JPS63143940A - Fluid cracking catalyst - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cracking catalyst for 7i dynamic catalytic cracking for producing high octane gasoline.

Cracking catalysts using certain forms of faujasite Y-type zeolite can be used for fluid catalytic cracking (F
CC) process to produce high-octane gasoline. U.S. Patent No. 3,758,403, No. 3,
No. 894,931, No. 3.1 + No. 94,933, No. 4,
Nos. 309,279 and 4,309,280 use zeolite Y mixed with zeolite ZSM-5 to produce higher octane gasoline.
C in catalyst particles, or a mixture of two F'CC catalysts, one conventional cracking catalyst with Y and the other with ZSM-5, or the charge (charge 5tock) using a conventional FCC with finely powdered ZSM-5 added. U.S. Patent No. 4.4340.4
No. 85 discloses the use of an FCC catalyst using a mixture of silicalite and clay-exchanged Y to produce higher octane gasoline.

Zeolite Beta is described in US Pat. No. 3,308,089 and Re 28,341, the entire contents of which are incorporated herein by reference. Zeolite Beta is used as a catalyst for various hydrocarbon conversion processes. For example, European Patent No. 140,
In issue 608, hydro dewaxing (hydrodew)
ax iB ) and hydrocracking (hydr
ocracking), and is used in U.S. Patent No. 4
, 501,926, on de-rolling, U.S. '44 Patent No. 4.
No. 301,316 for alkylation, and European Patent No. 98,040 for middle distillate
gas oil for production of distillate
l) Used in catalytic cracking.

There is also a disclosure of zeolite beta limited to use in k=' CC. European Patent No. 78,132 and U.S. Pat. No. 4,481,104 disclose that the zeolite in the catalyst has a framework with a silica to alumina ratio of greater than 100; a pore size of at least about 8 angstrom units;
and a catalyst of a zeolite in a substrate (s+atr+x) having an alpha value not exceeding 3 as a result of reducing its activity by treating the zeolite with an alkali metal cation at a pH of 4 to 6. has been used to crack gas oil to produce products with boiling points in the naphtha and distillate fuel range. These have a single catalyst particle and there is no discussion of any catalyst mixture.

It is an aim of the present invention to provide a highly active hydrocarbon conversion catalyst containing zeolites.

It is another object of the present invention to provide a cracking catalyst that is highly selective for the production of gasoline range olefins and aromatics and thus produces high octane gasoline.

It is another object of the present invention to provide a racking catalyst that enables the production of gasoline and distillates more economically and efficiently than hydrocarbon feedstocks using conventional equipment and processes. .

These and other goals will become apparent as the method of the invention is described.

By physically mixing two zeolite-containing catalysts, we have developed a hydrocarbon conversion catalyst composition that is highly selective for the production of gasoline-range olefins, aromatics, and, as a result, high-octane gasoline. was manufactured. For example, catalyst compositions prepared by physically mixing catalysts containing ion-exchanged Y74-jasite with catalysts containing zeolite beta exhibit high cracking activity, high yields of gasoline as well as gasoline range olefins. and has a combination of high selectivity for the production of aromatics. By mixing catalysts containing faujasite with other catalysts containing zeolite beta, composite catalysts with a unique combination of high activity and desirable selectivity are obtained. By using physical mixing, zeolite beta is separated from faujasite-containing particles. This separation minimizes hydrothermal inactivation of zeolite beta in commercial catalytic crackers and increases their efficiency.

The physically mixed catalyst composition according to the present invention comprises catalysts A and B.
It is produced by mixing two types of catalysts that can be called.

11tJI A: Inorganic oxide base material (matri
x, matrix) containing 1% by weight of 10 to 50 ion-exchanged faujasite zeolite.

1: Contains 20 to 65% by weight of zeolite beta in an inorganic oxide base material.

The two catalysts should preferably be physically mixed using 50 to 98% by weight of catalyst A and 2 to 50% by weight of catalyst B. A more preferable mixture is 5 to 25
% by weight of catalyst B.

The story of ion-exchanged faujasite is X and Y.
It encompasses all catalytically active cation-exchanged forms of faujasite.

Synthetic faujasites (usually NaX, NaY) and natural faujasites are usually ion-exchanged with cations that impart acidity to the zeolite. These cations are NH, ", L a".

