WO1999061552A1

WO1999061552A1 - New catalytic silicoaluminophosphates having an ael structure, and their use in catalytic cracking

Info

Publication number: WO1999061552A1
Application number: PCT/US1999/011465
Authority: WO
Inventors: Javier Agundez Rodriguez; Joaquin Perez Pariente; Antonio Chica Lara; Avelino Corma Canos; Tan-Jen Chen; Philip Andrew Ruziska; Brian Erik Henry; Gordon Frederick Stuntz; Stephen Mark Davis
Original assignee: Exxon Research And Engineering Company
Priority date: 1998-05-26
Filing date: 1999-05-25
Publication date: 1999-12-02
Also published as: AU4311999A; TW473540B; US6303534B1; US20010053744A1; EP1062294A1; WO1999061555A1; US6294493B1; EP1062295A1; WO1999061556A1; EP1062299A1; AU4201199A; AU4201499A; AU4201599A; US6300537B1; WO1999061553A9; WO1999061559A1; WO1999061558A1; AU4201399A; EP1062304A1; EP1054835A1

Abstract

Disclosed are silicoaluminophosphates (SAPOs) having unique silicon distributions, a method for their preparation and their use as catalysts for the catalytic cracking of hydrocarbon feedstocks. More particularly, the new SAPOs have a high silica:alumina ratio, and are prepared from microemulsions containing surfactants.

Description

NEW CATALYTIC SILICOALUMINOPHOSPHATES HAVTNG AN AEL

STRUCTURE. AND THEIR USE IN

CATALYTIC CRACKING

FIELD OF THE INVENTION

This invention relates to using silicoalummophosphates ("SAPO"s) ha\ ιng unique silicon distributions and their use as catalytic cracking catalysts for cracking hydrocarbon feedstocks More particularl} , the SAPOs have a high silica alumina ratio, and are prepared from microemulsions containing surfactants

BACKGROUND OF THE INVENTION

Conventional microporous crystalline silicoalummophosphates such as SAPO- 1 1 may be prepared by hydrothermal crystallization of sihcoaluminophosphate gels containing a molecular structure forming template SAPOs are members of a class known as non-zeohtic molecular sieves SAPO molecular sieves have a framework of A10₄. Sι0₄ and P0₄ tetrahedra linked by oxygen atoms The negatn e charge m the network is balanced bv the inclusion of exchangeable protons or cations such as protonated amines or alkylamonmm The interstitial spaces of channels formed by the crystalline network enables SAPOs to be used as molecular sieves m a manner similar to zeolites, which are crystalline alummosihcates

More recenth a new silicoalummophosphates have been prepared that are lsostructural with conventional SAPO-1 1. but having a dramatically higher silicon aluminum ratio and appropπate silicon distribution Such matenals are prepared from microemulsions Conventional SAPOs may be used as catalysts in petroleum processing. For example, SAPO catalysts may be used in lubricating oil hydroconversion procedures, hydrocrackmg, dewaxing, and combinations thereof Conventional SAPO catalysts may also be used in catalytic cracking processes such as fluid catalytic cracking ("FCC") processes.

There remains a need, though, for improved silicoalummophosphates for use in hydrocarbon processing

SUMMARY OF THE INVENTION

In one embodiment, the invention is a fluidized catalytic cracking method comprising injecting a feed into an FCC riser reactor having a reaction zone and catalytιcall cracking the feed in the reaction zone under catalytic cracking conditions in the presence of a cracking catalyst in order to form a cracked product, the cracking catalyst containing a major amount of a large-pore zeolite catalyst and a minor amount of a SAPO catalyst, the SAPO catalyst having a total silicon amount ranging from about 0.2 molar % to about 40 molar %, a total aluminum amount ranging from about 30 molar % to about 49 9 molar %. and a total phosphorus amount ranging from about 10 molar % to about 49.9 molar V the molar percents being based on the total amount of aluminum, phosphorus, and silicon present in the composition, and the SAPO catalyst being lsostructural with a SAPO-11 having the AEL structure and containing silicon, aluminum, and phosphorus, wherein

(a) the silicon present in the SAPO catalyst is distributed among silicon sites, each site having a first, a second, a third, and a fourth nearest neighbor position, and each position being independently occupied by one atom selected from silicon and aluminum, and (b) the composition has a first number of silicon sites having silicon atoms in the four nearest neighbor positions ( Sι4Sι), a second number of silicon sites having silicon atoms in three of the four nearest neighbor positions ( Sι3Sι), and a third number of silicon sites having silicon atoms in two of the four nearest neighbor positions (Sι2Sι), wherein

(1) the sum of the first, second, and third number of silicon sites ranges from about 10 to about 80 molar %, and

(n) the molar ratio of the sum of the third and second number of silicon sites to the first number of silicon sites ranges from about 0 7 to about 1 4. the molar % being based on the total number of silicon sites

In another embodiment, the invention is a composition comprising a major amount of a large-pore zeolite catalyst and a minor amount of a SAPO catalyst, the SAPO catalyst having a total silicon amount ranging from about 0.2 molar % to about 40 molar %, a total aluminum amount ranging from about 30 molar % to about 49 9 molar %, and a total phosphorus amount ranging from about 10 molar % to about 49 9 molar %, the molar percents being based on the total amount of aluminum, phosphorus, and silicon present in the composition, and the SAPO catalyst being lsostructural with a SAPO- 1 1 having the AEL structure and containing silicon, aluminum, and phosphorus, wherein

