂O ₃The meter 15～40 % by weight al compositions, with P ₂O ₅The phosphorus component of meter 45～80 % by weight and in the first clay of butt 1～40 % by weight, and its P/Al weight ratio is 1.0～6.0; Described modification MFI molecular sieve, its anhydrous chemical expression is counted with the weight of oxide: (0～0.3) Na ₂O (0.5～6) Al ₂O ₃(1.3～10) P ₂O ₅(0.7～15) M _xO _y(70～97) SiO ₂, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more among Fe, Co, Ni, Cu, Mn, Zn, Sn, the Bi; The infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm ^-1The place is without absworption peak, its Phosphorous distribution D satisfies 0≤D≤0.8, D=P (S)/P (C) wherein, described P (S) expression adopt zeolite crystal that the TEM-EDX method characterizes from the edge 1/5th phosphorus content to the center, the phosphorus content of P (C) expression zeolite crystal center.Wherein said VIII family metallic addition does not comprise the transition metal in the modification MFI molecular sieve.

The present invention also provides a kind of preparation method of assistant for calalytic cracking, comprise modification MFI molecular sieve, the phosphorus aluminium inorganic binder that contains the first clay, other inorganic binder are mixed, add or do not add the second clay, making beating, spray-drying and the step of introducing VIII family metallic addition; Wherein, the described phosphorus aluminium compound inorganic binder that contains the first clay take its butt weight as benchmark, contains with Al ₂O ₃The meter 15～40 % by weight alumina component, with P ₂O ₅The meter 45～80 % by weight phosphorus component and in butt 1～40 % by weight clay, its P/Al weight ratio is that 1.0～6.0, pH is 1.0～3.5, this binding agent solid content is 15～60 % by weight; Described modification MFI molecular sieve, its anhydrous chemical expression is counted with the weight of oxide: (0～0.3) Na ₂O (0.5～6) Al ₂O ₃(1.3～10) P ₂O ₅(0.7～15) M _xO _y(70～97) SiO ₂, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably, and described modification MFI molecular sieve carries out IR Characterization with trimethylpyridine as probe, and its spectrogram is at 1633cm ^-1The place is without absworption peak, its Phosphorous distribution D satisfies 0≤D≤0.8, D=P (S)/P (C) wherein, described P (S) expression adopt zeolite crystal that the TEM-EDX method characterizes from the edge 1/5th phosphorus content to the center, the phosphorus content of P (C) expression zeolite crystal center.

Described VIII family metallic addition is preferably one or more among Fe, Co and the Ni, wherein more preferably comprises iron, more preferably the Fe additive.The existence form of described VIII group 4 transition metal additive in auxiliary agent can be one or more of oxide, phosphate, phosphite, subphosphate or acid phosphate of described metal.

Described the first clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and the diatomite.

Described the second clay is selected from and well known to a person skilled in the art in the clay that is customarily used in Cracking catalyst or auxiliary agent one or more, for example be selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, rectorite, diatomite, galapectite, saponite, boron-moisten soil and the hydrotalcite one or more, be preferably one or more the mixture in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and the rectorite.

Cracking additive provided by the invention also contains other inorganic binder that contains the first clay inorganic binder except described.Described other inorganic binder is selected from one or more in the inorganic oxide binder that is customarily used in assistant for calalytic cracking or catalyst binder component, for example be derived from one or more the mixture in boehmite, aluminium colloidal sol, phosphorus aluminium glue, silicon-aluminum sol, the waterglass, wherein one or more in preferred boehmite, aluminium colloidal sol, the phosphorus aluminium glue.

Can also contain with P in the catalyst aid provided by the present invention ₂O ₅The phosphorus additive of meter 0～25 % by weight, described phosphorus additive is selected from compounds of phosphorus and comprises the inorganic compound of phosphorus and in the organic compound one or more, can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound, for example be selected from the oxide, phosphoric acid, phosphate, phosphite, hypophosphites, subphosphate, acid phosphate of phosphorus and in the phosphorous organic compound one or more.Preferred phosphorus compound is one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate and the phosphorus aluminium colloidal sol.In the resulting catalyst, phosphorus additive exists with the form of phosphorus compound (such as oxide, phosphate, phosphite, subphosphate, the acid phosphate of phosphorus).When containing other phosphorous binding agent except the described phosphorus aluminium inorganic binder that contains the first clay in the auxiliary agent for example during phosphorus aluminium colloidal sol, this part phosphorus also is considered as phosphorus additive, and the total content of the phosphorus that the phosphorus that other inorganic binder is introduced and other phosphorus additive are introduced is no more than 25 % by weight.Described phosphorus additive may reside in any position that may exist of auxiliary agent, as the duct that may reside in zeolite is inner, the surface of zeolite, may reside in the described host material, the duct that can also be present in simultaneously zeolite is inner, in the surface and described host material of zeolite.Do not comprise the phosphorus in the modification MFI molecular sieve in the content of described phosphorus additive, do not comprise the phosphorus that the described phosphorus aluminium inorganic binder that contains the first clay is introduced yet.

Assistant for calalytic cracking provided by the invention, have preferably anti-wear performance and Catalytic Cracking Performance, be used for the catalytic cracking reaction process, can improve the RFCC liquefied gas yield, improve significantly low-carbon alkene concentration especially propylene and isobutylene concentration in the catalytic cracking liquefied gas, improve liquid and receive, improve the productive rate of ethene, propylene and isobutene, coke and dry gas selectively low, and can improve the heavy oil conversion performance of carbon monoxide-olefin polymeric, improve octane number.For example, industrial DVR-3 poising agent is 16h at 500 ℃, weight (hourly) space velocity (WHSV) ^-1, oil ratio is to react under 5 the condition, liquefied gas yield is 16.36 % by weight, heavy oil yield is 14.21 % by weight, it is 77.01 % by weight that liquid is received, and productivity of propylene is 5.27 % by weight, and density of propylene is 32.21 % by weight in the liquefied gas, the isobutene productive rate is 1.55 % by weight, isobutylene concentration is 9.47 % by weight in the liquefied gas, and coke selectivity is 10.53 % by weight, and dry gas selectively is 2.24 % by weight.And the phosphorous and iron ZSM-5 molecular sieve that contains 50 % by weight silicon modifications provided by the invention, 10 % by weight kaolin, 24 % by weight contain the phosphorus aluminium inorganic binder of the first clay, 8 % by weight boehmites, the auxiliary agent of 6 % by weight aluminium colloidal sols and 2 % by weight iron additives, with 10: 90 weight ratios with after above-mentioned DVR-3 poising agent mixes, under similarity condition, react, liquefied gas yield is 22.34 % by weight, heavy oil yield is 13.35 % by weight, it is 77.87 % by weight that liquid is received, productivity of propylene is 9.45 % by weight, density of propylene is 42.30 % by weight in the liquefied gas, the isobutene productive rate is 2.34 % by weight, isobutylene concentration is 10.47 % by weight in the liquefied gas, coke selectivity is 10.29 % by weight, and dry gas selectively is 2.19 % by weight.

The specific embodiment

Cracking additive provided by the present invention preferably includes the phosphorus aluminium inorganic binder that contains the first clay of 8～25 % by weight, the modification MFI molecular sieve of 20～60 % by weight, the clay of 10～45 % by weight, other inorganic binder of 5～25 % by weight and the phosphorus additive of 0～10 % by weight.Wherein said phosphorus additive does not comprise the phosphorus that relates in the modification MFI molecular sieve, does not comprise the phosphorus that relates in the phosphorus aluminium inorganic binder that contains the first clay.

