CN103007990B - Cracking assistant for improving low-carbon olefin concentration - Google Patents

Cracking assistant for improving low-carbon olefin concentration Download PDF

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CN103007990B
CN103007990B CN201110284452.3A CN201110284452A CN103007990B CN 103007990 B CN103007990 B CN 103007990B CN 201110284452 A CN201110284452 A CN 201110284452A CN 103007990 B CN103007990 B CN 103007990B
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phosphorus
clay
molecular sieve
aluminium
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CN103007990A (en
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朱玉霞
沈宁元
陈蓓艳
罗一斌
欧阳颖
邓景辉
田辉平
蒋文斌
黄志青
宋海涛
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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 and other inorganic binders, 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 ethane, 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 for producing low-carbon alkene by catalytically cracking.
Background technology
Low-carbon alkene is important Organic Chemicals, and its demand increases year by year.Fluid catalytic cracking is the important method of producing low-carbon alkene, in order to increase the productive rate of low-carbon alkene, 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, add in containing 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.
USP 5,318, proposed to be less than based on a kind of large pore zeolite and silica alumina ratio the hydrocarbon conversion process process of the catalyst that 30 the zeolite with MFI structure forms 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 shape slective cracking auxiliary agents in heavy charge catalytic cracking process in 728.Said auxiliary agent adds 12～40% ZSM-5 zeolite to form in [amorphous, and system reserve at least 10% makes the ratio of ZSM-5 in catalyst surpass 3%.The method can, when increasing substantially low-carbon alkene, additionally 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, 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 for hydro carbons pyrolytic conversion.
In CN 1034223C, disclose a kind of catalyst for cracking for the production of low-carbon alkene, by the clay of 0～70% (take catalyst weight as benchmark), 5～99% inorganic oxide and 1～50% zeolite, formed.Zeolite is wherein the mixture of the five-membered ring silica-rich zeolite of the REY of 0～25 heavy % or the phosphorous and rare earth of Y-type high-Si zeolite and 75～100 heavy %.This catalyst has take higher hydrothermal activity stability, conversion ratio and the C of catalyst that ZSM-5 zeolite is 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 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 more than 4.5 phosphorus-containing compound aqueous solution of pH value, makes the phosphorus of zeolite-loaded at least 10 heavy % (with P 2o 5meter), then pull an oar with matrix and other zeolite component, spray drying forming.Gained catalyst has higher productivity of low carbon olefin hydrocarbon.
USP 5,171, disclose a kind of ZSM-5 zeolite with phosphorus modification in 921.This zeolite has 20～60 silica alumina ratio, with phosphorus-containing compound, floods by after 500～700 ℃ of steam treatment, for C 3～C 20hydrocarbon changes into C 2～C 5during the reaction of alkene, the ZSM-5 relatively processing 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, 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.
USP 5,472, disclose the hydrocarbon conversion process process of the catalyst forming 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.
Except ZSM-5 zeolite is carried out, phosphorus modification, also report and introduce phosphorus compound in matrix, 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, the inorganic binder component that also contains the mesopore zeolites such as ZSM-5 and there is cracking performance.Phosphorous in 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 in USP 2002/0049133A1.The ZSM-5 zeolite that this catalyst contains 30～85 heavy %, the phosphorus of 6～24 heavy % is (with P 2o 5meter), and lower than the Al of 10 heavy % 2o 3with other components such as clay 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, disclose the catalyst containing MFI or MEL structural zeolite in 880.Wherein zeolite Shi Jing VIII used family metal, preferably with Ni modification, 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 transforming 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 active, wherein said silica-rich zeolite is ZSM-5, β zeolite or the modenite that contains 0.01～3.0 heavy % phosphorus, 0.01～1.0 heavy % iron or 0.01～10 heavy % 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 ℃, with 0.1～10 hour -1volume space velocity obtain after passing into the halide solution of aluminium, the halide solution of iron 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 a kind of in transition-metal Fe, Co and Ni.When this zeolite is applied to the catalytic cracking process of petroleum hydrocarbon, although can improve C 2～C 4the productive rate of alkene and selective, have higher liquefied gas yield, but dry gas and coke selectivity are poor, and in liquefied gas, density of propylene is not high.
