CN1006687B

CN1006687B - Catalytic cracking catalyst and application thereof

Info

Publication number: CN1006687B
Application number: CN 85109361
Authority: CN
Inventors: 里吉斯·约瑟夫·佩利特; 彼得·凯文·库格林
Original assignee: Union Carbide Corp
Current assignee: Union Carbide Corp
Priority date: 1984-11-27
Filing date: 1985-11-26
Publication date: 1990-02-07
Also published as: CN85109361A; FI863823A; AU5190486A; WO1986003138A1; FI863823A0; DK486386D0; EP0202325A1

Abstract

Multiple catalyst for cracking and their application in cracking technology are disclosed.The mixture of the alumo-silicate molecular sieve that utilizes catalytic cracking catalyst and select from No. 4440871, United States Patent (USP) can be prepared this cracking catalyst.

Description

Catalytic cracking catalyst and application thereof

The present invention relates to the cracking catalyst that the mixture by the alumo-silicate molecular sieve of a kind of particular types of No. 4440871, zeolite aluminosilicate and United States Patent (USP) obtains.New catalyst mixture is applied in the cracking process, and the products therefrom mixture is more useful than the product of the cracking catalyst gained of making matrix with zeolite.

The prior art relevant with various catalytic cracking catalysts, major part are with as the component of cracking catalyst about preparation improvement zeolite.Following patent has been represented the prior art relevant with zeolite and matrix.

In United States Patent (USP) No. 3140249 and No. 3352796, disclose to adopt and be dispersed in the conversion catalyst that forms in the siliceous matrix by zeolite.

Disclose the use of fusion matrix component in No. 3312615, United States Patent (USP), as contained the catalyzer of zeolite, inorganic oxide matrix and fine inert material, fine inert material can be an Alpha-alumina.In No. 3542670, United States Patent (USP), disclose and contained amorphous silica-aluminum oxide, add the catalyzer of aluminum oxide and zeolite respectively, in No. 3428550, United States Patent (USP), disclose the catalyzer that contains zeolite, amorphous hydrated aluminum oxide and aluminum oxide-hydrate.

Show, use basic metal with low levels and unit cell dimension can improve Y zeolite steam and thermostability less than the zeolite of about 24.45 dusts (see United States Patent (USP) No. 3293192 and announce (bulletins again that No. 3402996, United States Patent (USP)) again No. 28629).

In addition, (No. 3591488, United States Patent (USP)) shows, the zeolite of Hydrogen or ammonium type can be used H at about 427 ℃ (800 °F) to the temperature of about 816 ℃ (1500) ₂O handles, then, with the zeolite of steam and water treatment with can be that the cationic multiple positively charged ion of rare earth metal carries out cationic exchange.United States Patent (USP) shows that the hydrogen faujusite (faujasite) of rare earth exchanged contains 6～14% rare earth oxide for No. 3676368.United States Patent (USP) shows that it is 1～10%(weight that the zeolite of rare earth exchanged has total amount for No. 3957623) rare-earth oxide.It is 0.3～10%(weight that United States Patent (USP) has been introduced content of rare earth for No. 3607043) the prepare zeolite method.

United States Patent (USP) has been introduced the Y zeolite of hydrothermally stable and ammonia stability for No. 4036739, wherein, part sodium ion in the sodium Y zeolite is exchanged into ammonium ion, subsequently, with steam calcination and further with ammonium ion exchange, so that last sodium oxide content is reduced to 1%(weight) below, calcine the product of exchange again again or press United States Patent (USP) No. 3781199, after zeolite and refractory oxide fusion, carry out the calcining second time.

The product that obtains with above-mentioned this class catalyzer is not all to be optimal in all cases.Therefore, various Catalyst And Methods have been developed to improve the product of cracking process.Have several patents by the agency of use various additives as the component of cracking catalyst to improve the distribution of product.United States Patent (USP) discloses that to use the catalyst additive that contains zeolite, the α value of this zeolite to be not less than about 5 for No. 4284529, and in fact to cracking normal hexane non-activity.United States Patent (USP) discloses a kind of catalyzer synthetics for No. 4239654, and it contains unusual stable Y type crystalline aluminosilicate zeolite, catalyzer inorganic oxide matrix and aperture crystalline ZSM type zeolite.No. 4289606, United States Patent (USP) and No. 4239654 similar parts of United States Patent (USP) are that one of aperture crystalline ZSM-5 type zeolite and unusual stable Y crystal silicon-aluminate zeolite are as catalyzer.United States Patent (USP) 4309279 and relate to for No. 4309280 cracking process is used zeolite additive, in cracking process, being characterized as of zeolite: the constraint rate is about 1 to 12, and the ratio of silicon oxide and aluminum oxide is greater than about 12.Aforesaid method relates to the use zeolite mixture, and is limited to zeolite certainly.

United States Patent (USP) discloses a kind of novel crystalline microporous alumo-silicate molecular sieve for No. 4440871.These alumo-silicates comprise that for various hydrocarbon conversion processes it is useful that the catalyzer cracking process shows usually.Disclose the alumo-silicate that utilizes No. 4440871, United States Patent (USP) component in the common pending application of the U.S. serial of submitting in May 2 nineteen eighty-three 490952, be used to transform the crude oil material that contains carbon-hydrogen cracking compound as common cracking catalyst.Though above-mentioned prior art usually discloses the use of alumo-silicate in cracking process, not as following the discussion, propose to use specific alumo-silicate to improve products distribution.

Utilize alumo-silicate molecular sieve to be disclosed in meanwhile submitting to of U.S. numbering (act on behalf of case number be No. 14698) and the common common pending application application of transferring the possession of as cracking catalyst.

The present invention relates to utilize component and the catalyst cracking method of specific alumo-silicate molecular sieve as cracking catalyst.When such alumo-silicate molecular sieve joins in the cracking catalyst and is applied to catalytic cracking method, such catalytic cracking method just can make product not compare with there being the product that this class alumo-silicate molecular sieve obtains, and has the difference of the essence on the products distribution and more valuable.

Method of the present invention relates to the catalytic cracking of crude oil material to produce than lower boiling hydrocarbons, present method is included under the effective catalytic cracking condition, above-mentioned raw material is contacted with the pellet type catalyst that the cracking crude oil material is had catalytic activity, and this catalyzer for example is at least a zeolite aluminosilicate that is applied to the cracking catalyst type usually and at least aly can adsorbs 2%(weight at least under 20 ℃ of temperature, dividing potential drop 667 handkerchiefs (500 torr)) the calcinated form of (No. 4440871, United States Patent (USP)) alumo-silicate molecular sieve of Trimethylmethane.The characteristics of zeolite aluminosilicate are that it is a kind of zeolite as cracking component, for example commonly use those various forms of zeolite Y in above-mentioned cracking catalyst before this.The alumo-silicate molecular sieve of Ying Yonging is not the zeolite aluminosilicate of using in technology before this in the present invention, but the member of the new alumo-silicate molecular sieve class of No. 4440871, United States Patent (USP).

