JPH02173188A - Method for raising octane value - Google Patents

Abstract

PURPOSE: To provide a structure for controlling a twisting diffusion factor and raise the octane value of gasoline by using a middle pore size NZMS (composition) as an octane value raising catalyst.

CONSTITUTION: A petroleum fraction is subjected to catalytic cracking condition in the presence of 20 wt.% or less (preferably less than 3 wt.%) of an octane value raising catalyst consisting of (A) a petroleum cracking catalyst and (B) a composition consisting of the combination of a middle pore size NZMS with another NZMS having the same framework structure as the above whereby the petroleum fraction is cracked into a material having a lower boiling point. As a preferable example of the component B, SAPO-11 and AlPO₄-11 are given as one of the middle pore size ZNMS and as the other non-zeolite molecular sieve having the same framework structure, respectively.

COPYRIGHT: (C)1990,JPO

Description

Detailed Description of the Invention In a heterogeneous catalytic reaction, a phenomenon called torsion diffusion is observed. The purpose of tortuous diffusion is to transport the gaseous or liquid reactants or reaction products and the catalyst material in the porous network of the catalyst to the reactants in the catalyst bed. and the reaction product for a period of time longer than the predetermined residence time of the reaction product.The length of contact time between the reactants and the reaction product in the catalyst depends on the complexity of the pores and the pore size. In the case of catalysts with a large surface area, the porosity is quite high and the residence time of the reactants or reaction products is relatively long, exceeding the theoretical value. If the reactants and/or reaction products form undesirable products during this transit period, the efficiency of the reaction will be significantly reduced. One way to avoid such negative effects due to tortuous diffusion is to create catalysts with small surface areas. That is, it is preferable to use a solid catalyst having a relatively small number of pores and a considerable number of large pores.

However, not all catalysts can be shaped like this. Some catalysts have a structure with a small surface area and are not effective, and some catalysts cannot adopt such a structure.

This specification describes a novel multi-component catalyst that provides groove control to control tortuosity diffusion factors to an extent that increases the octane number of gasoline in FCC (fluid catalytic cracking) processes. This catalyst consists of a specific type of non-zeolitic molecular sieve catalyst with an unaltered crystalline micropore size structure.

Co-pending U.S. Patent Application No. 058,259 states:
New classes of molecular sieves based on composites or combinations of micropore size non-zeolitic molecular sieves (NZMS) with other micropore size non-zeolitic molecular sieves (NZMS) or zeolitic molecular sieves (Z!IS) have been taught. Co-pending U.S. patent application Ser. No. 058,275 discloses that SAP
The use of composites of NZMS-37 and other "fajasite" molecular sieves, such as O-7 molecular sieves, has been taught.

Both applications provide a detailed discussion of the prior art regarding the formation of microporous non-zeolitic molecular sieves and molecular sieve composites used in the preparation of composites for use in the present invention. This specification incorporates the above discussion by reference. Particularly relevant to the present invention is the NZMS listed in Table A shown in each application. To avoid redundancy, I will not repeat them here.

Composites encompassed by co-pending U.S. patent application Ser.
Medium pore diameter NZM of SO, ELAPO and ELAPSO etc.
Those containing S are included. These medium pore diameter structures NZ
Examples of MS are shown in the table below.

Table A Medium pore size structure NZMS NZMS-40 structure has large pore size NZMs and medium pore size NZMS.
Although it falls in a category intermediate between MS and MS, for the purpose of the present invention it is here considered to be medium pore size NZMS. These NZMS are microporous non-zeolitic molecular sieves and are described in the various patents and patent applications listed in Table A of the co-pending application filed on the same date as this specification. As a representative example of such a description, April 1987
Examples include the SAPO compound type of medium pore structure NZMS described in US Pat. Examples 15-22 describes the structure of SAPO-11 and its manufacturing method, and Examples 51-53 describe the structure of SAPO-11 and its manufacturing method.
The structure of PO-31 and its manufacturing method are described, Examples 46 and 47 describe the structure of SAPO-40 and its manufacturing method, and Example 54 describes the structure of SAPO-41 and its manufacturing method. In the above specification, SA
PO-11 is described as a crystalline microporous silicoaluminophosphate with a unique X-ray powder diffraction pattern containing at least the d-spacings shown in Table B below.

The above specification states that 5APQ-20 is a crystalline microporous silicoaluminophosphate with a unique X-ray powder diffraction pattern containing at least the d-spacings shown in Table C below.

The above specification states that SAPO-41 is a crystalline microporous silicoaluminophosphate with a unique X-ray powder diffraction pattern containing at least the d-spacings shown in the table below. .

The above specification states that SAPO-40 is a crystalline microporous silicoaluminophosphate with an X-ray powder diffraction pattern containing small d-spacings as shown in the table below.

These medium pore structure SAPOs are suitably described in the above specification as well as in US Pat. No. 4,440,871.

The expression "medium pore size" refers to crystalline molecular sieves that are considered in the art to fall between "large pore size" and "small pore size" by standard gravimetric adsorption. Regarding this, F tan igen was included in the 7th International Zeolite Conference Report "New Developments in Zeolite Science and Technology".
A paper entitled “Aluminophosphate molecular sieves and the periodic table” by Y., Murarkami, A. Iijima et al.
and J.W., WardW., pp. 103-112.

(1986). The pore size of the medium pore crystalline molecular sieve is between 0.4 nm and 0.8 r+m, especially about 0
．． It is 6 nm. The medium pore size crystalline molecular sieve used for achieving the purpose of the present invention has a pore size of about 0.5 to about 0.7.
Examples include nmO.

LOK et al. (J. Am. Chem. Soc. 1984.
6092 and 6093) describes the medium pore diameter SAPO as follows.

SAPO-11, -31, -40 and -41 have pores of medium to large diameter. SAPO-11 and SA
PO-41 is both 2,2-dimethylpropane (radius 6
．． It is easier to accept cyclohexane (6.0 people) than 2 people). SAPO-31 and SAPO-
40 adsorbs 2,2-dimethylpropane but excludes the larger triethylamine (7.8 radial diameter). The pore size of these structures is measured by either open 10-rings or puff card 12-rings in silicalite (6 people). SAPO-31 and -4
For 0, the method using 12-rings is considered to be the most reliable.

A new series of crystalline microporous molecular sieve oxides is the subject of further improvements in said co-pending application;
You may have recently received a patent or have a patent application pending. See Table A of these applications, these 17J qualities are based on the presence of aluminum and phosphorous in the crystalline framework structure. These molecular sieves are not aluminosilicates; many of them have a novel crystal structure related to known zeolites, and Ike's have a framework structure comparable to that of zeolites in terms of topology. These substances are
In fact, it is not zeolite (1) J
, V, Sm1th is Amer, Mineralso
c, 5 pec.

paper (1963) I, p. 281, ``Zeolites are aluminosilicates with a framework structure containing cavities occupied by large ions and water molecules, in which the ions and water molecules have considerable freedom of movement, and the ions Exchange and reversible dehydration are also possible.”
It is written as follows. J, Rabo, Zeolite Chemistry and Catalysis,
Ameri-can Chemical 5ociet
Published by y, Washington, D.C.

ASC Monograph 171, 1979. See Chapter 1, Page 3 (J, V, S+++i th).

For convenience, these molecular sieves are considered herein to belong to the "non-zeolitic molecular section" (commonly referred to by the acronym r NZlIS j). Patents and patent applications relating to NZMS and a description of their subject matter are set out in Schedule A of the above patent application. In carrying out the present invention, methods for producing these new substances will be adopted.

Since the NZMS of these new species of lily is extremely important in the present invention, it seems appropriate to quote the above-mentioned explanation of the nomenclature of these substances by Flanigen et al.

“Depending on the number of elements contained in the cationic framework structure of a given structure, these substances can be classified as binary, ternary, quaternary, or
Classified into ternary and aqueous compositions. The normal TO□ formula is the composition (El, AlyP,)O□ (where Eg indicates the included element, and x, y.

Z represents the relative concentration of the framework elements in each composition (indicating the mole fraction of each element in the composition). Acronyms indicating framework composition are listed in Table 1. In other words, SAPO is (Si
, AI, represents the PlO□ composition.

The structure type is indicated by an integer following the composition acronym. For example, SAPO-5 is a type 5 (Si, AI, P)
0□ means composition. The structure type number is arbitrarily determined and is completely unrelated to the structure number found in prior documents such as ZSM-5. These structure type numbers were established solely to identify structures found in aluminophosphate-based molecular sieves. Even if the frame composition is different, if the structure type is the same, the same structure number is used. Table 1 Acronyms for Framework Composition Descriptions of how the particular phases of the composites of the present invention are formed will follow the nomenclature given above. For example, consider that the phase produced by the method of forming SAPO-11 is SAPO-11, and the phase produced by the method of forming AlPO4-11 is AIPO,-11. The same applies below.

The aforementioned co-pending application Schedule A and Flanige
The molecular sieve shown in the report by et al. has unique catalytic and adsorption abilities not found in other molecular sieves (especially zeolite molecular sieves). The activity of these molecular sieves is wide-ranging, and in most cases these materials have excellent stability with respect to heat and hydrothermal water, which is highly desirable.

The relative acidity of zeolite molecular sieve is @thin (2 mol%)n
- It is known in the art that this is indicated by the resolution for butane. Ra5telli et al., The
Canada Journal of Chen+1c
al Engineering.

See No. 60, pages 44-49, February 1982. This also applies to molecular planes belonging to NZMS.

Lok et al., Journal of American
Chemical 5ociety.

1984, No. 106, pp. 6092-6093. In this specification, when referring to the acidity of a molecular sieve, the acidity is defined by the dilute n-butane resolution as previously described by Ra5telli et al. It is determined based on the KA of the substance. More broadly, acidity generally refers to activity in catalytic reactions catalyzed by acids.

U.S. Patent No. 4.440.871, specification No. 8'u 10-1, which is one of the patents listed in Table A of the co-pending application specification.
Line 6 states the following:

Although not essential when synthesizing the rsAPo composition, stirring the reaction mixture or using other means of moderate agitation and/or the desired SAP
Crystallization can be promoted by seeding the reaction mixture with O or an aluminophosphate or aluminosilicate composition having a similar composition in terms of topology. Similar statements can be found in numerous other patents and patent applications listed in Table A of the co-pending application specification.

See notes in the margins of Table A. Among the examples of patents and patent applications listed in Table A above, those implementing the seeding method are particularly helpful. Many of the patents and patent applications listed in Table A discuss and disclose the use of molecular sieves containing aluminum and phosphorus as sources of aluminum and/or phosphorus in the manufacture of molecular sieves. None of the patents and patent applications listed in Table A discuss the formation of composites or the formation of multiphase compositions in which the phases are distinct from each other and inhomogeneous with respect to each other; There is also no mention of an octane number raising catalyst using structure NZMS.

Co-pending application No. 058゜25, which is a reference in this specification
No. 9 discloses NZ? containing different inorganic crystalline compositions (preferably molecular sieve compositions) as phases. Multiphase composites made from IS are disclosed in which at least one phase is formed by crystal growth in the presence of another phase. The characteristics of this multiphase composite are as follows.

(a) the different phases are continuous and have a common crystalline framework; (b) at least one phase includes phosphorus and aluminum atoms as part of the crystalline framework; and (C) One phase in the composition of the composite exhibits distinct heterogeneity with respect to the other phases. In a preferred practice of the invention, the multiphase composite contains at least 50% by weight of the multiphase composite (different crystalline compositions, preferably molecular sieve compositions, as phases, and at least one phase is different from the other phase). is a particulate composition containing (formed by crystal growth in the presence of) The characteristics of the multiphase composite are as follows.

(a) the different phases are continuous and have a common crystalline framework; Φ) at least one phase contains phosphorus and aluminum atoms as part of the crystalline framework; and (C) the composite. One phase in the composition exhibits distinct heterogeneity with respect to the other phases.

The remaining components of the particulate composition are independent particles made from molecular sieves having the same framework structure and composition as one phase of the composite. The multiphase composites of the present invention can be defined in several ways. For example, the multiphase composite may contain different inorganic crystalline compositions (preferably molecular sieve compositions) as phases, at least one phase containing an attached substrate and another phase as an external phase on said substrate. It is attached or multiphase is formed jointly, and its characteristics are as follows.