CN 1611299A discloses a kind of MFI structure molecular screen 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 a kind of 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, the disclosed propylene additive that comprises phosphorus and transition metal modified MFI molecular sieve of prior art is for catalytic cracking process, and in liquefied gas, density of propylene is lower, and dry gas and coke yield are higher, and when addition is larger, can weaken heavy oil conversion performance.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of cracking additive that improves catalytic cracking liquid gas propylene concentration, and this auxiliary agent can improve the density of propylene of catalytic cracking liquefied gas for catalytic cracking, reduces coke and dry gas yied.
The invention provides a kind of assistant for calalytic cracking, the butt weight of described auxiliary agent of take is benchmark, contain modification MFI molecular sieve in butt 10～75 heavy %, 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 heavy % containing the phosphorus aluminium inorganic binder of the first clay, in other inorganic binder of oxide 3～30 heavy % with in the second clay of butt 0～60 heavy %; Wherein, the described phosphorus aluminium inorganic binder butt weight containing the first clay of take is benchmark, and the described phosphorus aluminium inorganic binder containing the first clay comprises with Al 2o 3meter 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, 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, D=P (S)/P (C) wherein, 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 present invention also provides a kind of preparation method of assistant for calalytic cracking, comprises modification MFI molecular sieve, the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder mixing, adds or do not add the second clay, making beating, and spraying is dry; Wherein, the described phosphorus aluminium compound inorganic binder containing the first clay, in butt, 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, and y represents to meet the required number of oxidation state of described transition metal M, and described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably; 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, D=P (S)/P (C) wherein, 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 first described clay is one or more in kaolin, sepiolite, concave convex rod, tired de-soil, imvite and diatomite.
The second described clay is selected from one or more that well known to a person skilled in the art in clay, for example be selected from one or more in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil and hydrotalcite, be preferably one or more the mixture in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.
Cracking additive provided by the invention, also contains other inorganic binder except described phosphorus aluminium inorganic binder argillaceous.Described other inorganic binder is selected from one or more in the inorganic oxide binder of the binder component that is customarily used in assistant for calalytic cracking or catalyst, for example can be derived from one or more in boehmite, aluminium colloidal sol, phosphorus aluminium glue, silicon-aluminum sol, waterglass, wherein preferred one or more of 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 0～15 heavy %, the compound that described phosphorus additive is selected from phosphorus comprises the inorganic compound of phosphorus and one or more in organic compound, 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 one or more in phosphorous organic compound.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 resulting catalyst, phosphorus additive exists with the form of phosphorus compound (as the oxide of phosphorus, phosphate, phosphite, subphosphate, acid phosphate).In auxiliary agent, contain except described containing other the phosphorous binding agent the phosphorus aluminium inorganic binder of the first clay for example during phosphorus aluminium colloidal sol, the phosphorus of other described inorganic phosphor-contained binding agent introducing is considered as phosphorus additive.The total content of the phosphorus that phosphorus additive is introduced is no more than 15 % 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 inside, duct of zeolite, in the surface and described host material of zeolite simultaneously.Described phosphorus additive does not comprise modification MFI molecular sieve and contains the phosphorus relating in the phosphorus aluminium inorganic binder of the first clay.
Assistant for calalytic cracking provided by the invention, there is good anti-wear performance and Catalytic Cracking Performance, for heavy oil catalytic cracking reaction, can increase RFCC liquefied gas yield, improve significantly propylene in catalytic cracking liquefied gas and isobutene low-carbon alkene concentration, improve the ethylene concentration in dry gas, the productive rate of ethene, propylene and isobutene is high, coke and dry gas selectively low, and can improve heavy oil conversion performance, and improve the octane number of gasoline, improve light oil productive rate.Compare with existing auxiliary agent, there is higher heavy oil transformation active, higher ethene, propylene and selective isobutene, in liquefied gas, ethene, propylene and isobutylene concentration are higher, have better coke and dry gas selective, are unexpectedly also to have higher liquid to receive.For example, industrial MLC-500 poising agent is 16h at 480 ℃, weight (hourly) space velocity (WHSV) -1, react under the oil ratio condition that is 5, liquefied gas yield is 15.31 % by weight, and heavy oil yield is 15.78 % by weight, and it is 76.69 % by weight that liquid is received, productivity of propylene is 4.76 % by weight, isobutene productive rate is 1.36 % by weight, and ethylene yield is 0.42 % by weight, and in liquefied gas, density of propylene is 31.09 % by weight, isobutylene concentration is 8.88 % by weight, ethene in dry gas is 28.57 % by weight, and coke selectivity is 9.34 % by weight, and dry gas is selectively 2.26 % by weight.And the 50 % by weight modified zsm-5 zeolites that contain provided by the invention, 12 % 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, after mixing with above-mentioned MLC-500 poising agent with the weight ratios of 10: 90, under similarity condition, react, liquefied gas yield is 23.84 % by weight, heavy oil yield is 14.81 % by weight, it is 77.68 % by weight that liquid is received, productivity of propylene is 9.89 % by weight, , isobutene productive rate is 2.14 % by weight, ethylene yield is 0.48 % by weight, in liquefied gas, density of propylene is 41.48 % by weight, in liquefied gas, isobutylene concentration is 8.98 % by weight, ethene in dry gas is 32.88 % by weight, coke selectivity is 8.98 % by weight, dry gas is selectively 2.17 % by weight.