(a) the silicon present m the SAPO catalyst is distπbuted among silicon sites, each site having a first, a second, a third, and a fourth nearest neighbor position, and each position being independently occupied by one atom selected from silicon and aluminum, and

(b) the composition has a first number of silicon sites having silicon atoms in the four nearest neighbor positions (Sι4Sι), a second number of silicon sites ha\ ιnε silicon atoms m three of the four nearest neighbor positions (Sι3Sι), and a third number of silicon sites having silicon atoms in two of the four nearest neighbor positions (Sι2Sι), wherein

(n) the molar ratio of the sum of the third and second number of silicon sites to the first number of silicon sites ranges from about 0 7 to about 1 4, the molar % being based on the total number of silicon sites

BRIEF DESCRIPTION OF THE DRAW INGS

Figure 1 schematically illustrates the local arrangement of Si atoms in a SAPO framework

Figure 2 is a simulated deconvolution of a ^" Si MAS NMR spectrum

Figure 3 is a deconvolution of a ²⁹Sι MAS NMR spectrum of conventionally-prepared SAPO-1 1 with a 2 47 wt Si content

Figure 4 shows power x-ray diffraction results for the samples described herein Figure 4-a corresponds with sample 1 -a. 4-b with sample 1 -b. 4-c with sample 1 -c, 4-d with sample 1 -d, 4-e with sample 2-a, and 4-f with sample 2-b

Figure 5 shows ²⁹Sι MAS NMR result for the samples descπbed herein Figure 5-a corresponds with sample 1-a. 5-b with sample 1 -b, 5-c with sample 1 -c, 5-d with sample 1 -d, 5-e with sample 2-a, and 5-f with sample 2-b DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a new SAPO having an AEL structure as defined in the "Atlas of Zeolite Structure Types," 4th Ed, by W M Meiei, D H Olson and Ch Baerlocher, Elsevier, 1996 The new SAPO is prepared by adding an aqueous solution of phosphoπc acid to alumina. The mixture is stirred and an aqueous mixture of alcohol with a low solubility in water, such as n- hexanol, pentanol, butanol, and mixtures thereof, and a neutral or cationic surfactant, such as hexadecylamme, decylamme, hexadecyltπmethylamrnon m salt, and mixtures thereof is added to the mixture of phosphoπc acid and alumina To this mixture is added a silicon source material such as silicon alkoxide. and pieferably tetraethylorthosihcate. and the resultant mixtuie stirred The result gel may be calcined in order to form the SAPO mateπals of this invention It has been discovered that such matenals are effective catalysts for reaction such as lubπcatmg oil hydroprocessmg and catalytic cracking, including naphtha cracking The new SAPO mateπals have much improved activity and selectivity over SAPOs having an AEL structure and prepared by methods not described m the current invention

While not wishing to be bound, it is believed that the enhanced catalvtic m these nev% SAPO mateπals results from modifwng the synthesis of a silicon-substituted alummophosphate by changing the composition of the svnthesis mixture and the length of time taken to crystallize the product in order to modify the silicon distribution in the sihcoalummophosphate thus formed The changed distribution of silicon is believed to have a major beneficial influence on the catalytic activity of the sihcoalummophosphate

The following sections set forth the synthesis and use of the preferred A.EL-type SAPOs Section A descπbes the molecular sieve synthesis processes. Section B descπbes preferred SAPO molecular sieve catalysts. Section C descπbes the physical differences between the preferred SAPO mateπals and conventional SAPO- 1 1 , and Section D descπbes the use of the molecular sieve catalysts for hydrocarbon processing

4. Synthesis of the Preferred AEL-Type SAPO Molecular Sieves

When AEL-type molecular sieve mateπals are synthesized following the procedure descπbed herein, the distribution of Si and therefore the total number and strength of acid site? is quite different, and much higher than those of previously reported forms of SAPO-1 1

The preferred sihcoalummophosphate composition has the structure of AEL which corresponds to SAPO-1 1 The AEL structure is defined in the '" Atlas of Zeolite Structure Types," 4th Ed, b\ W M Meier, D H Olson and Ch Baerlocher, Elseuer, 1996 Although the preferred composition is isostructural with other AEL molecular sieve mateπals, it is a distinct molecular sieve composition because the silicon, aluminum, and phosphorus atoms present in the composition of this invention are not arranged the same way as in AEL- type SAPO molecular Those skilled m the art will recognize that two isostructural molecula

es

be entirely different compositions having entirely different properties depending on. for example, the nature and distπbution of the constituent atoms One such example invoh es isostructural s\ nthetιc ferπeπtes disclosed in L S Patent Nos 3,033,974, 3 966.883, 4 000,348, 4,017.590. and ZSM-35 U S Patent No 4.016.245

The prefeπed molecular sieve compositions are phvsically different from other SAPOs having the AEL structure because the silicon atoms are distributed differently m the molecular sieve framework The physical structure of the preferred composition (and its silicon distπbution) is illustrated schematically in Figure 1 While the actual structure is three dimensional and contains oxygen in addition to silicon, aluminum and phosphorus, the figure's atomic positions are represented on a two-dimensional array and oxygen atoms are omitted for claπtλ As is shown in the figure, each lattice site in the framework has four nearest neighbor lattice sites In the compositions of this invention, as with all AEL-type SAPOs, a lattice site occupied by a silicon atoms, l e , a "silicon site," ordinarily may not have a phosphorus atom as a nearest neighbor The four next nearest neighbor lattice sites may therefore be occupied by one silicon and three aluminum atoms, two silicon and two aluminum atoms, three silicon and one aluminum atom, four silicon atoms, or four aluminum atoms, as shown in figure 1 As discussed, conventional AEL- type SAPOs with increased silicon concentration contain an undesirable high proportion of silicon atoms forming part of the inteπor of the silicon islands, I e , silicon atoms having four silicon atoms nearest neighbors Nevertheless, and w hile not w ishing to be bound by any theorv or model, the formation of silicon island is believ ed to be desirable, for the silicon atoms in the border of the island are belie ed to lead to a negative charge that, if balanced by protons, would produce materials with acid centers whose acid strength is higher than that of isolate Si sites with the four nearest neighbor lattice sites occupied by aluminum atoms