(a) the different phases are continuous and have a common crystalline framework; (b) at least one phase contains phosphorus and aluminum atoms as part of the crystalline framework; and (C) an attached substrate. The phase containing or one of the phases jointly formed constitutes the attachment substrate and contains at least about 20% by weight of the total weight of the composite-forming phase.

The mainstream of gasoline production in the United States is the fluid catalytic cracking method. This process is generally carried out by contacting the catalyst with a feedstock (typically vacuum gas oil) and circulating it through the ascending reaction section of the cracker. The temperature in the riser reactor is approximately 500°C (932°F
). This reaction completes in a few seconds. Thus, by the time the feed and catalyst reach reactor temperature, the reaction is complete. The catalyst is separated from the product stream in a stripper and sent to a regenerator. In this regenerator, air and steam are used to regenerate about 760% of the catalyst.
Heat to 1400°F (°C). The regenerated catalyst is then reintroduced into the reaction feed stream. These decomposition reactions produce the following products.

Gasoline, light circulation oil, heavy circulation oil, coke and gas, gasoline accounts for about 60 volume% of the product, light circulation oil accounts for about 20 volume 1%, heavy circulation oil accounts for about IO volume %, about 4-6 Juyo% is coke and the rest is gas. The selectivity of this process is measured by the yield of gasoline or gunlin and light circulating oil obtained from the feed (vacuum gas oil) used as reactant. All currently used FCC catalysts contain zeolite as an essential cracking catalyst. Approximately 98% of these zeolites are of the zeolite-Y type. Zeolite-Y has a fajasite crystal framework structure. This material is an aluminosilicate obtained by ice crystallizing aluminate and silicate raw materials. The preparation and performance of this material are described in the aforementioned Rabo chapter 11, pages 615-664.

Some commercially available FCCY-type zeolites contain significant amounts of calcined rare earth oxides, up to about 18% by weight or more. These substances are known by the acronym r CREY J. Another particularly preferred cracking catalyst includes stabilized Y, known as USY or Y-82.

In this catalytic process, the catalyst is typically treated in a regenerator with large amounts of steam at temperatures above 760° C., typically in the presence of air. The temperature within the regenerator is much higher than the temperature within the reactor.

The purpose of this treatment with gas and air is to burn off the coke deposited during the decomposition reaction stage and promote catalyst regeneration.

In order to effectively remove coke from a catalyst, the catalyst must have excellent thermal and hydrothermal stability. Performing the process under such harsh conditions requires extremely strong compositions. The lifetime of these catalysts is
It is often v13-6 months.

A very important issue in the FCC process is the residence time in the reactor and the tortuous diffusion present in the zeolite microcrystals of 1-5μ, pore size of about 8 people. This decomposition process is carried out at high temperatures in the presence of acidic microcrystals of the catalyst (zeolite 1-Y). If the reactants are in contact with the catalyst or present in the catalyst for too long, undesirable secondary reactions can occur as described above, producing undesirable by-products such as coke and gases, and gasoline The octane rating is also affected. The tortuous diffusion of the feed and reaction products through the catalyst crystal increases the contact time of the large fractions of molecules present, thereby increasing the space velocity dependent capacity by which the engineer determines the residence time. It will drop. Because of this sensitivity to catalyst activity, the overall ability of a catalyst to selectively produce gasoline products is a function of process conditions such as catalyst acidity and residence time, and catalyst to oil ratio. It can only be determined partially. Some catalysts, by their nature, produce more coke, while others produce more gas. The effect of tortuosity diffusion on results needs to be considered in conjunction with process conditions.

Recently, octane number has emerged as an important issue in gasoline production. With the advent of unleaded gasoline as a result of regulations in the United States, it is considered desirable to increase the octane number of gasoline as high as possible in the FCC process.

In the United States, large amounts of FCC gasoline are blended to increase the octane number. According to a recent study, FCC accounts for about 35% of the gasoline produced in the United States. F
The octane rating of CC gasoline is approximately 86.5-87.5, while the octane rating of the US gasoline octane pool is approximately 85.9. This difference in octane ratings is quite large. This fact indicates that FCC gasoline is extremely useful in increasing the octane number of other low octane gasoline sources. Refining processes such as reforming, isomerization, alkylation, and FCC are required to achieve lead phase removal as mandated by the EPA and to increase the U.S. gasoline octane pool number above 88 as required by the auto industry. There is a need to make extensive use of components that can increase the octane number of the gasoline produced by the process.

The octane-enhancing FCC catalyst currently in use is Y-zeolite (rUSY).

It is a catalyst that contains USY or US-Y is an acronym for ultra-stable Y. The properties of these catalysts and their preparation are described in the aforementioned Rabo Nos. 102.164.249 and 318-32.
It is listed on page 9. The performance of USY can be improved by using calcined tongue Y (CRE), a more widely used gasoline catalyst.
Y) Compared to zeolite, USY not only has the effect of increasing the octane number but also has the effect of reducing the amount of coke produced. However, from the perspective of gasoline selectivity, USY is CR
It seems to be less effective than EY.

A decrease in gasoline selectivity (yield) often results in an increase in gas production (compared to liquid).

Furthermore, although USY is based on a catalyst that is rapidly deactivated in steam, contact between the FCC catalyst and steam is unavoidable in the gasoline manufacturing process. Therefore, the activity of SY falls below that of the CREY catalyst within a short period of time. If the uSY concentration in the catalyst is increased, US
Although the activity of Y can be improved, this increases cost and reduces the attrition resistance of the catalyst. An alternative is to use small quantities on the tongue through cation exchange, but the gasoline produced using the catalyst thus obtained has a low octane number.

The USY catalyst can produce gasoline that is rich in olefins and has a slightly lower content of aromatic compounds, so it is suitable for CRE.
Superior to Y catalyst. The higher the content of olefins, the higher the octane number. As the olefinicity increases, the concentration of acidic sites decreases, and the polarity of USY zeolite used in FCC decreases. the result,
Hydrogen transfer activity is reduced compared to CREY-based catalysts. As shown in the equation below, olefins are consumed by hydrogen transfer to produce paraffins and aromatics.

3-year-old lefin + 1 + phthene → 3 paraffin + 1 aromatic compound Although olefins and aromatics are both high-octane gasoline components, one molecule of aromatic compound is produced from three olefins, so this hydrogen transfer reaction substantially converts octane into will be lost. The CREY-containing catalyst has the highest acid site concentration as well as reactant concentration under the FCC environment and therefore has a higher H-shift rate. F.C.
As a result of prolonged exposure to C conditions, the steamed USY converts to a zeolite molecular sieve product with very low acid site concentration as well as reaction@IJ concentration. Thus, since the USY FCC catalyst does not have secondary hydride shift activity, it is possible to produce gasoline with a higher olefinicity and higher octane number than when using a CREY-containing catalyst. Unified Principles of Rabor Zeolite Chemistry and Catalysis J, Catal, Rev.

See Sci, Eng., No. 23 (l and 2), pp. 293-313 (1981).

USY-containing catalysts produce higher octane crude gasoline, but yields are lower due to increased secondary cracking activity. CREY-containing catalysts, on the other hand, produce high yields of gasoline, but with lower octane numbers due to another secondary reaction, hydrogen transfer.

Recently, additive technology has been developed for the purpose of increasing the octane number of gasoline. Examples of such techniques are described in US Pat. Nos. 4,309,279, 4,309,280 and 4,289,606. These patent specifications include ZS? A method is described for increasing the octane number of the resulting gasoline by adding an octane number increasing additive such as 1-5 to the FCC process. This addition @JZSFI-5 removes low octane gasoline components such as paraffins from the gasoline mixture by cracking these components into gases. Using this method, you can obtain gasoline with a high octane number,
Its yield is low.

US Pat. No. 4,309,279 describes the use of octane raising catalysts in FCC operations. The FCC process described therein and the octane elevating process using an octane elevating catalyst are incorporated herein by reference.

U.S. Patent No. 4,51, granted April 23, 1985.
No. 2,875 discloses hydrocarbon cracking of a physical mixture of non-zeolite eight IPO, silicalite and SAPO in combination with a conventional zeolite catalyst to transform a crude oil feed containing certain hydrocarbon cracking compounds. Use in the process is described. Co-pending Application No. 675.283 (co-designated), filed November 27, 1984, is directed to the use of SAPO molecular sieves as catalysts for the cracking of crude oil feeds. Co-pending Application No. 675.279 (joint designation) filed on November 27, 1984 is filed under S.
The present invention relates to the use of a mixture of APO molecular sieve and zeolite aluminosilicate molecular sieve as a catalyst for increasing the octane number of gasoline by increasing the ratio of side-chain olefins to linear olefins and isoparaffins to normal paraffins. December 18, 1984
Co-pending Application No. 682.946 (co-designated), filed on 1999, relates to the use of a mixture consisting of a SAPO molecular sieve, a hydrogenation catalyst, and, if desired, one or more conventional water-splitting catalysts. Such conventional water splitting catalysts include conventional zeolite aluminosilicates.

Co-pending Application No. 68 filed December 18, 1984
No. 3.246 (joint designation) is directed to a catalytic dewaxing and water dewaxing process in which a mixture of a conventional dewaxing catalyst containing a zeolite aluminosilicate and a SAPO molecular sieve catalyst is used. . The mixed catalysts shown in these co-pending applications are superior to conventional zeolite catalysts.

In the present invention, "octane number increase" refers to the use of a small amount of a specific added catalyst (hereinafter referred to as "octane number increase agent" or "octane number increase catalyst") in co-pending U.S. Patent Application No. 05
This is done by feeding a standard FCC catalyst containing a composite according to the invention of No. 8.259 or in combination with a novel FCC catalyst.

In other words, by adding another catalyst, an ``octane number increasing agent'' or an ``octane number increasing catalyst,'' to the gasoline formation step in the FCC process, a gasoline component that provides a higher octane number can be obtained at a higher yield.

Certain composites described in co-pending application Ser. It has been found that it can be used to increase As an active component of such an octane number raising catalyst, another comparable medium pore size NZMS deposited on the NZ main gate is mentioned.

The object of the present invention is to use medium pore size non-zeolitic molecular sieves (NZMS).
) and another non-zeolitic molecular sieve having a similar framework structure, a combination of the above octane number increasing catalyst and a catalytic cracking catalyst, and an increase in the octane degree of the resulting gasoline. The purpose of this invention is to provide a method for cracking petroleum fractions.

The present invention provides a method for catalytic cracking of petroleum in the presence of a petroleum cracking catalyst and an octane number raising catalyst, in which a blend (composite This invention relates to a petroleum catalytic cracking method characterized by using a petroleum catalytic cracking method.

The present invention uses a petroleum fraction as a petroleum cracking catalyst and a medium pore diameter NZ
The present invention relates to the cracking of such petroleum fractions by subjecting them to catalytic cracking conditions in the presence of an octane raising catalyst consisting of a combined formulation of MS and another non-zeolitic molecular sieve having a similar frame structure. In a highly preferred embodiment of the invention, a combination of medium pore size SAPO and another medium pore size NZMS having a similar 7-reme structure is used as the octane raising catalyst.

In a preferred embodiment, the amount of octane boosting catalyst incorporated is about 50% or less of the combined weight of the petroleum cracking catalyst and octane boosting catalyst.

In a highly preferred embodiment of the invention, the ultrastable YM is a fluid catalytic cracking (FCC) catalyst, such as a catalyst containing LZ-210, as well as a relatively small amount of medium-pore structure NZ.
MS and another NZ with similar frame medium pore size structure
The cracking is carried out by the FCC method using an octane-enhancing catalyst consisting of a combined MS formulation.

The present invention further relates to novel octane number raising catalysts and blends of these new octane number raising catalysts with FCC cracking catalysts.

The octane number increasing catalyst exhibits superior performance in terms of activity, selectivity and stability that exceeds conventional octane number increasing catalysts in the octane number increasing catalytic action which is the object of the present invention.