Ce2, Ce”, Nd co+, P, co+, p
r-4+, s12+, S M 3 +, M g", A
The term ion exchange faujasite, which can be selected from, but not limited to, 13+, H+ and mixtures thereof, also refers to ultrastable
It also includes stabilized faujasite structures such as faujasite dealuminated using ble) Y and chemical reagents such as S iC1, or (NH=)2 S iFa. These reagents may be used for moe Y-faujasite mixed into the catalyst, or may be used for a catalyst containing Y-faujasite.

Methods for preparing various types of catalytically active ion-exchanged faujasites have been described in the prior art. Zeolites are usually mixed with binders, fillers and functional additives to form hybrid catalysts. The term substrate refers to the non-zeolite component in the catalyst.
Various substrate components have been filmed in the prior art. This includes silica, alumina, silica-alumina, and silica-alumina.
Includes zirconia, silica-magnesia and mixtures thereof.

Methods for manufacturing these base components are also disclosed in the prior art. Base components selected from all these disclosed inorganic oxide materials were considered for the dual zeolite catalyst according to the present invention.

The catalytically active ion exchange form of zeolite beta is contemplated as one of the components of the subject binary zeolite mixture.

Preferred exchange cations include NH4 and M
g 2+ is included. Methods for producing zeolite beta are also disclosed in the prior art.

In other preferred embodiments, the total weight of faujasite in the mixture is greater than the total weight of zeolite beta in the mixture.

How the present invention enables hydrothermal inactivation of zeolite beta (
hydrothermal deactivation
) is not known, but the following may be useful to understand one mechanism that may be involved. Coke, one of the byproducts of catalytic crabbing, is deposited in the pores of the cracking catalyst. The amount of coke produced depends, inter alia, on the type and substrate of zeolite used in the catalyst, and on the time of use of the catalyst (a
ge). The catalyst that has produced coke is sent to a regenerator where the coke is incinerated by an exothermic reaction. It is believed that the temperature of the coke-forming particles varies depending on the coke concentration in the catalyst. Particles with sufficiently high concentrations of coke have hotspots of high temperature (i.e., above 700°C).
oot) may occur. The tendency of catalyst particles containing faujasite to form coke is greater than that of catalyst particles containing zeolite beta.

Therefore, catalyst particles containing faujasite reach higher temperatures in the regenerator than particles containing zeolite beta. If faujasite and beta are present in the same particle, the zeolite beta is exposed to high temperatures and undergoes more inactivation than if the two zeolites were present in separate particles. Therefore, the mixed catalyst of the present invention is designed to minimize hydrothermal inactivation of zeolite beta.

The blended hybrids have high activity and selectivity for gasoline range olefins and aromatics, making them useful in fluid catalytic cracking. By mixing preferably 5 to 25% by weight of the catalyst containing zeolite beta with another catalyst containing ion-exchanged faujasite, compared to that with a faujasite catalyst,
It is possible to reduce the paraffin content and increase the olefin content and aromaticity of gasoline to produce higher octane gasoline. This catalytic cracking process uses added hydrogen
Preferred temperatures are in the range 400 to 700°C and pressures are in the range 0 to 5 atmospheres, carried out under cracking conditions in the absence of.

Having described the basic aspects of the invention, the following non-limiting examples are presented to illustrate specific embodiments thereof.

This example describes the preparation of a catalyst containing 1-1-beta zeolite. This catalyst is an example of one component that may be used in the preferred physical mixture of the present invention.

Proton-exchanged zeolite beta (H-beta) was prepared according to the method described in Example 1 of U.S. Patent Application Serial No. 842,519, filed March 21, 1986. The contents of this application are incorporated herein by reference. This zeolite S io zl
The Altos ratio is about 21, and the weight percent of Na, O
was 0.2, and the particle size was less than 0.1 micron. Commercially available 50% containing 23.5 weight percent alumina
Aluminum chlorohydrol solution (2553g+a)
was placed in a 10 gallon stainless steel mixing tank. 3067 grams of Nakta kaolin (total volatiles = 15.2% by weight) was then added to the bath. Next, 872 grams of H-beta (total volatiles = 8.3% MX amount) was added to a Wearing (11aring)
In a mixer, it was mixed with a sufficient amount of deionized water to obtain a homogeneous dispersion of zeolite in water. The measured p I-1 value of this zeolite slurry was 4.8. Then, this mixed zeolite slurry was placed in the above liquid tank. Each component in the mixing tank was sufficiently stirred and spray-dried using a gas introduction temperature of 316°C and a gas discharge temperature of 149°C. The spray-dried catalyst particles were calcined in a Matsufuru furnace at a temperature of 538° C. for 2 hours with air flow. The calcined catalyst was analyzed to contain 0.1 wt. % Na2O, 0.1 wt. % mixed rare earth ff! i (aluminium and 46.1% by weight Al
It was found that it contains zO*. This calcined catalyst has a bulk density of 0.74 gm/ee and 126 ta"/g
It had a surface area of va.