The silicon atoms in the preferred composition are physically distributed so that the size of the silicon island, and therefore the concentration of Si atoms having four silicon as neighbors is greatlv reduced compared with other AEL-type SAPOs having the same total silicon concentration

The molecular sieve compositions useful in this invention may be formed in accordance with conventional molecular sieve synthesis techniques from a sihcoalummophosphate gel having the formula

X,CA X₂DPA A1₂0₃ P₂0, X,Sι0₂ X4F O X.SOL

wherein CA is a surfactant such as hexadecylamme, dodecylamme or decylamme or mixtures of two or more surfactants, DPA is a template such as di-n-propylamme, dnsopropylamine or tetrabutylammomum hydroxyde or mixtures of two or more templates. SOL is a solvent of low solubihtv m w ater nonhmiting examples of which are C₄-Cι₀ alcohols, such as heptanol, pentanol or butanol, polyalcohols, phenols, ketones, polyethers or mixtures of two or more solvents. Additionally, other solvents of high solubility in water could also be present, as ethanol or methanol

X] ranges from about 0.001 to about 0.5, X₂ ranges from about 0.5 to 2, X ranges from about 0.01 to about 3, X₄ ranges from about 4 to about 300, and X ranges from about 0.1 to about 50.

Alumina, phosphoπc acid, and water may be combined, and preferably agitated, for a time sufficient to form a uniform solution. The molar ratio of phosphoπc acid to alumina is in the range specified m the previous paragraph All the water or only a portion of the water required is combined w ith the alumina and the phosphoric acid This portion is m the range 5-99% of total w ater, preferably in the range 10-50%. A preferred temperature for the combination is 20°C, but temperatures in the range of about 4-70°C are suitable as well. A template such as di-n-propylamme, diisopropylamme. dodecylamme or tetrabutylammomum hydroxide may then be added, followed by surfactant such as hexadecylamaine or decylamme, an alcohol such as hexanol, pentanol or butanol. and a silica source such as tetraethyl orthosihcate. tetramethyl orthosilicate or tetrabuthyl orthosihcate in order to complete the synthesis mixture.

Stirring the synthesis mixture for about 15 minutes to about 24 hours, preferably 2 hours at room temperature, results in the formation of the synthesis gel.

The preferred molecular sieve composition mav be formed by heating the gel in a microwave autoclave for a time ranging from about 6 hours to about 1 week, at a temperature ranging from about 150°C to about 210°C, and at a pressure ranging from about 0 to about 40 bar in order to form the molecular sieve In cases where other products, unreacted gel, or a mixture thereof is present at the conclusion of the reaction, the molecular sieve may be recovered by a separation process such as centπfϊigation The process may also include conventional product washing and drying such as an ethanol πnse, followed by a de-ionized water πnse, followed by air oven drying at a temperature ranging from about 40°C to about 1 10°C It should be noted that conventional heating may be substituted for microwave heating in this process, and that a substantialh pure molecular sieve composition having the AEL-structure will result with either heating method Stoichiometπes for some of the gels exemplified herein are set forth in Table 2

B. AEL-Type Molecular Sieve Catalysts

Prefeπed molecular sieve mateπals prepared in accordance with these methods are useful as catalytic materials While not wishing to be bound, it is behe\ ed that the silicon distπbution withm the molecular sieve crystal, as measured for example by ^" Si NMR, is one important characteristic influencing catalytic activ ity in SAPO mateπals Since silicon is responsible for the aciditv in SAPO mateπals. it is desirable that silicon be well dispersed m the alummophosphate framework for high catalvtic activin It is known that silicon can form large silicon islands in SAPO mateπals Although large silicon islands are undesirable because those silicon atoms at the inteπor of the islands are catalytically inactiv e the small silicon-rich regions present m the prefeπed molecular

e matenal are desirable because the strongest acid sites are belie ed to form at the borders of the Si -πch regions and the alummophosphate domains This is because those silicons at the borders have fewer aluminum atoms as nearest neighbors, which leads to decreasing acidity resulting from aluminum's lower electronegativity The preferred AEL-type SAPO mateπals are believed to possess their desirable catalytic activity and selectivity because the Si atoms are well dispersed withm the molecular sieve framework As is known to those skilled in the art, molecular sieve mateπals may possess an intrinsic or added catalytic functionality, and such mateπals are frequently referred to as "molecular sieve catalysts " Additional catalytic functionalities may be provided for molecular sieve mateπals by conventional methods Accordingly, the molecular sieve mateπal formed from the gel as set forth above may be calcined to remove the template The sample may then be allowed to cool, preferably in a dry environment , and then loaded with an additional catalytic functionality