The present invention relates to new catalytic cracking catalyst, their preparation method and their using method in the catalytic cracking method that crude oil material transforms.Catalytic cracking catalyst of the present invention makes by the novel alumo-silicate molecular sieve of a specific type with in any suitable cracking catalyst that effectively has cracking activity under the catalytic cracking condition, know in the art.The alumo-silicate of Ying Yonging is a kind of alumo-silicate that is called the particular variety of " SAPOs " in No. 4440871, United States Patent (USP) in the present invention, can be with reference to this patent at this.

Have been found that when specific alumo-silicate when common zeolite aluminosilicate cracking catalyst is used in combination, this class alumo-silicate can make the distribution of product improve.Before this, variable or product property (as the octane value) optimizing of the catalyzer of prior art in order to make an ad hoc approach, its performance can be affected.For example, when using the catalyzer of zeolite aluminosilicate base, observed the improvement of the gasoline octane of product, the ratio that it is expressed as branched-chain alkene and normal olefine and isoparaffin and n-paraffin increases, and the decline of gasoline yield and materials conversion rate takes place simultaneously.As mentioned above, as the indication of higher octane product, their increase or minimizing are as the relative indication of gasoline products octane always in the existence of isoparaffin and branched-chain alkene.Present method is characterised in that and has improved isoparaffin and branched-chain alkene product, has also reduced the relative quantity of normal alkane and normal olefine, and the loss of gasoline yield and materials conversion rate simultaneously reduces to minimum.

The alumo-silicate molecular sieve that No. 4440871, United States Patent (USP) is known as the microporous crystalline alumo-silicate, and its hole is uniformly and has than the big specific diameter of about 3 dusts that in synthetic and its anhydrous form, its basic empirical chemical constitution is:

mR：（Si _xAl _yP _z）O ₂

Wherein " R " representative is present at least a organic formwork agent in the intracrystalline hole system; " m " represents each mol (Si _xAl _yP _z) O ₂In have the mole number of " R ", " m " value is 0.02 to 0.3, " x " " y " and " z " represent the mole fraction of the silicon, aluminium and the phosphorus that exist with tetrahedral oxide respectively, above-mentioned mole fraction is such mole fraction, so that they drop in the area of being made up of the ABCD of ternary diagram and the definite pentagon of E point, and this ternary diagram is Fig. 1 of No. 4440871 accompanying drawings of United States Patent (USP).The SAPO molecular sieve that No. 4440871, United States Patent (USP) is also referred to as has PO ⁺ ₂, AlO ^- ₂And SiO ₂The three-dimensional microporous framework structure of tetrahedron element, its basic experience chemical constitution, the form when anhydrous is: mR:(Si _xAl _yP _z) O ₂Herein: " R " represents at least a organic formwork agent that is present in the intracrystalline hole system, and " m " represents each mol (Si _xAl _yP _z) O ₂In have the mole number of " R ", it is worth from zero to 0.3, " x " " y " and " z " represent the mole fraction of the silicon, aluminium and the phosphorus that exist respectively in the oxide compound part, above-mentioned mole fraction is in the area of the composition that limits of A, B, C, D on Fig. 1 ternary diagram and E point, above-mentioned alumo-silicate has the X-ray powder diffraction figure of feature, and this figure contains the minimum d spacing in any one table of the table I, III, V, VII, IX, XII, X VII, X XI, XX III or the XX V that are presented at No. 4440871, following United States Patent (USP).In addition, above-mentioned crystalline aluminium silicophosphate can be enough to remove some organic formwork agent at least that is present in the intracrystalline hole system at sufficiently high temperature lower calcination.The alumo-silicate that No. 4440871, United States Patent (USP) is called " SAPO-n " usually there, is called one type, or is called " SAPO-n ", and n is the integer of a kind of specific SAPO of expression herein, and its preparation is reported in No. 4440871, the United States Patent (USP).The specific SAPOs of Ying Yonging in the present invention, its other characteristics are under 20 ℃ of dividing potential drop 667 handkerchiefs (500 torr), temperature, the Trimethylmethane of adsorbable at least 2% weight of their calcinated form.In addition, that better is above-mentioned SAPOs, and its calcinated form is also adsorbable triethylamine less than 5% weight under 22 ℃ of dividing potential drop 3.5 handkerchiefs (2.6 torr), temperature.Applicable SAPOs includes, but not limited to SAPO-5, SAPO-11, SAPO-31, SAPO-37, SAPO-40 and SAPO-41.

The above-mentioned feature that is applied to alumo-silicate class of the present invention (SAPOs) relates to the adsorpting characteristic that adsorbs on SAPO, this SAPO has stood synthetic aftertreatment, for example calcining or chemical treatment is to remove the quite most of template " R " that exists as synthetic product.Although specific here, its calcinated form, SAPO is characterised in that its adsorb isobutane and not necessarily do not adsorb triethylamine, use non-incinerating SAPO required in this invention comprising, the latter's characteristics are that its calcinated form can carry out above-mentioned absorption, because when under catalytic cracking condition, using above-mentioned non-calcining SAPO in present method, SAPO will calcine or the original place hydrothermal treatment consists, so that have the minimum absorption of the feature of Trimethylmethane.Therefore, can make SAPO become form in the original place with above-mentioned characterization of adsorption.For example, although the calcinated form of SAPO-11 has the characterization of adsorption of above-mentioned Trimethylmethane or triethylamine, the SAPO-11 when synthetic owing to there is synthetic product template " R ", does not have the characterization of adsorption of above-mentioned Trimethylmethane.Therefore, its calcinated form of touching upon has the SAPO of specific adsorpting characteristic, and does not mean that the SAPO that get rid of to use its synthesized form, it through calcining, hydrothermal treatment consists and/or other handle (as with suitable cationic exchange), just have above-mentioned characterization of adsorption.

Have been found that this alumo-silicate can provide the cracking catalyst that only contains zeolite aluminosilicate (not containing alumo-silicate) the products distribution that can not form.Till now, the catalyzer of prior art as the octane of gasoline product, reaches the optimizing aspect making particular procedure variable or product property, demonstrates the minimizing of gasoline yield and/or transformation efficiency.Utilize this catalyzer just to reduce above-mentioned loss.In addition, the minimizing of the raising of isoparaffin and branched-chain alkene output and this catalyzer n-paraffin and normal olefine amount is the sign of higher octane product.

Use term " crude oil material " to be meant any crude oil material or its part here, " crude oil material " comprises by common oil field or submarine oil field by elementary, secondary or three grades of crude oil materials that reclaim entire areas." crude oil material " also can be " synthetic crude " that can obtain from coal, shale oil, Tar sands and pitch earth.Crude oil material can be the synthetics of direct-distilled (straight run) or process fusion.Such crude oil material is wanted desalination before use usually, because sodium-chlor is a kind of " poisonous substance " in many cracking operations.In addition, term " crude oil material " also comprises the integral part of crude oil, up to the present, they are generally as catalytic cracking charging or standby charging, comprise the fraction that distills gas oil, heavy vacuum gas oil, vacuum gas oil (VGO), normal pressure and decompression residual oil, synthetic crude, fine coal and surpass the gasoline boiling range, gasoline boiling range fraction generally comprises greater than the compound of 11 carbon atoms and their composition.