The purpose of petroleum catalytic cracking is to create more valuable and useful substances. As mentioned above, FCC is one of the superior gasoline production methods. However, from a commercial standpoint, there is a strong demand for cracking to obtain the highest octane level, but the economic benefits are lost or reduced due to lower gasoline yields. , there is little benefit from increasing the octane rating. This drawback is explained in the US patent specification! No. 4,309,279 (see column 2, lines 12 to 18). In the above patent, ZSM-5
Zeolite molecular sieves are used as shape-selective octane number raising catalysts. Examples in the above patent specification state that the use of an octane increasing catalyst reduces C5 gasoline yield. These yield losses are offset by an increase in "potential alkylate yield." The economic benefits of using ZSM-5 as an octane raising catalyst will then be realized through downstream processing.

An object of the present invention is to provide a cracking method for cracking petroleum fractions into fractions with lower boiling points while preventing or minimizing a decrease in the yield of low-boiling fractions. More specifically, the present invention provides a cracking method that minimizes the decrease in gasoline yield, increases the octane number, and produces nine-gum lin by using a combination of the above-mentioned petroleum cracking catalyst and the selected blended catalyst according to the present invention. The purpose is to provide a method. Therefore, the octane number can be increased without reducing the gasoline yield as described in US Pat. No. 4,309,279.

More broadly stated, the invention subjects a petroleum fraction to catalytic cracking conditions in the presence of a catalytic cracking catalyst as well as an octane number raising catalyst according to the invention! The purpose of this invention is to provide a petroleum cracking method for cracking petroleum fractions into lower boiling fractions. As the catalytic cracking catalyst, any catalytic cracking catalyst known in the art and the catalytic cracking catalyst disclosed in the presently filed and co-pending US Patent Application Serial No. 058,275 can be used. Representative examples of suitable decomposition catalysts are shown below. AgX, AgY.

AJHY, BaX, BaY, Be-Y
, Ca-germanium near-phojasite (Ca-ge
rman4c near-faujasite), C
a -HX r Ca -X r Ca -Y, C
dX * CdY r CeY+ CoX.

CoY r CrYa C5Xa CsY+ Cu-X
5 Cu-Y, diethylammonium Y, ethylammonium Y.

Fe X, Fe-Y, IAX group, IAY group,
IIAY tribe, HY, KX.

KY, La-X, La-Y, LiX, Li
Y, LZ-10, LZ-210.

MgHY, MgNaX and Y, MgNH4Y,
MgX, MgY.

MnXa MnY+ Na-Kermanium near-phojasite.

Na-X, Na-Y, NH4-germanium near phosphorescence t NH4x, NH4y, N1-X*
N1-Ya dilute tank top, tank top Y.

RbX, RhY, SrX, SrY, vapor stabilized or ultrastable Y.

Tetramethylammonium Y, triethylammonium Y,
10゜Na-Y, NH4X, NH4Y, tank top X, rare earth Y, CREY steam stabilized or ultra-stable Y,
X, Y, Y-62 and Y-82 are mentioned. Consists of composite materials. In its most preferred embodiment, the present invention has a medium pore structure S
It consists of a composite in which APO is deposited as an external phase on a microporous crystalline molecular sieve having a similar framework structure.

The present invention provides that medium-pore structure NZMS (particularly SAPO molecular sieves) together with micro-pore size inorganic materials of equivalent structure (including the NZMS shown in Table A of the co-pending application filed on the same date as this application) This invention relates to an octane number increasing catalyst that utilizes a composite in the integral lattice association 2) state.

Note 2) The integral lattice association (ie, epitaxial matching) of the composite of the present invention is considered to include direct chemical bonding between the phases that make up the composite.

At present, other microporous inorganic materials with equivalent structures include NZMS (7) r-11J, r-31J, '
-40J and r-41J species, examples of which are as follows. AIPO411, SAPO11
, MeAPQ 11 (Me=Go, Fe, Mg,
Mn, Zn), MeAPSO-11 (Me=G
o+ Fe, ML Mr++ Zn), ELAPO
-11 (EL=As, Be.

a+ Cr, Gal t, i, v, Ti)l E
LAPSO-11 (EL=As.

Be, B, Cr, Gat Li+ V
tTi), AlPO4-40+ SAPO-
40, ELAPO-40 (EL-^s+ Be, a,
cr, Gal Lt.

V), ELAPO-40 (EL=As, Be, B
, Cr, Ga, Li.

V), AIPO,-31, SAPO-31, MeAP
SO-31(Me, =Co, Fe, Mg, Mn
+ Zn), ELAPO-31 (EL=As, Be
.

B, Cr, Ga, Li, V, Ti
), ELAPO-31 (EL=8s to BeB,
Cr, Ga, Li, V, Ti),
AlPO441, SAPO41MeAPO-41(
Me=Go, Fe, Mg, Mn, Zn), E
LAPO-41 (EL"As, Be, B, Cr,
Ga, Li, V) and ELAPSO41 (EL
-As, 8e+ Bt Cr, Ga, Lt+ V
) a These types of materials are hereinafter referred to as “medium pore size structure NZM”.
It's called SJ.

The active component of the octane number raising catalyst of the present invention should be (orientated) to an essentially crystalline composite structure. Although not departing from the scope of the decomposition process of the present invention, the crystalline materials described above are "crystalline" in the sense understood in the art and in the sense set forth below. The composite consists of multiple phases, at least one of which contains aluminum and phosphorous as part of the crystalline framework structure in the medium pore size structure NZ?IS.

Each phase of the composite is interconnected and integrated through crystal faces grown from other phases. This causes the crystal structure of these phases to become a composite with a heterogeneous chemical composition. In this sense, the framework structures of these phases are crystallographically common to each other. As I pointed out earlier, the phases of the composite are in a state of integral lattice association with each other. These phases appear to be interconnected by direct chemical bonds. The phases of the composites of the present invention are not mere formulations or physical mixtures held together by an adhesive created by a third component that cannot satisfy the crystallographic properties and epitaxial relationships in the composites of the present invention. In the most preferred practice of the invention, the composite is a shell (S
The core particles are surrounded by a shell or a mantle, and in the mantle, the core and shell constitute different phases that are arranged continuously with each other, and the crystal framework structure is based on material crystallography. are the same in a sense. In a preferred embodiment of the invention,
The shell or mantle is constituted by the medium-pore structure of the SAPO, while the core consists of a molecular sieve (a material that is inert from the point of view of the invention) with a different chemical composition that does not significantly inhibit the octane-raising effect of the medium-pore structure SAPO.

It is known that many of the advantages of NZMS as a catalyst are derived from the outer surface portion (mantle) of the sieve particles. When NZMS is used as a catalyst in a chemical reaction in which irreversible secondary reactions that generate by-products occur, most of the secondary reactions proceed in the external mantle, whereas the secondary reactions occur mostly within the core region of the molecular sieve particles. Proceed with This phenomenon is thought to be caused by tortuous diffusion when the adsorbate passes through the core of the molecular sieve particles.

This prolonged contact with the active catalyst will promote undesirable secondary reactions.

The efficiency or selectivity of a chemical reaction is determined by the ability of the catalyst to produce -secondary reaction products while irreversibly preventing or minimizing the production of second-order products in the reaction system. Secondary reaction products must therefore be considered as undesirable reaction products. It is an object of the present invention to provide a NZMS that increases the octane number of gasoline with increased efficiency or selectivity towards secondary reaction products and minimizes undesirable secondary reactions.

The present invention aims to improve the catalytic activity and/or
or provide selectively differentiated particulate composite products. The above objectives are achieved by selecting the composition of the phases of the composite as well as their location in the composite structure. If the phase forming the core of the composite is inert or less active than the outer phase (layer) of the composite, the reactants will be more active than if the entire particle had the same composition as the more active outer layer. The amount of secondary reaction products is reduced as a result of torsional diffraction relative to the core. As a result, selectivity increases.

The present invention is directed to the utilization of a single phase in a sufficient amount in a multiphase composite in which the heterogeneity of the various phases is preserved. Therefore, when one phase is used as an attachment substrate for another phase, the attachment substrate must be present in such an amount that it maintains its identity as a single phase in the final composite. That is, the phases constituting the composite are mutually heterogeneous in terms of composition, and compatible with each other in a topological sense. In the present invention, the above characteristics mean that the deposited substrate accounts for at least about 20% by weight of the total weight of the phases making up the composite. In other words, the expression "at least about 20% by weight" means that such attached substrate phase is present in an amount that may have an independent, heterogeneous compositional identity relative to other phases in the composite. means.

In the present invention, the composition of the gasoline fraction is changed by using the octane number increasing catalyst of the present invention in the second reaction to increase the amount of octane. Therefore, the efficiency or selectivity of chemical reactions that result in octane increases or octane increases is important because the efficiency or selectivity of the chemical reactions that result in octane increases is such that the -order reaction products are inhibited or minimized while preventing or minimizing secondary reactions, which tend to be at odds with the economic benefits of octane increases. Determined by the ability of the catalyst to produce. Therefore, secondary reaction products such as coke and gas must be considered as undesirable side reaction products. The purpose of the present invention is to increase the octane number of the gasoline obtained by increasing the production efficiency or selectivity of secondary reaction products, and to prevent the formation of secondary reaction products that have negative effects such as a decrease in gasoline yield. The purpose of the present invention is to provide a catalyst for increasing the octane number and a method for using the same.

Crystalline molecular sieves, either zeolites or NZMS, take the form of small crystals with diameters from about 0.1 μ (0.4Xl0-5 inches) to about 75 μ (0.003 inches), usually from 0.1 to 10 μ . For both molecular sieves, the diameter distribution is within a range of approximately lOμ. Crystalline molecular sieves are not spherical and can vary from regular to irregular structures in most crystals. Often formed as part of crystalline aggregates. In this specification, the cross section of a molecular sieve will be explained using the diameter of a sphere. This diameter is a nominal value indicating the difference in size between individual crystals, not crystal aggregates.

The present invention also includes an octane raising catalyst containing a heterogeneous mixture having the following characteristics.

(A) In a multicomponent, multiphase composite consisting of different inorganic crystalline molecular sieve compositions, in which at least one phase has grown by crystal growth in the presence of the other, (a) the different phases are continuous with each other; (b) at least one phase contains phosphorus and aluminum atoms as part of the crystalline framework; (C) each phase of the composite is distinct from the other; exhibiting compositional heterogeneity; (d) one phase (preferably an outer layer or a mantle phase);
contains medium pore size NZMS (preferably SAPO).

(B) Chairs that are arranged so continuously and do not have the same crystalline framework structure as the multi-composition multi-phase composite (A), but are connected to the multi-composition multi-phase composite (8). Inorganic crystalline composition.

(C) Amorphous composition combined with (A) multicomponent multiphase composite proboscis.

The heterogeneous mixture described above may contain an amorphous catalyst matrix that renders the mixture a shape and size suitable for catalytic cracking processes.

As previously indicated, it is desirable that the medium pore structure NZMS constitute the outer layer or mantle of the composite. The medium pore size NZMS used for the core of the composite can be arbitrarily selected as long as it has a crystallographically common medium pore size structure with the medium pore size NZMS phase used. At present, there is no known synthetic zeolite molecular sieve having a framework micropore crystal structure compatible with or equivalent to the medium pore size NZMS, so it is necessary to use the medium pore size NZMS for the other phases of the composite. It is desirable to manufacture the core of the composite with a material of lower catalytic activity, such as AIPO, especially one with a framework compatible with molecular sieves that is inert to octane raising catalysts. As a particularly desirable phase composition, AIP
O, -11, -31, -41 and -40 are mentioned.

These manufacturing methods are described in U.S. Patent No. 4.31 (No. 1,440 and No.
U.S. Patent Application No. 880 filed June 30, 986
．． It is described in the specification of No. 059. For example, Patent Specifications Examples 32-36 described above describe patent X-ray powder diffraction patterns of AlPO4-11 containing at least the d-spacings shown in Table 9 below.

Table F Other useful AIPOs, as well as other medium pore size NZMS are:
mentioned above. AlPO4-31 is taught in US Pat. No. 4,310,440, Example 54. AIPO,-41 is also taught in concurrently assigned U.S. patent application Ser. No. 880,059, filed June 30, 1986.

In characterizing the various phases of the composites of the present invention, reference is made to specific chemical compositions known in the art. This is because phases using existing chemical compositions as starting materials or manufacturing methods (see SAPO-11) may have such known chemical compositions.