C. Structural Analysis of AEL-Type Molecular Sieve Catalysts

The SAPO molecular sieve compositions useful m this invention have a Si content ranging from about 4 molar percent to about 10 molar percent silicon content based on the total amount of silicon in the molecular sieve composition Preferably, the proportion between silicon atoms hav ing one. two or three silicon atoms as nearest neighbors to those having four silicon atoms should be balanced, so that two conditions are simultaneously fulfilled the molar ratio between (Sι2Sι -+- Sι3Sι) to Sι4Sι should be m the range of about 0 7 to about 1 4, and the sum of Si atoms with 2Sι, 3Sι and 4Sι nearest neighbors should be m the range of about 10 to about 80 molar % based on the total amount of silicon the molecular sieve's framework As is known bv those skilled m the art, the molar percent of Si atoms with one, two, three, and four Si atom nearest neighbors may be obtained, for example, by deconvolutmg the integrated intensities from ²⁹Sι NMR measurements, as illustrated m Figure 2 and Table 1 Table 1 gives the mole fraction of framework silicon m each type of silicon site for samples l a through I d and 2a and 2b from the examples TABLE 1

Si Environment 4Al , 0Sι 3A1 , I Si

1 2Al , 2Si l Al , 3Si 0Al , 4Si j 1

Chemical shift in -89 10 -91 _[ -97 ppm -103 ppm -108 ppm -1 10 to -1 13 j ppm from TMS ppm ppm

EXAMPLE la 17.5 , 9.7 4.4 1.2 67.2

| lb 4.6 34.3 6.4 7.3 47.4 lc 4.4 , 13.9 8.9 8.5 64.3

!

Id 1 17.0 15.1 10.4 56.5

2a 15.5 28.9 14.3 13.9 27.4

2b 5 4 25.3 19.7 18.2 31.4

In a particularly preferred embodiment, the number of Si atoms having no Si nearest neighbor ranges from about 1 mol. % to about 20 mol. %. the number of Si atoms having one Si nearest neighbor ranges from about 10 mol. % to about 35 mol. %, the number of Si atoms having two Si nearest neighbors ranges from about 10 mol. % to about 30 mol. %. the number of Si atoms having three Si nearest neighbors ranging from about 10 mol. % to about 30 mol. %, and the number of Si atoms having four Si nearest neighbors ranging from about 15 mol. % to about 50 mol. %.

D. Use of New AEL-Type Molecular Sieves as Catalysts

The molecular sieves of this invention are useful as catalysts in a number of applications including, but not limited to, catalytic dewaxmg, isodewaxing/isomerization. hydrocracking, alkylation of aromatic hydrocarbons ( e.g., benzene) with long chain olefms (e.g.. C_! olefιn), alkylation of aromatic hydrocarbons (e.g., benzene and alkylbenzenes) in presence of an alkylating agent (e g , olefms, formaldehyde, alkyl hahdes and alcohols having 1 to about 20 carbons atoms), alkylation of aromatic hydrocarbons (e g., benzene) with light olefms to produce short chain aromatic compounds (e.g , alkylation of benzene with propylene to give cumene), transalkylation of aromatic hydrocarbons m the presence of polyalkvlaromatic hydrocarbons, isomeπzation of aromatic feedstock components (e g , xylene), naphtha cracking to make olefms. ohgomeπzation of straight and branched chain olefms having from about 2 to 5 carbons atoms, disproportionation of aromatics (e.g , the disproportionation of toluene to make benzene and paraxylene), and conversion of naphtha (e g , , - C]₀) and similar mixtures to highly aromatic mixtures

Accordingly, the preferred catalytic molecular sieve compositions are useful as FCC catalysts, both alone and in combination with other FCC catalysts The preferred SAPO molecular sieve catalysts may be used in combination with a conventional, large-pore FCC catalyst A preferred catalyst composition contains the large-pore FCC catalyst and a SAPO molecular sieve catalyst More preferably, the conventional, large pore FCC catalyst is present in an amount ranging from about 50 wt % to about 99 wt %, and the S APO molecular sieve catalyst is present in an amount ranging from about 1 wt % to about 50 w t %. the wt % being based on the total w eight of the FCC catalyst employed Such catalysts have a dramatically increased catalytic activity for such processes over FCC catalysts containing SAPO molecular sieve catalysts prepared bv conventional techniques

The conventional FCC catalyst may contain other reactive and e components, such catalysts are descπbed in European patent document \o 0 600 686A1. incorporated bv reference herein

The SAPO catalyst may be in the form of particles, and mav include fines, inert particles, particles containing a metallic species, and mixtures thereof Inert particles may contain species such as silica, alumina, cla , and mixtures thereof. More than one type of catalyst particle may be present in the catalyst. For example, individual catalyst particles may contain large pore molecular sieve catalyst, the preferred SAPO molecular sieve catalyst, other shape selective molecular sieve such as zeolite, and mixtures thereof

The SAPO catalyst particles may contain promoter species such as phosphorous-containing species, clay filler, and species for imparting additional catalytic functionality (additional to the cracking functionality) such as bottoms cracking and metals passivation Such an additional catalytic functionality may be provided, for example, by alummum-contammg species More than one type of catalyst particle may be present m the catalyst For example, individual catalvst particles may contain large pore molecular sieve catalyst, the AEL-type SAPO catalysts of this invention, other shape selective molecular sieve such as zeolite, and mixtures thereof