Cracking catalyst is a particle shape, contains inorganic, porous refractory oxide usually, as silica-alumina, also can be aluminum oxide and/or silicon oxide and/or clay.This class catalyzer generally also contains at least a silico-aluminate.Zeolite aluminosilicate cracking component in this class catalyzer can be any silico-aluminate that always is used as the cracking catalyst component so far.Up to the present openly can be used as the zeolite aluminosilicate of the component of cracking catalyst, its representative is zeolite Y, X zeolite, zeolite beta (No. 3308069, United States Patent (USP)), zeolite KZ-20(United States Patent (USP) 3445727), zeolite ZSM-3(United States Patent (USP) 3415736), No. 2014970, faujusite (faujasite), LZ-10(United States Patent (USP), June 9 nineteen eighty-two), ZSM type zeolite and their mixture.Contain Na in traditional cracking catalyst ₂The amount of O is pressed the weight of total catalyst and is calculated, less than about 6% better, and Na ₂The amount of O is also fine less than 1%.

Here, thinking that applicable representational Y type boils includes, but not limited to the zeolite introduced in the following U.S. Patent number: 3130007,3835032,3830725,3293192,3449070,3839539,3867310,3929620,3929621,3933983,4058484,4085069,4175059,4192778,3676368,3595611,3594331,3536521,3293192,3966643,3966882 and 3957623.

Here, another kind of applicable zeolite aluminosilicate is " LZ-210 ", and it is presented in No. 82211, the E.P.C publication published June 29 nineteen eighty-three.

The zeolite of term " ZSM-type " generally is applied to relate in the technology of those zeolites of naming by nomenclature " ZSM-n ", and n is an integer herein.ZSM-type silico-aluminate includes, but not limited to ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-48 and other similar material.

No. 3702886, United States Patent (USP) and announce again and describe ZSM-5 in 29948 in detail.Contained complete description in these patents, especially wherein the X-ray diffractogram of disclosed ZSM-5 is hereby incorporated by.

United States Patent (USP) has been described ZSM-11 No. 3709979.The description of this patent, the X-ray diffractogram of especially above-mentioned ZSM-11 is hereby incorporated by.

United States Patent (USP) has been described ZSM-12 No. 3832449.The description of this patent, the X-ray diffractogram that especially wherein shows is hereby incorporated by.

United States Patent (USP) has been described ZSM-23 No. 4076842.Whole contents wherein, the detailed description of the X-ray diffractogram of especially disclosed zeolite is incorporated herein for referencial use.

United States Patent (USP) has been described ZSM-35 No. 4016245.Be hereby incorporated by about the explanation of zeolite and X-ray diffractogram especially wherein in the patent.

United States Patent (USP) has more ad hoc illustrated ZSM-38 No. 4046859.Wherein describe about zeolite, especially its specific X-ray diffractogram is hereby incorporated by.

United States Patent (USP) has been narrated ZSM-48 No. 4423021 specially.Wherein the X-ray diffractogram about description, especially its feature of zeolite also is hereby incorporated by.

Cracking catalyst

Catalyzer of the present invention comprises at least a zeolite aluminosilicate cracking component and at least a SAPO molecular sieve component.Every kind of products distribution that the relative amount of component depends on the crude oil material of selecting for use at least in part and therefrom wants to obtain, but in many cases, use at least a SAPO of significant quantity, with with zeolite aluminosilicate but the distribution that does not have SAPO molecular sieve component to obtain compare, reach different products distribution.The zeolite aluminosilicate weight ratio relative with SAPO generally between about 1: 10 and about 500: 1, wish between about 1: 10 and about 200: 1, and be more desirable between about 1: 2 and about 50: 1, is preferably between about 1: 1 and about 20: 1.Zeolite aluminosilicate and/or SAPO can be with the cationic exchange of selection and/or are being mixed front or rear or their adding back or while and one or more inorganic oxide matrix component mixing postheat treatment separately each other.When exchange, the preferential and hydrogen evolution cationic exchange of SAPO molecular sieve is as NH ⁺ ₄, H ⁺, quaternary ammonium cation or the like.SAPO preferably at least partial cation exist with the hydrogen evolution ionic species.

Heat calcining and the hydro-thermal of using " thermal treatment " term to call in the presence of air or rare gas element such as nitrogen are here calcined (the heat calcining in the presence of steam).Thermal treatment is under efficient temperature and time, and carries out in the presence of the steam of significant quantity when hydrothermal treatment consists.Typical thermal treatment temp surpasses 300 ℃, and the time surpasses 0.25 hour, and when hydrothermal treatment consists, typical thermal treatment will be at least about 20% steam (by volume of air) with carry out in the presence of about 100% steam.Vapour source is not important, and it can be provided or can be produced on the spot being used under the temperature of hydrothermal treatment consists by external source.When the form of above-mentioned SAPO when synthetic is applied to present method, because on the spot, so can under catalytic cracking condition, introduce SAPO this process and hydrothermal treatment consists is provided.

Any ion-exchange of zeolite aluminosilicate and SAPO, no matter any silico-aluminate or SAPO can be through Overheating Treatment, can be undertaken by they are contacted with at least a cationic solution, comprise being selected from by ammonium, II A family, III A family, III B to those positively charged ion groups of III B group composition be selected from by Ce, La, Pr, Nd, Pm, Sm, those positively charged ion groups and be selected from the rare-earth cation group of forming by Ce, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dg, Ho, Er, Tm, Yb, Lu and composition thereof.At present, also do not observe the activity that existence of rare-earth cation and SAPO molecular sieve can help the SAPO component.The definite character of rare-earth cation and SAPOs mutual relationship is not also very understood so far.Because the result of ion-exchange, positively charged ion as rare-earth cation, can be replaced at least a portion and be present in positively charged ion among zeolite aluminosilicate or the SAPO at first.The positively charged ion that provides by ion-exchange can reach effective quantity, calculates by initial zeolite aluminosilicate or SAPO weight, can be in about 0.1%(weight) arrive about 20%(weight) between, typically about 0.5% to about 10%(weight) between.

Cracking catalyst of the present invention generally is and application of inorganic oxide matrix component, the inorganic oxide matrix component can be up to the present to be applied to form any in the inorganic oxide matrix component of FCC catalyzer, comprise various unbodied catalysis inorganic oxides, for example have the silica-alumina, clay, silicon oxide, aluminum oxide, silica-alumina, silicon oxide-zirconium white, silicon oxide-magnesium oxide, aluminum oxide-boron oxide (boria), aluminium oxide-titanium oxide or the like of catalytic activity and their mixture.Zeolite and SAPO can mix with the matrix component separately, and then mixing or zeolite and SAPO mixing earlier, and then mix with the matrix component.

