JPS61209049A - Production of y-faujasite-containing catalyst minute small sphere - 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 Lead is a cumulative poison. Government regulations limit its use, particularly in gasoline as an octane improver, because even small amounts can have significant adverse effects both on living organisms and on many common catalysts. There is. Therefore, oil refiners are in urgent need of a method for the production of high octane lead-free Ganlin. Fluid catalytic pyrolysis processes are central to modern petroleum refining, and such modifications to produce naphtha, which generally yield high octane gasoline, sacrifice gasoline selectivity for its increased octane. , ie, an increase in the amount of product that cannot be used in gasoline results from such changes.

One method for increasing the octane number of gasoline is the use of Y-faujasite, which is ammonium-exchanged and smoked, as an alternative to the rare earth-exchanged form of Y-faujasite commonly used in fluidized pyrolysis catalysts. include.

Unfortunately, the application of ammonium-exchanged and smoked Y-forujasite catalysts is limited due to the disadvantages often imposed on gasoline selectivity.

The present invention relates to a novel fluidized pyrolysis catalyst for the production of naphtha that provides surprisingly high octane gasoline.Furthermore, the catalyst of the present invention improves the gasoline yield typically provided by previously known octane improvement methods. To achieve gasoline octane improvement without major sacrifices.

In general, the present invention relates to a method of making and using a catalyst to obtain high octane gasoline in high yield. Furthermore, these new catalysts and processes achieve low coke, hydrogen and gas production while maintaining satisfactory layer loss resistance and excellent hydrothermal stability. The catalyst of the invention also finds use in the upgrading of resid oils to provide middle distillates with increased octane numbers. The catalyst of the present invention consists of Y-phasiasite of reduced unit cell size crystallized in situ in a silica-alumina matrix of controlled microporosity and preferably contains rare earth oxides. do not have.

The sodium content of the reduced lattice size Y-phasiasite is less than 7.5% based on the weight of the catalyst. The catalyst microspheres of the present invention have a size of about 2.0 mm to about 10 mm. O
Onm range from about O6O2 to about 0.25cc/g
pores and as described in U.S. Pat. No. 4,493,902 (
more than about 40% by weight in the macropores of microspheres derived from a mixture of metakaolin clay and kaolin clay that is teriyakid through at least a characteristic exotherm, as described in (herein included for reference). It is produced by crystallizing Y-phodiasite zeolite. After forming microspheres, crystallizing and washing, the sodium content is reduced to less than about 7.5% and the crystallized Y
The BET surface area is increased by at least partially exchanging the lithium ions in Forjasai 1 with ammonium ions and then smoking the partially ammonium exchanged catalyst in the presence of water vapor.
The unit cell size of the Y-forujasite is reduced by at least about 0.03^ while keeping the size between 300 and 425 m''/().
”/g (approximately 40% more than Y-71-Jasite)
% larger surface area) surface area; 24.35-24.
Y-phasiasite with unit cell dimensions to 55;
Sodium form Y-phosiasite having a sodium content of about 0.3-0.5% (as NaeO) based on the weight of the catalyst and having a molar ratio of silica to nalumina of at least about 4.8. manufactured from microspheres containing . The most preferred catalysts of the invention are substantially free of catalytic transition metals such as iron, cobalt, nickel and platinum group metals. In most applications, the catalyst is introduced into the pyrolysis unit as a combination of zeolite-containing catalyst particles and catalytically less active additive particles. U.S. Patent No. 4.493゜90
Terminated kaolin clay microspheres may be used as described in No. 2, or e.g.
Vanadium immobilizing additives such as those disclosed in 691244, 691245 and 691257@ can also be used. The most preferred additive for vanadium immobilization is microspheres formed by terminating a spray dry mixture of hydrous kaolin and dolomitic limestone.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Zeolite-containing microspheres that can be used as starting materials for the present invention are substantially as described in U.S. Pat.
．． Manufactured according to the teachings of No. 902. It is believed to be highly advantageous to form Y-phasiasite by a crystallization reaction occurring within the MacO pores (>60 nm 1 ) of the microspheres. For the purposes of the present invention, the formation of zeolite in this manner will be referred to as "in situ crystallization" and the resulting product will be referred to as "in situ crystallized Y-phasiasite". I'll decide. A preferred starting composition is made wA according to Example 1 of the above patent, except that the rare earth exchange is omitted. That is, the starting materials produced are substantially the same as those described in Part 1 of Example 1 of the above-mentioned US patent. Desirably, the unit cell size of the zeolite in the microspheres is from about 2.464 nm to about 2.473 nm. The silica to alumina ratio of the zeolite is from about 4.1 to about 5.2 at a unit cell size of about 2.464 to 2.473 n.
On the other hand, the overall silica to alumina ratio of the catalyst is about 1.7 to about 3.4. It is important that the content of Y-phasiasite in the starting microspheres is greater than about 40%;
A range of about 50-70% Y-phasiasite by weight is preferred, whereby a desired combination of properties of the final catalyst, including activity, selectivity and octane-forming ability, can be obtained. There is no reason why a zeolite content of more than 70% cannot also be used, as long as the resulting microsphere structure is acceptable.