The specific embodiment
Cracking additive provided by the present invention, what preferably include 8～25 heavy % contains the phosphorus aluminium inorganic binder of the first clay, the phosphorus additive of the modification MFI molecular sieve of 20～60 heavy %, the clay of 10～45 heavy %, other inorganic binder of 5～25 heavy % and 0～10 heavy %.In the content of wherein said phosphorus additive, do not comprise modification MFI molecular sieve and contain the phosphorus amount relating in the phosphorus aluminium inorganic binder of the first clay.Described modification MFI molecular sieve is phosphorous and the molecular sieve with MFI structure 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 structure molecular screen, carries out IR Characterization with trimethylpyridine as probe, and its spectrogram is at 1633cm -1place is without absworption peak.With trimethylpyridine, as probe, carrying out IR Characterization is existing method, and its process is as follows: by sample compressing tablet, the original position pond that is placed in infrared spectrometer seals, and at 450 ℃, 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.Described MFI molecular sieve is one or more in ZSM-5, ZSM-8 and ZSM-11 for example, 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, described the first clay containing in the phosphorus aluminium inorganic binder of the first clay comprises tired de-soil, and more preferably the first described clay is rectorite.Take butt weight as benchmark, and 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 5the phosphorus component of meter 50～75 % by weight and in the first clay of butt 8～35 % by weight, and not chloride, and 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, take its butt weight is benchmark, contains with Al 2o 3meter 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, this binding agent solid content is 15～60 % by weight.The described phosphorus aluminium compound 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; In wherein said P/Al, P is the weight of the phosphorus in simple substance in phosphoric acid, and Al is in the weight of the aluminium of simple substance in alumina source;
(3) slurries that step (2) obtained react 15～90 minutes at 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 is 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 are 50～75 % by weight P preferably 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 2～5.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, tired de-soil, 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.
Described phosphorus aluminium inorganic binder argillaceous is due to 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, can regulate more neatly the pH value of binding agent, obtain the binding agent of high solids content, and do not need high temperature depolymerization, the step such as concentrated, preparation method is simple.The adhesive property of resulting binding agent is with not introduce phosphorus al binder prepared by clay mitigation suitable; And the method introduces clay, especially there is the tired de-soil of layer structure, improved the heavy oil conversion performance of carbon monoxide-olefin polymeric, the auxiliary agent that makes to obtain has better selective.
The preparation method of modification MFI structure molecular screen of the present invention, the baked phosphorous and MFI structure molecular screen that has transition metal is mixed with silicon source, in 145～190 ℃ of reaction crystallization 2～80 hours, then reclaim the MFI structure molecular screen of the phosphorous and transition metal that obtains silicon modification, with SiO 2the silicon source of meter is 0.03～0.3: 1 with take the weight ratio of MFI structure molecular screen of described baked phosphorous and transition metal of butt, is 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, silicone grease more preferably, and described estersil is methyl silicate and/or ethyl orthosilicate for example.
The preparation method of the MFI structure molecular screen of modification of the present invention, with silicon-containing compound, phosphorous and MFI structure molecular screen transition metal are carried out to modification, comprise the baked phosphorous and MFI structure molecular screen that has transition metal is mixed with silicon source, then gained mixture is reacted to crystallization (also claiming crystallization) for 2～80 hours in 145～190 ℃ of maintenances.With SiO 2the silicon source of meter is 0.03～0.3: 1 with take the weight ratio of MFI structure molecular screen of described baked phosphorous and transition metal of butt, is preferably 0.05～0.15: 1.Described reaction crystallization temperature is preferably 150～190 ℃ more preferably 170～190 ℃, and reaction crystallization time is preferably 5～50 hours more preferably 12～24 hours.