The inorganic oxide matrix component can be the form of colloidal sol, the water-sol or gel, be typically aluminum oxide, silicon oxide, clay and/or as those silica-alumina component of normally used silica-alumina cracking catalyst, commercial can buy of combination of good several models and model.Matrix component itself can play catalytic effect or it comes down to inert.In some cases, the effect of matrix can be used as " tackiness agent ", although do not need tackiness agent can make final catalyst spraying drying and moulding in some cases.Can resemble and prepare these materials silicon oxide and aluminum oxide cogelled, perhaps also can resemble alumina deposit and prepare these materials on the hydrogel of ready-formed and preliminary ageing.Silicon oxide can be used as a component in the solid of above-mentioned gel and exists, between content can be about 5% to about 40% (by weight), between preferably about 10% to about 30% (by weight).Silicon oxide also can be applied to contain in the cogelled form of aluminum oxide of the silicon oxide of 75% weight of having an appointment and about 25% weight, perhaps also can be applicable to contain in the cogelled form of aluminum oxide of the silicon oxide of 87% weight of having an appointment and about 13% weight.The general content of inorganic oxide matrix component in catalyzer will be for about 0% to about 99%(weight), be preferably about 5% and arrive 95%(weight), all calculate by total catalyst weight.Except zeolite aluminosilicate, outside the inorganic oxide matrix component in SAPO molecular sieve and the final cracking catalyst, the material of using other also be model thing matrix group of the present invention especially, the material of using other also is a scope of the present invention, comprises zeolite, the clay of various other types, promotor of silicon monoxide oxidation or the like.

Introduced applicable typical matrix system herein in No. 3446727,4086187, No. 1315553, british patent specification of publishing on May 2nd, 1973 and the United States Patent (USP), here also be incorporated herein by reference.

As mentioned above, catalyzer of the present invention can with use of a kind of matrix component, this component can be the aluminum oxide component.The aluminum oxide component can contain the discrete particle of various aluminum oxide, as Pseudobeohmite.The aluminum oxide component can be the discrete particle form with certain total surface area, uses Brunauer, Emmett and Teller(BET) method measures its total surface area and is greater than about 20 meters ²/ gram is more preferably greater than 145 meters ²/ gram is as at about 145 meters ²/ restrain about 300 meters ²Between/the gram.The volume of voids of aluminum oxide component is generally greater than 0.35 centimetre ³/ gram.The mean size of alumina particle is generally less than 10 microns, preferably less than 3 microns.Aluminum oxide can be used alone as matrix or with other matrix component combination.The aluminum oxide component can be any aluminum oxide, preferably moulding in advance and place a tangible form, in order that make its surface-area and pore texture keep stable, so that when in the inorganic gel that aluminum oxide is joined the impure residual soluble salt that contains significant quantity, salt neither can change surface and hole characteristic, also can not promote chemical corrosion on the porous alumina of the pre-setting that will change.For example, aluminum oxide can be any a kind of aluminum oxide, and it has been aging by suitable chemical reaction, slurry, filter, dry, flush away salt residue and heating then, makes its volatilizable thing content be reduced to less than about 15%(weight) and form.Alumina hydrosol or hydrogel or hydrated aluminum oxide slurry can be used for Preparation of Catalyst in addition.

The inorganic oxide matrix component, can arrive about 99%(weight about 5% as amounts in final catalyst such as aluminum oxide, silicon oxide, clays), preferable is to about 95%(weight about 5%), preferably arrive about 85%(weight about 10%), press total catalyst weight and calculate.

Form technology with standard catalyst, the mixture of zeolite aluminosilicate, SAPO molecular sieve and inorganic matrix can be shaped, obtain the final form of catalyzer, these technology comprise spraying drying, granulation, extruding and other suitable general method.Such catalyzer typically can prepare by spraying drying, and these methods are very familiar to for the staff who is proficient in catalytic cracking catalyst technology.Only pipe is at present to the also imprecise understanding of catalyzer of the present invention, but observe, this catalyzer is in some cases in the cracking process time, according to zeolite aluminosilicate and SAPO be simultaneously or respectively with matrix component blended situation, can obtain different results.

Catalytic cracking catalyst can be by any preparation the in several methods of commonly using.A kind of method that application silica-alumina and porous alumina prepare above-mentioned catalyzer is to make water glass and alum liquor reaction form silica hydrogel slurry, make the aging ideal hole character that obtains of slurry then, filtration becomes it into slurry then again to remove a large amount of irrelevant and unwanted sodium ion and sulfate ion in water.Sodium aluminate solution and Tai-Ace S 150 react under appropriate condition can prepare aluminum oxide, aging simultaneously slurry is to obtain the aluminum oxide of desirable hole character, filtration drying, in water, become slurry to remove sodium ion and sulfate ion again, dry again, so that volatile matter content is reduced to the weight less than 15%().Aluminum oxide can become slurry then in water, with appropriate amount and impure silica-alumina hydrogel slurry fusion.Zeolite aluminosilicate and SAPO molecular sieve are added in this adulterant then.Each component that uses q.s is to obtain the final composition of ideal.Filter the mixture obtain then from salt, to remove the remaining irrelevant soluble salt of a part.Dry then the solid of filtering mixture to obtain doing.Dried solid becomes slurry then again in water, washing is to the soluble salt that needs invariably again.Catalyzer is dried to quantity of residual less than about 15%(weight then), after calcining, catalyzer generally just obtains regeneration.

Can under effective catalytic cracking condition, in any catalytic cracking method, carry out catalytic cracking with catalyzer of the present invention.Suitable catalytic cracking condition comprises that temperature is between about 204 ℃ (400 °F) to about 871 ℃ (1600 °), be preferably between about 371 ℃ (700 °F) to about 871 ℃ (1600 °F), pressure is from being lower than barometric point to several normal atmosphere, typically from normal pressure to about 6.895 * 105 handkerchiefs (100 pounds/square inch) (gauge pressure).Present method can be applicable to the fixed fluidized-bed, movably in fluidized-bed, ebullated bed, slurry, line of pipes, vertical pipe reactor and the fluidized bed process.Can use catalyzer of the present invention to transform any common hydrocarbon charging that is used for catalytic cracking, can and have the Residual oil that the high-content metal pollutes with the thick gas and oil of its cracking, gas oil.Be particularly useful for the hydrocarbon of cracking boiling point in gas oil range, promptly, under the normal pressure, the hydrocarbon ils of boiling point from about 216 ℃ (420) to about 982 ℃ (1800) (concerning raw gasline) not only can obtain than the low-boiling product of initial charge but also can obtain having the gasoline product of octane value preferably.

Cracking catalyst commonly used and the mixing of SAPO can achieve in any way, as long as this method can make above-mentioned substance contact with crude oil material simultaneously under catalytic cracking condition.For example, can use and both contain cracking catalyst commonly used, also contain the catalyzer of single catalyst particulate SAPO, perhaps contain or do not contain the SAPO of matrix component, join in the cracking catalyst commonly used as discrete component.In one embodiment, can be added to SAPO in the cracking process as a kind of make-up catalyst, replace the cracking catalyst commonly used of having worn and torn.

