CN103007989B - Cracking assistant for improving low-carbon olefin concentration - Google Patents

Cracking assistant for improving low-carbon olefin concentration Download PDF

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CN103007989B
CN103007989B CN201110284435.XA CN201110284435A CN103007989B CN 103007989 B CN103007989 B CN 103007989B CN 201110284435 A CN201110284435 A CN 201110284435A CN 103007989 B CN103007989 B CN 103007989B
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molecular sieve
phosphorus
clay
aluminium
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CN103007989A (en
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陈蓓艳
宋海涛
欧阳颖
邓景辉
朱玉霞
罗一斌
蒋文斌
田辉平
黄志青
沈宁元
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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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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 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 that to contain catalyst or the auxiliary agent with MFI structural zeolite be effective technological approaches in catalytic cracking process.
USP3,758,403 are early disclosed in the method for adding ZSM-5 zeolite in catalytic cracking catalyst can improve the octane number of gasoline and increase C 3～C 4the productive rate of alkene.For example, containing adding in the conventional catalyst of 10%REY from 1.5,2.5,5 to 10% ZSM-5 zeolite, octane number improves, and the productive rate of low-carbon alkene increases; While using the auxiliary agent that contains ZSM-5 zeolite, also there is same effect.
In USP 5,318,696, propose to be less than based on a kind of large pore zeolite and silica alumina ratio the hydrocarbon conversion process process of the catalyst of 30 the zeolite composition with MFI structure.This technique is produced high-knock rating gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly propylene.
A large amount of methods that use shape slective cracking auxiliary agent in heavy charge catalytic cracking process are disclosed in USP 5,997,728.Said auxiliary agent is made up of the ZSM-5 zeolite that adds 12～40% in [amorphous, and system reserve at least 10% makes the ratio of ZSM-5 in catalyst exceed 3%.The method can be in increasing substantially low-carbon alkene, additionally do not increase aromatic production and loss gasoline yield.
ZSM-5 zeolite carries out after modification with phosphorus-containing compound, and its cracking activity stability can improve, and reduces the consumption of zeolite.
In CN 1049406C, disclose a kind of phosphorous and rare earth and had the zeolite of MFI structure, it is aRE without hydrochemical compositions 2o 3bNa 2oAl 2o 3cP 2o 5dSiO 2, wherein a=0.01～0.25, 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 for hydro carbons pyrolytic conversion.
In CN 1034223C, disclose a kind of catalyst for cracking for the production of low-carbon alkene, formed by the clay of 0～70% (taking catalyst weight as benchmark), 5～99% inorganic oxide and 1～50% zeolite.Zeolite is wherein the mixture of the five-membered ring silica-rich zeolite of the REY of 0～25 % by weight or the phosphorous and rare earth of Y-type high-Si zeolite and 75～100 % by weight.This catalyst has higher hydrothermal activity stability, conversion ratio and the C of catalyst taking ZSM-5 zeolite as active component 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.Gained catalyst does not increase dry gas and coke yield in 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 more than 4.5 phosphorus-containing compound aqueous solution of pH value, makes the phosphorus of zeolite-loaded at least 10 % by weight (with P 2o 5meter), then with matrix and the making beating of other zeolite component, spray drying forming.Gained catalyst has higher productivity of low carbon olefin hydrocarbon.
A kind of ZSM-5 zeolite with phosphorus modification is disclosed in USP 5,171,921.This zeolite has 20～60 silica alumina ratio, with after phosphorus-containing compound dipping after 500～700 DEG C of steam treatment, for C 3～C 20hydrocarbon changes into C 2～C 5when the reaction of alkene, relatively there is higher activity without the ZSM-5 of phosphorus processing.
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, then by the zeolite of processing through phosphorus and AlPO 4gel combination.The method can be improved activity and the hydrothermal stability of aperture and mesopore zeolite.
The hydrocarbon conversion process process of the catalyst based on a kind of large pore zeolite and phosphorous MFI structure mesopore zeolite composition is disclosed in USP 5,472,594.This technique is produced high-knock rating gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly C 4/ C 5.
, phosphorus modification, also report and introduce phosphorus compound in matrix 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 in USP 2002/0003103A1.This technical process is except entering at least part of gasoline product in second riser and re-start cracking reaction, in the carbon monoxide-olefin polymeric adopting, except containing macropore USY zeolite, also contain the mesopore zeolites such as ZSM-5 and there is the inorganic binder component of cracking performance.Phosphorous in inorganic binder component wherein, its P/Al ratio is 0.1～10.Significantly increased low carbon olefine output of this technical process, particularly increases productivity of propylene.
The catalyst of a kind of high zeolite content, high abrasion resistance strength is disclosed in USP 2002/0049133A1.The ZSM-5 zeolite that this catalyst contains 30～85 % by weight, the phosphorus of 6～24 % by weight is (with P 2o 5meter), and lower than the Al of 10 % by weight 2o 3with other components such as the clays of surplus, phosphorus is wherein present in matrix.This catalyst, 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, discloses the catalyst containing MFI or MEL structural zeolite in 880.Wherein zeolite used is through VIII family metal, preferably with Ni modification, and this zeolite is introduced after Ni, experiences heat or hydrothermal treatment consists at harsh control temperature, makes VIII family metal and aluminium at surface enrichment.Said catalyst can improve octane number while conversion for alkane, increases C 3～C 4the productive rate of alkene.
A kind of catalyst for cracking containing silica-rich zeolite is disclosed in CN 1057408A, there is higher catalytic pyrolysis activity, 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, silica alumina ratio to be greater than to 15 Hydrogen or potassium type ZSM-5 zeolite, β zeolite or modenite be heated to 350～820 DEG C, 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.
The MFI structural zeolite that discloses a kind of phosphorous and transition metal in CN 1465527A, the anhydrous chemical expression of this zeolite, counts (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 the one in transition-metal Fe, Co and 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 in its liquefied gas, density of propylene is not high, and dry gas and coke selectivity are poor.
CN 1611299A discloses a kind of MFI molecular sieve of phosphorous and metal component, and its anhydrous chemical expression, counts 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 the one in transition-metal Fe, Co and Ni, and M2 is selected from any in Metal Zn, Mn, Ga and Sn.
At present, for most catalytic cracking units, under the prerequisite of identical liquefied gas yield, the density of propylene improving in liquefied gas is the important channel of improving catalytic cracking unit economic benefit, but existing catalyst aid is for catalytic cracking process, Propylene Selectivity is not high, and in liquefied gas, density of propylene is not high; In the time that 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, for catalytic cracking, can improve density of propylene in catalytic cracking liquefied gas, improves heavy oil conversion performance.