The baked phosphorous and MFI structure molecular screen that has transition metal is mixed with silicon source, preferably also add dispersant in 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 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 the MFI structure molecular screen that has 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 structure molecular screen 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 template and silicon source, the mol ratio of silicon is preferably 0.4～0.6: 1.Described template is that MFI structure molecular screen is prepared conventional template, is preferably one or more in tetraethyl ammonium hydroxide, TPAOH, tetraethylammonium bromide or 4-propyl bromide.Preferably, template and water mix and react with the MFI structure molecular screen that has 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 resulting modified molecular screen keeps.
The preparation method of the MFI structure molecular screen of the phosphorous and transition metal of modification provided by the invention, the step that also comprises recovery, described recovery comprises the mixture obtaining after reaction crystallization separated, dry, roasting, the MFI structure molecular screen 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 ℃, and the time of roasting is preferably 1～5 hour.
The MFI structure molecular screen of described baked phosphorous and transition metal can for example, by introducing the method preparation of phosphorus and transition metal, roasting in having the molecular sieve of MFI structure (ammonium type or Hydrogen have MFI structure molecular screen).Described introducing phosphorus and transition gold can have MFI structure molecular screen by phosphorous and solution impregnation transition metal, described dipping can successively flood with the solution that contains transistion metal compound and the solution of 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: ammonium type and/or Hydrogen are had to the phosphorus-containing compound solution of MFI structure molecular screen and amount of calculation and containing transistion metal compound solution in room temperature (being generally 15～30 ℃) to 95 ℃ of hybrid infusions, dry roasting under 400～800 ℃ 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 into ammonium type and/or Hydrogen to have in MFI structure molecular screen; 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; Containing transistion metal compound, be selected from the water soluble salt of described transition metal, described water soluble salt is selected from a kind of in sulfate, nitrate, chlorate.Described silicon modification can be one or many, but have at least, is once to carry out after the transition metal of all measuring is introduced.Under preferable case, whole phosphorus and transition metal are introduced in the described molecular sieve with MFI structure before silicon modification.
Described ammonium type has the molecular sieve of MFI structure, can be according to existing method the molecular sieve by sodium type being there is to MFI structure with obtaining after ammonium ion exchange.Molecular sieve sodium type to MFI structure is 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 ℃ after, dry, the molecular sieve with MFI structure that obtains ammonium exchange is ammonium type molecular sieve.The molecular sieve that described Hydrogen has MFI structure can obtain by above-mentioned ammonium type being had to the molecular sieve roasting of MFI structure, or obtains with hydrogen ion exchange by sodium type being had to the molecular sieve of MFI structure.
A kind of specific embodiment 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) sodium type is had after MFI structure molecular screen exchanges 0.3～1 hour at room temperature to 100 ℃ filter, 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 ℃; 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 use the solution that contains phosphorus compound and flood respectively the solution that contains transistion metal compound; Described dipping can carry out one or many, preferred, with the solution that contains phosphorus compound and transistion metal compound simultaneously, floods;
(3) the MFI structure molecular screen 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 ℃ in airtight reaction vessel, then filter, be dried, roasting, obtain the MFI structure molecular screen of the phosphorous and transition metal of 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 structure molecular screen 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.
Modification MFI molecular sieve preparation method provided by the invention carries out modification by phosphorous and the MFI structure molecular screen that has transition metal with silicon compound, this modifying process mixes the baked phosphorous and MFI structure molecular screen that has transition metal with silicon source, resulting mixture reacts crystallization 2～80 hours in 145～190 ℃, can carry out one or many, phosphorous and the transition metal of the modification obtaining by the inventive method there is MFI structure molecular screen molecular sieve, can also further with silicon-containing compound, carry out modification.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)the zeolite crystal that represent to adopt TEM-EDX method to characterize to record is from edge to 1/5th the phosphorus content at center, P (C)represent to adopt TEM-EDX method to characterize the phosphorus content of the zeolite crystal center recording, the distribution D of phosphorus preferably meets 0≤D≤0.8.Preferably the phosphorus of the modification described in 0.1≤D≤0.5 and transition metal modified MFI molecular sieve, carry out IR Characterization with trimethylpyridine as probe, 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, the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder mixing, making beating, its reinforced order does not have specific (special) requirements, for example, 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 and the second clay can be mixed to (can omit relevant addition step when not containing the second clay time) making beating.