The catalyst particles may contain an inorganic oxide matπx component for binding the particles' components together so that the catalyst particle product is hard enough to survive lnterparticle and reactor wall collisions The inorganic oxide matπx may be made according to conventional methods from an inorganic oxide sol or gel which is dried to "glue" the catalyst particle's components together Preferably , the inorganic oxide matπx is not catalytically active and comprises oxides of silicon, aluminum, and mixtures thereof It is also preferred that separate alumina phases be incorporated into the inorganic oxide matπx Species of aluminum oxyhydroxides-γ-alumma, boehmite. diaspore. and transitional aluminas such as α-alumina, β-alumma, γ- alumma, δ-alumma. ε-alumma. κ-alumma, and p-alumma can be employed Preferabh . the alumina species is an aluminum tπhydroxide such as gibbsite, baveπte, nordstrandite, or doyehte The matπx mateπal may also contain phosphorous or aluminum phosphate The amount of molecular sieve in the catalyst particle will generally range from about 1 to about 60 wt.%, preferably from about 1 to about 40 wt.%, and more preferably from about 5 to about 40 wt.%, based on the total weight of the catalyst Generally, the catalyst particle size will range from about 10 to 300 microns in diameter, with an average particle diameter of about 60 microns. The surface area of the matrix mateπal will be about >350 m²/g, preferably 50 to 200 m7g, more preferably from about 50 to 100 m²/g. While the surface area of the final catalysts will depend on factors such as the type and amount of zeolite mateπal used, it will usually be less than about 500 irf/g, preferably from about 50 to 300 m /g, more preferably from about 50 to 350 m7g, and most preferably from about 100 to 250 irT'g

Conventional FCC catalysts useful m the invention also include catalysts containing zeolite Y, Zeolite beta, and mixtures thereof, and catalysts containing a mixture of zeolite Y and a shape selective molecular sieve species such as ZSM-5, or a mixture of an amorphous acidic material and ZSM-5. Such catalysts are described U.S. Patent No. 5.3 18.692, incorporated by reference herein. The zeolite portion of the catalyst particle will typically contain from about 5 wt.% to 95 wt.% zeolite-Y (or alternatively the amorphous acidic mateπal ) and the balance of the zeolite portion being ZSM-5 Shape selectiv e zeolite useful in the second catalyst include medium pore size molecular sieves such as ZSM-5, which is described in U.S. Patent Nos. 3,702,886 and 3,770,614. ZSM-1 1 is described in U.S. Patent No. 3,709,979; ZSM-12 in U.S. Patent No. 3.832,449; ZSM-21 and ZSM-38 in U.S. Patent No. 3,948,758; ZSM-23 m U.S. Patent No. 4.076.842; and ZSM-35 in U.S. Patent No, 4,016,245. All of the above patents are incorporated herein by reference.

The large pore and shape selective catalysts may include "crystalline admixtures" which are thought to be the result of faults occurring withm the crystal or crystalline area duπng the synthesis of the zeolites. Examples of crystalline admixtures of ZSM-5 and ZSM-1 1 are disclosed in U.S Patent No 4,229,424 which is incorporated herein by reference The crystalline admixtures are themselves medium pore, i.e., shape selective, size zeolites and are not to be confused with physical admixtures of zeolites in which distinct crystals of crystallites of different zeolites are physically present in the same catalyst composite or hydrothermal reaction mixtures

As discussed, one aspect of the invention is the use of an effective amount of the preferred SAPO molecular sieve catalysts in catalytic cracking processes, especially in FCC processes for producing naphtha and C₂ and C₄ olefms Suitable FCC conditions and the types of feeds that maybe used therein are as follows

Suitable hydrocarbonaceous feeds for the catalytic cracking process of the present invention include naphtha, hydrocarbonaceous oils boiling in the range of about 430°F to about 1050°F, such as gas oil, heavy hydrocarbonaceous oils comprising mateπals boiling above 1050°F, heavy and reduced petroleum crude oil, petroleum atmospheπc distillation bottoms, petroleum vacuum distillation bottoms, pitch, asphalt, bitumen, other heavy hydrocarbon residues, tar sand oils, shale oil, liquid products deπved from coal liquefaction processes, and mixtures thereof

The cracking process of the present invention may be performed in one or more conventional FCC process units under conventional FCC conditions in the presence of the catalyst of this invention Each unit compπses a πser reactor having a reaction zone, a stripping zone, a catalyst regeneration zone, and at least one fractionation zone The feed is conducted to the πser reactor where it is injected into the reaction zone wherein the heavy feed contacts a flowing source of hot, regenerated catalyst The hot catalyst apoπzes and cracks the feed at a temperature from about 500°C to about 650°C, preferably from about 500°C to about 600°C The cracking reaction deposits carbonaceous hydrocarbons, or coke, on the catalyst, thereby deactivating the catalyst The cracked products may be separated from the coked catalyst and a portion of the cracked products may be conducted to a fractionator The fractionator separates at least a naphtha fraction from the cracked products.