The invention provides a kind of assistant for calalytic cracking, taking the butt weight of described auxiliary agent as benchmark, contain in the modification MFI molecular sieve of butt 10～75 % by weight, with the al composition containing in the phosphorus aluminium inorganic binder of the first clay (with Al 2o 3meter), phosphorus component is (with P 2o 5meter) and the first clay butt weight sum meter 3～30 % by weight containing the phosphorus aluminium inorganic binder of the first clay, in other inorganic binder of oxide 3～30 % by weight, in oxide 0.5～15 % by weight be selected from VIII family metal one or more metallic addition and in the second clay of butt 0～60 % by weight; Wherein, taking the described phosphorus aluminium inorganic binder butt weight containing the first clay as benchmark, the described phosphorus aluminium inorganic binder containing the first clay comprises with Al 2o 3meter 15～40 % by weight al compositions, with P 2o 5count the phosphorus component of 45～80 % by weight and the first clay in 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, counts 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 meet the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi; The infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm -1place is without absworption peak, the distribution D of its phosphorus meets 0≤D≤0.8, wherein D=P (S)/P (C), described P (S) represent to adopt zeolite crystal that TEM-EDX method characterizes from edge 1/5th the phosphorus content to center, P (C) represents the phosphorus content of zeolite crystal center.Wherein said VIII family metallic addition does not comprise the transition metal in modification MFI molecular sieve.
The present invention also provides a kind of preparation method of assistant for calalytic cracking, comprise modification MFI molecular sieve, mix containing phosphorus aluminium inorganic binder, other inorganic binder of the first clay, add or do not add the second clay, making beating, spraying is dried and introduces the step of VIII family metallic addition; Wherein, the described phosphorus aluminium compound inorganic binder containing the first clay, taking its butt weight as benchmark, contains with Al 2o 3meter 15～40 % by weight alumina component, with P 2o 5meter 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, counts 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 meet 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 -1place is without absworption peak, the distribution D of its phosphorus meets 0≤D≤0.8, wherein D=P (S)/P (C), described P (S) represent to adopt zeolite crystal that TEM-EDX method characterizes from edge 1/5th the phosphorus content to center, P (C) represents the phosphorus content of zeolite crystal center.
Described VIII family metallic addition is preferably one or more in Fe, Co and Ni, wherein more preferably comprises iron, more preferably 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.
The first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and diatomite.
The second described clay is selected from and well known to a person skilled in the art one or more in the clay that is customarily used in Cracking catalyst or auxiliary agent, for example be selected from one or more in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, rectorite, diatomite, galapectite, saponite, boron-moisten soil and hydrotalcite, be preferably one or more the mixture in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite.
Cracking additive provided by the invention, also contains except described other inorganic binder the first clay inorganic binder that contains.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, waterglass, wherein preferred one or more in boehmite, aluminium colloidal sol, phosphorus aluminium glue.
In catalyst aid provided by the present invention, can also contain with P 2o 5the phosphorus additive of meter 0～25 % by weight, the compound that described phosphorus additive is selected from phosphorus comprises one or more in inorganic compound and the organic compound of phosphorus, can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound, for example, be selected from one or more in oxide, phosphoric acid, phosphate, phosphite, hypophosphites, subphosphate, acid phosphate and the phosphorous organic compound of phosphorus.Preferred phosphorus compound is one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate and phosphorus aluminium colloidal sol.In the catalyst obtaining, phosphorus additive exists with the form of phosphorus compound (as the oxide of phosphorus, phosphate, phosphite, subphosphate, acid phosphate).When containing in auxiliary agent except described containing other the phosphorous binding agent the phosphorus aluminium inorganic binder of the first clay for example when phosphorus aluminium colloidal sol, this part phosphorus is also 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 may reside in the inside, duct of zeolite, the surface of zeolite, may reside in described host material, can also be present in the surface and described host material of inside, duct, zeolite of zeolite simultaneously.In the content of described phosphorus additive, do not comprise the phosphorus in modification MFI molecular sieve, do not comprise the phosphorus that the described phosphorus aluminium inorganic binder containing the first clay is introduced yet.
Assistant for calalytic cracking provided by the invention, there is good anti-wear performance and Catalytic Cracking Performance, for catalytic cracking reaction process, can improve RFCC liquefied gas yield, improve significantly especially propylene and the isobutylene concentration of low-carbon alkene concentration in 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 DEG C, weight (hourly) space velocity (WHSV) -1, react under the oil ratio condition that is 5, 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 in liquefied gas, density of propylene is 32.21 % by weight, isobutene productive rate is 1.55 % by weight, in liquefied gas, isobutylene concentration is 9.47 % by weight, and coke selectivity is 10.53 % by weight, and dry gas is selectively 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 are containing 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, after mixing with above-mentioned DVR-3 poising agent with the weight ratios of 10: 90, 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, in liquefied gas, density of propylene is 42.30 % by weight, isobutene productive rate is 2.34 % by weight, in liquefied gas, isobutylene concentration is 10.47 % by weight, coke selectivity is 10.29 % by weight, dry gas is selectively 2.19 % by weight.
Detailed description of the invention
Cracking additive provided by the present invention, preferably includes the phosphorus aluminium inorganic binder containing the first clay of 8～25 % by weight, the modification MFI molecular sieve of 20～60 % by weight, clay, other inorganic binder of 5～25 % by weight and the phosphorus additive of 0～10 % by weight of 10～45 % by weight.Wherein said phosphorus additive does not comprise the phosphorus relating in modification MFI molecular sieve, does not comprise containing the phosphorus relating in the phosphorus aluminium inorganic binder of 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 2.The phosphorus distribution D of described modification MFI molecular sieve meets 0.1≤D≤0.5.Described MFI molecular sieve, carries out IR Characterization as probe with trimethylpyridine, and its spectrogram is at 1633cm -1place is without absworption peak.Carrying out IR Characterization with trimethylpyridine as probe is existing method, and its process can be as follows: by sample compressing tablet, the original position pond that is placed in infrared spectrometer seals, and at 450 DEG C, is evacuated down to 10 -3pa, roasting 1.5h, is cooled to room temperature; Then the trimethylpyridine steam importing to original position pond, maintains adsorption equilibrium 30min, takes the photograph spectrum.Described M is preferably Fe.One or more in described MFI molecular sieve for example ZSM-5, ZSM-8 and ZSM-11, are preferably ZSM-5.MFI molecular sieve is also referred to as having MFI structure molecular screen or MFI structure molecular screen.