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.
While containing phosphorus additive in auxiliary agent, one of its introducing mode of described phosphorus additive is following method or the combination of several method, but is not limited to these methods:
1, before spray drying forming, in slurries, add phosphorus compound;
2, by other inorganic binder, be incorporated in auxiliary agent, when containing phosphorus aluminium colloidal sol in inorganic oxide binder, after roasting, in auxiliary agent, both brought phosphorus into, phosphorus aluminium colloidal sol can play the effect of host material and binding agent again, 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, wherein said dry temperature is room temperature to 400 ℃, preferably 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.
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 1～30 heavy % of FCC catalyst and catalyst mixture total amount provided by the invention, be preferably 3～20 heavy %, 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 impurities such as nickel, vanadium and sulphur, nitrogen impurity, and as the content of sulphur can be up to 3.0 % by weight, 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 ℃, 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, for example fixed bed reactors, fluidized-bed reactor, riser reactor, multi-reaction-area reactor.
The following examples will be further described the present invention, but not thereby limit the present invention.
Part material used is as follows: boehmite is Shandong Aluminium Industrial Corp's manufacture product, the heavy % of solid content 60; Aluminium colloidal sol is the industrial products that catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, Al 2o 3content is 21.5 heavy %; Waterglass is the industrial products that catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, SiO 2the heavy % of content 28.9, Na 2o content 8.9%; Kaolin is the special-purpose kaolin of Cracking catalyst that Kaolin of Suzhou company produces, the heavy % of solid content 78; Tired de-soil: Hebei Zhongxiang Mingliu Rectorite Development Co., Ltd., 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; 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 heavy %, the heavy % of degree of crystallinity 85, silica alumina ratio (SiO 2/ Al 2o 3, mol ratio, lower same) 50.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 ℃ 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 was dissolved in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ 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), (Guangzhou has greatly Fine Chemical Works to produce to 0.333kg 4-propyl bromide, analyze pure, 99%) and the mixture of 1.2L water mix, be placed in the crystallizing kettle that contains polytetrafluoro lining, in 150 ℃ of static crystallizations, after 20 hours, be cooled to room temperature, afterwards, molecular sieve is dried 4 hours at 120 ℃, 550 ℃ 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
By the method for CN1425567A, prepare phosphorous and transition metal and there is the molecular sieve of MFI structure.
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 ℃ 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 ℃ 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 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.93kg H 3pO 4(concentration 85 % by weight) and 3kg Co (NO 3) 26H 2o is dissolved in 9kg water obtaining maceration extract, by 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), (Guangzhou has greatly Fine Chemical Works to produce to 817g tetraethyl ammonium hydroxide, 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, in 180 ℃ of static crystallizations, after 20 hours, be cooled to room temperature, afterwards, at 120 ℃, dry 4 hours, 550 ℃ 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 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 ℃ 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 ℃ 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, 8iO 2/ Al 2o 3=50),, after 90 ℃ 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 ℃ 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, in 170 ℃ of static crystallizations, after 20 hours, be cooled to room temperature, afterwards, molecular sieve is dried 4 hours at 110 ℃, 550 ℃ 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 ℃ 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 ℃ 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 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 ℃ 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 ℃ 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 has greatly Fine Chemical Works to produce, containing TPAOH 25 % by weight, water 75 % by weight) mixture mixes, and is then placed in the crystallizing kettle that contains polytetrafluoro lining, in 180 ℃ of static crystallizations, after 24 hours, is cooled to room temperature, afterwards, molecular sieve is dried 4 hours at 110 ℃, and 550 ℃ 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 ℃ 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 ℃ 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 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.52kg H 3pO 4(concentration 85 % by weight), 0.82kgFe (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 ℃ 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 ℃ of reactions 12 hours, be then cooled to room temperature, afterwards, molecular sieve is dried 4 hours at 110 ℃, and 550 ℃ 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 ℃ 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 ℃ 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.