The coked catalyst flows through the stπppmg zone where volatiles are stπpped from the catalyst particles with a stπppmg material such as steam. The stripping may be performed under low seventy conditions m order to retain absorbed hydrocarbons for heat balance The stπpped catalyst is then conducted to the regeneration zone where it is regenerated by burning coke on the catalyst in the presence of an oxygen containing gas, preferably air. Decoking restores catalyst activity and simultaneously heats the catalyst to, e.g., 650°C to 750°C The hot catalyst is then recycled to the πser reactor at a point near or just upstream of the second reaction zone Flue gas formed by burning coke in the regenerator may be treated for removal of particulates and for conversion of carbon monoxide, after which the flue gas is normally discharged into the atmosphere

The feed may be cracked in the reaction zone under conventional FCC conditions in the presence of the catalyst of this inv ention Preferred process conditions m the reaction zone include temperatures from about 500°C to about 650°C, preferably from about 525°C to 600°C, hydrocarbon partial pressures from about 10 to 40 psia, preferably from about 20 to 35 psia; and a catalyst to feed (wt/wt) ratio from about 3 to 20, preferably from about 4 to 15, where catalyst weight is total weight of the catalyst composite Though not required, it is also preferred that steam be concurrently introduced with the feed into the reaction zone, with the steam comprising up to about 10 wt.%, and preferably ranging from about 2 wt % to about 3 wt % of the feed Also, it is preferred that the feed's residence time m the reaction zone be less than about 10 seconds, for example from about 0.01 to 60 seconds, preferably from 0.1 to 30 seconds The invention is further exemplified by the following non-hmitmg examples

EXAMPLES

Example 1

Preparation of a Conventional Sample of SAPO-11

A sample of conventional SAPO- 1 1 was prepared in accordance with the procedure set forth in Zubowa et al. J Chem Soc Faradav Trans 86 230^~ (1990 More specifically the synthesis used was as follows

FLPO , (Riedel-de-Haen. 85% ) was agitated during 10- 15 minutes with the required amount of H.O (Milli Q) On this solution the pseudobohemite

(Catapal B, 73 ⁷% Al.O,) was added and the mixture was agitated for two hours

Dipropylamme (DPA. Aldrich) and Ludox AS40 (Aldrich 40%o) were then added successivelv After two more hours of agitation, the preparation of the gel was concluded Gels prepared in accord with this process have stoichiometπes m the range of

wherein x is ranges from about 1 to about 1.2. y ranges between about 1 and about 2.5, and Z ranges between about 0 and about 1.5 More specifically, the sample prepared m this example was

A1_0.- P,0_^ DPA: 0.6 SiO,: 62 H,0

The gel was introduced in 60 ml Teflon lined autoclaves, which were about 50% filled up. and was crystallized at 195°C for about 16 hours The crystallized products were washed and centπfuged 3 times at 14.000 rpm The resultant solid was dried at 100°C The samples were calcined in accordance with the following program

(a) Flow of N₂ (150 ml mm '), at 2°C. mm^{" 1} until reaching 550°C

(b) At 550°C are kept under the N₂ flow duπng 1 hour

(c) N₂ is changed to air (150 ml.min^'1) and kept at 550° during 3 hours.

(d) The system is let to cool down under the flow of air

(e) During the calcination procedure the height of the bed was 0 5 cm

The powder

diffraction pattern for these samples, shown in Figure 4(a), demonstrates that a substantially pure SAPO- l 1 resulted The sample is designated herein as Sample 1 -a.

Sample 1-a was further characteπzed using Si MAS NMR spectroscopy and the data generated is shown on Figure 5-a This solid state Si MAS NMR spectrum and all others appearing hereafter were recorded on a \ aπan NXR S 400 WB spectrometer at 79.5 MHz using 7 mm CP/MAS Naπan probe with zircoma rotors To acquire the spectra, pulses of 4 2 us coπesponding to π 3 rad pulse length were applied, with a 40s rec cle delav and a rotor spinning rate of 5 KHz

Three additional samples of conventional SAPO-1 1 were prepared m accordance with the procedure set forth in U.S. Patent No 4.440,871 Accordingly, Al isopropoxide was introduced into a polypropylene flask, which w as provided with a tope for passage of a stirrer A solution of H P0₄ was prepared with the total amount of water (milli Q) required for the synthesis The H-P0₄ solution was added to the polypropylene flask, located in a H₂0 bath at 20 - 2°C The mixture was stirred during 2 hours using a teflon stirrer at 350 rpm After two hours time, the stirπng was stopped and the necessary silica was added from LUDOX AS40, and the mixture was stirred for 2 hours. Finally, the DPA was added and the synthesis mixture was stirred for 2 hours to form the synthesis gel. The gel prepared in this way is white, and had the Ph as given in Table 2.

The general composition of the gel was

1.0 A1₂0₃ : 1.00 P₂0₅ : 0.9 DPA : xSi0₂ : 57.0 H₂0

The gel composition and the yield of the solid product obtained are also given in Table 2

The gel was distπbuted among 6 teflon-lined autoclaves of 60 ml of capacity each (40 g of synthesis gel in each autoclave), and the crystallization was conducted m static mixing at 195°C for 48 hours. After this, the product of each autoclave was washed with 240 ml of H₂0 and centrifuged The three solid samples of SAPO-1 1 were dπed at 40°C, and are designated herein as Samples 1-a. 1 -b, 1 -c. and 1 -d. Powder x-ray diffraction patterns for the samples, shown respectively m Figures 4b. 4c and 4d, demonstrate that a substantially pure SAPO-1 1 resulted

^2QSι MAS NMR results from samples 1 -a, 1 -b, 1 -c, and 1-d are set forth respectively in Figures 5-a. 5b, 5c. and 5d As is evident from the spectra, all conventional SAPO-1 1 samples (Fig. 5a through 5d) show substantial silicon islanding as indicated by the number of silicon atoms in the framework having four silicon atom nearest neighbors. TABLE 2

Example 2

Synthesis of a SAPO-11 Using a Surfactant-Containing Synthesis Solution

20.34g of A1₂0, (Condea Pural SB 74.6%) were introduced in a 500 ml polypropylene flask, which was provided with a tope for passage of an agitator.