Under preferable case, the first clay in the inorganic binder of the described phosphorus aluminium compound containing the first clay comprises rectorite, and more preferably the first described clay is rectorite.Taking butt weight as benchmark, the described phosphorus aluminium compound binding agent containing the first clay contains with Al 2o 3the al composition of meter 15～35 % by weight, with P 2o 5count the phosphorus component of 50～75 % by weight and the first clay in butt 8～35 % by weight, it is 1.0～3.5 that its P/Al weight ratio is preferably 2.0～5.0, pH.
In the preparation method of assistant for calalytic cracking provided by the invention, the described phosphorus aluminium inorganic binder containing the first clay, taking its butt weight as benchmark, contains with Al 2o 3meter 15～40 % by weight al compositions, with P 2o 5count the phosphorus component of 45～80 % by weight and the first clay in butt 1～40 % by weight, its P/Al weight ratio is that 1.0～6.0, pH is 1.0～3.5, and solid content is 15～60 % by weight.The described phosphorus aluminium inorganic binder preparation method containing 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) in the slurries that obtain to step (1) under stirring, add SPA according to the part by weight of P/Al=1.0～6; In wherein said P/Al, P is the weight of the phosphorus in simple substance in phosphoric acid, and Al is the weight in the aluminium of simple substance in alumina source;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 DEG C of temperature.
Wherein, the consumption of alumina source, SPA and the first clay, makes the obtained phosphorus aluminium inorganic binder containing the first clay, taking its butt weight as benchmark, comprises: 15～40 % by weight preferably 15～35 % by weight are derived from the Al of described alumina source 2o 3, 45～80 % by weight 0～75 % by weight P 2o 5, 1～40 % by weight is the first clay of 8～35 % by weight preferably; 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 boehmite, and described al composition is derived from described alumina source.The first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and 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/Kg alumina source, more preferably 0.03-0.07Kg phosphoric acid/minute/Kg alumina source.
The described phosphorus aluminium inorganic binder containing the first clay is due to the introducing of clay, mass transfer, the heat transfer of storeroom not only in preparation process, are 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 obtaining is with not introduce phosphorus al binder prepared by clay mitigation suitable; And the method introduces clay, especially there is the rectorite of layer structure, improve the heavy oil conversion performance of carbon monoxide-olefin polymeric, the auxiliary agent that makes to obtain has better selective.
Described modification MFI molecular sieve, for the MFI molecular sieve of 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 silicon source, react crystallization 2～80 hours in 145～190 DEG C, reclaim again the MFI molecular sieve of the phosphorous and transition metal that obtains silicon modification, with SiO 2the silicon source of meter with the weight ratio of the MFI molecular sieve taking 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 one or more in silane, siloxanes, estersil and Ludox, more preferably silicone grease, for example methyl silicate of described estersil and/or ethyl orthosilicate.
The preparation method of modification MFI molecular sieve of the present invention, phosphorous and MFI molecular sieve transition metal is carried out to modification with silicon-containing compound, comprise baked phosphorous and MFI molecular sieve transition metal is mixed with silicon source, then gained mixture is reacted to crystallization (also claiming crystallization) for 2～80 hours in 145～190 DEG C of maintenances.With SiO 2the silicon source of meter with the weight ratio of the MFI molecular sieve taking 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 DEG C more preferably 170～190 DEG C, and reaction crystallization time is preferably 5～50 hours, more preferably 12～24 hours.
Baked phosphorous and MFI molecular sieve transition metal is mixed with silicon source, preferably also add dispersant in the mixture forming, 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 C10 alkane, is preferably one or more in C5, C6 and C7 alkane, wherein dispersant with SiO 2the weight ratio in silicon source of meter is 5～90: 10～95, preferably 10～80: 20～90.After preferably described dispersant being first mixed to form to silicon source mixture with silicon source, again this silicon source mixture is phosphorously mixed with MFI molecular sieve transition metal with baked, this is conducive to silicon source and is scattered in more equably in molecular sieve, thereby the character of the MFI molecular sieve of the phosphorous and transition metal of gained modification is more even, the mixture that dispersant and silicon source form comprises the preferably dispersant of 10～80 % by weight of 5～90 % by weight.
In described reactant mixture, preferably also introduce template and water, wherein water and template weight ratio are 0.5～19: 1, in the molal quantity of template and silicon source, the ratio of the molal quantity of silicon is 0.3～1: 1, and in the agent of masterplate plate and silicon source, the mol ratio of silicon is preferably 0.4～0.6: 1.Described template is the masterplate template that MFI molecular sieve is conventional, is preferably one or more in tetraethyl ammonium hydroxide, TPAOH, tetraethylammonium bromide or 4-propyl bromide.Preferably, masterplate template and water mix and react with the MFI molecular sieve of described baked phosphorous and transition metal again after first mixing with silicon source.Crystallization is carried out in the silicon source of containing silicon-containing compound and phosphorous and transition metal molecular sieve under the existence of template, and it is higher that the degree of crystallinity of the modified molecular screen obtaining keeps.
The preparation method of the MFI molecular sieve of the phosphorous and transition metal of modification provided by the invention, also comprise the step of recovery, described recovery comprises the mixture separation obtaining after reaction crystallization, dry, roasting, the MFI molecular sieve of the phosphorous and transition metal of the modification described in obtaining after roasting; Wherein, described separation is for example filtered, and the temperature of roasting is preferably 530～550 DEG C, and the time of roasting is preferably 1～5 hour.
The MFI molecular sieve of described baked phosphorous and transition metal can for example, by introducing the method preparation of phosphorus and transition metal, roasting in MFI molecular sieve (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 successively flood with the solution of the solution that contains transistion metal compound and phosphorus compound respectively, also can flood with the solution that contains transistion metal compound and phosphorus compound simultaneously, 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: by 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 DEG C) to 95 DEG C of hybrid infusions, dry roasting under 400～800 DEG C of conditions.Described phosphorus and the compound of transition metal dipping can adopt saturated dipping or supersaturation impregnation method once or to be several times incorporated in ammonium type and/or Hydrogen MFI molecular sieve; The dipping of phosphorus and transition metal can carry out also can carrying out respectively simultaneously, preferred, and described phosphorus is at least partially in before transition metal or introduce with transition metal simultaneously.Phosphorus-containing compound can be selected from one of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate or its mixture; The water soluble salt that is selected from described transition metal containing transistion metal compound, described water soluble salt is selected from the one in sulfate, nitrate, chlorate.Described silicon modification can be one or many, is once to carry out after the transition metal of all measuring is introduced but have at least.Under preferable case, whole phosphorus and transition metal are introduced in described MFI molecular sieve before silicon modification.