This does not mean that the chemical composition of the phase is identical in all these characteristics; the phase may be manufactured using an existing composition as a starting material or using a method intended to produce a known composition. However, it is believed that the phase in the resulting composite of the invention will have a chemical composition that is substantially different from either the starting material or the target material of the process.

These differences in chemical composition are not due to changes in crystal structure, but are due to the chemical composition at the phase interface. This is due to the substantial ionic mobility of specially structured cations in the manufacturing process of molecular sieves. This results in a significant amount of ion transfer due to ion exchange. Such ion migration tends to occur when one composition is deposited onto another composition of different chemical composition, as is the case with the present invention. One phase (composition 171)
In the process of adhering to another phase, the other phase redissolves and chemically bonds with the composition of the phase at the interface portion that ostensibly belongs to the phase that serves as the adhesion substrate. Since such a phenomenon occurs at the atomic level, the degree of change in composition is extremely small, and it is thought that it does not cause a large change in the composition of any phase. The reason for this is that, in typical cases, the adhering substrate occupies a considerable portion of the entire composite. As a result, in this composite, no major compositional changes in the framework structure detectable by magnetic resonance (NMR) are observed in the chemical composition of either phase. If such a change were to occur, the crystal structure would be predictable and consistent with the crystal structure of the phase. However, the extent of compositional changes and the manner in which compositional changes occur are unknown.

For example, the SAPO-31 or SAPO-11 phase in the compositions of the present invention may be
SA produced according to Examples 51-53 of the specification
PO-31 or SAPO-1 made according to U.S. Pat. No. 4,440,871 Examples 16-22
It is thought that it is not exactly the same as 1. This is because, in the composite according to the invention, these compositions are in contact with other molecular sieve compositions at the interface.

It is contemplated that the deposition of one phase onto another in the composites of the present invention will take the form of a layer being deposited directly onto the surface of the other phase. In such expressions, the deposited layer is referred to herein as the "outer layer," while the substrate phase that provides the deposition surface is referred to as the "deposition substrate." Even when three or more types of phases are present in the composite, the bonding relationship of the outer layer to the adhering substrate using this expression is as described above.

The crystal structure of the composite of the invention or any phase thereof is determined by standard analytical methods used in the art.

In the industry, X-ray powder diffraction analysis is often used to define new molecular sieves or to distinguish them from conventional ones. However, it should be noted that this method is not the only way to determine the crystal structure. In some cases, it is not possible to obtain an X-ray powder diffraction pattern that allows the crystal structure to be appropriately determined. In such a case, the structure is not necessarily non-crystalline. Other methods may also be used to reveal the existence of a crystal structure. Typically, several types of analytical means are used to determine the crystal structure, including X-ray powder diffraction analysis. Examples of such analytical means include electron diffraction analysis, molecular adsorption data, and adsorption isothermal analysis. Some of the phases used in the composites of the invention may not exhibit distinct X-ray spectroscopic diffraction patterns suitable for determination of crystal structure.

This is because by combining it with other techniques, it is possible to elucidate the properties of the crystal lattice of the phase. There are also cases where the crystal structure cannot be clearly determined even when several analytical methods are combined, but even in such cases, if signs of alignment are seen, it can be concluded that the structure is crystalline compared to a specific structure. think. Such a similar crystalline structure is also considered to be a crystal for the purpose and understanding of the present invention.

The phases of the composite used in the present invention are interrelated because they have an essentially common framework structure. This is true in all details except that the X-ray powder diffraction pattern of the multiphase composite (or the data underlying the pond crystallinity) is actually affected by changes in the size of the different framework cations. It means that they are essentially the same. It is acceptable for the X-ray diffraction patterns of each phase to be different, but even in such a case, it is necessary that such differences can be regarded as sufficient compatibility between the different structural frameworks from a crystallographic point of view. This means that each phase has a crystal structure that imitates each other when viewed from the frame structure topology.

The composites used in the present invention, compared to using a composition having a composition corresponding to one of the phases in the composites of the present invention alone, or using a formulation consisting of such a composition. has the following major advantages. In other words, excellent effects can be obtained by using this composite as a catalyst for increasing the octane number.

The advantages of the present invention are obtained when the outer layer is less than 80% by weight of the composite. In most cases, it is desirable for the outer layer to be less than about 60% by weight of the composite, and more preferably less than about 50% by weight. In most if not all cases, secondary reactions are less likely to occur when the weight of the outer layer is less than the weight of the composite molecular sieve. When the weight of the outer layer exceeds 80% by weight of the composite, the composite becomes 100%
It behaves as if it had the composition and structure of an outer layer, and when used as a catalyst, secondary reactions occur significantly. Such secondary reactions tend to decrease as the weight of the outer layer decreases.

In another version B of the invention, the attachment substrate comprises at least about 20% to about 99% by weight of the total weight of the composite.
Composites can be produced in which the phase forming the outer layer is from about 80% to about 1% by weight of the total weight of the composite. In a preferred embodiment of the invention, the attachment substrate is at least about 40% to about 99% by weight of the total weight of the composite. The phase forming the outer layer accounts for approximately 6% of the total weight of the composite.
Composites are produced that are 0% to about 1% by weight. More preferably, the composite is comprised of two phases, with the amount of attached substrate being about 50% to about 98% by weight of the total weight of the composite, and the outer layer comprising about 2% to about 50% by weight of the composite. occupy

In a typical case, the thickness of the outer layer (mantle) is
Less than the thickness of the deposited substrate layer. In typical cases, the weight of the outer layer is less than the weight of the deposited substrate, and the NZMS forming the outer layer preferably has a higher catalytic activity than that used in the deposited substrate. This is because, in typical cases, a medium-pore structure SAPO, which is generally highly active and stable, is selected for the outer layer. It is desirable to combine the pore structure A f PO with the catalytically active medium pore structure NZMS; in such cases, the outer layer consisting of the medium pore structure NZMS accounts for about 2 to about 50% by weight of the total weight of the composite. (Preferably!4+J2～
(approximately 40% by weight), with the remainder corresponding to the medium-pore structure Al
It is desirable to use a medium-pore structure NZMS with lower activity such as PO4.

In a preferred practice of the invention, the composite is small particles having an average cross-sectional diameter of about 0.2 to about 10 microns. Preferably, the particles also include an inner core region surrounded by one or more mantles.

When there are two or more types of mantle, one of them serves as the outer layer for the other mantles and the core.

In describing the invention herein, the internal mantle surrounding the core, as well as any other internal mantle present as appropriate, will be referred to as the core, as opposed to the mantle that exists outside of it.

Each mantle in contact with each other has a different chemical composition, and the mantle and core in contact with each other also have different chemical compositions. To achieve the objectives of the present invention, it is not necessary for the particles to be spherical in order to maintain the above-described core-mantle relationship. The core is a collection of particles surrounded by an outer layer.

Typically, the particles are polyhedral and may include dendrites and/or spherules. Also, ultimately,
The particles may be part of a particle aggregate.

The as-manufactured shape of typical medium pore structure composites is spherical. When used as an octane number raising catalyst, the composite may be used in the as-prepared spherical form or may be bonded together to form other forms. The shape of the catalyst is determined depending on the respective decomposition reaction in which the catalyst is used.

In the case of FCC catalysis, the composite can be used in its as-prepared form or it can be transformed into a more robust form by using binder-free methods or by using other components as binders. Various methods of changing the shape of particles are known in the art, such as fog drying, bonding via bonding rules, and the like. The catalyst is transformed into a form appropriate for the reactor or reaction mode. However, special effects can be obtained using the composite structure of the present invention. For example, rather than depositing an outer layer onto the attachment surface before bonding the composite with the bond, the attachment substrate may be formed into pellets, extrudates, etc. by a combination of spray drying or bond bonding. It is possible to hydrothermally crystallize the molded body containing the adhered substrate or surface in a preparation of the precursor forming the outer layer.

In this way, the outer layer is deposited on the attachment surface in the formation.

This method minimizes the amount of outer layer required for the composite/part molded product. In a preferred practice, the composite is made prior to forming the compact containing the composite.

The advantages of the present invention can be appreciated by recognizing that microporous molecular sieves have pores that extend throughout the crystal structure. Most of the catalyst surface area resides in these pores. This pore surface portion provides virtually all of the catalytic active sites. When the feedstock enters the interior of the catalyst, it travels through a labyrinth or tortuous path either as it is or as a reaction product generated in the catalyst. Meandering diffusion is an indication that sufficient contact time has been provided, and some of the secondary reaction products react with active sites on the surface of the catalyst pores to form lower molecular weight products. Problems with tortuous diffusion can be reduced by reducing the labyrinth of channels that most active catalysts have. As a result, the contact time within the most active sites in the catalyst can be controlled to minimize the occurrence of secondary reactions, thereby increasing selectivity to the product.

A particular advantage of the composite structures of the present invention is that the layer depth of a given phase in the composite provides a mechanism for controlling the catalytic functional properties of that phase. If the acidity is too high and this phase is highly active, the catalytic activity can be kept at a high level while minimizing the decomposition properties (eg, secondary reactions) due to high acidity. It is known that the decomposition type B of an acidic and therefore active catalyst depends on the residence time of the reactants in the catalyst. By depositing a small layer of the active phase onto a surface that is relatively inert to the reactants in contact with the outer layer, the contact time of the reactants with the catalyst (particularly its outer layer) can be controlled to improve the decomposition characteristics of the catalyst. Shorten it to the extent that it is the minimum.

For relatively new catalysts, the rate of decomposition of secondary reaction products to produce undesirable by-products is naturally lower than the rate of desired catalytic reaction. Otherwise, there is no point in using a catalyst. Reducing the thickness of the active catalyst layer also reduces the diffusion contact time in the active catalyst. This allows selection of catalysts that produce the desired reaction products and minimize the amount of secondary reaction products. The layered composite catalyst according to the present invention has the advantage that the activity of the outer layer can be adjusted according to the desired reaction and reaction product by adjusting the depth of the outer layer and controlling tortuosity diffusion. .

Another factor in the design of the composite catalyst according to the present invention is consideration of various reactions that may be affected by the catalyst. In the case of a reaction with a simple change as shown below, the selectivity regarding the amount and size of the -B outer layer is hardly limited, but as shown below, irreversible by-products (C)
For reactions in which k is formed, the undesirable by-products C
Therefore, it is preferable to limit the contact in the catalyst to the more active outer layer, so that K becomes the main reaction, and K2 and/or K2 is preferably kept to a minimum, even if it is unavoidable. Using such means, the catalytic action of these layered catalysts becomes more selective than in catalyst particles where the composition of the outer layer is the composition of the entire particle.

To control the catalytic performance of the octane boosting catalyst of the present invention in terms of gasoline product selectivity, the dimensions of the outer layer and its relationship to the deposition substrate can be adjusted to minimize coke and gas production. .

The composites used in the present invention can be prepared by hydrothermal crystallization of a reactive gel of a precursor to the crystal structure in the presence of a supporting surface for crystal growth.

A gel precursor is used depending on the desired structure.

For crystalline framework structures based on silicoaluminum and phosphorus, the precursors are typically the phosphate, aluminate and silicate compositions used in their manufacture. In fact, one of the features of the composite used in the present invention is that each phase can be manufactured by composition manufacturing methods known in the art. In utilizing the advantages of the present invention, it is generally not necessary to employ new methods of producing one phase in the presence of another phase.

A typical method for producing non-zeolitic molecular sieves based on aluminum and phosphorus is to prepare a reactive gel containing aluminum and phosphorus, and optionally other framework elements and an organic template, by preparing about 50% °C (122 °F) to approximately 250 °C (482 °C)
°F), preferably from about 100 °C (212 °F) to about 2
A synthetic method involves hydrothermal crystallization at a temperature of 25'C (437'F).

The optimum crystallization temperature is determined by composition and structure. A
IPO and SAPO are approximately 125°C (257'F
) It tends not to crystallize at temperatures below ). On the other hand, M
Some eAPOs readily crystallize at about 100°C (212°F).