The following examples can but be not limited to those in order to explanation the present invention.The preparation that shows for No. 82211 by the E.P.C. publication of publishing June 29 nineteen eighty-three at each example mesolite LZ-210.The SAPO molecular sieve is pressed No. 4440871 preparations of United States Patent (USP).The SAPO molecular sieve is calcined in air earlier before use in the following Example.In No. 4440871, United States Patent (USP), disclose to removing the method for calcinating of template.The catalyzer for preparing in the following example is estimated by the step identical with D-3907 basically.Therefore, about ASTM methods of test D-3907, be meant to have following four improved ASTM methods of test hereinafter.The first, the product full boiling point that is accredited as gasoline product is 222 ℃ (431 °F).The second, it is 30 ml/min that the back gas of the nitrogen of catalyzer was carried in 23 minutes to 27 minutes time.The 3rd, transform and to be meant the conversion that records rather than the standard conversion of ASTM methods of test.The 4th, the raw material A PI proportion that uses in test method (American Petroleum Institute's api gravity index) is 24.0 °, the IBP(initial boiling point) 179 ℃ (354), FBP(full boiling point) 581 ℃ (1077 °F), the k-factor of Praxair Technology, Inc (UOP) is 11.8.

Example 1

By the present invention, use the mixture of SAPO-5 and LZ-210 to prepare cracking catalyst.Preparation contains the cracking catalyst of LZ-210 as reference catalyst in addition.The preparation catalyzer is to use SiO ₂/ Al ₂O ₃Than the LZ-210 and the APO-5 that are 9.0.Prepare two kinds of catalyzer.Catalyst A is a reference catalyst, and catalyst B is a catalyzer of the present invention.The preparation method of catalyst A is: with 18%(weight) LZ-210,18%(weight) Pseudobeohmite aluminum oxide, 60%(weight) kaolinton, 4%(weight) silicon oxide and the water of q.s blend together slurry, the slurry that obtains, solids content accounts for 25%(weight).The percentage ratio of above-mentioned solid constituent is to calculate by dry weight.Then, but the slurry spraying drying is obtained the fluidizing catalyst complex, pass through 150 microns sieve (USS) again.Then, catalyzer is 600 ℃ of down calcinings 1 hour, again in 100% steam 740 ℃ of following steam deactivationizations 2 hours.The preparation method of catalyst B is mixed catalyst A and SAPO-5.SAPO-5 is with before catalyst A is mixed, in 100% steam under 760 ℃ with steam deactivationization 2 hours.It is the envrionment conditions that lives through for the simulate commercial cracking catalyst that the steam deactivation step is provided.Catalyst B contains the SAPO-5 of its gross weight 10%.

By ASTM methods of test D-3907, evaluate catalysts A and B separately.In this example and subsequently example, " the weight % of conversion ", as ASTM methods of test D-3907 definition with above-mentioned discussion, be the conversion weight percentage that records." the weight % of gasoline " is defined as product from C ₅Hydrocarbon is lower than those hydrocarbon between 431 hydrocarbon to boiling point, represents with the weight percentage of charging.Term " alkylide " is meant propylene, butylene and Trimethylmethane at this." the weight % of gas " is defined as the product mid-boiling point and is lower than C ₄Those hydrocarbon, calculate with the weight percentage of charging." the weight % of coke " is defined as in the back desorb and stays residue on the catalyzer of use later on, represents with the weight percentage of charging." C ₄The weight % of hydrocarbon " be defined as the weight percentage of Trimethylmethane, normal butane and the butylene of product." C ₆-C ₈The weight % of aromatic substance " be defined as the weight percentage of benzene in the gasoline product, ethylbenzene, toluene and dimethylbenzene here.The result is as follows:

Catalyzer

The catalyst A catalyst B

Transformation efficiency weight % 70.3 71.0

The weight % 50.0 49.3 of gasoline

(gasoline+alkylide) weight % 60.9 61.6

C ₆-C ₈The weight % 14.6 15.4 of aromatic substance

The weight % 4.9 4.8 of coke

The weight % 6.2 6.7 of gas

C ₄The weight % 9.1 10.2 of hydrocarbon

Above-mentioned data declaration, catalyst B is suitable with catalyst A aspect the weight % of weight % that transforms and gasoline, and produces some more slightly aromatic substance, and these aromatics beings are being useful aspect the octane value that improves gasoline product.

Example 2

Prepare two kinds of catalyzer, wherein catalyzer C is the reference catalyst that contains LZ-210, SiO among the LZ-210 ₂/ Al ₂O ₃Than being 9.0, catalyzer D is a catalyzer of the present invention, contains LZ-210 and SAPO-11.The preparation method of catalyzer C is: preparation contains 15%(weight in the water of q.s) LZ-210,18%(weight) Pseudobeohmite aluminum oxide, 60%(weight) kaolin and 4%(weight) slurry of silicon oxide, solid weight accounts for 25% in the slurry that obtains.But the slurry spraying drying obtains fluidized catalyst then, and its granular size can be passed through 150 tm screen (USS).Catalyzer is 600 ℃ of calcinings 1 hour, then in 100% steam 765 ℃ of following steam deactivations 2 hours.

Prepare catalyzer D by the step that is used for catalyzer C, just 10%(weight wherein) kaolin 10%(weight) the SAPO-11 replacement, promptly kaolinic consumption is a 50%(weight).

Come evaluate catalysts C and catalyzer D by ASTM methods of test D-3907, just service temperature is 482 ℃ (900) of 454 ℃ (850) rather than ASTM methods of test D-3907 suggestion.

The result is as follows:

Catalyzer

Catalyzer C catalyzer D

Transform: 61.9 62.9

The weight %:46.5 47.6 of gasoline

(gasoline+alkylide) weight %:55.3 56.7

The weight % that paraffinic hydrocarbons is analyzed: ¹

C ₄Different/positive 4.8 5.7

C ₆Different/positive 13.6 17.1

C ₇Different/positive 15.6 16.8

C ₈Different/positive 7.1 8.1

The weight % that gaseous product is analyzed: ²

C ₃Alkene/paraffinic hydrocarbons 2.8 3.8

C ₄Alkene/paraffinic hydrocarbons 0.55 0.66

The weight %:4.1 4.0 of coke

1, has the isoparaffin of the compound that shows carbonatoms and the ratio of n-paraffin.

2, have the alkene of the compound that shows carbonatoms and the ratio of paraffinic hydrocarbons.

The The above results explanation adds the component of SAPO-11 as catalyzer D, makes product have the weight % of similar gasoline and the weight % of gasoline+alkylide, has also improved isoparaffin and n-paraffin ratio, has therefore shown higher octane product.As indicated in the gaseous product analysis, the raising explanation gaseous product of gaseous product alkene content has more useful, more valuable alkene product.

Example 3

Prepare two kinds of catalyzer, wherein catalyzer E contains LZ-210(SiO ₂/ Al ₂O ₃Ratio be 9.0) reference catalyst, catalyzer F is by of the present invention, contains the catalyzer of LZ-210 and SAPO-5.

The preparation method of catalyzer E is: earlier the LZ-210 of 15% weight, the Pseudobeohmite aluminum oxide of 18% weight, kaolin, 4% weight silicon oxide and the enough water of 63% weight are made slurry, solids weight accounts for 25% in this slurry.Then, slurry spraying drying, calcining are reached by the method that is used for catalyzer C in the example 2 and handle.

The preparation method of catalyzer F is: use 15%(weight) LZ-210,10%(weight) SAPO-5,18%(weight) Pseudobeohmite aluminum oxide, 53%(weight) kaolin, 4%(weight) silicon oxide and enough water gagings form slurry, solids weight accounts for 25% in the slurry, then, make slurry spraying drying, calcining reach by the method that is used for catalyzer C in the example 2 and handle.