The corresponding surface area ranges from about 300 to about 7501/g. The micropore structure of the finished catalyst is not substantially different from that of the starting material, and therefore, in order to obtain the desired coke selectivity, especially for the catalyst of the present invention, the pore structure of the starting microspheres must be controlled. It is also important that In this regard, it is of particular importance that the pore volume in the range 2-1001 is from about 0.02 to about 0.25 CG/+II. The micropore volume of the zeolite-containing particles can be varied and controlled using silica retention. Silica retention can also be used to modify other properties of the microsphere pore structure, if desired.

In a particularly preferred embodiment for the purposes of the present invention, the microspheres are produced by external initiation using a clear zeolite initiator with sodium silicate acting as a binder during the spray drying process and thereafter. Ru.

For products prepared using external initiation, it is preferred to use a transparent initiator to prevent excessive fines formation during crystallization.

However, it is possible to achieve satisfactory results using internal initiation or cloudy initiators or a combination of both.

After crystallizing the zeolite (as desired to retain silica) and recovering and drying the microspheres, the sodium content of the zeolite is reduced to form microspheres containing Y-phasiasite of reduced lattice size. The reduction must occur in one or more stages consisting of successive ammonia-cum exchange and smoldering stages. The overall sodium content must ultimately be reduced to less than about 7.5% (based on the weight of the catalyst). In the laboratory, it has been found desirable to perform two ammonium exchanges on the dried catalyst before the first smoldering stage. These exchanges are about 30% to about 40% by weight.
% solids of catalyst, approximately 3.0 l) by addition of nitric acid
This is accomplished by slurrying in 1807'' 2N ammonium nitrate maintained at 180°C and stirring for a period ranging from about 10 minutes to several hours.

After ammonium exchange, the microspheres are smoked in the presence of water vapor. Generally, the lattice dimensions should be reduced by at least about 0.001 to 0.002 nm as measured after the initial ion exchange and smoldering steps. The sodium content after the first ammonium exchange is usually about 3%.

Typical smoke concentration and time for the first smoke is approximately 70
0° to about 1600'F, preferably 900-1500'F
"F1" is more preferably 1000-1500"F for about 1-10 hours, but it is important that the zeolite is not exposed to conditions so severe that its cage structure collapses during smoking. However, on the other hand, it is important that the smoldering be severe enough to be able to subsequently remove residual sodium without inducing collapse of the zeolite cage structure during the subsequent ammonium exchange. be. Approximately 3 hours of smoking at 1000"F appears to adequately satisfy both of these conditions. Approximately 1 by weight
Addition of 5% water appears to provide sufficient water vapor for lattice size reduction in a closed system. After the first smoking stage, the unit cell dimension of the zeolite is approximately 2.46
Preferably, the range is from 0 nm to about 2.469 nm.

Paradoxically, the zeolite index (determined by comparison using X-ray diffraction with a standard of commercially available pure sodium form of Y-phasiasite) is actually lower during the ammonium exchange and smoldering steps. It was found that the zeolite was far more severely degraded, thus indicating that the ammonium exchange and smoking had been too severe.