Described modification MFI molecular sieve is phosphorous and MFI molecular sieve transition metal, and its anhydrous chemical expression is preferably: (0～0.2) Na ₂O (0.9～5.5) Al ₂O ₃(1.5～7) P ₂O ₅(0.9～10) M _xO _y(82～92) SiO ₂The phosphorus distribution D of described modification MFI molecular sieve satisfies 0.1≤D≤0.5.Described MFI molecular sieve carries out IR Characterization with trimethylpyridine as probe, and its spectrogram is at 1633cm ^-1The place is without absworption peak.Carry out IR Characterization with trimethylpyridine as probe and be existing method, its process can be as follows: with the sample compressing tablet, place the original position pond of infrared spectrometer to seal, be evacuated down to 10 under 450 ℃ ^-3Pa, roasting 1.5h is cooled to room temperature; Then the trimethylpyridine steam that imports to the original position pond is kept adsorption equilibrium 30min, takes the photograph spectrum.Described M is preferably Fe.Described MFI molecular sieve is one or more among ZSM-5, ZSM-8 and the ZSM-11 for example, are preferably ZSM-5.The MFI molecular sieve is also referred to as has MFI structure molecular screen or MFI structure molecular screen.

Under the preferable case, the first clay in the inorganic binder of the described phosphorus aluminium compound that contains the first clay comprises rectorite, and more preferably described the first clay is rectorite.Take butt weight as benchmark, the described phosphorus aluminium compound binding agent that contains the first clay contains with Al ₂O ₃The al composition of meter 15～35 % by weight is with P ₂O ₅The phosphorus component of meter 50～75 % by weight and in the first clay of butt 8～35 % by weight, it is 1.0～3.5 that its P/Al weight ratio is preferably 2.0～5.0, pH.

Among the preparation method of assistant for calalytic cracking provided by the invention, the described phosphorus aluminium inorganic binder that contains the first clay take its butt weight as benchmark, contains with Al ₂O ₃The meter 15～40 % by weight al compositions, with P ₂O ₅The phosphorus component of meter 45～80 % by weight and in the first clay of butt 1～40 % by weight, its P/Al weight ratio is that 1.0～6.0, pH is 1.0～3.5, solid content is 15～60 % by weight.The described phosphorus aluminium inorganic binder preparation method who contains the first clay comprises:

(1) alumina source, the first clay and water making beating are dispersed into the slurries that solid content is 8～45 % by weight; Described alumina source is can be by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt and with Al ₂O ₃The weight ratio of the alumina source of meter is 1～40: 15～40;

(2) stir that the part by weight according to P/Al=1.0～6 adds SPA in the lower slurries that obtain to step (1); P is the weight in the phosphorus of simple substance in the phosphoric acid among the wherein said P/Al, and Al is in the weight of the aluminium of simple substance in the alumina source;

(3) slurries that step (2) obtained reacted 15～90 minutes under 50～99 ℃ of temperature.

Wherein, the consumption of alumina source, SPA and the first clay makes the resulting phosphorus aluminium inorganic binder that contains the first clay, and take its butt weight as benchmark, comprise: preferred 15～35 % by weight of 15～40 % by weight are derived from the Al of described alumina source ₂O ₃, 45～80 % by weight, 0～75 % by weight P ₂O ₅, the first clay of preferred 8～35 % by weight of 1～40 % by weight; Described P/Al weight ratio is preferably 1.2～6.0, and more preferably 2.0～5.0.Alumina source is one or more in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and the boehmite, and described al composition is derived from described alumina source.Described the first clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and the diatomite, is preferably rectorite.Its concentration of described SPA is 60～98 % by weight, more preferably 75～90 % by weight.The charging rate of phosphoric acid be preferably 0.01-0.10Kg phosphoric acid/minute/the Kg alumina source, more preferably 0.03-0.07Kg phosphoric acid/minute/the Kg alumina source.

The described phosphorus aluminium inorganic binder of the first clay that contains is because the introducing of clay, mass transfer, the heat transfer of storeroom not only in preparation process, have been improved, the adhesive cures of having avoided the inhomogeneous local moment vigorous reaction heat release overtemperature of material to cause, the adhesive property of the binding agent that obtains is suitable with the phosphorus al binder of not introducing the clay mitigation preparation; And the method introduces clay, and the rectorite that especially has layer structure has improved the heavy oil conversion performance of carbon monoxide-olefin polymeric, and it is better selective that the auxiliary agent that obtains is had.

Described modification MFI molecular sieve, MFI molecular sieve for the phosphorous and transition metal of modification, its preparation method comprises baked phosphorous and MFI molecular sieve MFI molecular sieve transition metal is mixed with the silicon source, reacted crystallization 2～80 hours in 145～190 ℃, reclaim again the MFI molecular sieve of the phosphorous and transition metal that obtains the silicon modification, with SiO ₂The silicon source of meter with take the weight ratio of the MFI molecular sieve of the described baked phosphorous and transition metal of butt as 0.03～0.3: 1, be preferably 0.05～0.15: 1.Wherein said silicon source is one or more in the material of silicon compound or silicon-containing compound, is preferably in silane, siloxanes, estersil and the Ludox one or more, silicone grease more preferably, and described estersil is methyl silicate and/or ethyl orthosilicate for example.

The preparation method of modification MFI molecular sieve of the present invention, with silicon-containing compound phosphorous and MFI molecular sieve transition metal are carried out modification, comprise baked phosphorous and MFI molecular sieve transition metal is mixed with the silicon source, then the gained mixture was reacted crystallization (also claiming crystallization) in 2～80 hours in 145～190 ℃ of maintenances.With SiO ₂The silicon source of meter with take the weight ratio of the MFI molecular sieve of the described baked phosphorous and transition metal of butt as 0.03～0.3: 1, be preferably 0.05～0.15: 1.Described reaction crystallization temperature is preferably 150～190 ℃ more preferably 170～190 ℃, and the reaction crystallization time is preferably 5～50 hours, more preferably 12～24 hours.

Baked phosphorous and MFI molecular sieve transition metal is mixed with the silicon source, preferably also add dispersant in the formed mixture, the weight ratio in dispersant and silicon source is 5～90: 10～95, is preferably 10～80: 20～90.Described dispersant is selected from one or more in C5, C6, C7, C8, C9 and the C10 alkane, is preferably in C5, C6 and the C7 alkane one or more, wherein dispersant with SiO ₂The weight ratio in the silicon source of meter is 5～90: 10～95, preferred 10～80: 20～90.Preferably described dispersant is mixed with the silicon source first behind the mixture of formation silicon source again this silicon source mixture is phosphorously mixed with MFI molecular sieve transition metal with baked, this is conducive to the silicon source and is scattered in more equably in the molecular sieve, thereby the character of the MFI molecular sieve of the phosphorous and transition metal of gained modification is more even, comprises the dispersant of preferred 10～80 % by weight of 5～90 % by weight in the mixture that dispersant and silicon source form.

Preferably also introduce template and water in the described reactant mixture, wherein water and template weight ratio are 0.5～19: 1, the ratio of the molal quantity of silicon is 0.3～1: 1 in the molal quantity of template and the silicon source, and the mol ratio of silicon is preferably 0.4～0.6 in the agent of masterplate plate and the silicon source: 1.Described template is MFI molecular sieve masterplate template commonly used, is preferably in tetraethyl ammonium hydroxide, TPAOH, tetraethylammonium bromide or the 4-propyl bromide one or more.Preferably, masterplate template and water react with described baked phosphorous the mixing with MFI molecular sieve transition metal first with after mix in the silicon source again.Silicon source and the phosphorous and transition metal molecular sieve that will contain silicon-containing compound carry out crystallization in the presence of template, it is higher that the degree of crystallinity of resulting modified molecular screen keeps.