A solution of 34.31 g of H,P0 (Riedel-de-Haen 85%), and 30g of H₂0 (milli Q) was prepared by agitation dunng 10-15 minutes. The H.PO , solution was added to the polypropylene flask, which was placed into a water bath at 20 = 2°C. The mixture was stirred during 2 hours with a Teflon stirrer, at 350 rpm. After this time the stirring was stopped and 15.2 lg of DPA were added, and the mixture was stirred during 2 hours.

68.27g of 1 hexanol (Aldπch 95%), 30g of H₂0 and 5.75g of hexadecilamme (Aldrich 99%) were combined in a glass flask, and the resultant solution was stirred during 1 hour. The hexanol solution, together with 9.30g of tetraethylorthosilicate (TEOS) (Merck-Schuchardt >98%) and 26 81g of H₂0 (milli Q) were added to the polypropylene flask, and the mixture was stirred during 2 hours in order to form the synthesis gel

The resultant gel was white, and the pH was 4.33

40g of the synthesis gel were introduced in the 60 ml teflon-lmed autoclaves, and the crystallization was earned out at 195°C in static mixing (without stirring) duπng 24 hours

The resultant samples were washed first with 240 ml of H₂0, followed by 30 ml ethanol. and finally 240 ml of H^O while centrifugmg The y ield was 0 17g dried solid g gel A portion of the uncalcined SAPO-1 1 was enclosed This material was calcined using the protocol as was used for sample 1 -a The resulting sample is referred to herein as sample 2-a

The composition of the gel was

A1₂0₃ P₂0, 0 3 TEOS DPA 0 144 Hexadecilamme 4 40 Hex 40 H₂0

Powder \-rav diffraction data, shown m Figure 4. demonstrates that the product is isostructural with SAPO- 1 1 ² Sι MAS NMR was used to characteπze the local atomic environment of Si atoms in the SAPO framework That data is shown Figure 5(e) As is clear from the data. Sample 2-a exhibits a greatly reduced amount of silicon islanding when compared to Samples 1 -a through 1-d, for approximately the same amount of silicon in the synthesis solution

A second SAPO sample was prepared from a surfactant-containing synthesis solution in order to investigate the degree of Si islanding at higher silica concentration Accordmgly, a sample of SAPO-1 1 was synthesized using surfactants and with a higher Si content than any of the previously prepared samples This sample was prepared according to the same synthesis procedure as Sample 2-a, and the gel composition and solid yield is given in Table 2 Figure 4 shows the powder XRD This sample referred to as Sample 2-b herein The powder x-ray diffraction data reveals the presence of some tndimite impunties in Sample 2-b Si MAS NMR results show that Sample 2-b has substantially fewer Si framework atoms m lattice sites having four Si nearest neighbors than does conventionally-prepared SAPO- 11 with about half the silicon content (Figure 5-a)

Example 3

Acidity Measurements

The total amount of Bronsted and Lewis acid sites, as well as the acid strength distπbution of all samples was determined by adsorption and thermal desorption of pyndme is accordance with known procedures In this example, it is assumed that at 150°C of pyndme desorption temperature all the acid sites are measured While at 350°C only the strongest acid sites will be able to retain pyndme

IR spectroscopy was used to probe hydroxyl stretching modes in the samples before and after pyndme adsorbtion Pyndme adsorbtion at Bronsted ( 1545 cm ') and Lewis (1455 cm ') acid sites are determined by calculating the integrated intensities of the IR absorbtion bands The results are set forth in Table 3 TABLE 3 Bronsted (micromole py/gr cat.) Lewis (micromole py/ gr cat.)

Table 3 shows that the sample synthesized with surfactant (2-a and 2-b) have a higher total Bronsted acidity than the conventionally synthesized samples. Importantly, Sample 2-b has more Bronsted acid sites than do Samples 1-b and 1 -d with lower (Sample 1 -b) and higher (Sample 1 -d) Si content in the synthesis solution. These data are in agreement with the NMR data which shows increased proportion of Si-O-Al bonding which inherently means higher and stronger acidity.

Example 4

Catalytic Activity

The surfactant-prepared SAPO materials described herein were evaluated for effectiveness in catalytic cracking processes.

The preferred SAPO-1 1 catalysts are useful as FCC Catalysts for generation light olefms such as of propylene. A series of tests were conducted with a conventional SAPO-1 1 and a commercial ZSM-5 additive catalyst. The tests were carried out under conventional catalytic cracking conditions with 75 wt.% conventional large pore zeolite catalyst as the base cracking catalyst and

25 wt. % of the preferred SAPO-11 catalyst. The test conditions included a

51 1 °C reaction temperature, 2.5-5.0 catalyst to oil ratio, and a heavy gas oil feed.

As can be seen from the data presented in Table 4 even conventionally prepared SAPO-1 1 is a selective catalyst for olefm generation. At 74-75wt.% conversion, the propylene-to-butylene ratio from addition of conventional SAPO-1 1 is 3.0, which compares favorably to the commercial FCC additive catalyst, which showed a propylene-to-butylene ratio of 1.3. In addition to the superior propylene-to-butylene selectivity, the propane and butane light saturate yields were also lower with conventional SAPO-1 1.