By ASTM methods of test D-3907 each appraisal catalyzer E and catalyzer F.The result is as follows:

Catalyzer

Catalyzer E catalyzer F

Transformation efficiency weight %:77.2 76.8

The weight of gasoline+alkylide

Percentage ratio: 63.8 60.3

C ₆-C ₈The weight of aromatic substance

Amount percentage ratio: 33.4 37.8

The weight percentage of coke: 7.7 7.9

The weight ratio of catalyst/oil: 53

Above-mentioned data show to have much bigger activity by catalyzer F of the present invention than catalyzer E, and catalyzer F is that 5 catalyzer E similarly transforms as long as the ratio of catalyst/oil is 3 ratios that just can reach catalyst/oil.Can reach similar conversion with 40% catalyzer less, prove that the activity of such catalysts increase that contains LZ-210 and SAPO-5 is surprising.In addition, catalyzer F much more about C of 4.4% in the gasoline product that forms ₆-C ₈Aromatic substance, simultaneously the amount of gasoline+alkylide has reduced about 3.5%(weight).The higher octane product of increase prompting of aromatic substance output.In addition, the component of aromatic substance is valuable as the component that generates with other chemical process.

Compare with the mixed catalyst of example 1, above-mentioned data illustrate that also the variation of component mixing order can cause the change of mixed catalyst performance in catalyzer F.In slurry, adding SAPO-5, rather than the mixing of SAPO-5 and Y zeolite/substrate mixture machinery, can obtain than the bigger active catalyzer of above-mentioned example 1 catalyst B.As for mixing the definite reason that order causes active aspect to change, present solve unclear.

Example 4

Prepare two kinds of catalyzer, wherein catalyzer G contains ZSM-5(SiO ₂With Al ₂O ₃Than being 30) reference catalyst, as described in No. 4239654, United States Patent (USP); And catalyzer H is the catalyzer that contains SAPO-5 by the present invention.

Utilize mixed rare earth chlorides solution, prepare the catalyzer base by rare earth exchanged LZ-210.The weight that earth solution contains various rare earth oxides is 46.0%, wherein La(La ₂O ₃) account for 60.0%, Nd(Nd ₂O ₃) account for 21.5%, Ce(CeO ₂) account for 10.0%, Pr(Pr ₆O ₁₁) account for 7.5%, and other rare earth oxide account for 1.0%.The LZ-210 of final rare earth exchanged contains rare earth 9.9%(weight), it is the oxide compound (RE to record ₂O ₃, " RE " represents rare-earth cation herein) expression.Fusion 14.3%(weight) rare earth LZ-210,80% silica-alumina (the Davison group of W.R.Grace is sold, and trade mark MS13/110 contains 86%(weight) SiO ₂With 13%(weight) Al ₂O ₃) and 5.0%(weight) the Microcrystalline Cellulose extrusion aid form a kind of mixture.This mixture is through extruding, in air 110 ℃ dry 16 hours down, deactivation 5 hours in 760 ℃ 100% steam then.Pulverize extrudate then, sieve is got the particulate matter of 60～200 orders (USS) size.

Catalyzer G and catalyzer H are for respectively with 5%(weight) ZSM-5 and 5%(weight) SAPO-5 and the above-mentioned 95%(of making weight) the catalyzer base mix and prepare.Estimate this two kinds of catalyzer by ASTM methods of test D-3907.The result is as follows:

Catalyzer

Catalyzer G catalyzer H

The weight %:65.2 66.8 that transforms

The weight %:42.8 47.3 of gasoline

C in the gasoline ₆-C ₈Aromatic substance

Weight %:11.5 14.1

C ₆Different/the direct ratio of paraffinic hydrocarbons: 7.3 11.2

Above-mentioned data declaration when SAPO-5 is used as the component of cracking catalyst, is compared the weight % and the C of aromatic substance in the weight % of conversion, the weight % of gasoline, the gasoline with using ZSM-5 ₆The ratio (weight ratio) different and just of paraffinic hydrocarbons all has significant improvement.

Example 5

By two kinds of catalyzer of method preparation of 2 couples of catalyzer C of example and catalyzer D, just the temperature of steam deactivationization is a temperature represented in the following table 1.By the parent of catalyzer C without steam deactivationization, the catalyzer that obtains by change steam deactivation temperature is called " catalyzer C-n ", and n is an integer herein.Can represent with similar fashion without the catalyzer that the parent of steam deactivationization makes by catalyzer D.Estimate these catalyzer by ASTM methods of test D-3907, obtain following result (seeing Table 1).

1. test temperature is 482 ℃ (900) among 850 ℃ rather than the ASTA test method D-3907.

2. the C of Ce Dinging ₆Branched-chain alkene is 2-methyl-2-amylene and 2-Methyl-1-pentene.The C that measures ₆Normal olefine is 1-hexene, anti--the 2-hexene, suitable-2-hexene and anti--3-hexene.

3. the C of Ce Dinging ₆Isoparaffin is 2-methylpentane, 3-methylpentane and 2, the 2-dimethylbutane.The C that measures ₆N-paraffin is a normal hexane.

These data declarations, the catalyzer that contains SAPOs can keep its selectivity after hydrothermal treatment consists.Compare with the catalyzer that does not contain SAPO-11 for the catalyzer that contains SAPO-11, when transformation efficiency is suitable with the gasoline yield, the weight ratio that contains the weight ratio of its branched-chain alkene of catalyzer of SAPO-11 and normal olefine and isoparaffin and n-paraffin is higher, and therefore just prompting has higher octane product.Therefore also explanation, the advantage that hydrothermal deactivation condition and not obvious influence use SAPOs to obtain.

Example 6

Prepare two kinds of catalyzer, wherein reference catalyst J contains the Y-zeolite that is called LZ-10 of steam stable, and catalyzer K contains LZ-10 and SAPO-11.By English Patent 2014970 preparation LZ-10, exchange with ammonium then.

Preparation contains 18%(weight in the water of q.s) LZ-10,62%(weight) kaolin and 20%(weight) the mixture of silicon oxide, can form squeezable material and obtain catalyzer J.Such mixture has pasty consistency and is also ground, pushes, and calcines 16 hours down for 500 ℃ in air.Granular size (USS) between 60 order to 200 orders is pulverized, sieved, gets to extrudate.

The method for making of catalyzer K is identical with catalyzer J's, and just original stock is LZ-10,6% weight SAPO-11,56% weight kaolin and the 20% weight silicon oxide of 18% weight.