The preparation method of the MFI molecular sieve of the phosphorous and transition metal of modification provided by the invention, the step that also comprises recovery, described recovery comprises that the mixture that will reaction obtains after the crystallization separates, drying, and roasting obtains the MFI molecular sieve of the phosphorous and transition metal of described modification after the roasting; Wherein, described separation is for example filtered, and the temperature of roasting is preferably 530～550 ℃, and the time of roasting is preferably 1～5 hour.

Described baked MFI molecular sieve phosphorous and transition metal can be by introducing the method preparation of phosphorus and transition metal, roasting in MFI molecular sieve (for example ammonium type or Hydrogen MFI molecular sieve).Described introducing phosphorus and transition gold can be with phosphorous and solution impregnation MFI molecular sieves transition metal, described dipping can be respectively with containing the solution of transistion metal compound and the solution of phosphorus compound successively floods, also can flood with the solution that contains simultaneously transistion metal compound and phosphorus compound, it is that phosphorus and transition metal can once or several times be introduced that described dipping can carry out one or many.The mode of dipping can be saturated dipping or supersaturation dipping.A kind of preferred preparation method can comprise: with the phosphorus-containing compound solution of ammonium type and/or Hydrogen MFI molecular sieve and amount of calculation and contain transistion metal compound solution in room temperature (being generally 15～30 ℃) to 95 ℃ of hybrid infusions, oven dry, roasting under 400～800 ℃ of conditions.The compound dipping of described phosphorus and transition metal can adopt saturated dipping or supersaturation impregnation method once or several times to be incorporated in ammonium type and/or the Hydrogen MFI molecular sieve; The dipping of phosphorus and transition metal can carry out also can carrying out respectively simultaneously, and is preferred, and described phosphorus is at least partially in introducing simultaneously before the transition metal or with transition metal.Phosphorus-containing compound can be selected from one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture; Contain the water soluble salt that transistion metal compound is selected from described transition metal, described water soluble salt is selected from a kind of in sulfate, nitrate, the chlorate.Described silicon modification can be one or many, once is to carry out after all the transition metal of amount is introduced but have at least.Under the preferable case, whole phosphorus and transition metal are introduced in the described MFI molecular sieve before the silicon modification.

Described ammonium type MFI molecular sieve can be according to existing method by obtaining sodium type MFI molecular sieve after with ammonium ion exchange.With sodium type MFI molecular sieve according to molecular sieve: ammonium salt: H ₂O=1: (0.1～1): the weight ratio of (5～10) is filtered after 0.3～1 hour in room temperature to 100 a ℃ lower exchange, drying, the MFI molecular sieve that obtains the ammonium exchange is ammonium type molecular sieve, and preferred described exchange makes the content of sodium oxide molybdena in the molecular sieve that obtains be no more than 0.2 % by weight.Described Hydrogen MFI molecular sieve can be by the roasting of above-mentioned ammonium type MFI molecular sieve is obtained, perhaps by sodium type MFI molecular sieve is obtained with the hydrogen ion exchange.

A kind of specific embodiment of preparation method provided by the invention comprises:

(1) according to molecular sieve: ammonium salt: H ₂O=1: (0.1～1): the weight ratio of (5～10) with sodium type MFI molecular sieve filter after 0.3～1 hour in the lower exchange of room temperature to 100 ℃, drying;

(2) flood dry, roasting after the modification with phosphorus-containing compound solution and the solution that the contains transistion metal compound molecular sieve after to the ammonium exchange; Described sintering temperature is 400～800 ℃; The described molecular sieve dipping of using after phosphorus-containing compound solution and transistion metal compound solution exchange ammonium, can be to flood with the solution that contains simultaneously phosphorus compound and transistion metal compound, also can be to flood respectively with the solution that contains phosphorus compound and the solution that contains transistion metal compound; Described dipping can carry out one or many.Preferably, flood with the solution that contains simultaneously phosphorus compound and transistion metal compound.；

The MFI molecular sieve of the baked phosphorous and transition metal that (3) step (2) is obtained mixes with the silicon source of containing silicon-containing compound, the mixture that obtains reacted crystallization 2～80 hours in 145～190 ℃ in airtight reaction vessel, then filter, dry, roasting, obtain the MFI molecular sieve of the phosphorous and transition metal of described silicon modification.The described consumption that contains the silicon source of silicon-containing compound makes in the described mixture, with SiO ₂The weight ratio of the MFI molecular sieve of the silicon source of meter and phosphorous and transition metal is 0.03～0.3, is preferably 0.05～0.15.Described crystallization condition is more preferably: 170～190 ℃ of crystallization temperatures, crystallization time 20～24 hours.

Preparation method provided by the invention carries out modification with phosphorous and MFI molecular sieve transition metal with silicon compound, this modifying process mixes baked phosphorous and MFI molecular sieve transition metal with the silicon source, resulting mixture reacted crystallization 2～80 hours in 145～190 ℃, can carry out one or many, the MFI molecular sieve molecular sieve of the phosphorous and transition metal of the modification that namely obtains with the inventive method can also further carry out modification with silicon-containing compound.Described modifying process makes that Phosphorous distribution D satisfies 0≤D≤0.8, wherein D=P in the molecular sieve that described mixture obtains through crystallization _(S)/ P _(C), described P _(S)Expression adopt zeolite crystal that the TEM-EDX method characterizes from the edge 1/5th phosphorus content to the center, P _(C)The phosphorus content of the zeolite crystal center of TEM-EDX method sign is adopted in expression, and Phosphorous distribution D preferably satisfies 0≤D≤0.8.The phosphorus of preferred 0.1≤D≤0.5 described modification and transition metal modified MFI molecular sieve carry out IR Characterization with trimethylpyridine as probe, and its spectrogram is at 1633cm ^-1The place is without absworption peak.

The preparation method of assistant for calalytic cracking provided by the invention, described with modification MFI molecular sieve, the phosphorus aluminium inorganic binder that contains the first clay, other inorganic binder mixes, making beating, its reinforced order does not have specific (special) requirements, for example can the phosphorus aluminium inorganic binder of the first clay will be contained, other inorganic binder (when not containing other inorganic binder, then can omit relevant addition step), modification MFI molecular sieve, the second clay mixes (then can omit relevant addition step when not containing the second clay) making beating, preferably, first with the second clay, molecular sieve and other inorganic binder add the described phosphorus aluminium inorganic binder that contains the first clay after mixing making beating again, and this is conducive to improve the activity and selectivity of auxiliary agent.

Assistant for calalytic cracking preparation method provided by the invention also comprises the spray-dired step of the slurries that described making beating is obtained.Spray-dired method is known for those skilled in the art, and the present invention does not have specific (special) requirements.

Among the cracking additive preparation method provided by the invention, can introduce described metallic addition by the form of introducing the VIII group transition metal compound, VIII group 4 transition metal additive can any step before the spray drying forming of auxiliary agent preparation process in the slurries interpolation transistion metal compound and introducing; Also can after the auxiliary agent spray drying forming, introduce by roasting behind dipping or the chemisorption transition metallic compound, comprise that the transistion metal compound aqueous solution floods or chemisorbed is processed with containing with auxiliary agent, then carry out Separation of Solid and Liquid (if necessary), drying and roasting, wherein dry temperature is room temperature to 400 ℃, preferred 100～300 ℃, the temperature of roasting is 400～700 ℃, be preferably 450～650 ℃, roasting time is 0.5～100 hour, is preferably 0.5～10 hour.Described VIII group transition metal compound is selected from their inorganic compound and in the organic compound one or more, can be soluble in water, also can be to be insoluble in water or water-fast compound.The example of transistion metal compound comprises oxide, hydroxide, chloride, nitrate, sulfate, the phosphate of transistion metal compound, organic compound of transition metal etc.Preferred transistion metal compound is selected from one or more in their chloride, nitrate, sulfate and the phosphate.