The medium pore structure NZi'lS composition is a medium pore structure rQAPA which is an anhydrous based experimental chemical composition of the formula
Belongs to SOJ.

mR: (QwAlxPySiz)Oz (() where Q is an n-valently charged framework structure oxide unit rQo,'
at least one element present in the form j (wherein n is -3, -2, -1, 0 or +1); R is at least one organic templating agent present on the intracrystalline pore system; ; m is (QwAlxPySiz)Oz R per molecule
The molar amount of is from 0 to about 0.3; w
, x, y, z are QO□ +A10z −, pot” l5I, which exist as skeleton structural oxide units
In each mole fraction of OZ, Q is an element with an average rT-OJ open-0 of about 1.51 to about 2.06 in the tetrahedral oxide structure. Q is approximately 125Kca
It has a cation electronegativity of 1/Dulham atom to about 310 Kcal/Dulham atom. Also, Q is 298°K
"Q-0" of about 59 Kcal/Durham atom or more in
A stable Q-0-P, Q-0-AIAI or Q-0-Q bond can be formed in a crystalline three-dimensional oxide structure having bond dissociation properties.

Note 3) European Patent Application No. 0.159.624 Specification 8a
.

See pages 8b and 8C, rEL in verse, and explanation of "M".

Q in this specification is the same as these.

The range of the mole fraction is as follows.

W is 0 to 98 mol%; y is 1 to 99 mol%; X is 1 to 99 mol%; 2 is 0 to 98 mol%.

Q in the molecular sieve QAPSO in formula (I) is defined as at least one element capable of forming a framework tetrahedral oxide, including arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, Selected from magnesium, manganese, titanium, vanadium and zinc.

Further, in the present invention, Q may be a combination of a plurality of elements. In this case, this combination is QA
The mole fraction of Q component in the PSO structure is 1 to 99
The amount shall be within the range of %. Also, in equation (1), Q
It should be noted that there are cases where Si and Si are not present. In such a case, the above-mentioned AIPOa becomes the functional structure. If Z has a positive value, the functional structure is SAPO above. In other words, the term QAPSO does not necessarily mean that the elements Q and S (actually Si) are present; if Q is more than one element, the world of those elements is not included in this specification. The functional structure shall be determined by the above ELAPSO, ELAPO, MeAP.
O or MeAPSO structure. However, if a QAPSO molecular sieve in which Q is another element is invented, that molecular sieve is included in the present invention as suitable for carrying out the present invention.

The compositional structure of QAPSO is described in the patents and patent applications listed in Table A and in the report entitled "Aluminophosphate Molecular Sieves and the Periodic Table" by Flanigen et al., supra.

Medium-pore structured QAPSO compositions generally contain an active source of element Q (if required), silicon (if required), aluminum and phosphorus, and preferably an organic templating agent (i.e., preferably an element belonging to group VA of the periodic table). A reaction mixture containing a structural director (which is a compound) and/or optionally an alkali or other metal is synthesized by hydrothermal crystallization. The reaction mixture is generally placed in a sealed pressure vessel, preferably lined with an inert plastic material such as polytetrafluoroethylene, and heated, preferably under self-heating pressure, until crystals of the particular type of QAPSO product are obtained. , preferably from about 100°C (212°F) to about 225'C (43°C).
7°F), more preferably 100°C (212°F) to 200°C (424°F). The effective crystallization period is usually several hours to several weeks. Generally, the effective crystallization period is about 2 hours to about 30 days,
It also takes from 4 hours to about 20 days to obtain a variety of QAPSO products. The resulting product is recovered by any convenient method such as centrifugation or filtration.

When synthesizing the QAPSO composition used in the present invention, it is preferable to use a reaction mixture composition represented by the following molar ratio.

aR: (QwAIxPySiz)Oz:bHzO where R is an existing template agent capable of forming a 111 framework structure; and preferably an effective amount within the range of greater than O up to about 6; b is from O to about 50
a value of 0, preferably from about 2 to about 300;
Q is as mentioned above.

5ioz, Aloz- and PO□゛ is at least one element capable of forming a framework structure-11 oxide unit with the tetrahedral oxide unit; n is a numerical value of -3, -2, -1, 0 or +1; ; w, x, y, and z shall be defined previously.

In the description of the reaction composition above, it is standard that the sum of w, x, y and 2 is w + x + y + z = 1.00 mol, while in the example in the reaction mixture:
The molar oxide ratio is based on the mole of P2O. To convert the latter to the former, simply divide the number of moles of each component, including template and water, by the total number of moles of Q, aluminum, phosphorous, and silicon elements to obtain the standard moles based on the total molar dispersion of the aforementioned components. All you have to do is calculate the fraction.

Preferably, an organic templating agent is used to prepare the reaction mixture for producing medium-pore structure QAPSO molecular sieves. The organic templating agent can be any known material used in conventional zeolite aluminosilicate synthesis. In either case, however, the template is a material taught in the art to produce the desired QAPSO. Generally, these compounds contain elements of group VA of the periodic table, especially nitrogen, phosphorus, arsenic, and antimony. Nitrogen or phosphorus is preferred, nitrogen being most preferred. These compounds have a small amount (
and one alkyl group or aryl group (carbon number L ~
8). Particularly preferred compounds as template agents include amines, quaternary phosphoniums, and quaternary ammonium compounds. Quaternary phosphonium and quaternary ammonium are represented by the general formula R,X'.

In the formula, X is nitrogen or phosphorus, and each R is 1
It is an alkyl or aryl group having from 5 to 8 carbon atoms. Polymeric quaternary ammonium salts of the following formula are also suitable for the above use: ((CzHzJz)(OH)z) x where X has a value of 2 or more. Mono-, di-, and triamines may also be used alone or in combination with quaternary ammonium compounds or other template compounds. By using a mixture of two or more templating agents, a desired mixture of QAPSOs may be obtained, or the more active templating agent may control the others in the reaction process and primarily determine the pH conditions of the reaction gel. In some cases, it may have the effect of In most cases, the initial gel pH value is slightly acidic, allowing elements in the form of hydrolyzable metal ions to easily enter the framework structure.
It is also less likely to precipitate as an apparent hydroxide or oxide. Representative examples of template agents are shown below. Ammonium ions such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium and tetrapentylammonium, as well as di-n-propylamine, tripropylamine, triethylamine, triethanolamine, piperidine, cyclohexylamine, 2-methyl pyridine,
N,N-dimethylbenzylamine, N,N-dimethylethanolamine, choline, N,N'-tumethylpiperazine, 1,4-diazabicyclo(2,2,2)octane,
N-methylgetanolamine, N-methylethanolamine, N-methylpiperidine, 3-methylpiperidine, N-methylcyclohexylamine, 3-methylpyridine, 4-methylpyridine, quinacridine, NN'-dimethyl-1,4- Diazabicyclo(2゜2.2)octane, di-n-butylamine, neopentylamine, di-n
- Amines such as pentylamine, isopropylamine, L-butylamine, ethylenediamine, diethylenetriamine, triethylenetetraamine, pyrrolidine, and 2-imidazolitone. Not all templating agents direct the formation of all species 1QAPso. That is, by appropriately adjusting the experimental conditions, several types of QAPSO compositions can be formed from one template agent. Also, several different templating agents can be used to produce a given QAPSO composition.

In the report entitled "Aluminophosphate molecular sieves and the periodic table" mentioned above, Flanigen et al. make the following conclusions.

"The organic template appears to play a crucial role in determining the structure. As the crystal grows,
The template fits into the structural cavity or is included. More than 85 amines and quaternary ammonium compounds, including primary amines, secondary amines, tertiary amines, and cyclic amines, have been used for growth purposes as crystallization templates. The degree of template structural specificity varies from the crystallization of AlPO4-5 with 23 types of templates to the crystallization of AI with only one type of template.
+71 Table 6 summarizes typical templates that form the main structures, ranging from the formation of PO, -20, and provides a good explanation of how one template forms multiple structures. (di-n-propylamine forms each structure of 11, 31, 41, 46)
. Also temperature, template concentration, gel oxide composition, pF
(We attempted to control the structure by varying other synthesis conditions, such as the value of
It shows a stoichiometrically neat space-filling structure as seen in and -11.

Table 6 Structure and Template Relationship The role of the templating agent described above is characteristic of the general role of templating agents for the production of other QAPSOl.

Silicon sources include silica [silica sols or humed silica 1, reactive solid amorphous precipitated silicas, silica gels, silicon alkoxides, silica-containing clays, silicic acids, alkali metal silicates and mixtures thereof.

The best phosphorus source for aluminophosphates known so far is phosphoric acid, but organic phosphates such as triethyl phosphate are also effective, as well as the AI! Crystalline or amorphous aluminophosphates such as , PO, etc. are also effective. Staged phosphorus compounds such as tetrabutylphosphonium bromide do not appear to be effective as sources of reactive phosphorus. However, these compounds act as template agents.

Conventional phosphorus salts such as sodium metaphosphate can be used as at least part of the phosphorus source, but are not preferred.

Preferred as aluminum are either aluminum alkoxides such as aluminum isopropoxide or pseudo-boehmite. Crystalline or amorphous aluminophosphate, which is preferred as a source of phosphorus, is naturally also preferred as a source of aluminum. Other aluminum sources used in zeolite synthesis such as gibbsits, aluminum-containing clays, sodium aluminate and aluminum trichloride may be used, but are not preferred.

Element Q can be introduced into the reaction system in any form that can take an elemental reaction form in situ (that is, can form a skeleton structure oxide of element Q). Non-limiting examples of elemental compounds that can be used are shown below. Oxides, hydroxides, alkoxides, nitrates, sulfates, halides, carboxylates and mixtures thereof.

Some representative compounds are specially mentioned below. Arsenic and beryllium carboxylates, large aqueous phase cobalt chloride, α-
Cobalt iodide, cobaltous sulfate, cobalt acetate, cobaltous bromide, cobaltous chloride, boron alkoxide, chromium acetate, gallium alkoxide, zinc acetate, zinc bromide, zinc formate, zinc iodide, zinc sulfate , heptahydrate, germanium dioxide, iron acetate (■), lithium acetate, magnesium acetate, magnesium bromide, magnesium chloride, magnesium iodide, magnesium nitrate, magnesium sulfate, manganese acetate, manganese bromide, manganese sulfate, tetrachloride Titanium, titanium carboxylate, titanium acetate, zinc acetate, etc.

After crystallization, the QAPSO-forming proboscis may be isolated, washed with water, and dried in air. QAP as synthesized
SO generally contains in its mesopore system at least one template agent used in its manufacture. However, in the case of boat fishing, this stepped portion derived from any existing template may be present, as is commonly seen in the case of as-synthesized aluminosilicate zeolites obtained by organic-containing reaction systems. Some of the organic moieties are present in the form of charge-balancing cations. However, in the case of certain QAPSOs, it is also possible that some or all of the organic moieties are occluded species. In principle, the template agent (and hence the occluded organic species) are too large to move freely within the pores of the QAPSO product;
It is necessary to remove the organic molecular species by heating and baking them at 200°C to 700°C to thermally decompose the organic molecular species. In some cases, the QAPSOm acid particles have a size that allows the migration of the templating agent (particularly when the templating agent molecules are small), and therefore in such cases it is difficult to The templating agent can be completely or partially removed by conventional deposition means. The expression "as synthesized" as used herein means that m is 0.0 in the following compositional formula.
It is to be understood that this does not include types of QAPSO in which the organic moieties present in the intracrystalline pore system as a result of the hydrothermal crystallization step are reduced by post-synthesis treatments, such as less than 2 be.

mR: (QwAl, PySiJOz In the formula, the pond symbol is as defined above. In these production methods, if an alkoxide is used as a source of element Q, aluminum, phosphorus and/or silicon, hydrolysis of the alkoxide The product, the corresponding alcohol, must necessarily be present in the reaction mixture.NZMS
As reported repeatedly in the patent literature, it is unclear whether this alcohol is involved as a templating agent in the synthesis process. However, for the purpose of this application, Even in the case where a substance is included in the template, it can be arbitrarily excluded from the scope of the template agent.