We believe that this apparent decrease in zeolite index is due, at least in part, to a significant structural rearrangement of the zeolite cage structure, resulting in a shift in peak position from that in the unexchanged, unsmoked material. Curiously, a significant degree of reduction in the apparent zeolite index is actually desirable in intermediates and final products and the zeolite has been reduced dramatically, perhaps to the extent of 10 or 12% zeolite. Even if the apparent zeolite index dictates, excellent products can still be obtained.Thus, using starting materials with a zeolite index in the range 45-70%, the apparent zeolite index is lower than the initial ion It seems quite surprising that excellent results can be obtained even with a reduction of 40, 30 or even 20% or even less after the exchange.After the first ion exchange step, the aluminum in the zeolite lattice The catalyst must be tempered with the presence of water vapor, which is believed to be necessary to permit the hydrolysis of This should be understood as the numerical value obtained by the procedure.First, the sample was analyzed by X-ray diffraction.
Adjust the detector to a 2θ increment of 0.01 and test for each fR No. 11J shown in Table A while holding the detector at that increment for the indicated time. For each peak, calculate the ratio of the counts thus obtained to the counts similarly obtained for the standard, and then calculate the apparent zeolite index by calculating the arithmetic ratio of these 10 ratios expressed as a percentage. Find it as an average.

Table A Apparent zeolite index of faujasite for 10 peaks Angle lower limit Angle upper limit Peak number for each increment 2θ 2θ standing'1 residue 1L standing second'-1
5,026,500,05 214,6016,090,50 318,0019,001,00 419,6020,800,50 523,0024,200,50 626,2027,400,50 730,2430,921,00 830 , 9231, 720, 70 931, 9232, 641, 20 1033, 5034, 301, 20 This can be done in substantially the same manner as above.

After such ammonium exchange, re-smoking at a temperature in the range of about 1000"F to about 1600"F is preferred, but when the catalyst is added to the regenerator of a fluid catalytic cracking (FCC) unit, It is also conceivable that proper castle yaki may be achieved.

However, a separate smoldering step would further stabilize the catalyst for intermediate storage steps, and more importantly, moisture control during smoldering would allow the zeolite to be controlled. A separate smoldering step is preferred, as it appears to be important for stabilization and reduction of unit cell dimensions.A suitable combination of time, temperature and moisture can be used in a closed system for ammonia exchange. This is achieved by steaming for 3 hours at 1500'F in the presence of water retained from the later wash.

The catalyst produced during this smoldering process is at least about 2501/2
g, preferably 300 m”/g or more, usually 5001/g
less than 300 m2/g to about 4 g, but preferably about 300 m2/g to about 4 g
It should have a surface area in the range of 25 m"/g. Although the zeolite index as generally calculated for these catalysts does not correlate precisely with the zeolite content, ''/g surface area corresponds to a zeolite content that exceeds Y''-phasiasite with a reduced lattice size of substantially 40% by weight. Surprisingly, the apparent zeolite index of the final product is often 40. 30 or even less than 20, yet with excellent results.

Excellent results have been obtained with final products exhibiting an apparent zeolite index of about 10-12%.

After ammonium exchange, the filtered, dried and smoked product exhibits a reduced unit cell size, a reduced sodium content of less than 7.5% and is often at least about 20, usually less than the zeolite index of the starting material. at least about 3
0, often exhibiting a markedly reduced zeolite index (measured as described above), often as much as 50% lower. Preferred methods to reduce the unit cell size are by a combination of ammonium exchange and smoldering, but dealumination with hydrochloric acid or chelation with ethylenediaminetetraacetic acid, oxalic acid, reaction with tetrachlorosilane, etc. It is also within the scope of this invention to reduce the grating size by known methods such as. In many cases, these methods can also be used following a combination of ammonium exchange and terminating treatment to further reduce the lattice size. Following ammonium exchange and teriyaki <2.424 by HCI leaching
The catalyst of the invention with lattice dimensions as low as nm
It is possible to make 4 pieces.

The final catalytic microspheres of the present invention preferably have less than 2.5% rare earth oxidation anastomoses! (based on the weight of the catalyst), more preferably substantially free of rare earth oxides and transition metals such as iron, cobalt, nickel and platinum group metals. It is also preferable that the material does not substantially contain any of the following compounds. The expression "substantially free" of these metals shall mean that the amounts present must not significantly exceed those typically found as impurities in raw materials. For transition metals other than iron group metals, rare earth oxides, and platinum group metals, the expression ``substantially free'' shall correspond to a content of less than approximately 7.0% of these impurities. You should understand. Increasing the amount of rare earth usually leads to a decreased gasoline octane yield from the product.