In the cracking additive provided by the present invention, described transition metal additives may reside in any position that may exist of auxiliary agent, as the duct that may reside in zeolite is inner, the surface of zeolite, may reside in the host material, the duct that can also be present in simultaneously zeolite is inner, in the surface and described host material of zeolite, preferably be present in the host material.The transition metal additives of described VIII family can exist with their oxide, phosphate, phosphite, subphosphate, the form of acid phosphate.

Catalyst aid preparation method provided by the present invention, when containing phosphorus additive in the auxiliary agent, said phosphorus additive can adopt the combination of one of following method or several method, introduces in the auxiliary agent but be not limited to these methods:

1, before the auxiliary agent spray drying forming, in slurries, adds phosphorus compound;

2, be incorporated in the auxiliary agent by inorganic oxide binder, when containing phosphorus aluminium colloidal sol in the inorganic oxide binder (other inorganic binder), both brought phosphorus after the roasting in the auxiliary agent into, phosphorus aluminium colloidal sol can play again the effect of host material and binding agent, and this part phosphorus also belongs to phosphorus additive of the present invention;

3, after the auxiliary agent spray drying forming through the dipping or the chemisorbed phosphorus compound, introduce through Separation of Solid and Liquid (if necessary), drying and roasting process, the temperature of said drying is room temperature to 400 ℃, preferred 100～300 ℃, the temperature of roasting is 400～700 ℃, be preferably 450～650 ℃, roasting time is 0.5～100 hour, is preferably 0.5～10 hour.Described phosphorus compound is selected from the various inorganic compounds of phosphorus and in the organic compound one or more.Described phosphorus compound can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound.The embodiment of phosphorus compound comprises the oxide, phosphoric acid, phosphate, phosphite, hypophosphites of phosphorus, phosphorous organic compound etc.Preferred phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate and the phosphorus aluminium colloidal sol.

Thereby, described phosphorus additive may reside in any position that may exist of auxiliary agent, as the duct that may reside in zeolite is inner, the surface of zeolite, may reside in the described host material, and the duct that can also be present in simultaneously zeolite is inner, in the surface and described host material of zeolite.Described phosphorus additive exists with the form of phosphorus compound (such as oxide, phosphate, phosphite, subphosphate, the acid phosphate of phosphorus).

Cracking additive provided by the invention is applicable to hydrocarbon oil catalytic cracking.When being used for catalytic cracking process, can in catalyst cracker, add separately, use after also can mixing with Cracking catalyst.Generally speaking, auxiliary agent provided by the invention accounts for the FCC catalyst and agent mixture total amount provided by the invention is no more than 30 % by weight, be preferably 1～25 % by weight, 3～15 % by weight more preferably, described hydrocarbon ils is selected from various petroleum distillates, such as crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/in heavily de-oiling, wax tailings and the coal liquefaction products one or more.Described hydrocarbon ils can contain the beavy metal impurities such as nickel, vanadium and sulphur, nitrogen impurity, can be up to 3.0 % by weight such as the content of sulphur, and the content of nitrogen can be up to 2.0 % by weight, and the content of the metal impurities such as vanadium, nickel is up to 3000ppm.

Cracking additive provided by the invention is used for catalytic cracking process, and the cracking hydrocarbon oil condition is conventional catalytic cracking condition.In general, this cracking hydrocarbon oil condition comprises that reaction temperature is 400～600 ℃, is preferably 450～550 ℃, and weight (hourly) space velocity (WHSV) is 10～120 hours ^-1, be preferably 10～80 hours ^-1, oil ratio (weight ratio) is 1～20, is preferably 3～15.Cracking additive provided by the invention can be used for existing various catalyst cracker, as carrying out in fixed bed reactors, fluidized-bed reactor, riser reactor, multi-reaction-area reactor etc.

The following examples will be further described the present invention, but be not therefore and restriction the present invention.Part material character used among the embodiment is as follows:

Boehmite is Shandong Aluminium Industrial Corp's manufacture product, solid content 60 % by weight; Aluminium colloidal sol is the industrial products that China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, Al ₂O ₃Content is 21.5 % by weight; Waterglass is the industrial products that China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, SiO ₂Content 28.9 % by weight, Na ₂O content 8.9%; Kaolin is the special-purpose kaolin of Cracking catalyst that Kaolin of Suzhou company produces, solid content 78 % by weight; The ZRP-5 zeolite is the industrial products of the conventional MFI structural zeolite of China Petrochemical Industry's catalyst asphalt in Shenli Refinery production, wherein P ₂O ₅2.5 % by weight, degree of crystallinity 85 % by weight, silica alumina ratio (SiO ₂/ Al ₂O ₃, mol ratio, lower same) 50.Concentration of hydrochloric acid is 36 % by weight.Rectorite is Hebei Zhongxiang Mingliu Rectorite Development Co., Ltd.'s product, quartz sand＜3.5 % by weight, Al ₂O ₃39.0 % by weight, Fe ₂O ₃2.0 % by weight, Na ₂O 0.03 % by weight, solid content 77 % by weight; The SB aluminium hydrate powder: German Condex company produces, Al ₂O ₃Content 75 % by weight; The gamma oxidation aluminium powder: German Condex company produces, Al ₂O ₃Content 95 % by weight.Hydrochloric acid: chemical pure, concentration 36～38 % by weight, the Beijing Chemical Plant produces.

Embodiment 1

With 5kg NH ₄Cl is dissolved in the 100kg water, and (China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 0.9kg H ₃PO ₄(concentration 85 % by weight) and 0.81kgFe (NO ₃) ₃9H ₂O was dissolved in the 9kg water, with this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ of roastings 2 hours; Get the above-mentioned baked molecular sieve of 1kg, with its with contain the 0.536kg ethyl orthosilicate (Beijing chemical reagents corporation, analyze pure, SiO ₂Content 28 % by weight), (there is greatly Fine Chemical Works production in Guangzhou to the 0.333kg 4-propyl bromide, analyze pure, 99%) and the mixture of 1.2L water mix, place the crystallizing kettle that contains the polytetrafluoro lining, be cooled to room temperature in 150 ℃ of static crystallizations after 20 hours, afterwards, molecular sieve was 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 2 hours namely get molecular sieve of the present invention.Gained molecular sieve elementary analytical chemistry consists of 0.07Na ₂O2.9Al ₂O ₃5.3P ₂O ₅1.5Fe ₂O ₃89.6SiO ₂, Phosphorous distribution D value and IR Characterization the results are shown in Table 1.

Comparative Examples 1

Method by CN1425567A prepares phosphorous and MFI molecular sieve transition metal.