Described ammonium type MFI molecular sieve, can according to existing method by by sodium type MFI molecular sieve with obtaining after ammonium ion exchange.By sodium type MFI molecular sieve according to molecular sieve: ammonium salt: H 2o=1: (0.1～1): the weight ratio of (5～10) filters exchange 0.3～1 hour at room temperature to 100 DEG C after, dry, the MFI molecular sieve that obtains ammonium exchange is ammonium type molecular sieve, and in the molecular sieve that preferred described exchange makes to obtain, the content of sodium oxide molybdena is 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, or by sodium type MFI molecular sieve is obtained with hydrogen ion exchange.
A kind of detailed description of the invention of preparation method provided by the invention, comprising:
(1) according to molecular sieve: ammonium salt: H 2o=1: (0.1～1): the weight ratio of (5～10) filters after sodium type MFI molecular sieve is exchanged to 0.3～1 hour at room temperature to 100 DEG C, dry;
(2) with phosphorus-containing compound solution and the solution that contains transistion metal compound, the molecular sieve after to ammonium exchange floods dry, roasting after modification; Described sintering temperature is 400～800 DEG C; The described molecular sieve after phosphorus-containing compound solution and transistion metal compound solution exchange ammonium of using floods, can be to flood with the solution that contains phosphorus compound and transistion metal compound simultaneously, can be also to flood respectively with the solution that contains phosphorus compound with containing the solution of transistion metal compound; Described dipping can carry out one or many.Preferably, flood with the solution that contains phosphorus compound and transistion metal compound simultaneously.；
(3) the MFI molecular sieve of baked phosphorous and transition metal step (2) being obtained mixes with the silicon source of containing silicon-containing compound, the mixture obtaining reacts crystallization 2～80 hours in 145～190 DEG C in airtight reaction vessel, then filter, be dried, roasting, obtain the MFI molecular sieve of the phosphorous and transition metal of described silicon modification.The consumption in the described silicon source of containing silicon-containing compound makes in 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 DEG C of crystallization temperatures, crystallization time 20～24 hours.
Preparation method provided by the invention carries out modification by phosphorous and MFI molecular sieve transition metal with silicon compound, this modifying process mixes baked phosphorous and MFI molecular sieve transition metal with silicon source, the mixture obtaining reacts crystallization 2～80 hours in 145～190 DEG C, can carry out one or many, the MFI molecular sieve molecular sieve of the phosphorous and transition metal of the modification obtaining by the inventive method, can also further carry out modification with silicon-containing compound.Described modifying process, makes the distribution D of phosphorus in molecular sieve that described mixture obtains through crystallization meet 0≤D≤0.8, wherein D=P (S)/ P (C), described P (S)represent to adopt zeolite crystal that TEM-EDX method characterizes from edge 1/5th the phosphorus content to center, P (C)represent the phosphorus content of the zeolite crystal center that adopts TEM-EDX method sign, the distribution D of phosphorus preferably meets 0≤D≤0.8.The preferably phosphorus of the modification described in 0.1≤D≤0.5 and transition metal modified MFI molecular sieve, carries out IR Characterization as probe with trimethylpyridine, and its spectrogram is at 1633cm -1place is without absworption peak.
The preparation method of assistant for calalytic cracking provided by the invention, described by modification MFI molecular sieve, containing the phosphorus aluminium inorganic binder of the first clay, other inorganic binder mixes, making beating, its reinforced order does not have particular/special requirement, for example can be by the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder (can omit relevant addition step when not containing other inorganic binder time), modification MFI molecular sieve, the second clay mixes (can omit relevant addition step when not containing the second clay time) making beating, preferably, first by the second clay, molecular sieve and other inorganic binder add the described phosphorus aluminium inorganic binder containing the first clay after mixing making beating again, 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 particular/special requirement.
In cracking additive preparation method provided by the invention, can introduce described metallic addition by the form of introducing VIII group transition metal compound, VIII group 4 transition metal additive is introduced toward adding transistion metal compound in slurries in can any step before the spray drying forming of auxiliary agent preparation process; Also can after auxiliary agent spray drying forming, introduce by roasting after dipping or chemisorption transition metallic compound, comprise auxiliary agent with flooding or chemisorbed processing containing the transistion metal compound aqueous solution, then carry out Separation of Solid and Liquid (if necessary), dry and roasting, wherein dry temperature is room temperature to 400 DEG C, preferably 100～300 DEG C, the temperature of roasting is 400～700 DEG C, be preferably 450～650 DEG C, roasting time is 0.5～100 hour, is preferably 0.5～10 hour.Described VIII group transition metal compound is selected from one or more in their inorganic compound and organic compound, can be soluble in water, can be to be also 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 phosphate.
In cracking additive provided by the present invention, described transition metal additives may reside in any position that may exist of auxiliary agent, as may reside in the inside, duct of zeolite, the surface of zeolite, may reside in host material, can also be present in the surface and described host material of inside, duct, zeolite of zeolite simultaneously, preferably be present in host material.The transition metal additives of described VIII family can exist with the form of their oxide, phosphate, phosphite, subphosphate, acid phosphate.
Catalyst aid preparation method provided by the present invention, in the time containing phosphorus additive in auxiliary agent, said phosphorus additive can adopt the combination of one of following method or several method, introduces in auxiliary agent but be not limited to these methods:
1, before auxiliary agent spray drying forming, in slurries, add phosphorus compound;
2, be incorporated in auxiliary agent by inorganic oxide binder, when containing phosphorus aluminium colloidal sol in inorganic oxide binder (other inorganic binder), after roasting, in auxiliary agent, both brought phosphorus 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 auxiliary agent spray drying forming through dipping or chemisorbed phosphorus compound, through Separation of Solid and Liquid (if necessary), dry and roasting process introducing, said dry temperature is room temperature to 400 DEG C, preferably 100～300 DEG C, the temperature of roasting is 400～700 DEG C, be preferably 450～650 DEG C, roasting time is 0.5～100 hour, is preferably 0.5～10 hour.Described phosphorus compound is selected from one or more in various inorganic compounds and the organic compound of phosphorus.Described phosphorus compound can be soluble in water, can be to be also 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 phosphorus aluminium colloidal sol.
Thereby, described phosphorus additive may reside in any position that may exist of auxiliary agent, as may reside in the inside, duct of zeolite, the surface of zeolite, and may reside in described host material, can also be present in the surface and described host material of inside, duct, zeolite of zeolite simultaneously.Described phosphorus additive exists with the form of phosphorus compound (as the oxide of phosphorus, phosphate, phosphite, subphosphate, acid phosphate).