The medium-pore structure QAPSO composite oxide according to the present invention has net charges of -1, +1, o and n, respectively (where n is -
3, -2, -1, 0 or +1), POz'', Sing and qO2r'
Bone Mi structure is formed from oxidized proboscis units. Therefore, the cation exchange properties of this composition would ideally be AIO□
- Significant reconstitution compared to zeolite molecular sieves, where a stoichiometric relationship holds between tetrahedra and charge-balanced cations. In the composition of the invention, the AIQ□-tetrahedron is P
The electrical balance is maintained between either the O□′ tetrahedron or simple cation (alkali metal cation or proton), the cation of element Q present in the reaction mixture, or the organic cation derived from the templating agent. . Similarly, QO□′ oxides may be PO□° tetrahedra, simple cations such as alkali metal cations, gold EQO cations, organic cations derived from templating agents, or other divalent or polyvalent cations obtained from foreign sources. Maintains electrical balance with metal cations.

When QAPSO compositions are analyzed using ion exchange techniques commonly used for zeolite aluminosilicate, they show cation exchange capacity and also have unique pore sizes (
Approximately 3 to 8 people). Ion exchange of QAPSO compositions is usually possible as long as the organic moieties present as a result of the synthesis are removed from the pore system. Dehydration of the water present in the as-synthesized QAPSO generally does not remove the organic moieties (although it can be accomplished, at least to some extent, by conventional methods; however, in the absence of organic species, the adsorption-desorption process is significantly The hydrothermal and thermal stabilities of QAPSO rostrum range widely and some are quite remarkable.

The composites of the invention are further prepared by hydrothermal crystallization of one phase in the presence of another phase.

That is, the desired phase in the composite is formed by hydrothermal crystallization of the precursor in the presence of an adhering substrate that grooves other phases in the composite. In practicing the present invention, the deposited substrate is always fully formed (i.e., fully crystallized) 44! It doesn't have to be a commercial product. For example, when forming a molecular sieve structure, before the crystal structure is completely formed, a method is used in which hydrothermal crystallization is first performed, and this is used as an adhesion substrate and a precursor for outer JiW formation is added. I can also do things. In such cases, the attached substrate may be
It is expressed as being in a state of "GJ-n)". In some cases, the cations may be removed from the deposition substrate after the outer layer has been deposited onto the deposition substrate. The cations can thus be removed after the deposition is complete and the composite structure is formed.

In the composites used in the present invention, there need not be a sharp boundary between the framework composition of one phase and the other phase, either during the manufacturing process of the composite or in the final composite.

As pointed out earlier, deformation is often observed at the phase interface. In such cases, the interface appears to form an apparent third framework in a desired two-phase system, or an apparent fourth or fifth framework in a desired Mita system. It looks like there is. In fact, this transition from one tearbone structure composition to another looks like a gradient composition change that exists between phases. However, this gradient is essentially distinguishable around the interface from other phases having a mutually homogeneous composition.

In a broad sense, the compositional heterogeneity of the composite of the present invention is brought about by differences in the composition of each phase, the framework structure composition at the interface, and differences in the t-order interrelationships between the phases.

The ice packed crystallization conditions for synthesizing the composite are as described above with respect to the molecular sieve composition used in the hydrothermal crystallization phase. If a ready-made molecular sieve is used as a substrate for depositing aluminium- and phosphorus-based non-zeolitic molecular sieves, it is natural that the reactive aluminophosphate gel must be hydrothermally crystallized in the presence of the ready-made molecular sieve. does not mean that the phases obtained by this synthesis perfectly mimic the composition of the molecular sieve that is the object of the hydrothermal crystallization synthesis; each composition formed differs in details, and therefore at the interface Although the above-mentioned phenomenon is observed, it is thought that they have similarities to the extent that they are included in the characteristics of such molecular sieves. It is preferred that one of these phases, which functions as the adhesion substrate, has a fully formed crystal structure. The template may or may not be removed before contacting the composition with the components used for the formation of the other phases.The one-dimensional substrate is a support for the subsequently formed outer layer. , providing the basis for epitaxial growth. When one tear crystallizes in the presence of a pond crystalline phase, the resulting association can be used as a support to form another solid phase as well.

By repeating this operation a desired number of times or until a sufficient number of molecular sieves with different compositions but with the same crystal framework structure are formed, a composite having essentially the same crystal structure can be obtained. By this method, it is possible to produce a composite having different molecular sieves in overlapping layers of onions. Except in the case of the composites of the invention,
These skins are chemically bonded to each other. Blends of components of different molecular sieve compositions may be hydrothermally crystallized to form mixed phase compositions encompassed by the present invention. Typically, such composites are produced by hydrothermal crystallization of a molecular sieve formulation by contacting it with another (at least partially) ready-made crystalline molecular sieve of the appropriate crystal structure. .

The composite is believed to be formed by epitaxial growth of crystals on a deposited substrate. [It is possible that the attachment substrate may promote this growth. This is called the "seeding effect," but this is nothing compared to the role that the attached substrate plays in forming composites with unique and unexpected properties.1 Such growth A substrate support surface is obtained on which a layer of crystalline molecular sieves is attached.

This adherent molecular sieve layer is epitaxially bonded to the crystalline framework structure of the substrate surface by hydrothermal crystallization. In this way it is possible to obtain a core surrounded or enveloped by other molecular sieve layers, films or mantles. By producing a composite with multiple films deposited on top of each other on a core, it is also possible to obtain membranes with different exchange properties depending on the depth of the composite. Composites in which each layer undergoes a different catalytic action can have multipurpose catalytic deposition capabilities.

The following examples illustrate the use of the composites encompassed by the present invention as octane raising catalysts for the purpose of raising the octane number of gasoline produced by fluid catalytic cracking (Fcc). A very small amount of medium-pore structure composite (for example, medium-pore structure SAPO attached to medium-pore structure AlPO4 having a similar crystal type)
when used in combination with a conventional Y zeolite FCC catalyst or an Fcc catalyst based on other composites described in Co-pending Application No. 058.275.
The ability to increase the octane number of gasoline can be further increased.

These composites, in the form of unbound or bound particles,
There are many methods of combining with Fcc catalyst as described below.

In the production example for the purpose of producing a composite according to the present invention, a stainless steel vessel lined with polytetrafluoroethylene, an inert plastic material, is used to prevent contamination of the reaction mixture.

Generally, the final reaction mixture for crystallizing the composite is prepared by mixing all ingredients before adding the attachment substrate and then adding the attachment substrate. Alternatively, the attachment substrate may be placed in the reactor first, and then the components for the aqueous gel forming the outer layer may be added. Subsequently, hydrothermal crystallization is performed. There are conditions in which the components of one phase have different hydrothermal crystallization kinetics than the components of the pond phase. Under these circumstances, the components combine simultaneously and the difference in kinetics provides an attachment substrate for crystal growth. Each mixed component may retain its unique properties in the mixture, or some or all of the components may react to form new components. In both cases the term "mixture" is used. Also, unless otherwise specified, each intermediate mixture as well as the final mixture is stirred until substantially homogeneous.

As previously noted, the composites used in the present invention allow the adhesion substrate to function as a growth site for crystal formation.
It can be manufactured with good luck. This method is called "seeding". However, in the present invention, the use of an attachment substrate in the hydrothermal crystallization of the outer layer is not intended to promote crystal formation. Typically, the attached substrate forms the largest phase in the composite. The function of this phase as a composite phase is influenced by the ratio of its effects on the composition of the formulation. In other words, the larger the deposited substrate, the more selective the outer layer will be. This means that the attached substrate must be at least 5% of the weight of the composite.
This is evidenced by the fact that the octane boosting catalyst containing 0% by weight of medium pore structure NZMS shows higher selectivity.

There are many uses for the composites of the present invention as octane increase catalysts. A number of octane raising catalyst applications are described in U.S. Pat. No. 4,309,279;
No. 4,289,606 and the aforementioned U.S. patent application Ser. No. 675,279. In this specification, these methods are taken as reference.

In the simplest method of using the octane number increasing catalyst according to the present invention, the composite particles themselves are used as the octane number increasing catalyst, or they are externally or internally bonded to an Fcc catalyst or the like. If you use the particles themselves,
Simply add the desired amount of composite particles to the catalytic blender that can increase the octane number of gasoline. This method has problems due to the difference in size between the Fcc catalyst and the composite particles. When handling this formulation, be careful when transferring the formulation from the blender to other filling operations or when handling the Fcc.
Care must be taken to avoid unwanted separation of the composite particles and Fcc catalyst when feeding the unit. There are also different ways to do an inner or outer join. One such method involves the use of "wet" composite particles. The composite particles are moistened with distilled water, deionized water or petroleum feedstock prior to compounding with the Fcc catalyst. This causes the particles to stick together or adhere to the surface of the Fcc catalyst. Either case is preferable. However, when performing external coupling in this manner, it is necessary to carefully increase the amount of composite particles added to the Fcc catalyst already present in the blender and blender. In another method, unburned composite proboscis particles are added to the Fcc catalyst in a catalyst blend in a similar manner. Another method of adding composite particles to the Fee catalyst is to feed the composite particles to the riser of the cracker and draw the desired amount of particles from the feed stream into the cracking reaction. In the presence of unsuitable negative pressures that adversely affect the desired metering of composite particles into the decomposition reaction in the riser, it is possible to avoid Positive pressure is applied to feed the desired 1 composite particles into the riser and mixture with the Fcc catalyst.

In the slurry process described in U.S. Pat. Adjust the concentration to the desired level. This method is also suitable for obtaining the advantages of the present invention.

It is also widely practiced to "glue" composite particles together to form catalyst particles of the desired shape using methods known in the art, such as spray drying, extrusion, pelletization, and the like. According to the above-mentioned article, composite particles are blended with company rules (typical examples include substances that are inert to reactants and reaction products in catalytic reactions), and then spray-dried, pelletized, or It can also be formed into a desired shape by extrusion or other methods.

Although the shape of the composite according to the invention is not critical to the practice of the invention, it is important in certain Fcc operations.

Octane-enhancing catalyst pellets made from composite particles are typically a physical mixture of small composite particles and a silent oxidizing agent component.

As this inorganic oxide component, any substance commonly used in the production of catalysts can be used, examples of which are as follows. Amorphous inorganic oxide catalysts, i.e. silica-alumina or zeolites with catalytic activity, such as amorphous aluminum silicate or Y zeolite, clay silica, alumina, silica-alumina, silica-zirconia, silica-magnesia, alumina- boria, alumina
Titania etc. and mixtures thereof. Such composites are usually mixed with proprietary ingredients and then formed into the appropriate catalyst form.

The content of non-oxidizing components such as alumina, silica, clay, etc. in the final carp medium ranges from about 5 to about 99% by weight, based on the total weight of the catalyst, and from about 5 to about 95% by weight, based on the total weight of the catalyst. %
is preferred, and about 10 to about 85% by weight is more preferred.

The inorganic oxide matrix component takes the form of a sol, an aqueous sol, or a sol, and typical examples include alumina, silica, clay, and/or silica-alumina used in conventional silica-alumina catalysts. Ingredients include. Several seeds of these substances and compositions are commercially available. The corporate component may itself be catalytic or may be essentially inert. For example, company regulations may serve as a "binding agent." However, the final product, the octane number raising catalyst, may be spray dried or shaped using a method that does not require a binder. These materials may be prepared in the form of silica and alumina cogels, or may be alumina precipitated in preformed aged aqueous gels. Silica is present as a solid component in such gels in an amount of about 5 to about 40% by weight;
Preferably it is present from about 10 to about 30% by weight. or,
Silica may be used in the form of a cogel containing about 75% silica and about 25% alumina, or about 87% silica and about 13% alumina.

The alumina component may be thousands of individual particles of alumina, such as pseudo-bomite. The alumina component may be in the form of split particles;
BET)? Its total surface area, measured using B, is approximately 2
0 bo/g or more, preferably about 145 bo/g or more (
For example, about 145 to about 300 bo/g). Typically, the pore volume of the alumina component is greater than or equal to 0.35 cc/g. The average particle size of the alumina particles is generally less than ↓ 10μ,
Preferably less than 3μ. Alumina may be used alone or in combination with other constituents mentioned above, such as silica.

The alumina component is preferably made of alumina, which is caulked and has a stable surface area and pore structure. For some reason, when alumina is added to an impure inorganic gel containing significant amounts of residual soluble salts, these salts do not appreciably change the surface or pore properties, nor do they affect the ready-made material that is subject to modification. It also does not promote chemical changes in porous alumina.