This example describes four physical mixtures of catalysts. 4
All physical mixtures of species are examples of preferred physical mixtures according to the present invention.

Ten grams of mixed catalyst were prepared as described in Table 1 below. Brace Co. (l11. R, Grace &C
Davison Chemistry Department, )
A commercially available DA-300 fluidized cracking catalyst, believed to contain rare earth-exchanged Y zeolite, manufactured by ical Division) was the main component of this mixture.

This physical mixture was thoroughly mixed before subsequent catalyst testing.

Fire 111-''--This example and subsequent examples are based on each catalyst and Example 2.
microactivity test on physical mixtures of (s+1croa
cLivityLest). Oil and Gas Journal
urnal).

Volume 65, pages 89-93, October 16, 1967
Chiavec (F, G, C1apetta) listed in the day number
) and Henderson (D, S, Hender
“Micro activity test of Crab King catalyst @
(MicroactiviLyTe5tforCr
We used a microactivity test method published in a paper entitled ``Acking Catalysts''. Petroleum fractions cracked with these catalysts were
0il), and the following test was used.

Temperature = 499℃ Catalyst contact time = 75 seconds 1 violet hourly space velocity (WH8V) = 18W if necessary
The HSV was varied to vary the conversion for a particular catalyst. The liquid product of the microactivity test was analyzed by high-resolution capillary gas chromatography to determine the PONA of gasoline.
(paraffins, olefins, naphthenes and aromatics) composition was determined. The test results for the mixtures of 2!4 (Examples 2a and 2b) were compared to D
A-300 (a commercially available catalyst with lower cracking activity than A-300) and the calcined catalyst of Example 1 were measured and listed in Table II below.

Example 4 Test results for two mixtures containing steam-deactivated beta catalysts (Examples 2c and 2d in Table 1) were determined along with the results for the steam-treated catalyst of Example 1 and are summarized in Table Ill below. Listed.

Example 11-i This example describes the preparation of a catalyst containing 40% H-beta zeolite. This catalyst is one example of a component that may be used in the preferred physical mixture of the present invention.

The catalyst manufacturing method used was the same as that in Example 1.

Ingredients: 1,256 grams of H-beta, 2,170 grams of aluminum chlorohydrol solution, and 1 gram of nato cacaolin.
It weighed 522 grams. The weight of each component was selected to provide 40% 11-beta by weight in the formulation.

Shakuragai-1 This example describes the preparation of three physical mixtures of catalysts. All mixtures are examples of preferred physical mixtures according to the invention.

The mixed catalyst was prepared as described in Table IV below. Davison Z-14 manufactured by Brace Company, Davison Chemical Department
A commercially available Octaeat® fluid crabbing catalyst believed to contain standard ultra-stable Y was the main component of this mixture.

Table ■ Smell u? jL-D-1・One dog use 1 circle L 1 bear ('' ingredient) (6a Steam treatment 1 octacut
7,86b Steam treatment 1 octacut
7. ()6c Steam treatment Octacut 7,51 Total pressure 1 atm, steam 20% by weight, 827°C, 12 hours m2 Total pressure 1 atm, steam 1.
00% by weight, 760°C, 5:00 p.m.
*'JL Bokmin Components Steam treatment 2 catalyst of Example 5 0.2 Steam treatment 2 catalyst of Example 5 0.4 Steam treatment 1 catalyst of Example 5
2.5 The physical mixture was thoroughly mixed before subsequent catalyst testing.

1-L This example describes the results of microactivity testing on Octacut and the two-way mixture of Example 6. A reactor temperature of 499°C was used in this test. The results are summarized in Table V below.

This example describes the results of a microactivity test conducted at a reactor temperature of 538°C. Octacut and Example 6 (
The mixture of c) was tested at this temperature. The results are summarized in Table F. Vl.

t, O@7 ;, hei ・, Oη0 i-treρ The results described in Example 2-7 show a lower degree of paraffinicity and a higher degree of paraffinicity compared to Octacut for the binary zeolite catalyst. It is shown that gasolines having a degree of olefinicity or degree of aromaticity are obtained. Linear and monomethyl branched paraffins were the predominant (rough-in isomers) produced with this catalyst. It has a higher mixed offtane number than branch paraffins.