Cracking additive provided by the invention is applicable to hydrocarbon oil catalytic cracking.During for catalytic cracking process, can in catalyst cracker, add separately, after also can mixing with Cracking catalyst, use.Generally, auxiliary agent provided by the invention accounts for FCC catalyst and agent mixture total amount provided by the invention is no more than 30 % by weight, be preferably 1～25 % by weight, more preferably 3～15 % by weight, described hydrocarbon ils is selected from various petroleum distillates, as crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/one or more in heavily de-oiling, wax tailings and coal liquefaction products.Described hydrocarbon ils can contain the beavy metal impurity such as nickel, vanadium and sulphur, nitrogen impurity, can be up to 3.0 % by weight 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 for catalytic cracking process, and cracking hydrocarbon oil condition is conventional catalytic cracking condition.In general, this cracking hydrocarbon oil condition comprises that reaction temperature is 400～600 DEG C, is preferably 450～550 DEG C, 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 carried 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 not thereby limit the present invention.Part material character used in 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 catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, Al 2o 3content is 21.5 % by weight; Waterglass is the industrial products that catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, SiO 2content 28.9 % by weight, Na 2o content 8.9%; Kaolin is the special kaolin of Cracking catalyst that Kaolin of Suzhou company produces, solid content 78 % by weight; ZRP-5 zeolite is the industrial products of the conventional MFI structural zeolite of catalyst asphalt in Shenli Refinery of China Petrochemical Industry 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; SB aluminium hydrate powder: German Condex company produces, Al 2o 3content 75 % by weight; Gamma oxidation aluminium powder: German Condex company produces, Al 2o 3content 95 % by weight.Hydrochloric acid: chemical pure, concentration 36～38 % by weight, Beijing Chemical Plant produces.
Embodiment 1
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake; By 0.9kg H 3pO 4(concentration 85 % by weight) and 0.81kg Fe (NO 3) 39H 2o was dissolved in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry, 550 DEG C of roastings 2 hours; Get the above-mentioned baked molecular sieve of 1kg, by its with contain 0.536kg ethyl orthosilicate (Beijing chemical reagents corporation, analyze pure, SiO 2content 28 % by weight), 0.333kg 4-propyl bromide (Guangzhou have greatly Fine Chemical Works produce, analyze pure, 99%) and the mixture of 1.2L water mix, be placed in the crystallizing kettle that contains polytetrafluoro lining, after 20 hours, be cooled to room temperature in 150 DEG C of static crystallizations, afterwards, molecular sieve is dried 4 hours at 120 DEG C, 550 DEG C of roastings 2 hours, obtain 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, distribution D value and the IR Characterization of phosphorus the results are shown in Table 1.
Comparative example 1
Prepare phosphorous and MFI molecular sieve transition metal by the method for CN1425567A.
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake; By 0.9kg H 3pO 4(concentration 85 % by weight) and 0.81kgFe (NO 3) 39H 2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample, 550 DEG C of calcination process 2 hours, obtains contrast molecular sieve, is designated as B 1.Elementary analytical chemistry consists of 0.08Na 2o3.0Al 2o 35.4P 2o 51.5Fe 2o 389.3SiO 2.
Embodiment 2
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry of China Petrochemical Industry produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake; By 0.93kg H 3pO 4(concentration 85 % by weight) and 3kgCo (NO 3) 26H 2o is dissolved in 9kg water obtaining maceration extract, by this maceration extract and filter cake hybrid infusion, oven dry, 550 DEG C 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), 817g tetraethyl ammonium hydroxide (Guangzhou have greatly Fine Chemical Works produce, wherein, tetraethyl ammonium hydroxide accounts for 27 % by weight, water accounts for 73 % by weight) mixture mix, be placed in the crystallizing kettle that contains polytetrafluoro lining, after 20 hours, be cooled to room temperature in 180 DEG C of static crystallizations, afterwards, dry 4 hours at 120 DEG C, 550 DEG C of roastings 2 hours, obtain 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, distribution D value and the IR Characterization of phosphorus the results are shown in Table 1.
Comparative example 2
By 5kgNH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake; By 0.93kgH 3pO 4(concentration 85 % by weight) and 3kgCo (NO 3) 26H 2o is dissolved in 9kg water, by this maceration extract and the even hybrid infusion of filter cake, oven dry; Gained sample, 550 DEG C of calcination process 2 hours, obtains contrast molecular sieve, 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
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake, by 0.25kg H 3pO 4(concentration 85 % by weight) and 0.38kgNi (NO 3) 26H 2o is dissolved in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry, 550 DEG C of calcination process 2 hours, obtains the ZSM-5 molecular sieve sample of baked phosphorous and transition metal, by 0.1428kg ethyl orthosilicate (Beijing chemical reagents corporation, analyze pure, SiO 2content 28 % by weight), (Guangzhou has greatly Fine Chemical Works to produce to 0.1815kg 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 obtaining is mixed with the above-mentioned baked molecular sieve of 1kg, stir 20 minutes, then be placed in the crystallizing kettle that contains polytetrafluoro lining, after 20 hours, be cooled to room temperature in 170 DEG C of static crystallizations, afterwards, molecular sieve is dried 4 hours at 110 DEG C, 550 DEG C of roastings 2 hours, obtain 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, distribution D value and the IR Characterization of phosphorus the results are shown in Table 1.
Comparative example 3
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (Shandong catalyst branch company produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake; Add 0.25kg H 3pO 4(concentration 85 % by weight) and 0.38kgNi (NO 3) 26H 2o dissolves in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry; Gained sample, 550 DEG C of calcination process 2 hours, obtains modification MFI molecular sieve, is designated as B 3.Elementary analytical chemistry consists of 0.1Na 2o3.2Al 2o 31.5P 2o 51.0NiO94.2SiO 2.
Embodiment 4
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake; By 0.35kg H 3pO 4(concentration 85 % by weight) and 0.66KgZn (NO 3) 26H 2o was dissolved in 9kg water, by this maceration extract and the even hybrid infusion of filter cake, oven dry, 550 DEG C of roastings 2 hours; Get the above-mentioned baked molecular sieve of 1kg, by it, (Guangzhou has greatly Fine Chemical Works to produce, SiO with containing 0.35kg Ludox 2content 40 % by weight, water content 60 % by weight) and 1.516kg TPAOH (Guangzhou have greatly Fine Chemical Works produce, containing TPAOH 25 % by weight, water 75 % by weight) mixture mix, be then placed in the crystallizing kettle that contains polytetrafluoro lining, after 24 hours, be cooled to room temperature in 180 DEG C of static crystallizations, afterwards, molecular sieve is dried 4 hours at 110 DEG C, and 550 DEG C of roastings 2 hours, obtain 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, distribution D value and the IR Characterization of phosphorus the results are shown in Table 1.