Although highly selective, the conventional SAPO-1 1 showed lower activity than the ZSM-5 additive catalyst, as is shown by the naphtha yield reduction of 0.9% when the conventional SAPO- 1 1 was used as a FCC additive. This contrasts with the SAM-5 additive, which reduced naphtha yield by 4.0 wt.%. From these data, one can estimate that commercial FCC additive catalysts is about four times more active than the SAPO- 1 1 which was made in the conventional manner.

As can be seen from Table 5, the activity of the preferred surfactant-prepared SAPOs described herein are substantially more active than conventional SAPO-1 1. The conventional SAPO-1 1 showed 42-44 wt.% conversion at a WHSN of 14 hr^"1 in cracking of hexene/hexane model compounds at 575°C, whereas the surfactant-prepared SAPO (Sample 2-a) catalyst of this invention showed 43 wt.% conversion at 144 hr^" WHSN. From these data, it can be estimated that the surfactant-prepared SAPO-11 is about 10 times more active than conventional SAPO-1 1. Equally important, the conventional SAPO-1 1 and the preferred AEL-type SAPO catalyst of this mvention are equally selective, at 74-80%, in spite of the tremendous activity difference.

TABLE 4

All data snown are delta yields at 74-^'75 wt.% conversion

TABLE 5

(50/50 hexane/hexene, 575C. 44 wt.% conversion)

Catalvst UOP SAPO-11 Sample 2-a Sample 2-b

WHSV, Hr-1 14 144 192

Conversion. Wt.% 44.3 42.5 44.3

Key Results, Wt.% 2.4 2.1 2.1 Ethylene

Propylene 32. δ 33.9 ~ X . '

Butenes 5.0 4.2 4.8

Light Saturates 3.0 2.4 2.2

Aromatics 1.1 0.5 1.5

Selectivity, % 74.0 79.8 76.1 Propylene

The third column of Table 5 shows that even greater activity for a mixture of surfactant-prepared SAPO- 1 1 and SAPO-41. The surfactant-prepared SAPO mateπals described herein are also effective naphtha cracking catalysts A conventionally-prepared SAPO-1 1 and Sample 2-a were compared under conventional naphtha cracking conditions (575°C temperature, 48 hr- 1 WHSV) in order to demonstrate the catalytic effectiveness of the surfactant-prepared material with a light cat naphtha feed. As shown in Table 6, the surfactant- prepared material (Sample 2-a) was nearly twice as active (and substantially more selective) than the conventionally-prepared SAPO- 1 1.

TABLE 6

Claims

CLAIMS:

1 A fluidized catalytic cracking method comp╧Çsing injecting a feed into an FCC nser reactor having a reaction zone and catalytically cracking the feed in the reaction zone under catalytic cracking conditions in the presence of a catalytically effective amount of a cracking catalyst in order to form a cracked product, the cracking catalyst containing a major amount of a large-pore zeolite catalyst and a minor amount of a SAPO catalyst, the SAPO catalyst having a total silicon amount ranging from about 0 2 molar % to about 40 molar %, a total aluminum amount ranging from about 30 molar % to about 49 9 molar %, and a total phosphorus amount ranging from about 10 molar % to about 49 9 molar %, the molar percents being based on the total amount of aluminum, phosphorus, and silicon present in the composition, and the SAPO catalyst being isostructural with a SAPO-1 1 having the AEL structure and containing silicon, aluminum, and phosphorus, wherein

(a) the silicon present the SAPO catalyst is dist╧Çbuted among silicon sites, each site having a first, a second, a third, and a fourth nearest neighbor position, and each position being independently occupied by one atom selected from silicon and aluminum, and

(b) the composition has a first number of silicon sites having silicon atoms in the four nearest neighbor positions ( S╬╣4S╬╣), a second number of silicon sites having silicon atoms in three of the four nearest neighbor positions ( S╬╣3S╬╣). and a third number of silicon sites having silicon atoms m two of the four nearest neighbor positions (S╬╣2S╬╣). wherein

(l) the sum of the first, second, and third number of silicon sites ranges from about t 10 to about 80 molar %, and (ii) the molar ratio of the sum of the third and second number of silicon sites to the first number of silicon sites ranges from about 0.7 to about 1.4, the molar % being based on the total number of silicon sites.

2. A composition comprising a major amount of a large-pore zeolite catalyst and a minor amount of a SAPO catalyst, the SAPO catalyst having a total silicon amount ranging from about 0.2 molar % to about 40 molar %, a total aluminum amount ranging from about 30 molar % to about 49.9 molar %, and a total phosphorus amount ranging from about 10 molar % to about 49.9 molar %, the molar percents being based on the total amount of aluminum, phosphorus, and silicon present in the composition, and the SAPO catalyst being isostructural with a SAPO-1 1 having the AEL structure and containing silicon, aluminum, and phosphorus, wherein

(a) the silicon present in the SAPO catalyst is distributed among silicon sites, each site having a first, a second, a third, and a fourth nearest neighbor position, and each position being independently occupied by one atom selected from silicon and aluminum, and

(b) the composition has a first number of silicon sites having silicon atoms in the four nearest neighbor positions (Si4Si), a second number of silicon sites having silicon atoms in three of the four nearest neighbor positions (Si3Si), and a third number of silicon sites having silicon atoms in two of the four nearest neighbor positions (Si2Si), wherein

(i) the sum of the first, second, and third number of silicon sites ran *gt es from about 10 to about 80 molar %, and

(ii) the molar ratio of the sum of the third and second number of silicon sites to the first number of silicon sites ranges from about 0.7 to about 1.4, the molar % being based on the total number of silicon sites.