With 5kg NH ₄Cl is dissolved in the 100kg water, and (China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 0.9kg H ₃PO ₄(concentration 85 % by weight) and 0.81kgFe (NO ₃) ₃9H ₂O is dissolved in the 90g water, dries with the filter cake hybrid infusion; The gained sample namely gets the contrast molecular sieve 550 ℃ of calcination process 2 hours, is designated as B ₁Elementary analytical chemistry consists of 0.08Na ₂O3.0Al ₂O ₃5.4P ₂O ₅1.5Fe ₂O ₃89.3SiO ₂

Embodiment 2

With 5kg NH ₄Cl is dissolved in the 100kg water, and (China Petrochemical Industry of China Petrochemical Industry catalyst asphalt in Shenli Refinery is produced, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 0.93kg H ₃PO ₄(concentration 85 % by weight) and 3kgCo (NO ₃) ₂6H ₂O is dissolved in the 9kg water getting maceration extract, with this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ of roastings 2 hours, obtains sample; Get the above-mentioned baked sieve sample of 1kg and contain 253g methyl silicate (Beijing chemical reagents corporation, analyze pure, 99 % by weight), (there is greatly Fine Chemical Works production in Guangzhou to the 817g tetraethyl ammonium hydroxide, wherein, tetraethyl ammonium hydroxide accounts for 27 % by weight, water accounts for 73 % by weight) mixture mix, place the crystallizing kettle that contains the polytetrafluoro lining, be cooled to room temperature in 180 ℃ of static crystallizations after 20 hours, afterwards, 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 2 hours namely got molecular sieve of the present invention.Gained molecular sieve elementary analytical chemistry consists of 0.10Na ₂O2.8Al ₂O ₃5.3P ₂O ₅8.5Co ₂O ₃83.2SiO ₂, Phosphorous distribution D value and IR Characterization the results are shown in Table 1.

Comparative Examples 2

With 5kgNH ₄Cl is dissolved in the 100kg water, and (China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 0.93kgH ₃PO ₄(concentration 85 % by weight) and 3kgCo (NO ₃) ₂6H ₂O is dissolved in the 9kg water, with this maceration extract and the even hybrid infusion of filter cake, oven dry; The gained sample namely gets the contrast molecular sieve 550 ℃ of calcination process 2 hours, is designated as B ₂, elementary analytical chemistry consists of 0.11Na ₂O2.8Al ₂O ₃5.5P ₂O ₅8.6Co ₂O ₃83SiO ₂

Embodiment 3

With 5kg NH ₄Cl is dissolved in the 100kg water, and (China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 0.25kg H ₃PO ₄(concentration 85 % by weight) and 0.38kgNi (NO ₃) ₂6H ₂O is dissolved in the 9kg water, with this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, gets the ZSM-5 molecular sieve sample of baked phosphorous and transition metal; With the 0.1428kg ethyl orthosilicate (Beijing chemical reagents corporation, analyze pure, SiO ₂Content 28 % by weight), 0.1815kg (there is greatly Fine Chemical Works production in Guangzhou to tetraethyl ammonium hydroxide, tetraethyl ammonium hydroxide 27 % by weight, water 73 % by weight) and 0.442kg n-hexane (Beijing Chemical Plant, analyze pure, n-hexane content 95 % by weight) mix, the mixture that obtains is mixed with the above-mentioned baked molecular sieve of 1kg, stirred 20 minutes, then place the crystallizing kettle that contains the polytetrafluoro lining, be cooled to room temperature in 170 ℃ of static crystallizations after 20 hours, afterwards, molecular sieve was 110 ℃ of oven dry 4 hours, 550 ℃ of roastings 2 hours namely get molecular sieve of the present invention.Gained molecular sieve elementary analytical chemistry consists of 0.1Na ₂O3.1Al ₂O ₃1.5P ₂O ₅1.0NiO94.3SiO ₂, Phosphorous distribution D value and IR Characterization the results are shown in Table 1.

Comparative Examples 3

With 5kg NH ₄Cl is dissolved in the 100kg water, and (catalyst branch company in Shandong produces, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; Add 0.25kg H ₃PO ₄(concentration 85 % by weight) and 0.38kgNi (NO ₃) ₂6H ₂O dissolves in 9kg water, with this maceration extract and filter cake hybrid infusion, oven dry; The gained sample namely gets modification MFI molecular sieve 550 ℃ of calcination process 2 hours, is designated as B ₃Elementary analytical chemistry consists of 0.1Na ₂O3.2Al ₂O ₃1.5P ₂O ₅1.0NiO94.2SiO ₂

Embodiment 4

With 5kg NH ₄Cl is dissolved in the 100kg water, and (China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 0.35kg H ₃PO ₄(concentration 85 % by weight) and 0.66KgZn (NO ₃) ₂6H ₂O was dissolved in the 9kg water, with this maceration extract and the even hybrid infusion of filter cake, oven dry, 550 ℃ of roastings 2 hours; Get the above-mentioned baked molecular sieve of 1kg, (there are greatly Fine Chemical Works production, SiO in Guangzhou with containing the 0.35kg Ludox with it ₂Content 40 % by weight, water content 60 % by weight) and the 1.516kg TPAOH (there is greatly Fine Chemical Works production in Guangzhou, contain TPAOH 25 % by weight, water 75 % by weight) mixture mixes, and then places the crystallizing kettle that contains the polytetrafluoro lining, is cooled to room temperature in 180 ℃ of static crystallizations after 24 hours, afterwards, molecular sieve was 110 ℃ of oven dry 4 hours, and 550 ℃ of roastings 2 hours namely get molecular sieve of the present invention.Gained molecular sieve elementary analytical chemistry consists of 0.10Na ₂O3.0Al ₂O ₃2.5P ₂O ₅1.8ZnO92.6SiO ₂, Phosphorous distribution D value and IR Characterization the results are shown in Table 1.

Comparative Examples 4

With 5kg NH ₄Cl is dissolved in the 100kg water, and (China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 0.35kg H ₃PO ₄(concentration 85 % by weight) and 0.66kgZn (NO ₃) ₂6H ₂O is dissolved in the 9kg water, with this maceration extract and filter cake hybrid infusion, oven dry; The gained sample gets modification MFI molecular sieve 550 ℃ of roastings 2 hours, is designated as B ₄Elementary analytical chemistry consists of 0.12Na ₂O3.1Al ₂O ₃2.5P ₂O ₅1.8ZnO92.5SiO ₂, Phosphorous distribution D value and IR Characterization the results are shown in Table 1.

Embodiment 5

With 5kg NH ₄Cl is dissolved in the 100kg water, and (China Petrochemical Industry's catalyst asphalt in Shenli Refinery is produced, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; With 0.52kg H ₃PO ₄(concentration 85 % by weight), 0.82kg Fe (NO ₃) ₃9H ₂O and 0.22kgBi (NO ₃) ₃5H ₂O is dissolved in the 9Kg water, and this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ of roastings were obtained sample in 2 hours.Get 1 kilogram of above-mentioned baked sieve sample, with its with contain the 0.357kg ethyl orthosilicate (Beijing chemical reagents corporation, analyze pure, SiO ₂Content 28%) and 0.9366kg n-hexane (Beijing Chemical Plant, analyze pure, 95%) mixture mixes, be placed in the crystallizing kettle that contains the polytetrafluoro lining, in 170 ℃ of reactions 12 hours, then be cooled to room temperature, afterwards, 110 ℃ of oven dry 4 hours, 550 ℃ of roastings 2 hours namely got molecular sieve of the present invention with molecular sieve.Gained molecular sieve elementary analytical chemistry consists of 0.1Na ₂O3.0Al ₂O ₃3.0P ₂O ₅1.6Fe ₂O ₃1.0Bi ₂O ₃91.4SiO ₂, also can be expressed as 0.1Na ₂O3.0Al ₂O ₃3.0P ₂O ₅2.6M ₂O ₃91.1SiO ₂, wherein the calculating atomic weight of M is 82.9, Phosphorous distribution D value and IR Characterization the results are shown in Table 1.