Comparative example 4
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake; By 0.35kg H 3pO 4(concentration 85 % by weight) and 0.66kgZn (NO 3) 26H 2o is dissolved in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry; Gained sample, 550 DEG C of roastings 2 hours, obtains modification MFI molecular sieve, is designated as B 4.Elementary analytical chemistry consists of 0.12Na 2o3.1Al 2o 32.5P 2o 51.8ZnO92.5SiO 2, distribution D value and the IR Characterization of phosphorus the results are shown in Table 1.
Embodiment 5
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain filter cake; By 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 9Kg water, and this maceration extract and filter cake hybrid infusion, oven dry, 550 DEG C of roastings are obtained to sample for 2 hours.Get 1 kilogram of above-mentioned baked sieve sample, by its with contain 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 polytetrafluoro lining, in 170 DEG C of reactions 12 hours, be then cooled to room temperature, afterwards, molecular sieve is dried 4 hours at 110 DEG C, and 550 DEG C of roastings 2 hours, obtain molecular sieve of the present invention.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, distribution D value and the IR Characterization of phosphorus the results are shown in Table 1.
Comparative example 5
By 5kg NH 4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (Shandong catalyst branch company produces, and has amine method synthetic, SiO 2/ Al 2o 3=50),, after 90 DEG C of exchange 0.5h, filter to obtain 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, by this maceration extract and filter cake hybrid infusion, oven dry; Gained sample, 550 DEG C of calcination process 2 hours, obtains modified molecular screen, is designated as B 5.Elementary analytical chemistry consists of 0.1Na 2o3.1Al 2o 33.1P 2o 51.6Fe 2o 31.0Bi 2o 391.1SiO 2.Also 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
Sample TEM-EDS and infrared sign that embodiment 1～5 and comparative example 1～5 are made, the results are shown in Table 1.
Embodiment 7～10 preparation the present invention phosphorus aluminium inorganic binder argillaceous used, formula and composition are in table 2.
Embodiment 7
This example is prepared phosphorus aluminium inorganic binder argillaceous of the present invention.
0.74 kilogram of boehmite (is contained to 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, under stirring, in slurries, add 2.03 kilograms of SPAs (concentration 85 % by weight), phosphoric acid add speed be 0.03Kg phosphoric acid/minute/Kg alumina source, be warming up to 70 DEG C, then at this temperature, react 45 minutes, make phosphorus aluminium inorganic binder argillaceous.Material proportion is in table 2.
Embodiment 8～10
Example 8～10 preparation phosphorus aluminium inorganic binder argillaceous of the present invention.Material proportion is in table 2.
Comparative example 6
This comparative example is prepared phosphorus aluminium glue according to existing method.
By 0.66 kilogram of boehmite (0.40 kilogram of butt) and 1.75 kilograms of decationizing water making beating 30 minutes, under stirring, in slurries, add 2.6 kilograms of SPAs (chemical pure, phosphoric acid 85 % by weight), be warming up to 70 DEG C, then at this temperature, react 45 minutes, obtain phosphorus aluminium glue inorganic binder.Material proportion is in table 2.
Table 1
Embodiment 11～21 preparation auxiliary agent provided by the present invention.Auxiliary formula is in 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, under stirring, add FeCl 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 to 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 to prepare, stir after 30 minutes, by dry the slurries spraying obtaining, obtain microballoon, by microballoon roasting 1 hour at 500 DEG C, make ZJ 1, its proportioning is in table 3.
Table 2
Embodiment 12
Get molecular sieve-4 A 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl 36H 2the aqueous solution (the FeCl of O 3content 30 % by weight), obtain the slurries that solid content is 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3.0, continue making beating 45 minutes, then the phosphorus aluminium inorganic binder argillaceous that adds embodiment 7 to prepare, stirs 30 minutes, by the slurries that obtain 500 DEG C of dry gas inlet temperatures, under the condition that exhaust temperature is 180 DEG C, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 DEG C, obtain auxiliary agent ZJ 2.Auxiliary agent proportioning is in table 3.
Embodiment 13
Get molecular sieve-4 A 1and diatomite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries that solid content is 30 % by weight, be 3.0 by adding hydrochloric acid content to regulate the pH value of slurries, then pull an oar 45 minutes, then toward the phosphorus aluminium inorganic binder argillaceous (Binder3) that adds embodiment 9 to prepare in mixed serum, stir 30 minutes, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 500 DEG C.
Get thus obtained microsphere product, add FeCl 36H 2the O aqueous solution, is warming up to 60 DEG C under stirring, react after 20 minutes at this temperature, and by slurries vacuum filtration, dry, then roasting 2 hours at 500 DEG C, makes auxiliary agent ZJ 3.Auxiliary agent ZJ 3proportioning is in table 3.
Embodiment 14
Get molecular sieve-4 A 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add Co (NO 3) 26H 2the aqueous solution (concentration 30 % by weight) of O, obtain the slurries that solid content is 38 % by weight, adding hydrochloric acid to make the pH value of slurries is 3.0, pull an oar 45 minutes, then the phosphorus al binder providing toward the phosphorus aluminium inorganic binder argillaceous (Binder 4) that adds in slurries embodiment 10 to prepare and comparative example 6, stirs 30 minutes.The slurries that obtain, 500 DEG C of inlet temperatures, are sprayed under the condition that exhaust temperature is 180 DEG C dry, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 DEG C, obtain auxiliary agent ZJ 4, its proportioning is in 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, under stirring, add Ni (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 hydrochloric acid consumption makes the pH value of slurries, pull an oar 45 minutes, the phosphorus al binder argillaceous and the diammonium hydrogen phosphate solid that then add embodiment 7 to provide, stir 30 minutes, the slurries spraying obtaining is dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 DEG C, make ZJ 5.
Embodiment 16
Get molecular sieve-4 A 1, boehmite and kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl 36H 2the O aqueous solution (FeCl 3content 30 % by weight), obtain the slurries that solid content is 38 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3.0, continue making beating 45 minutes, the phosphorus al binder argillaceous that adds embodiment 9 to provide, stirs 30 minutes, then by dry the slurries spraying obtaining, obtain microballoon.By microballoon roasting 1 hour at 500 DEG C.