For example, alumina may be used which has been produced by a chemical reaction, removed by slurry aging, filtering, drying, and washing to remove residual salts, and then heated to reduce the entrained components to about 15% by weight. It is also possible to produce an octane number increasing catalyst using an aqueous alumina sol or gel, or an aqueous alumina slurry.

The mixture of composite particles and inorganic particles is formed into the final form of the octane boosting catalyst using any suitable method commonly used in catalyst manufacturing such as spray drying, pelletizing, extrusion, etc. Such an octane number increasing catalyst is often manufactured by spray drying 2.

This method is well known in the art.

Next, a method for producing an octane number increasing catalyst from the composite of the present invention will be explained. Sodium silicate is reacted with aluminum sulfate solution to produce a silica/alumina water gel slurry. The resulting slurry is aged to achieve the desired pore characteristics, filtered to remove significant amounts of excess undesired sodium and sulfate ions, and then reslurried in water.

To produce alumina, sodium aluminum butt C solution and aluminum sulfate solution are reacted under suitable conditions, the slurry is aged to achieve the desired alumina pore characteristics, filtered and dried, and then washed in water. It is slurried again to remove sodium ions and sulfate ions, and dried to reduce the content of explosive components to less than 15% by weight. The alumina is then slurried in water and a suitable amount of the resulting slurry is combined with a slurry of impure silica-alumina aqueous gel. A composite molecular sieve is then added to this formulation. Each component is used in sufficient amounts to yield the desired final composition. The resulting mixture is then filtered to remove any remaining excess soluble salts, and the filtered mixture is dried to produce a dry solid. The dried solids are then reslurried in water and washed to remove virtually any undesirable soluble salts. This octane number raising catalyst is then dried to a residual moisture content of less than about 15% by weight.
After calcination, the octane number increasing catalyst is recovered.

The present invention also includes an octane number raising catalyst containing zeolite, clay-carbon oxidation promoter, etc. in addition to the composite component and the non-oxidizing component.

A representative example of company regulations used in the present invention is May 2, 1973.
British Patent Specification 1 1,315,553 and US Patent Nos. 3,446,727 and 4,086.
No. 187 specification. These specifications are included as references for the present invention.

Preferably, the composite particles themselves are used as an octane raising catalyst in combination with an FCC catalyst such as ultrastable Y or L Z-210 zeolite.

The type of octane boosting catalyst used in the FCC process depends on the desired effect and the performance of the octane boosting catalyst at different concentrations. As the amount of octane raising catalyst used increases, the octane number increases up to a certain point. The specific points above are determined by the octane raising catalyst selected.

Normally, an increase in the octane rating of gasoline will cause off Y to F
When used as a CC catalyst, the octane number increasing catalyst and FC
The octane number increase reaches its maximum value when the combined weight with C catalyst is about 5% by weight.

However, this does not limit the effective usage amount of the octane number increasing catalyst. Any amount of octane raising catalyst capable of raising the octane number of the gasoline over the FCC catalyst alone is desirable. In a preferred embodiment, an amount of octane raising catalyst is used that maximizes the octane number of the gasoline produced. After all, the octane number increasing catalyst is less than 50% by weight of the total weight of the octane number increasing catalyst and the FCC catalyst.

In a more typical example, the amount of octane boosting catalyst is about 20% by weight or less based on the total weight of the cracking catalyst and octane boosting catalyst included in the cracking reaction, and about 10% by weight or less, based on the total weight of the cracking catalyst and octane boosting catalyst included in the cracking reaction.
More preferably, it is less than or equal to about 7% by weight, and most preferably less than about 7% by weight. In a typical and most preferred practice, the FC
The amount of octane number increasing catalyst used in decomposition reactions such as C decomposition is about 5% by weight or less based on the above criteria. usually,
the amount of octane boosting catalyst present during the cracking reaction is at least about 0.1 weight percent of the total weight of the cracking catalyst, such as an FCC catalyst, and the octane boosting catalyst included in the cracking reaction;
Preferably it is at least about 0.5 weight percent, more preferably at least about 0.7 weight percent, and most preferably at least about 0.9 weight percent.

The conditions for carrying out the cracking reaction shall be those employed in the art for the cracking of petroleum fractions to low boilers. The reaction temperature is about 350°C (662'F) to about 700°C.
1300°F (1300°F), and the temperatures mentioned above are representative. Pressures for decomposition reactions range from vacuum to pressurization. Decomposition reactions can be performed in either batch or continuous systems. However, a continuous system is of course preferable.The catalytic cracking process may be performed in a fixed bed, moving bed or fluidized bed.The hydrocarbon feedstock may also be fed in the same direction as the conventional catalyst flow. It can also be in the opposite direction.

Hydrocarbon or petroleum feedstocks to be cracked according to the present invention are generally hydrocarbons and have an initial boiling point at atmospheric pressure of at least 200°C (390F) and a 50% point at atmospheric pressure of at least 260°C (500F). Yes, the end point at normal pressure is at least 300°C (5
70'F). Such hydrocarbon fractions include gas oils obtained by hydrogenating coal, shale oil, tar, pinch, asphalt, etc., residual oils, recirculating feeds, whole top crude (Wh).
ole top crude) and heavy hydrocarbon fractions. It should be noted that distillation of petroleum fractions with higher boiling points above about 400° C. (750° F.) at atmospheric pressure should be carried out in vacuum to avoid thermal decomposition.

The invention is further illustrated by the following non-limiting examples.

Example 1 a) 85% by weight of 40.45' in water at 133.2F
Add di-n to a solution of orthophosphoric acid (H3PO4)
- 17.7F of propylamine (DPA) and 18.42F of jetanolamine (DEA) were slowly added. The liquids were stirred until mixed and then cooled to ambient temperature. HiSiJ (precipitated silica, 5i
o2ss wt%, I (,012 wt%)4. Add El, followed by hydric alumina (pseudo-Boehmian lithology, Al2O).

70% by weight, H, 030% by weight). The resulting mixture was mixed and homogenized. The elemental composition of this mixture expressed in molar oxide ratio is as follows.

1. ODPA: 1. ODEA: 0.4Si
O□: Al, 0. : PtOs : 50H,0
b) as-synthesized AlPO with the following elemental composition,
-1148,45', 0.18DPA: AJ tOs: P205:
The mixture was gently ground using a pestle in a 0.8H20 milk needle, and then slurried in 100 g of water. This A
j! Pot-11 slurry was immediately added to mixture a). Another 232 g of water was reserved to completely transfer the entire amount of Agpo,-11 into the final mixture. The elemental composition of the final mixture expressed as molar oxide ratio was as follows.

0.6DPA: 0.5DEA: 0.2Si
02: Al2O3: P2O5: 45u.

The final mixture was placed in a stainless steel pressure tank equipped with a stirrer and heated to 175°C. The reaction mixture was heated to 175°C for 2
It was held for 4 hours and then cooled. 72 products
Let it settle for a while, then decant the supernatant mother liquor.

The solid was resuspended in fresh water and allowed to settle for 1 hour. The cloudy supernatant was decanted and collected by centrifugation. Further, the precipitated solid matter was collected by filtration.

C) The weight of the recovered product was as follows:

Solid obtained from supernatant 57.4P Sedimented solid 20.31 From the starting material AlPO, -1148,4f, 29. Other substances of '1 were also recovered. This fact suggested that the SAPO-11 outer layer was about 38% by weight composite structure. X-ray analysis of the above two product fractions revealed that the precipitated solids were pure 11-type (SAPO-11χ formulated on AIPO, -11) and were obtained from the supernatant of crucible 5. The recovered solids were mainly 11-type (Alpo
SAPO-41) and a trace amount of 1-41
It turns out that it contains a structure type.

d) A sample of the settled solid was calcined in air at 500° C. for 16 hours, and the above n-butane decomposition activity was examined. The K of this sample was 0.2.

e) The elemental composition of the precipitated solid sample expressed in weight percent was as follows.

AJI! ,0. 37.2 pro! 46.5 S i 0. 1.9 Carbon 5.3 Nitrogen 1.0 f) A sample of the settled solid was calcined in air at 600° C. for 3 hours. Adsorption capacity was measured using a standard McPayne-Baker gravimetric adsorption apparatus, followed by vacuum activation at 350°C. The results were as follows.

Table H Adsorbate Pressure (Torr) Temperature Weight % Oxygen 100 -183℃ 9.5〃
700 -183℃ 12
．． 4g) synthetic Axpo added to the initial reaction mixture, -
u and SAPO-11/Ajl! Particle size analysis was performed on the settled solids of the PO,-11 formulation. Al
The average particle size of pO,-11 is 3.5μ, and it is dust, and S A
The average particle size of the P 0 11/AlPO4-11 blend was 4.8μ.

Example 2 This example demonstrates the preparation of a formulation consisting of a SAPO-11 deposited outer layer encapsulating the deposited substrate AlPO,-11. 85% by weight orthophosphoric acid 101.22 and distilled water 79.5? and water-containing aluminum oxide (pseudo-boehmite phase, Al, 0.74.4% by weight, H,.

25.6% by weight) 69.8r was added under high speed stirring to create a homogeneous gel. This gel was mixed with Hineemdoclica (5i
o292.8% by weight, H2O7.2% by weight) 19.4?
A mixture containing was added. While thoroughly stirring the obtained silicoaluminophosphate gel, 101.2 f of di-n-propylamine was added.

The composition of this reaction mixture, expressed in terms of molar oxide ratio, is as follows.

2) ORr, NH: 05 (TBA), O: AJ
, o, : PzOa : 0.6S to, :
16.75H, 0:24.3CH, the total weight of the surrounding gel is about 6902, and its pH value is 9.4
Met. Divide this gel into 5 batches of about 137f each7
'C, 5 equivalents of uncalcined Agpo, -11 molecular sieves (85 in solids, 15 in water) were added to each batch of SAPO-11 gel (137r). Each batch was stirred to homogenize and transferred to a polytetrafluoroethylene lined pipe bomb (250 cc).

p of each batch of this newly formed adherent gel reaction mixture.
The H value C9,5) did not change much. These cylinders were placed in a pre-equalized oven at 200° C. and each was cooked at 2.4.6° for 24 hours. Two batches were cooked for 6 hours. In this way, five cylinders were subjected to cooking.

After the desired cooking time, each cylinder was removed from the open and allowed to cool to room temperature. The reaction mixture in each bomb was centrifuged to remove solids. This solid substance was dispersed in distilled water and centrifuged to remove unreacted substances.9. This washing step was repeated, and the washed solid material was recovered and dried at 100°C.

Analysis of the added Alpo<-11 and the resulting formulation revealed that it contained the following components on a solids basis.

Table Air AlPO4-11 SAPO-11/A11P04-11 SAPO-11/AlPO,-11 SAPO-11/AlPO,-11 SAPO-11/AlPO4-11 41,20,058B 2 hours 40.9 1258.4 4 hours 40.2 2.0 5836 hours 40.
1 2,13 57924 hours 385 4.6
It should be noted that as the 572 cooking time increases from 2 to 24 hours, the amount of 5i02 on the slit substrate increases (note that this fact is consistent with the silica-free Al
This corresponds to the deposition of the SAPO-11 outer layer on the PO4-11 deposited phase.

X-ray powder diffraction analysis of all products showed typical diffraction patterns for AlPO2-11 and SAPO-11.

Example 3 In this example, the 6-hour cooking S produced in Example 2 above was used.
AP O-11/AI! Y-82 molecular sieve “Standard” F mixed with 1% by weight of PO,-11 blend by physical method
This is a comparison between the CC decomposition catalyst and the Y-82 molecular sieve "standard JFCC decomposition catalyst" mixed with 4% by weight of SAPO-LL by physical method. of gasoline with 1% by weight SAP O-11/AIPO.

-11 alone, it was possible to obtain the same effect as when using 4% by weight of SAPO-11.

The standard catalyst was J60 containing 18% by weight Y-82, 62% by weight kaolin fur, and 20% by weight silica binder.
．． D: Extruded into pellets and dried overnight at 110°C. This catalyst τi. The powder was ground to 0.0 ml and calcined at 500° C. for 1 hour.