-Red ■'' U series (AST fresh flood of the main body) 992 order Lr1-Hexane 19 222-Methylpentane 82 783-Methylpentane 86 801-Hexane
96 942-hexane (trans> 134 1293-methyl-1
-Pentene 114 1140-Hebutane
00 2-Methylhexane 40 423-
Methylhexane 56 571-hexene 64 602-Methyl-1-hexene 118 108 Therefore, the present binary zeolite catalyst is believed to produce gasoline with a higher octane number than that produced by Octacut.1 The present binary zeolite catalyst The heavy charge yield of gasoline is comparable to that obtained with Octacut.

It will be understood that the above detailed description is given for purposes of illustration only and that many variations may be made without departing from the spirit of the invention.

Claims (1)

[Scope of Claims] 1. a) a faujasite catalyst containing 10 to 50% by weight of ion-exchanged faujasite zeolite in an inorganic oxide base material, and b) beta zeolite in an inorganic oxide base material. a physical mixture of beta catalyst containing 20 to 65% by weight of 2 to 50 parts of faujasite catalyst on a 100 parts basis to about 50 to 98 parts of faujasite catalyst.
A fluidized cracking catalyst comprising 50% of beta catalyst. 2. The fluidized cracking catalyst according to claim 1, wherein the zeolite beta catalyst is present in an amount of 5 to 25 parts based on 100 parts of the catalyst mixture. 3. The above faujasite zeolite and the above zeolite beta are NH_4^+, La^3^+, Ce^3^
+, Ce^4^+, Nd^3^+, Pr^3^+, Pr
^4^+, Sm^2^+, Mg^2^+, Al^3^+
The fluidized cracking catalyst according to claim 1, which is ion-exchanged with a cation selected from the group consisting of , H^+, and mixtures thereof. 4. The above zeolite beta is NH_4^+ or Mg^
3. The fluidized cracking catalyst according to claim 3, which is ion-exchanged with 2^+. 5. Claim 1, wherein the faujasite zeolite is ultra-stable Y zeolite or faujasite dealuminated with a chemical reagent.
Fluidized cracking catalyst as described in section. 6. The above chemical reagent is SiCl_4 or (NH_4)_
6. The fluidized cracking catalyst according to claim 5, which is 2SiF_6. 7. The method according to claim 6, characterized in that the above reagent is used (a) for Y faujasite before being mixed into the catalyst, or (b) for a catalyst containing Y faujasite. Fluidized cracking catalyst. 8. The above inorganic oxide base material is silica, alumina, silica
A fluidized cracking catalyst according to claim 1, characterized in that it is selected from the group consisting of alumina, silica-zirconia, silica-magnesia and mixtures thereof. 9. A fluidized cracking catalyst mixture according to claim 1, characterized in that the total weight of faujasite zeolite in the mixture is greater than the total weight of beta zeolite in the mixture. 10. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of a catalyst as claimed in claim 1. A method of obtaining hydrocarbons with lower boiling points. 11. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of the catalyst of claim 2. A method of obtaining hydrocarbons with lower boiling points. 12. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of a catalyst according to claim 3. A method of obtaining hydrocarbons with lower boiling points. 13. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of the catalyst of claim 4. A method of obtaining hydrocarbons with lower boiling points. 14. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of the catalyst of claim 5. A method of obtaining hydrocarbons with lower boiling points. 15. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of the catalyst of claim 6. A method of obtaining hydrocarbons with lower boiling points. 16. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of the catalyst of claim 7. A method of obtaining hydrocarbons with lower boiling points. 17. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of the catalyst of claim 8. A method of obtaining hydrocarbons with lower boiling points. 18. Cracking a hydrocarbon feedstock to produce higher octane gasoline by subjecting the feedstock to cracking conditions in the absence of added hydrogen and in the presence of the catalyst of claim 9. A method of obtaining hydrocarbons with lower boiling points. 19. The method according to claim 10, characterized in that the temperature is maintained in the range of 400-700°C. 20. The method according to claim 10, characterized in that the pressure is maintained in the range of 0 to 5 atmospheres. 21. FCC comprising contacting a hydrocarbon feedstock under FCC cracking conditions in the absence of added hydrogen and in the presence of a catalyst mixture according to claim 1.
How to increase the octane rating of gasoline. 22. Claim 21, characterized in that the catalyst particles have a particle size of about 10 to 200 micrometers.
The method described in section.