Get thus obtained microsphere product, add ammonium dibasic phosphate aqueous solution, be warming up to 60 DEG C under stirring, react after 20 minutes at this temperature, by slurries vacuum filtration, dry, then roasting 2 hours at 500 DEG C, makes auxiliary agent ZJ 6.
Embodiment 17
Get molecular sieve-4 A 1, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl 36H 2the aqueous solution of O, obtains the slurries that solid content is 30 % by weight, regulates the pH value 3.0 of slurries with hydrochloric acid, then pulls an oar 45 minutes, and the phosphorus al binder argillaceous that then adds embodiment 7 to provide, stirs 30 minutes, by dry the slurries spraying obtaining, obtains microballoon.By microballoon roasting 1 hour at 400 DEG C, make auxiliary agent ZJ 7, its proportioning is in table 3.
Embodiment 18
Get molecular sieve-4 A 2, boehmite and kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl 36H 2the aqueous solution of O, obtain the slurries that solid content is 30 % by weight, be 3.0 by adding hydrochloric acid to regulate the pH value of slurries, then pull an oar 45 minutes, then, toward the phosphorus al binder argillaceous (binder4) that adds embodiment 10 to provide in slurries, stir 30 minutes, by dry the slurries spraying obtaining, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 400 DEG C, make auxiliary agent ZJ 8.
Embodiment 19
Get molecular sieve-4 A 3, kaolin and diatomite, add decationized Y sieve water and waterglass making beating 120 minutes, under stirring, add FeCl 36H 2the aqueous solution of O, obtain the slurries that solid content is 30 % by weight, add hydrochloric acid, it is 3.0 that hydrochloric acid consumption makes the pH value of slurries, then pulls an oar 30 minutes, the phosphorus al binder that adds phosphorus al binder argillaceous (binder2) that embodiment 8 provides and comparative example 6 to provide, pull an oar 30 minutes, then, by dry the slurries spraying obtaining, obtain microballoon, by microballoon roasting 1 hour at 500 DEG C, make auxiliary agent ZJ 9.
Embodiment 20
Get molecular sieve-4 A 4, kaolin and boehmite, add decationized Y sieve water making beating 120 minutes, under stirring, add FeCl 36H 2the aqueous solution of O, obtain the slurries that solid content is 30 % by weight, be 3.0 by adding hydrochloric acid to make the pH value of slurries, then pull an oar 30 minutes, the phosphorus al binder argillaceous (Binder4) that adds embodiment 10 to provide, pulls an oar 30 minutes, then by the slurries that obtain 500 DEG C of dry air inlet temperatures, under the condition that exhaust temperature is 180 DEG C, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 DEG C, make auxiliary agent ZJ 10.
Embodiment 21
Get molecular sieve-4 A 5and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl 36H 2o solid, adding hydrochloric acid to regulate the pH value of slurries is 3.0, pulls an oar 45 minutes, the phosphorus al binder argillaceous (Binder 2) that adds embodiment 8 to provide, stirs 30 minutes, by dry the slurries spraying obtaining, obtains microballoon, makes auxiliary agent ZJ 11.
Comparative example 7
Get A 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add hydrochloric acid, by the pH value 3.0 of hydrochloric acid content control slurries, by mixture continue making beating 45 minutes, by the slurries that obtain 500 DEG C of inlet temperatures, under the condition that exhaust temperature is 180 DEG C, spray dry, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 DEG C, make reference auxiliary agent DB 1.
Comparative example 8
Get A 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl 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 makes the pH value 3.0 of slurries, pull an oar 45 minutes, the slurries that obtain, 500 DEG C of inlet temperatures, are sprayed under the condition that exhaust temperature is 180 DEG C dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 DEG C, make reference auxiliary agent DB 2.
Comparative example 9
Get A 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, add iron nitrate solution (concentration 30 % by weight), obtain the slurries that solid content is 30 % by weight, under stirring, adding concentration is the hydrochloric acid of 36 % by weight, and the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued to making beating 45 minutes.Then toward the phosphorus aluminium glue that adds comparative example 6 to provide in mixed serum, after stirring, the spraying obtaining is dry, obtain microballoon.By microballoon roasting 1 hour at 500 DEG C, make reference auxiliary agent DB 3.
Comparative example 10
Get molecular sieve B 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries that solid content is 30 % by weight, under stirring, adding concentration is the hydrochloric acid of 36 % by weight, it is 3.0 that the consumption of hydrochloric acid makes the pH value of slurries, continue making beating 45 minutes, then the phosphorus aluminium inorganic binder argillaceous (Binder 2) that adds embodiment 8 to provide, stir 30 minutes, by the slurries that obtain 500 DEG C of inlet temperatures, under the condition that exhaust temperature is 180 DEG C, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 DEG C, make reference auxiliary agent DB 4
Comparative example 11
By the method for embodiment 11 is prepared to auxiliary agent, be not both and use molecular sieve B 1replace A 1, make reference auxiliary agent DB 5.
Comparative example 12
Get ZRP-5, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries that solid content is 30 % by weight, under stirring, adding concentration is the hydrochloric acid of 36 % by weight, and the consumption of hydrochloric acid makes the pH value 3.0 of slurries, then continues making beating 45 minutes, by dry the slurries spraying obtaining, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 DEG C, make reference auxiliary agent DB 6.
Comparative example 13
Get molecular sieve B 3, kaolin, diatomite and boehmite, add decationized Y sieve water making beating 120 minutes, under stirring, add FeCl 3.6H 2the aqueous solution of O, obtain the slurries that solid content is 30 % by weight, adding hydrochloric acid to make the pH value of slurries is 3.0, pull an oar 30 minutes, add diammonium hydrogen phosphate, then pull an oar 30 minutes, then by the slurries that obtain 500 DEG C of inlet temperatures, under the condition that exhaust temperature is 180 DEG C, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 DEG C, make auxiliary agent DB 7.
Comparative example 14
Get molecular sieve B 4with boehmite, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries that solid content is 30 % by weight, adding hydrochloric acid to make the pH value of slurries is 3.0, continue making beating 45 minutes, then by the slurries that obtain 500 DEG C of inlet temperatures, under the condition that exhaust temperature is 180 DEG C, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 DEG C, obtain reference auxiliary agent DB 8
Comparative example 15
Get molecular sieve B 5and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, by adding hydrochloric acid to regulate the pH value 3.0 of slurries, continue making beating 45 minutes, add ammonium dibasic phosphate aqueous solution, obtain the slurries that solid content is 30 % by weight, after stirring by the slurries that obtain 500 DEG C of dry gas inlet temperatures, under the condition that exhaust temperature is 180 DEG C, spray dry, obtain average particulate diameter and be the microballoon of 65 microns, make reference auxiliary agent DB 9.