Comparative Examples 5

With 5kg NH ₄Cl is dissolved in the 100kg water, and (catalyst branch company in Shandong produces, and has the amine method synthetic, SiO to add 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution ₂/ Al ₂O ₃=50), behind 90 ℃ of exchange 0.5h, filter to get filter cake; Add 0.52kg H ₃PO ₄(concentration 85 % by weight) and 0.82kgFe (NO ₃) ₃9H ₂O, 0.22kg Bi (NO ₃) ₃5H ₂O dissolves in 9kg water, with this maceration extract and filter cake hybrid infusion, oven dry; The gained sample namely gets modified molecular screen 550 ℃ of calcination process 2 hours, is designated as B ₅Elementary analytical chemistry consists of 0.1Na ₂O3.1Al ₂O ₃3.1P ₂O ₅1.6Fe ₂O ₃1.0Bi ₂O ₃91.1SiO ₂Also can be expressed as 0.1Na ₂O3.1Al ₂O ₃3.1P ₂O ₅2.6M ₂O ₃91.1SiO ₂, wherein the calculating atomic weight of M is 82.9.

Embodiment 6

The sample that embodiment 1～5 and Comparative Examples 1～5 are made the results are shown in Table 1. with TEM-EDS and infrared the sign

The used phosphorus aluminium inorganic binder argillaceous of embodiment 7～10 preparation the present invention, prescription and composition see Table 2.

Embodiment 7

This example prepares phosphorus aluminium inorganic binder argillaceous of the present invention.

0.74 kilogram of boehmite (is contained Al ₂O ₃0.45 kilogram), 0.39 kilogram of rectorite (0.30 kilogram of butt) and 1.6 kilograms of decationizing water making beating 30 minutes, in slurries, add 2.03 kilograms of SPAs (concentration 85 % by weight) under stirring, phosphoric acid adding speed be 0.03Kg phosphoric acid/minute/the Kg alumina source, be warming up to 70 ℃, then under this temperature, reacted 45 minutes, make phosphorus aluminium inorganic binder argillaceous.Material proportion sees Table 2.

Embodiment 8～10

Example 8～10 preparations phosphorus aluminium inorganic binder argillaceous of the present invention.Material proportion sees Table 2.

Comparative Examples 6

This Comparative Examples prepares the phosphorus aluminium glue according to existing method.

With 0.66 kilogram of boehmite (0.40 kilogram of butt) and 1.75 kilograms of decationizing water making beating 30 minutes, in slurries, add 2.6 kilograms of SPA (chemical pures under stirring, phosphoric acid 85 % by weight), be warming up to 70 ℃, then under this temperature, reacted 45 minutes, obtain phosphorus aluminium glue inorganic binder.Material proportion sees Table 2.

Table 1

Embodiment 11～21 preparations auxiliary agent provided by the present invention.Auxiliary formula sees Table 3, and preparation process is described below:

Embodiment 11

Get molecular sieve-4 A ₁, kaolin and boehmite, add decationized Y sieve water and and aluminium colloidal sol making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution (the FeCl of O ₃Content 30 % by weight), obtain the slurries that solid content is 30 % by weight, add hydrochloric acid and regulate the pH value 3.0 of slurries, then continue making beating 45 minutes, then toward the phosphorus aluminium inorganic binder Binder 2 argillaceous that adds embodiment 8 preparations, stir after 30 minutes, with the slurries spray-drying that obtains, obtain microballoon, microballoon in 500 ℃ of lower roastings 1 hour, is made ZJ ₁, its proportioning sees Table 3.

Table 2

Embodiment 12

Get molecular sieve-4 A ₁, kaolin and boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution (the FeCl of O ₃Content 30 % by weight), obtain the slurries that solid content is 30 % by weight, the pH value that adds hydrochloric acid adjusting slurries is 3.0, continue making beating 45 minutes, then add the phosphorus aluminium inorganic binder argillaceous of embodiment 7 preparation, stirred 30 minutes, with the slurries that obtain 500 ℃ of dry gas inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is obtained auxiliary agent ZJ ₂The auxiliary agent proportioning sees Table 3.

Embodiment 13

Get molecular sieve-4 A ₁And diatomite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, obtain the slurries that solid content is 30 % by weight, the pH value of regulating slurries by adding hydrochloric acid content is 3.0, then pulls an oar 45 minutes, then adds the phosphorus aluminium inorganic binder argillaceous (Binder3) that embodiment 9 prepares in mixed serum, stirred 30 minutes, slurries spray-drying with obtaining obtains microballoon, with microballoon in 500 ℃ of lower roastings 1 hour.

Get the thus obtained microsphere product, add FeCl ₃6H ₂The O aqueous solution is warming up to 60 ℃ under stirring, and with slurries vacuum filtration, drying, then in 500 ℃ of lower roastings 2 hours, makes auxiliary agent ZJ in reaction under this temperature after 20 minutes ₃Auxiliary agent ZJ ₃Proportioning sees Table 3.

Embodiment 14

Get molecular sieve-4 A ₁, kaolin and boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower Co of adding (NO ₃) ₂6H ₂The aqueous solution of O (concentration 30 % by weight), obtain the slurries that solid content is 38 % by weight, it is 3.0 that adding hydrochloric acid makes the pH value of slurries, pulled an oar 45 minutes, then in slurries, add the phosphorus aluminium inorganic binder argillaceous (Binder 4) of embodiment 10 preparations and the phosphorus al binder that Comparative Examples 6 provides, stirred 30 minutes.The slurries that obtain 500 ℃ of inlet temperatures, are carried out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon, microballoon in 500 ℃ of lower roastings 1 hour, is obtained auxiliary agent ZJ ₄, its proportioning sees Table 3.

Embodiment 15

Get molecular sieve-4 A ₁, kaolin and boehmite, add decationized Y sieve water and and aluminium colloidal sol making beating 120 minutes, stir the lower Ni of adding (NO ₃) ₂6H ₂The aqueous solution of O, obtain the slurries that solid content is 30 % by weight, add hydrochloric acid, it is 3.0 that the hydrochloric acid consumption makes the pH value of slurries, pulled an oar 45 minutes, and then added phosphorus al binder argillaceous and diammonium hydrogen phosphate solid that embodiment 7 provides, stirred 30 minutes, with the slurries spray-drying that obtains, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is made ZJ ₅

Embodiment 16

Get molecular sieve-4 A ₁, boehmite and kaolin, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The O aqueous solution (FeCl ₃Content 30 % by weight), obtain the slurries that solid content is 38 % by weight, the pH value that adds hydrochloric acid adjusting slurries is 3.0, continue making beating 45 minutes, add the phosphorus al binder argillaceous that embodiment 9 provides, stirred 30 minutes, then with the slurries spray-drying that obtains, obtain microballoon.With microballoon in 500 ℃ of lower roastings 1 hour.

Get the thus obtained microsphere product, add ammonium dibasic phosphate aqueous solution, be warming up to 60 ℃ under stirring, with slurries vacuum filtration, drying, then in 500 ℃ of lower roastings 2 hours, make auxiliary agent ZJ in reaction under this temperature after 20 minutes ₆

Embodiment 17

Get molecular sieve-4 A ₁, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution of O obtains the slurries that solid content is 30 % by weight, with the pH value 3.0 that hydrochloric acid is regulated slurries, then pulls an oar 45 minutes, then adds the phosphorus al binder argillaceous that embodiment 7 provides, and stirs 30 minutes, and the slurries spray-drying with obtaining obtains microballoon.Microballoon in 400 ℃ of lower roastings 1 hour, is made auxiliary agent ZJ ₇, its proportioning sees Table 3.

Embodiment 18

Get molecular sieve-4 A ₂, boehmite and kaolin, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution of O, obtain the slurries that solid content is 30 % by weight, the pH value of regulating slurries by adding hydrochloric acid is 3.0, then pulled an oar 45 minutes, and then in slurries, added the phosphorus al binder argillaceous (binder4) that embodiment 10 provides, stirred 30 minutes, with the slurries spray-drying that obtains, obtain average particulate diameter and be 65 microns microballoon, microballoon in 400 ℃ of lower roastings 1 hour, is made auxiliary agent ZJ ₈, its proportioning sees Table 3.