Table 1
Embodiment 6
The sample that embodiment 1～5 and comparative example 1～5 are made, with TEM-EDS and infrared sign, 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 tired de-soil (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 (mass concentration 85%), phosphoric acid add speed be 0.04Kg phosphoric acid/minute/Kg alumina source, be warming up to 70 ℃, then at this temperature, react 45 minutes, make the inorganic binder of phosphorous aluminium compound.Material proportion is in Table 2.
Embodiment 8～10
Example 8～10 preparations are containing the phosphorus aluminium inorganic binder of the first clay.Material proportion is in Table 2.
Comparative example 6
This comparative example is prepared comparative example of the present invention phosphorus aluminium glue used (phosphorus aluminium colloidal sol).
Phosphorus aluminium glue preparation: by 0.66 kilogram of boehmite (0.44 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, the heavy % of phosphoric acid 85), be warming up to 70 ℃, then at this temperature, react 45 minutes, obtain phosphorus aluminium glue (phosphorus aluminium inorganic binder).Material proportion is in Table 2.
Embodiment 11～18 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, obtain the slurries of solid content 30 % by weight, add hydrochloric acid to regulate the pH value 3.0 of slurries, then continue making beating 45 minutes, then the phosphorus aluminium inorganic binder argillaceous that adds embodiment 8 preparations, stir after 30 minutes, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, 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, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3.0, pull an oar after meal 45 minutes, then toward the phosphorus aluminium inorganic binder argillaceous that wherein adds embodiment 7 preparations.The slurries that obtain, 500 ℃ of dry gas inlet temperatures, are sprayed under the condition that exhaust temperature is 180 ℃ dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃.
Get thus obtained microsphere product, add ammonium dibasic phosphate aqueous solution, be warming up to 60 ℃ under stirring, react after 20 minutes at this temperature, by slurries vacuum filtration, dry, then roasting 2 hours at 500 ℃, makes auxiliary agent ZJ 2.Auxiliary agent proportioning is in Table 3.
Embodiment 13
Get molecular sieve-4 A 1with boehmite, kaolin, diatomite, add decationized Y sieve water and waterglass making beating 120 minutes, obtain the slurries of solid content 35 % by weight, add hydrochloric acid to make the pH value 3 of slurries, then pull an oar 45 minutes, to the phosphorus aluminium inorganic binder argillaceous that adds embodiment 9 preparations in mixed serum, stir 30 minutes, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ 3, its proportioning is in Table 3.
Embodiment 14
Get molecular sieve-4 A 1with boehmite, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 38 % by weight, add hydrochloric acid to make the pH value 3.0 of slurries, then pull an oar 45 minutes, then in mixed serum, add the phosphorus aluminium inorganic binder argillaceous of embodiment 10 preparations and the phosphorus al binder that comparative example 6 provides, stir 30 minutes.The slurries that obtain, 500 ℃ of dry air inlet temperatures, are sprayed under the condition that exhaust temperature is 180 ℃ dry, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ 4, its proportioning is in Table 3.
Embodiment 15
Get molecular sieve-4 A 2with boehmite, kaolin, add decationized Y sieve water making beating 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3, then pull an oar 45 minutes, then, toward the phosphorus al binder argillaceous that adds embodiment 7 preparations in slurries, stir 30 minutes.The slurries spraying obtaining is dry, obtain microballoon.By microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ 5, auxiliary agent proportioning is in Table 3.
Embodiment 16
Get molecular sieve-4 A 3, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3, continues making beating 45 minutes, then the phosphorus al binder argillaceous that adds embodiment 8 preparations, and after diammonium hydrogen phosphate solid stirs, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 400 ℃, make auxiliary agent ZJ 6.Proportioning is in Table 3.
Embodiment 17
Get molecular sieve-4 A 4with boehmite, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, with hydrochloric acid, regulating the pH value of slurries is 3.0, then continues making beating 45 minutes, the phosphorus al binder argillaceous that adds embodiment 9 preparations, stir 30 minutes, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ 7.Auxiliary agent proportioning is in Table 3.
Embodiment 18
Get molecular sieve-4 A 5, kaolin soil and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to make the pH value of slurries is 3, continues making beating 30 minutes, the phosphorus al binder argillaceous that adds embodiment 9 preparations, pull an oar again 30 minutes, then that the slurries spraying obtaining is dry, obtain, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ 8.Auxiliary agent proportioning is in Table 3.