Embodiment 22～32
The following examples, taking fixed fluidized-bed reactor as example, illustrate the cracking reaction effect of cracking additive provided by the invention.
Respectively by 30 grams of ZJ 1-ZJ 11under 800 DEG C, 100% steam atmosphere condition, carry out the burin-in process of 17 hours.Get respectively the ZJ through burin-in process of different amounts 1-ZJ 11industrial FCC equilibrium catalyst (the FCC equilibrium catalyst that the industrial trade mark is DVR-3 from different amounts, main character is in table 4) mix, catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, feedstock oil oil shown in his-and-hers watches 5 carries out catalytic cracking (feedstock oil character is in table 5).Table 6 and table 8 have provided the weight composition of used catalyst mixture, reaction condition and reaction result.
Comparative example 16～25
Comparative example below, taking fixed fluidized-bed reactor as example, illustrates the situation that uses reference auxiliary agent.
By the method in embodiment 22, same feedstock oil is carried out to catalytic cracking, different is that used catalyst is respectively 100% industrial FCC equilibrium catalyst (DVR-3), DB 1～DB 9mixture with industrial FCC equilibrium catalyst (DVR-3).Table 6, table 7 and table 8 have provided the weight composition of used catalyst mixture, reaction condition and reaction result.
Can be found out by table 6, table 7 and table 8, compared with reference auxiliary agent, catalyst aid provided by the invention, can effectively increase catalytic cracking liquefied gas yield, improve significantly propylene, isobutylene concentration in catalytic cracking liquefied gas, improve the concentration of ethene in 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; In the time that promoter additive amount is larger, still there is higher heavy oil transformation rate.
Table 3
Table 4
Table 5

Claims (19)

1. improve an assistant for calalytic cracking for density of propylene, contain the modification MFI molecular sieve in butt 10～75 % by weight, with Al 2o 3, P 2o 5and first clay butt weight sum meter 3～30 % by weight containing the phosphorus aluminium inorganic binder of the first clay, in other inorganic binder 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 VIII family metal that is selected from of oxide 0.5～15 % by weight; Wherein, taking the described phosphorus aluminium inorganic binder butt weight containing the first clay as benchmark, the described phosphorus aluminium inorganic binder containing the first clay comprises with Al 2o 3meter 15～40 % by weight al compositions, with P 2o 5count the phosphorus component of 45～80 % by weight and the first clay in 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, counts 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 meet the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi, and the infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm -1place is without absworption peak, the distribution D of its phosphorus meets 0≤D≤0.8, wherein D=P (S)/P (C), described P (S) represent to adopt zeolite crystal that TEM-EDX method characterizes from edge 1/5th the phosphorus content to center, P (C) represents the phosphorus content of zeolite crystal center;
The described phosphorus aluminium inorganic binder preparation method containing 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) and add SPA according to the part by weight of P/Al=1～6;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 DEG C of temperature.
2. according to auxiliary agent claimed in claim 1, it is characterized in that, the distribution D of described phosphorus is 0.1～0.5.
3. according to the auxiliary agent described in any one of claim l～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, the first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and diatomite; Described the second clay is selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite one or more mixture; Other described 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 in Fe, Co and Ni.
7. according to auxiliary agent claimed in claim 1, 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 the modification MFI molecular sieve containing the phosphorus aluminium inorganic binder of the first clay, 20～60 % by weight, 10～45 % by weight of 8～25 % by weight other inorganic binder, 1.0～10 % by weight be selected from 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, mix containing phosphorus aluminium inorganic binder, other inorganic binder of the first clay, add or do not add the second clay, making beating, spraying is dried and introduces the step of VIII family metallic addition; Wherein, the described phosphorus aluminium inorganic binder containing the first clay, taking its butt weight as benchmark, contains with Al 2o 3meter 15～40 % by weight alumina component, with P 2o 5meter 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, counts 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 meet the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi; The infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm -1place is without absworption peak, the distribution D of its phosphorus meets 0≤D≤0.8, wherein D=P (S)/P (C), described P (S) represent to adopt zeolite crystal that TEM-EDX method characterizes from edge 1/5th the phosphorus content to center, P (C) represents the phosphorus content of zeolite crystal center;
The described phosphorus aluminium inorganic binder preparation method containing 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) and add SPA according to the part by weight of P/Al=1～6;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 DEG C of temperature.
10. in accordance with the method for claim 9, it is characterized in that the described phosphorus aluminium inorganic binder containing the first clay, taking its butt weight as benchmark, comprises 15～35 % by weight and be derived from the Al of described alumina source 2o 3, 50～75 % by weight P 2o 5the first clay with 8～35 % by weight.
11. in accordance with the method for claim 9, it is characterized in that, described P/Al weight ratio is 2～5.
12. in accordance with the method for claim 9, 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 boehmite, and the first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and diatomite.
13. in accordance with the method for claim 9, it is characterized in that, the temperature described in step (3) is 65～90 DEG C.
14. 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 to reactant mixture, obtained reactant mixture is reacted to crystallization 2～80 hours in 145～190 DEG C.
15. in accordance with the method for claim 9, it is characterized in that, described reaction crystallization temperature is 150～190 DEG C, and reaction crystallization time is 5～50 hours.
16. in accordance with the method for claim 9, it is characterized in that, with SiO 2the silicon source of meter with the weight ratio of the MFI molecular sieve taking the described baked phosphorous and transition metal of butt as 0.03～0.3: 1.
17. methods of stating according to claim 16, is characterized in that, described silicon source comprises one or more in silane, siloxanes, estersil and Ludox.
18. according to the method described in claim 14～17 any one, it is characterized in that, in described reactant mixture, also introduce dispersant and/or template, described dispersant is selected from one or more in C5, C6, C7, C8, C9 and C10 alkane, dispersant with SiO 2the weight ratio in the silicon source of meter is 5～90: 10～95; In the time containing template in reactant mixture, also contain water, wherein water and template weight ratio are 0.5～19 simultaneously, and in the molal quantity of template and silicon source, the ratio of the molal quantity of Si is 0.3～1: 1.
19. in accordance with the method for claim 14, it is characterized in that, the preparation method of the MFI molecular sieve of described baked phosphorous and transition metal comprises:
(1) by sodium type MFI molecular sieve according to molecular sieve: ammonium salt: H 2o=1: (0.1～1): the weight ratio of (5～10) filters exchange 0.3～1 hour at room temperature to 100 DEG C after, dry;
(2) molecular sieve phosphorus-containing compound step (1) being obtained and containing transistion metal compound flood, be dried, roasting.
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