Embodiment 19

Get molecular sieve-4 A ₃, kaolin and diatomite, add decationized Y sieve water and waterglass making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution of O, obtain the slurries that solid content is 30 % by weight, add hydrochloric acid, it is 3.0 that the hydrochloric acid consumption makes the pH value of slurries, then pulls an oar 30 minutes, the phosphorus al binder that the phosphorus al binder argillaceous (binder2) that adding embodiment 8 provides and Comparative Examples 6 provide, pulled an oar 30 minutes, and then with the slurries spray-drying that obtains, obtained microballoon, microballoon in 500 ℃ of lower roastings 1 hour, is made auxiliary agent ZJ ₉, its proportioning sees Table 3.

Embodiment 20

Get molecular sieve-4 A ₄, kaolin and boehmite, add decationized Y sieve water making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution of O, obtain the slurries that solid content is 30 % by weight, making the pH value of slurries by adding hydrochloric acid is 3.0, then pulled an oar 30 minutes, add the phosphorus al binder argillaceous (Binder 4) that embodiment 10 provides, pulled an oar 30 minutes, then with the slurries that obtain 500 ℃ of dry air inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is made auxiliary agent ZJ ₁₀, its proportioning sees Table 3.

Embodiment 21

Get molecular sieve-4 A ₅And boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The O solid, the pH value that adds hydrochloric acid adjusting slurries is 3.0, pulls an oar 45 minutes, adds the phosphorus al binder argillaceous (Binder 2) that embodiment 8 provides, and stirs 30 minutes, the slurries spray-drying with obtaining obtains microballoon, makes auxiliary agent ZJ ₁₁, its proportioning sees Table 3.

Comparative Examples 7

Get A ₁, kaolin and boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower hydrochloric acid that adds, by the pH value 3.0 of hydrochloric acid content control slurries, mixture is continued to pull an oar 45 minutes, with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon, microballoon in 500 ℃ of lower roastings 1 hour, is made reference auxiliary agent DB ₁Reference auxiliary agent proportioning sees Table 4.

Comparative Examples 8

Get A ₁, kaolin and boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution of O, obtain the slurries of solid content 30 % by weight, adding concentration is the hydrochloric acid of 36 % by weight, the consumption of hydrochloric acid is so that the pH value 3.0 of slurries, pulled an oar 45 minutes, the slurries that obtain 500 ℃ of inlet temperatures, are carried out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is made reference auxiliary agent DB ₂

Comparative Examples 9

Get A ₁, kaolin and boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, add iron nitrate solution (concentration 30 % by weight), obtain the slurries that solid content is 30 % by weight, stirring lower adding concentration is the hydrochloric acid of 36 % by weight, and the consumption of hydrochloric acid is so that the pH value 3.0 of slurries.Mixture is continued making beating 45 minutes.Then add the phosphorus aluminium glue that Comparative Examples 6 provides in mixed serum, after stirring, the spray-drying with obtaining obtains microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is made reference auxiliary agent DB ₃

Comparative Examples 10

Get molecular sieve B ₁, kaolin and boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, obtain the slurries that solid content is 30 % by weight, stirring lower adding concentration is the hydrochloric acid of 36 % by weight, the consumption of hydrochloric acid is so that the pH value of slurries is 3.0, continue making beating 45 minutes, then add the phosphorus aluminium inorganic binder argillaceous (Binder 2) that embodiment 8 provides, stirred 30 minutes, with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is made reference auxiliary agent DB ₄

Comparative Examples 11

Prepare auxiliary agent by the method to embodiment 11, be not both and use molecular sieve B ₁Replace A ₁, make reference auxiliary agent DB ₅

Comparative Examples 12

Get ZRP-5, kaolin and boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, obtain the slurries that solid content is 30 % by weight, stirring lower adding concentration is the hydrochloric acid of 36 % by weight, and the consumption of hydrochloric acid is so that then the pH value 3.0 of slurries continues making beating 45 minutes, with the slurries spray-drying that obtains, obtain average particulate diameter and be 65 microns microballoon, microballoon in 500 ℃ of lower roastings 1 hour, is made reference auxiliary agent DB ₆

Comparative Examples 13

Get molecular sieve B ₂With boehmite, kaolin, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution of O, it is 3.0 that adding hydrochloric acid makes the pH value of slurries, then pulls an oar 45 minutes, add the phosphorus aluminium glue, stirred 30 minutes, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is obtained reference auxiliary agent DB ₇

Comparative Examples 14

Get molecular sieve B ₃, kaolin, diatomite and boehmite, add decationized Y sieve water making beating 120 minutes, stir the lower FeCl of adding ₃6H ₂The aqueous solution of O, obtain the slurries that solid content is 30 % by weight, it is 3.0 that adding hydrochloric acid makes the pH value of slurries, pulled an oar 30 minutes, add diammonium hydrogen phosphate, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is made auxiliary agent DB ₇

Comparative Examples 15

Get molecular sieve B ₄With boehmite, kaolin, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, obtain the slurries that solid content is 30 % by weight, it is 3.0 that adding hydrochloric acid makes the pH value of slurries, continue making beating 45 minutes, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of lower roastings 1 hour, is obtained reference auxiliary agent DB ₈

Comparative Examples 16

Get molecular sieve B ₅And boehmite, add decationized Y sieve water and aluminium colloidal sol making beating 120 minutes, regulate the pH value 3.0 of slurries by adding hydrochloric acid, continue making beating 45 minutes, add ammonium dibasic phosphate aqueous solution, obtain the slurries that solid content is 30 % by weight, after stirring with the slurries that obtain 500 ℃ of dry gas inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon, make reference auxiliary agent DB ₉

Embodiment 22～32

The following examples illustrate the cracking reaction effect of cracking additive provided by the invention take fixed fluidized-bed reactor as example.

Respectively with 30 gram ZJ ₁-ZJ ₁₁Under 800 ℃, 100% steam atmosphere condition, carry out 17 hours burin-in process.Get respectively the ZJ through burin-in process of different amounts ₁-ZJ ₁₁(the industrial trade mark is the FCC equilibrium catalyst of DVR-3 from the industrial FCC equilibrium catalyst of different amounts, main character sees Table 5) mix, catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, and feedstock oil oil shown in the his-and-hers watches 6 carries out catalytic cracking (feedstock oil character sees Table 6).The weight that table 7 and table 9 have provided the catalyst system therefor mixture forms reaction condition and reaction result.

Comparative Examples 17～26

Following Comparative Examples illustrates the situation of using the reference auxiliary agent take fixed fluidized-bed reactor as example.

By the method among the embodiment 22 same feedstock oil is carried out catalytic cracking, different is that catalyst system therefor is respectively 100% industrial FCC equilibrium catalyst (DVR-3), DB ₁～DB ₉Mixture with industrial FCC equilibrium catalyst (DVR-3).The weight that table 7, table 8 and table 9 have provided the catalyst system therefor mixture forms reaction condition and reaction result.

Can be found out by table 7, table 8 and table 9, compare with the reference auxiliary agent, catalyst aid provided by the invention, can effectively increase the catalytic cracking liquefied gas yield, improve significantly propylene, isobutylene concentration in the catalytic cracking liquefied gas, improve the concentration of ethene in the dry gas, significantly improve the productive rate of ethene, propylene and isobutene, and can improve the selective of coke and dry gas, improve the heavy oil conversion performance of carbon monoxide-olefin polymeric, improve liquid and receive; When the promoter additive amount is larger, still has higher heavy oil transformation rate.