Comparative example 7
Get A 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, under stirring, adding concentration is the hydrochloric acid of 36 % by weight, and the pH value that makes slurries is 3.0, then pulls an oar 45 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 ℃, make reference auxiliary agent DB 1.Reference auxiliary agent proportioning is in Table 4.
Comparative example 8
Get A 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, under stirring, add hydrochloric acid, by hydrochloric acid content, control the pH value 3.0 of slurries, mixture was continued to making beating after 45 minutes, the phosphorus al binder that adds comparative example 6 to make, then stir 30 minutes, by the slurries that obtain 500 ℃ of inlet temperatures, under the condition that exhaust temperature is 180 ℃, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃, make reference auxiliary agent DB 2.Reference auxiliary agent proportioning is in Table 4.
Comparative example 9
Method by embodiment 11 is prepared auxiliary agent, is not both and uses molecular sieve B 1replace A 1, make reference auxiliary agent DB 3.Reference auxiliary agent proportioning is in Table 4.
Comparative example 10
By the method for comparative example 7 is prepared to auxiliary agent, be not both with molecular sieve ZRP-5 and replace A 1, make reference auxiliary agent DB 4.Reference auxiliary agent proportioning is in Table 4.
Comparative example 11
By the method for embodiment 15 is prepared to auxiliary agent, be not both and use molecular sieve B 2replace A 2, make reference auxiliary agent DB 5.Reference auxiliary agent proportioning is in Table 4.
Comparative example 12
Get molecular sieve B 3, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, by adding hydrochloric acid to regulate the pH value 3.0 of slurries, then continue making beating 30 minutes, add diammonium hydrogen phosphate, pull an oar again 30 minutes, then by the slurries that obtain 500 ℃ of inlet temperatures, under the condition that exhaust temperature is 180 ℃, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃, make auxiliary agent DB 6.Reference auxiliary agent proportioning is in Table 4.
Comparative example 13
Get molecular sieve B 4and kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3.0, and the phosphorus al binder argillaceous that adds embodiment 9 to provide is provided 30 minutes, pull an oar 45 minutes, then by the slurries that obtain 500 ℃ of dry air inlet temperatures, under the condition that exhaust temperature is 180 ℃, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃, obtain reference auxiliary agent DB 7.Reference auxiliary agent proportioning is in Table 4.
Comparative example 14
Get molecular sieve B 5, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, by adding hydrochloric acid to make the pH value 3.0 of slurries, pull an oar 45 minutes, then that the slurries spraying obtaining is dry, obtain microballoon, make reference auxiliary agent DB 8.Reference auxiliary agent proportioning is in Table 4.
Embodiment 19～26
The following examples be take fixed fluidized-bed reactor as example, and the cracking reaction effect of cracking additive provided by the invention is described.
Respectively by 30 grams of ZJ 1-ZJ 8under 800 ℃, 100% steam atmosphere condition, carry out the burin-in process of 12 hours.Get the ZJ through burin-in process of different amounts 1-ZJ 8mix respectively from the industrial FCC equilibrium catalyst (the FCC equilibrium catalyst that the industrial trade mark is MLC-500, main character is in Table 5) of different amounts.Catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, feedstock oil oil shown in his-and-hers watches 6 carries out catalytic cracking (feedstock oil character is in Table 6).Table 7, table 8 and table 9 have provided used catalyst mixture weight and have formed, reaction condition and reaction result.
Comparative example 15～23
Comparative example below be take fixed fluidized-bed reactor as example, and the situation of using reference auxiliary agent is described.
By the method in embodiment 19, same feedstock oil is carried out to catalytic cracking, different is that used catalyst is respectively 100% industrial FCC equilibrium catalyst, DB 1～DB 8mixture with industrial FCC equilibrium catalyst.Table 7, table 8 have provided used catalyst mixture weight and have formed, reaction condition and reaction result.
From table 7 and table 8, can find out, compare with auxiliary agent prepared by existing method, catalyst aid provided by the invention, have higher catalytic cracking liquefied gas yield, the productive rate of ethene, propylene and isobutene is higher, and propylene, isobutylene concentration in catalytic cracking liquefied gas are higher, ethylene concentration in dry gas is higher, heavy oil conversion performance is higher, and coke and dry gas selective better is also to have higher liquid to receive unexpectedly.