By ASTM methods of test D-3907, estimate this two kinds of catalyzer, just test temperature is 866 °F.The all product ratios that provide are weight ratios.The result is as follows:

Catalyzer

Catalyzer J catalyzer K

The weight %:70.2 69.1 that transforms

The weight %:50.7 50.1 of gasoline

C ₃Alkene/C ₃Paraffinic hydrocarbons 1.76 1.86

C ₄Alkene/C ₄Paraffinic hydrocarbons 0.402 0.382

C ₄Isoalkane/C ₄Normal alkane 4.12 4.64

The weight % 10.9 10.9 of alkylide

C ₆Alkene/C ₆Alkane 0.154 0.166

C ₆Isoalkane/C ₆Normal alkane ¹13.4 15.4

C ₆Branched-chain alkene/C ₆Normal olefine ¹1.18 1.67

C ₇Alkene/C ₇Paraffinic hydrocarbons 0.769 0.86

C ₇Isoalkane/C ₇Normal alkane ²16.9 18.6

C ₇Branched-chain alkene/C ₇Normal olefine ²0.739 0.799

1. determined C ₆Isoparaffin is 2-methylpentane, 3-methylpentane and 2, the 2-dimethylbutane.Determined C ₆N-paraffin is a normal hexane.Determined C ₆Branched-chain alkene is 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-Methyl-1-pentene, 2-methyl-2-amylene and anti--3-methyl-2-amylene.Determined C ₆Normal olefine is 1-hexene, anti--the 2-hexene, suitable-2-hexene and anti--3-hexene.

2. the C of Ce Dinging ₇Isoparaffin is 3-methyl hexane, 2-methyl hexane and 2, the 4-dimethylpentane.The C that measures ₇N-paraffin be just-heptane.Measure all C ₇Alkene also therefrom deducts the C that records ₇Normal olefine obtains measured C ₇Branched-chain alkene.Determined C ₇Normal olefine is 1-heptene, suitable-the 2-heptene, anti--the 2-heptene, suitable-3-heptene and anti--3-heptene.

Above-mentioned data declaration when similar activity and gasoline yield, is pressed catalyzer K of the present invention at C ₆And C ₇Can obtain in the hydrocarbon higher different/n-paraffin than and the gasoline product of side chain/normal olefine ratio, higher ratio value representation higher octane product; And above-mentioned higher ratio

Be similarly to form under gasoline yield and the conversion situation.

Comparative example 7

Prepare two kinds of catalyzer, wherein reference catalyst L contains LZ-210, and relatively catalyzer M contains AIPO ₄-5 and catalyzer L.Press No. 4310440 preparations of United States Patent (USP) AIPO ₄-5.

By mixing the LZ-210(SiO of 15% weight ₂With Al ₂O ₃Than being 9.0), the silicon oxide of kaolin, 18% weight aluminum oxide and 4% weight of 63% weight prepares catalyzer L.Pulverize this catalyzer, and handle by the facture of the catalyzer that is similar to example 3, just steam deactivationization is carried out at 765 ℃.

Catalyzer M is by fusion 10%(weight) burnt ALPO ₄With 90%(weight) catalyzer L prepare.

With ASTM test method(s) D-3907 evaluate catalysts L and catalyzer M.The ratio of the ratio of the alkene/paraffinic hydrocarbons that provides and different/just is a weight ratio.The result is as follows:

Catalyzer

Catalyzer L catalyzer M

Transformation efficiency, weight %:69.9 67.1

The weight %:50.8 48.6 of gasoline

C ₃Alkene/paraffinic hydrocarbons 2.87 2.68

C ₄Alkene/paraffinic hydrocarbons 0.59 0.57

C ₄Isoparaffin/n paraffinic hydrocarbons 4.36 4.36

Above-mentioned data declaration AlPO ₄-5 have the matrix topology similar with SAPO-5, but lack SiO ₂Tetrahedral component, AlPO ₄-5 do not have SAPO-5 and usual cracking catalyst to use shown advantage simultaneously.

Comparative example 8

Three kinds of catalyzer (N, O and P) are produced.Catalyst n and P are the comparison catalyzer, and catalyzer O is the catalyzer by the present invention's preparation.The method of using by example 1 makes these catalyzer, and just catalyzer O and P use 54%(weight) kaolin and the zeolite and the SAPO of following component.Catalyst n contains SiO ₂/ Al ₂O ₃Ratio be 9.0 LZ-21018%(weight).Catalyzer O contains 18%(weight) LZ-210 that is used for catalyst n and 6%(weight) SAPO-11.Catalyst P contains 18%(weight) LZ-210 that is used for catalyst n and 6%(weight) SAPO-34.

Catalyst n, O and P respectively 740 ℃, 740 ℃ and 760 ℃ of following steam deactivationizations 2 hours, and estimate by ASTM methods of test D-3907 in 100% steam.Evaluation result is as follows:

Catalyzer

Catalyst n catalyzer O catalyst P

Transformation efficiency, weight % 72.7 71.5 72.0

The weight % 52.7 51.2 47.7 of gasoline

Gas+C ₄The weight % 15.6 15.8 19.5 of hydrocarbon

The weight % 4.05 4.27 of coke-

The above results shows that the catalyzer gasoline yield that contains SAPO-34 reduces.SAPO-34 has under 20 ℃ of temperature, 667 handkerchiefs (500 torr) air pressure and adsorbs 2%(weight at least not as SAPO of the present invention) the feature of Trimethylmethane.

Comparative example 9

The catalyzer of two kinds of comparisons of preparation, D-3907 estimates by ASTM methods of test.With alumo-silicate molecular sieve SAPO-5 and zeolite L Z-210(SiO ₂/ Al ₂O ₃Than being 9.0) two kinds of catalyzer of preparation.

After the SAPO-5 preparation, this material in 100% steam 760 ℃ of following steam deactivationizations 2 hours, to simulate the actual effect that is used in the cracking process.The LZ-210 component resembles the described and rare earth chloride mixture rare earth exchanged of example 4 then, with the LZ-210 of (being expressed as oxide compound) rare earth exchanged of obtaining containing 9.9% weight rare earth.

Mixing 90%(weight) SiO ₂/ Al ₂O ₃, it is sold by the Davison of W.R.Grace group, and the Microcrystalline Cellulose extrusion aid of trade mark MS13/110 and 10% weight can be prepared the matrix of SAPO-5 and LZ-210.Mixture is squeezed into 1/16 inch pill, and in air 110 ℃ dry about 16 hours down, 760 ℃ of following steam deactivationizations 2 hours in 100% steam then.Pulverize then by the material of steam deactivationization and also sieve the particle of getting between the 60-200 order (USS).

Mix the material of selecting for use of 15% weight and the matrix of 85% weight and prepare SAPO-5 and LZ-210 catalyzer separately.LZ-210 will be at 100% steam 760 ℃ of following steam deactivationizations 2 hours before being used for Preparation of Catalyst.The final catalyst mixture was calcined 3 hours under 590 ℃ in air then.By ASTM methods of test D-3907, estimate each catalyzer at conversion aspect.Evaluation result is as follows:

Catalyzer

SAPO-5 LZ-210

Transformation efficiency, weight % 57.7 57.2

The weight % 37.2 41.4 of gasoline

The weight % 6.6 5.5 of gas

The weight % 3.9 3.1 of coke

C ₄Weight % 10.0 7.33

The above results has illustrated that SAPO-5 and LZ-210 are as cracking catalyst activity separately.Although Lz-210 demonstrates the weight % of higher gasoline, under ASTM methods of test D-3907 condition, SAPO-5 forms more gaseous product and C ₄Product.As appreciable by above-mentioned example, use the catalyzer that contains common cracking catalyst and SAPO to compare the composition difference of the product that obtains with independent use SAPO or LZ-210 by the present invention.