Table 3

Table 4

Table 5

Table 6

Claims (20)

1. an assistant for calalytic cracking that improves density of propylene contains the modification MFI molecular sieve in butt 10～75 % by weight, with Al ₂O ₃, P ₂O ₅And the phosphorus aluminium inorganic binder that contains the first clay of the first clay butt weight sum meter 3～30 % by weight, in other inorganic binders of oxide 3～30 % by weight, in the second clay of butt 0～60 % by weight with in one or more the metallic addition in the VIII family metal of being selected from of oxide 0.5～15 % by weight; Wherein, take the described phosphorus aluminium inorganic binder butt weight that contains the first clay as benchmark, the described phosphorus aluminium inorganic binder that contains the first clay comprises with Al ₂O ₃The meter 15～40 % by weight al compositions, with P ₂O ₅The phosphorus component of meter 45～80 % by weight and in the first clay of butt 1～40 % by weight, and its P/Al weight ratio is 1.0～6.0; Described modification MFI molecular sieve, its anhydrous chemical expression is counted with the weight of oxide: (0～0.3) Na ₂O (0.5～6) Al ₂O ₃(1.3～10) P ₂O ₅(0.7～15) M _xO _y(70～97) SiO ₂, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably, and the infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm ^-1The place is without absworption peak, its Phosphorous distribution D satisfies 0≤D≤0.8, D=P (S)/P (C) wherein, described P (S) expression adopt zeolite crystal that the TEM-EDX method characterizes from the edge 1/5th phosphorus content to the center, the phosphorus content of P (C) expression zeolite crystal center.

2. according to auxiliary agent claimed in claim 1, it is characterized in that described Phosphorous distribution D is 0.1～0.5.

3. according to each described auxiliary agent of claim 1～2, it is characterized in that described its anhydrous chemical expression of modification MFI molecular sieve is: (0～0.2) Na ₂O (0.9～5.5) Al ₂O ₃(1.5～7) P ₂O ₅(0.9～10) MxOy (82～92) SiO ₂

4. according to auxiliary agent claimed in claim 1, it is characterized in that described MFI molecular sieve is ZSM-5.

5. according to auxiliary agent claimed in claim 1, it is characterized in that described the first clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and the diatomite; Described the second clay is selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and the rectorite one or more mixture; Described other inorganic matter binding agent is selected from one or more of boehmite, aluminium colloidal sol, silicon-aluminum sol, waterglass and phosphorus aluminium colloidal sol.

6. according to the auxiliary agent of claim 1, it is characterized in that described VIII family metal is selected from one or more among Fe, Co and the Ni.

7. according to each described auxiliary agent of claim 1～6, it is characterized in that described auxiliary agent contains with P ₂O ₅Meter is no more than the phosphorus additive of 25 % by weight.

8. according to auxiliary agent claimed in claim 7, it is characterized in that, this auxiliary agent comprise the second clay, 5～25 % by weight of modification MFI molecular sieve, 10～45 % by weight of the phosphorus aluminium inorganic binder that contains the first clay, 20～60 % by weight of 8～25 % by weight other inorganic binder, 1.0～10 % by weight be selected from the VIII family metal one or more metallic addition and the phosphorus additive of 0～10 % by weight.

9. the preparation method of an assistant for calalytic cracking, comprise modification MFI molecular sieve, the phosphorus aluminium inorganic binder that contains the first clay, other inorganic binder are mixed, add or do not add the second clay, making beating, spray-drying and the step of introducing VIII family metallic addition; Wherein, the described phosphorus aluminium inorganic binder that contains the first clay take its butt weight as benchmark, contains with Al ₂O ₃The meter 15～40 % by weight alumina component, with P ₂O ₅The meter 45～80 % by weight phosphorus component and in butt 1～40 % by weight the first clay, its P/Al weight ratio is that 1～6, pH is 1.0～3.5, this binding agent solid content is 15～60 % by weight; Described modification MFI molecular sieve, its anhydrous chemical expression is counted with the weight of oxide: (0～0.3) Na ₂O (0.5～6) Al ₂O ₃(1.3～10) P ₂O ₅(0.7～15) M _xO _y(70～97) SiO ₂, x represents the atomicity of described transition metal M, y represents to satisfy the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more among Fe, Co, Ni, Cu, Mn, Zn, Sn, the Bi; The infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm ^-1The place is without absworption peak, its Phosphorous distribution D satisfies 0≤D≤0.8, D=P (S)/P (C) wherein, described P (S) expression adopt zeolite crystal that the TEM-EDX method characterizes from the edge 1/5th phosphorus content to the center, the phosphorus content of P (C) expression zeolite crystal center.

10. in accordance with the method for claim 9, it is characterized in that the described phosphorus aluminium inorganic binder preparation method who contains the first clay comprises:

(1) alumina source, the first clay and water making beating are dispersed into the slurries that solid content is 8～45 % by weight; Described alumina source is can be by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt and with Al ₂O ₃The weight ratio of the alumina source of meter is 1～40: 15～40;

(2) stir in the lower slurries that obtain toward step (1) part by weight adding SPA according to P/Al=1～6;

(3) slurries that step (2) obtained reacted 15～90 minutes under 50～99 ℃ of temperature.

11., it is characterized in that the described phosphorus aluminium inorganic binder that contains the first clay take its butt weight as benchmark, comprises the Al that 15～35 % by weight are derived from described alumina source according to claim 9 or 10 described methods ₂O ₃, 50～75 % by weight P ₂O ₅The first clay with 8～35 % by weight.

12., it is characterized in that described P/Al weight ratio is 2～5 according to claim 10 or 11 described methods.

13. in accordance with the method for claim 10, it is characterized in that, described alumina source is one or more in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and the boehmite, and described the first clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and the diatomite.

14. in accordance with the method for claim 10, it is characterized in that the temperature described in the step (3) is 65～90 ℃.

15. in accordance with the method for claim 9, it is characterized in that, the preparation method of described modification MFI molecular sieve, comprise: baked phosphorous and MFI molecular sieve and silicon source transition metal are mixed to get reactant mixture, resulting reactant mixture was reacted crystallization 2～80 hours in 145～190 ℃.

16. in accordance with the method for claim 9, it is characterized in that described reaction crystallization temperature is 150～190 ℃, the reaction crystallization time is 5～50 hours.

17. in accordance with the method for claim 9, it is characterized in that, with SiO ₂The silicon source of meter with take the weight ratio of the MFI molecular sieve of the described baked phosphorous and transition metal of butt as 0.03～0.3: 1.

18. the method according to claim 17 is stated is characterized in that, described silicon source comprises one or more in silane, siloxanes, estersil and the Ludox.

19. according to each described method of claim 15～18, it is characterized in that, also introduce dispersant and/or template in the described reactant mixture, described dispersant is selected from one or more in C5, C6, C7, C8, C9 and the C10 alkane, dispersant with SiO ₂The weight ratio in the silicon source of meter is 5～90: 10～95; Also contain simultaneously water when containing template in the reactant mixture, wherein water and template weight ratio are 0.5～19, and the ratio of the molal quantity of Si is 0.3～1: 1 in the molal quantity of template and the silicon source.

20. in accordance with the method for claim 15, it is characterized in that the preparation method of the MFI molecular sieve of described baked phosphorous and transition metal comprises:

(1) with sodium type MFI molecular sieve according to molecular sieve: ammonium salt: H ₂O=1: (0.1～1): the weight ratio of (5～10) is filtered after 0.3～1 hour in room temperature to 100 a ℃ lower exchange, drying;

(2) molecular sieve that step (1) is obtained is with phosphorus-containing compound and contain that transistion metal compound floods, dry, roasting.