The octane number raising catalyst is SAP on a dry weight % basis.
O-11/A) po, -11 formulation and SAPO-1
Two copies were prepared by physically mixing 1 with Y-82 standard catalyst. Prior to mixing with Y-82, the formulation and S
Both APO-11 were fired at 550°C for 2 hours.

Each catalyst mixture was then steamed in 100% steam at 760°C and subjected to a microactivity test (M
AT) t-Done. Test conditions were in accordance with ASTM.

Table 5 shows the results of MAT and Ganlin analysis of these three catalysts. SAP O-11/AlPO4-1
1-containing catalyst has an octane number increasing substance content of SAPO
Despite being one-quarter the amount of -11-containing catalyst, it showed the same theoretical octane increase. The theoretical increase value is
The apparent increase in aromatic hydrocarbon concentration corresponded to approximately 2 units of theoretical ROM (weighted average octane number of all Ganlin components). All catalysts using SAPO showed a slight decrease in gasoline selectivity.

Table 5 MAT conversion (%) Gasoline selectivity (%) Dry gas yield (%) Coke yield (%) Theoretical ROM 63.6 75.4 5.2 2.7 89.5 63.7 74.9 5.4 6.6 Aromatic hydrocarbons 39.0 42fl
41.6 Paraffin 35
．． 5 341 321 Olefin
7.7 72 8.
4 naphthenes 12 yu 11 yu
12. Fiso/n-paraffin 8.
9 85 8B Ganrin selectivity = gasoline yield, 1L (%) / [conversion (%) XO, 1:
) Example 4 In this example, the SAPO-
11/AlPO4-11 blend octane number raising catalyst and S
This shows that when APO-11 was physically mixed into the Y-82 folding catalyst at an addition level of 1% by weight and subjected to calcination and steam treatment, the former was superior to the latter. . Y-82 touch fmUY-82 by 18%,
It contained 62% kaolin clay and 20% glue binder and was produced in the same manner as described in Example 3. The octane number increaser-containing catalysts were synthesized and SAP
O-11 and SAPO-11/AlPO4-11 blends on a 60/100 mesh Y-82 on an anhydrous basis.
It was produced by mixing with a catalyst and physical methods. These samples were fired at 1500°C in air for 1 hour and then steamed at 760°C or 790°C in 100% steam for 2 hours.

The table below shows 1% SAPO-11 and 1% SAPO-
11 shows MAT evaluation results for octane-enhancing FCC catalysts containing 11/AlPO4-11 blends. Figure 1 of the accompanying drawings shows the theoretical RO of the Ganlin product obtained using a catalyst physically mixed with SAPO-11 and Y-82.
Relationship between N value and MAT conversion (downward curve) and SAP O
11/kl The relationship between the theoretical RON value and MAT conversion (upper curve) of a gasoline product obtained by physically mixing an octane number raising catalyst consisting of a PO411 blend with Y-82 and using a nine catalyst is plotted on a graph. This is for comparison. After steam treatment, for SAPO-'11/AlPO4-11-containing catalysts, SAPO-11 at corresponding conversion
A product with a higher octane number was obtained, exceeding the theoretical RON value of the containing catalyst by 1 to 3 units. Ganrin selectivity and M
From the relationship with AT conversion, it can be seen that the RON value increases without decreasing gasoline selectivity. This result is also reflected in the attached drawing, Figure 2. Figure 2 shows SAPO-11
and SAPO-1t/AlpO,-11 blends with Y-
The relationship between gasoline selectivity and MAT conversion in both octane number increasing catalysts obtained by physically mixing with No. Additionally, the catalyst containing the above formulation also exhibits a much better octane number after FCC steam treatment compared to SAPO-11 itself.

K table MAT conversion 60B 59.9 548
632 octane 86.9 85.6
898 88.0 Ganrin selectivity 76.
0 76.0 772 75.0 Steam treatment temperature
760℃ 760℃ 7901: 760℃64.
6 90.5 75.4 760°C Example 5 This example shows the SA produced by the method described in Example 2.
PO-11/AA'PO,-11 blend (6 hours cooking)
The effect of ZSM-5 as an octane number increasing catalyst when mixed with Y-82 standard catalyst at an addition level of 1% by weight was investigated.
Y at an addition level of 3% by weight of zeolite molecular sieve equivalent to
This is for comparing the effect as an octane number increasing catalyst when mixed with -82 standard catalyst. The Y-82 standard catalyst to be mixed with both additives contained 1% Y-82, 62% kaolin clay and 20% silica binder, and was prepared according to Example 3 above. The octane number raising catalyst SAPO-11/AlPO,-11 blend and the zeolite molecular sieve equivalent to ZSM-5 are Y-8
Calcined at 550° C. for 2 hours on an anhydrous basis prior to physical mixing with 2 standard catalysts. All mixed catalysts were steamed in 100% steam at 790° C. for 2 hours and then subjected to the MAT test.

The table below shows the results of the MAT evaluation as well as the gasoline product analysis. Compared to the standard catalyst alone, both the 1% SAPO-11/AlPO,-11-containing catalyst and the 3% ZSM-5 type molecular sieve-containing catalyst
The theoretical ROM value increases substantially at comparable MAT conversion rates. The Z S M-5 type molecular sieve-containing catalyst had considerably reduced gasoline selectivity, but the S APO-11
/A71PO4-11-containing catalyst K No significant decrease was observed. This reduction resulted in an increase in undesirable gas production. Both catalysts containing warm substances showed an increase in the aromatic hydrocarbon content in Ganlin and a corresponding decrease in the paraffin concentration. The Tomodashi ZSM-5 type molecular sieve-containing catalyst showed an undesirable decrease in the in/n ratio in the paraffin fraction compared to the standard catalyst. This phenomenon was not observed in the case of the 5apO-11/AI PO4-11 containing catalyst.

From these results, SAPO-117A! IPO, -1
It has been found that the catalyst containing the puctan number increasing agent exhibits a ROM increasing effect comparable to that of the catalyst containing the ZSMS type molecular sieve, without undesirable reduction in gasoline selectivity.

L table MAT conversion (%) Gasoline selectivity (%) Dry gas yield (%) Coke yield (5i) Theoretical ROM value 59.7 71.1 92.6 J3 D 92 yu 75.5 4.6 88:3

[Brief explanation of the drawing]

Figure 1 shows that the octane number increasing catalyst of the present invention is different from that of conventional N2M.
This shows that it is superior to the S catalyst in terms of the relationship between octane number and MAT conversion. FIG. 2 shows that the octane number raising catalyst of the present invention and conventional NZMS have comparable Ganlin selectivity. Patent Ratio M Union, Carbide, Corporation Aromatic Hydrocarbon Paraffin Olefin Naphthene/n-Paraffin 40.6 0B 6.9 1i3 11.0 36 U35.0 9.1 Gasoline Selectivity = Gasoline Yield/[Conversion ( %)Xo, 1
) Octane Number vs. Conversion (06) Conversion*<”6) Gasoline Selectivity vs. Conversion $(%) F I G.

Claims (32)

[Claims] (1) In a method for cracking a petroleum fraction into substances with a lower boiling point by subjecting the petroleum fraction to catalytic cracking conditions in the presence of a petroleum cracking catalyst and an octane number raising catalyst, the octane number raising catalyst is a medium pore diameter An improved method characterized by using a composite that combines NZMS and another NZMS having a similar framework structure. (2) The method according to claim 1, wherein the cracking is carried out by a fluid catalytic cracking method. (3) The method according to claim 2, wherein the amount of the octane number increasing catalyst is 20% by weight or less of the combined weight of the petroleum cracking catalyst and the octane number increasing catalyst. (4) The method according to claim 3, wherein the amount of the octane number increasing catalyst is 10% by weight or less of the combined weight of the petroleum cracking catalyst and the octane number increasing catalyst. (5) The method according to claim 4, wherein the amount of the octane number increasing catalyst is 5% by weight or less of the combined weight of the petroleum cracking catalyst and the octane number increasing catalyst. (6) The method according to claim 5, wherein the amount of the octane number increasing catalyst is 3% by weight or less of the combined weight of the petroleum cracking catalyst and the octane number increasing catalyst. (7) In the method according to claims 1 to 6, one of the medium pore diameter NZMS is a medium pore diameter SAPO.
A method characterized by: (8) The method according to claim 7, wherein the medium pore diameter SAPO is SAPO-11. (9) The method according to claim 7, characterized in that the other non-zeolite molecular sieve having a similar framework structure has a medium pore size of AlPO_4. (10) The method according to claim 8, wherein the other non-zeolite molecular sieve having a similar framework structure is AlPO_4-11. (11) A petroleum catalyst composition comprising an octane number increasing catalyst which is a composite of a petroleum cracking catalyst and a medium-pore diameter NZMS and another NZMS having a similar framework structure. (12) The composition according to claim 11, wherein the petroleum cracking catalyst is an FCC catalyst. (13) The composition according to claim 12, wherein the FCC decomposition catalyst is a crystalline fine pore diameter Y zeolite molecular sieve. (14) The composition according to claim 13, wherein the Y zeolite is ultra-stable Y. (15) The composition according to claim 13, wherein the Y zeolite is LZ-210. (16) In the composition according to claims 11 to 15, the medium pore diameter NZMS is SAPO.
A composition characterized by: (17) The composition according to claim 16, wherein the medium pore diameter SAPO is SAPO-11. (18) The composition according to claims 11 to 17, characterized in that the other non-zeolite molecular sieve having a similar framework structure is a medium pore size AlPO_4. (19) The composition according to claim 17, wherein the other non-zeolite molecular sieve having a similar framework structure is AlPO_4-11. (20) The composition according to claims 11 to 19, characterized in that the amount of the octane number increasing catalyst is 20% by weight or less of the combined weight of the petroleum cracking catalyst and the octane number increasing catalyst. composition. (21) The composition according to claim 20, wherein the amount of the octane number increasing catalyst is 10% by weight or less of the combined weight of the petroleum cracking catalyst and the octane number increasing catalyst. (22) The composition according to claim 21, wherein the amount of the octane number increasing catalyst is 5% by weight or less of the combined weight of the petroleum cracking catalyst and the octane number increasing catalyst. (23) The composition according to claim 22, wherein the amount of the octane number increasing catalyst is 3% by weight or less based on the combined weight of the petroleum cracking catalyst and the octane number increasing catalyst. (24) The composition according to claims 20 to 23, wherein the petroleum cracking catalyst is a Y zeolite molecular sieve. (25) The composition according to claim 24, wherein the petroleum cracking catalyst is an ultra-stable Y zeolite molecular sieve. (26) The composition according to claim 11, wherein the petroleum cracking catalyst comprises LZ-10, LZ-210, Na
-Y, NH_4X, NH_4Y, Rare Earth X, Rare Earth Y, Steam Stabilized or Ultra Stable Y, X, Y, Y-62 and Y-
A composition selected from No. 82. (27) The composition according to claims 20 to 26, wherein at least one phase of the petroleum cracking catalyst is grown by crystal growth in the presence of another phase, and (a) ) each of the different phases has continuity and a common crystalline framework structure; (a) at least one phase has SAPO-11 composition and structure; and (c) the composite has A microporous crystalline multicomposition multiphase containing a multiphase composite with phases consisting of different inorganic micropore crystalline molecular sieve compositions; A composition comprising a composite granular composition. (28) LZ-210 and SAPO-11 and AlP
A petroleum catalytic cracking composition characterized by comprising a combination of a compound with O_4-11. (29) Ultrastable Y zeolite and SAPO-11
A petroleum catalytic cracking composition characterized by comprising a combination of a composite of and AlPO_4-11. (30) Rare earth Y zeolite and SAPO-11 and A
A composition for petroleum catalytic cracking, characterized by comprising a combination of a compound with lPO_4-11. (31) At least one phase has grown by crystal growth in the presence of another phase, and (a) each of the different phases has continuity and a common crystal framework structure; ) at least one phase has a SAPO-11 composition and structure; and (c) each phase in the composite exhibits a composition that is clearly different from each other; however, phases consisting of different inorganic micropore size crystalline molecular sieve compositions; An octane number increasing catalyst comprising a micropore-sized crystalline multi-composition multi-phase composite granular composition containing. (32) The octane number increasing catalyst according to claim 31, wherein the composite is SAPO-11 deposited on AlPO_4-11.