Claims

1, a kind of cracking catalyst, this catalyzer contains at least a zeolite aluminosilicate and at least a alumo-silicate molecular sieve that has cracking activity under effective cracking conditions, this alumo-silicate molecular sieve be characterized as its calcinated form adsorbs at least 2% (weight) under 20 ℃ of temperature and 667 handkerchiefs (500 torr) pressure Trimethylmethane, in this cracking catalyst, the weight ratio of above-mentioned silico-aluminate and alumo-silicate is between about 1: 10 and about 500: 1, and this catalyzer also contains at least a inorganic oxide matrix component of 0～99% weight.

2, the catalyzer of claim 1, wherein the additional features of above-mentioned alumo-silicate molecular sieve is, its calcinated form adsorbs less than 5%(weight under 22 ℃ of temperature and 3.5 handkerchiefs (2.6 torr) pressure) triethylamine.

3, the catalyzer of claim 1, wherein alumo-silicate is the microporous crystalline alumo-silicate, and its hole is uniformly and has specific diameter greater than about 3 dusts, and its basic empirical chemical constitution is mR:(Si when synthetic and during anhydrous form _xAl _yP _z) O ₂, wherein " R " represents at least a organic formwork agent that is present in the crystal inner pore system; " m " represents every mol (Si _xAl _yP _z) O ₂In " R " mole number of existing, the value of " m " from 0.02 to 0.3; " x " " y " and " z " represent the mole fraction of the silicon, aluminium and the phosphorus that exist with tetrahedral oxide respectively, and the selection of above-mentioned mole fraction is that it is dropped in the area of being made up of the ABCD and the definite pentagon of E point of ternary diagram (accompanying drawings 1 that No. 4440871, United States Patent (USP)).

4, claim 1 or 2 catalyzer, wherein alumo-silicate is for having PO ⁺ ₂, AlO ^- ₂And SiO ₂The three-dimensional porous skeleton structure of tetrahedron element, its basic experience chemical constitution when anhydrous form is: mR:(Si _xAl _yP _z) O ₂, wherein " R " represents at least a organic formwork agent that is present in the intracrystalline hole system; " m " represents every mol (Si _xAl _yP _z) O ₂In " R " mole number of existing, its value from zero to 0.3; " x " " y " and " z " represent the silicon that exists respectively in the oxide compound part, the mole fraction of aluminium and phosphorus, above-mentioned mole fraction is that A, B, C, D and the E point on ternary diagram (Fig. 1) limits in the area of forming, above-mentioned alumo-silicate has the X-ray powder diffraction figure of feature, and this figure contains minimum d-spacing in any one table of the table I, III, V, VII, IX, XI, X VII, X XI, XX III or the XX V that are disclosed in No. 4440871, United States Patent (USP).

5, claim 1 or 2 catalyzer, wherein above-mentioned zeolite aluminosilicate is selected from zeolite Y, X zeolite, zeolite beta, zeolite KZ-20, faujusite (faujasite), LZ-210, LZ-10, ZSM type zeolite and its mixture.

6, the catalyzer of claim 5, wherein the weight ratio of zeolite aluminosilicate and above-mentioned alumo-silicate is between about 1: 2 and about 50: 1.

7, the catalyzer of claim 6, wherein the weight ratio of zeolite aluminosilicate and above-mentioned alumo-silicate is between about 1: 1 and about 20: 1.

8, the catalyzer of claim 5, wherein the content of inorganic oxide components about 5% and about 95%(weight) between, in the gross weight of catalyzer.

9, the catalyzer of claim 5, wherein the inorganic oxide matrix component is selected from clay, silicon oxide, aluminum oxide, silica-alumina, silicon oxide-zirconium white, silicon oxide-magnesium oxide, aluminum oxide-boron oxide, aluminum oxide-titanium dioxide and based mixtures.

10, the catalyzer of claim 1, wherein alumo-silicate is selected from SAPO-5, SAPO-11, SAPO-31, SAPO-37, SAPO-40, SAPO-41 and composition thereof.

11, the catalyzer of claim 1, wherein zeolite aluminosilicate is selected from Y zeolite, LZ-210, LZ-10 and its mixture, and described alumo-silicate is selected from SAPO-5, SAPO-11, SAPO-31, SAPO-41 and its mixture.

12, the catalyzer of claim 1, above-mentioned zeolite aluminosilicate contain weight and be selected from ammonium, II A family, III A family, the III B family positively charged ion to VII B family, rare earth and its mixture between about 0.1% and about 20%.

13, the catalyzer of claim 12 wherein contains and has an appointment 0.1% to about 20%(weight) above-mentioned polyvalent cation.

14, the catalyzer of claim 1, wherein alumo-silicate has at least partial cation to exist with hydrogen evolution form (hydrogen-forming species).

15, the catalyzer of claim 14, wherein the hydrogen evolution form is NH ⁺ ₄Or H ⁺

16, a kind of cracking catalyst, this catalyzer contains at least a alumo-silicate molecular sieve that has at least a cracking catalyst and the significant quantity of cracking activity under effective cracking conditions, and its calcinated form that is characterized as of this alumo-silicate molecular sieve adsorbs 2%(weight at least when 20 ℃ of temperature, pressure 667 handkerchiefs (500 torr)) Trimethylmethane.

17, the catalyzer of claim 16, wherein the weight ratio of cracking catalyst and above-mentioned alumo-silicate is between about 1: 10 and about 500: 1.

18, the catalyzer of claim 16, wherein cracking catalyst comprises at least a zeolite aluminosilicate.

19, the catalyzer of claim 16, wherein cracking catalyst is made up of silica-alumina basically.

20, the catalyzer of claim 16, wherein another characteristics of alumo-silicate are that its calcinated form adsorbs less than 5%(weight when 22 ℃ of temperature, pressure 3.5 handkerchiefs (2.6 torr)) triethylamine.

21, the method for preparing catalyzer, this method comprises:

(a) form at least a zeolite aluminosilicate and at least a alumo-silicate, the mixture of its weight ratio between about 1: 10 and about 500: 1, its calcinated form that is characterized as of this alumo-silicate adsorbs 2%(weight at least under the pressure of 20 ℃ of temperature, 667 handkerchiefs (500 torr)) Trimethylmethane.

(b) form the mixture that (a) goes on foot product and at least a inorganic oxide matrix component, constitute catalyzer.

22, the method for preparing catalyzer, this method comprises:

(a) mixture of at least a inorganic oxide matrix component of formation and at least a zeolite aluminosilicate.

(b) form the mixture of the alumo-silicate of No. 4440871, at least a inorganic oxide matrix component and at least a United States Patent (USP), this alumo-silicate be characterized as its calcinated form under 20 ℃ of temperature and 667 handkerchiefs (500 torr) pressure, adsorb the Trimethylmethane of 2% weight at least.

(c) form a kind of (a) step and (b) go on foot mixture of products, have the catalyzer of weight ratio between about 1: 10 and about 500: 1 of zeolite aluminosilicate and alumo-silicate with composition.

23, the described Application of Catalyst of claim 1～20, this catalyzer is used for the method that the catalytic cracking crude oil material prepares low boiling hydrocarbon.