Table 5
Table 6

Claims (18)

1. improve an assistant for calalytic cracking for density of propylene, contain modification MFI molecular sieve in butt 10～75 heavy %, in the phosphorus aluminium inorganic binder containing the first clay of al composition, phosphorus component and the first clay butt weight sum 3～30 heavy %, in other inorganic binder of oxide 3～30 heavy % with in the second clay of butt 0～60 heavy %; Wherein, the described phosphorus aluminium inorganic binder butt weight containing the first clay of take is benchmark, and the described phosphorus aluminium inorganic binder containing the first clay comprises with Al 2o 3meter 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 1～6; 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 2x 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 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, D=P (S)/P (C) wherein, 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 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) 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 ℃ of temperature.
2. according to auxiliary agent claimed in claim 1, it is characterized in that, the phosphorus distribution D of described modification MFI molecular sieve meets 0.1≤D≤0.5.
3. according to auxiliary agent claimed in claim 1, it is characterized in that, described MFI molecular sieve is ZSM-5, and described M is Fe.
4. according to auxiliary agent claimed in claim 1, it is characterized in that, this auxiliary agent comprises that 8～25 heavy %'s contains the phosphorus aluminium inorganic binder of the first clay, the phosphorus additive of the described modification MFI molecular sieve of 20～60 heavy %, the second clay of 10～45 heavy %, other inorganic binder of 5～25 heavy % and 0～15 heavy %.
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, tired de-soil, imvite and diatomite; Described the second clay is selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more; 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 described in claim 1～5 any one, 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) M xo y(82～92) SiO 2.
7. a preparation method for assistant for calalytic cracking, comprises modification MFI molecular sieve, the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder mixing, adds or do not add the second clay, making beating, and spraying is dry; Wherein, the described phosphorus aluminium compound inorganic binder containing the first clay, take its butt weight is benchmark, containing with Al 2o 3meter 15～40 % by weight al compositions, 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 1～6, pH value is 1～3.5, 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; It is multiple that 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, D=P (S)/P (C) wherein, 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 ℃ of temperature.
8. in accordance with the method for claim 7, it is characterized in that, the described phosphorus aluminium inorganic binder containing the first clay, take its butt weight is benchmark, comprises the Al that 15～35 % by weight are derived from described alumina source 2o 3, 50～75 % by weight P 2o 5the first clay with 8～35 % by weight.
9. according to the method described in claim 7 or 8, it is characterized in that, described P/Al weight ratio is 2～5.
10. in accordance with the method for claim 7, 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; The first described clay is one or more in kaolin, sepiolite, concave convex rod, tired de-soil, imvite and diatomite.
11. in accordance with the method for claim 7, it is characterized in that, the temperature described in step (3) is 65～90 ℃.
12. in accordance with the method for claim 7, it is characterized in that, described modification MFI molecular sieve preparation method comprises: by baked phosphorous and transition metal there is MFI structure molecular screen with silicon source is mixed to get reactant mixture, resulting reactant mixture is reacted to crystallization 2～80 hours in 145～190 ℃.
13. in accordance with the method for claim 12, it is characterized in that, described reaction crystallization temperature is 150～190 ℃, and reaction crystallization time is 5～50 hours.
14. in accordance with the method for claim 12, it is characterized in that, with SiO 2the silicon source of meter is 0.03～0.3: 1 with take the weight ratio of MFI structure molecular screen of described baked phosphorous and transition metal of butt.
15. methods of stating according to claim 14, is characterized in that, described silicon source comprises one or more in silane, siloxanes, estersil and Ludox.
16. according to the method described in claim 12～15 any one, it is characterized in that, also introduces dispersant and/or template in described reactant mixture; When introducing dispersant, 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; While 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.
17. in accordance with the method for claim 12, it is characterized in that, the preparation method of the MFI structure molecular screen of described baked phosphorous and transition metal comprises:
(1) molecular sieve that sodium type is had to a MFI structure is 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 ℃ after, dry;
(2) molecular sieve step (1) being obtained with phosphorus-containing compound and containing transistion metal compound flood, be dried, roasting.
18. in accordance with the method for claim 7, it is characterized in that, described the second clay be in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more; Other described inorganic matter binding agent is one or more of boehmite, aluminium colloidal sol, silicon-aluminum sol, waterglass and phosphorus aluminium colloidal sol.
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