Platinum group metals and their sulfides and oxides are significantly more catalytically active than others, so for these the expression ``substantially free'' is approximately 0.01
It should be understood that this corresponds to a content of less than %. As mentioned above, the pore structure of these catalysts is an important part of the invention, especially with regard to selectivity, especially to coke, hydrogen, dry gas and gasoline.

The volume of pores in the 2-10 nm size range in the catalyst of the present invention is about 0.02 to about 0.25 cc/g. In a preferred embodiment of the invention, the pore volume (micropore volume) ranges from 2 to 10 ni from about 0.05 to 0.
20 cc/g and the pore volume in the range 60-2.000 nn+ is less than about 0.2 CC/Q. In a more preferred embodiment, the micropore volume is about 0.08
to about 0.10 cc/g, while the total porosity (2n
m plus) is about o, less than 5cc10.

In the catalyst of the present invention, the size of the unit cell of Y-forujasite is at least about 0°003n17, preferably at least about 0.005nml, more preferably from the initial lattice size of Y-forujasite in the starting material. has decreased by at least about 0.10 nml. In another preferred embodiment, the unit cell size is 2.4
It is less than 6 On1, more preferably less than 2.455 nm. In this regard, there is no known lower limit for lattice size, but based on present data, the most suitable catalysts are between about 2.435 nm and about 2.455 nm.
Y-7 ogiasite, which indicates the size of the unit cell of i, is
have.

The sodium content of the catalyst of the invention is less than 165% by weight, based on the total weight of the catalyst, including both zeolite and matrix. In preferred embodiments, the sodium content (as NaOt) is less than 1°0%;
More preferably it is less than 0.8%.

In most preferred embodiments, the sodium content ranges from about 0.3 to about 0.03, again based on the total weight of the catalyst.
．． A preferred catalyst of the present invention is a starting Y-7 oasiasite-containing catalyst having a molar ratio of silica to alumina of greater than 4.5, more preferably greater than 4.5%. 1 meter is made from the material.

Figure 1 shows the sample conversion rate. Illmai Catalyst Total softening rate range data (60-90) shows.

The m2 diagram shows the catalyst/oil and catalytic coke production rates as a function of the 9-position lattice size for ultra-stabilized high zeolite catalysts.

The Pt53 diagram shows the relationship between the coke production rate (difference between the 24 and 44 ?■ lattice size samples) and the conversion rate of the ultra-stabilized high zeolite catalyst and the total conversion rate range data of the catalyst combined 1:1 with AM ( (50-':)0) is shown.

FIG. 4 shows the variation of unit cell dimensions and catalytic reaction coke "A" and catalyst/oil coke "I3" for catalyst composition.

Figure 5 shows the coke production rate of the ultra-stabilized high zeolite catalyst (
24 and 44 samples) and the conversion ratio (1:1), the range data of the catalyst nm4 order conversion ratio in combination with AM is shown.

The Pt56 diagram is Δ compared to the unit cell size of 24.40 people.
Coke production rate, conversion rate, and unit cell (relationship with r method - jp taste catalyst, the entire data range was used for ii calculation ((
10-90% conversion rate).

FIG. 7 shows the relationship between steaming temperature and activity for ultra-stabilized high zeolite catalysts with different unit cell dimensions.

In Figures 1, 3, and tjS5, the numbers in parentheses are the calculated coke yields at each corresponding conversion rate.

Practical Application-L A sample of the sodium form high zeolite catalyst prepared as in Example 1 of US Patent f:tS4.493,902 was used in this example. After crystallization and drying, this batch of material was first ammonia exchanged twice, each time by the addition of HNOx; l) slurrying the catalyst at 35% solids in a 2NN84NO3 solution with H kept at 3; After heating to 180"F for 1 hour with stirring, filter. After drying in a drying dish,
This sample had a NaeO content of 2.78%, a zeolite index of 51, and a zeolite unit cell size of 24.72 angstroms.

A 600 g sample of the product catalyst containing 2.78% NatO was packed into a cordierite smoking dish with a lid to provide the necessary water vapor during teriyaki (to reduce the unit cell size). Moisten with 1001 H2O. The samples were then fired at 1000'F for 3 hours. After smoking, the catalyst was again ammonium exchanged twice as before. After irradiation, the wet catalyst cake was packed into cordierite pans with lids and subjected to a second teriyakiing for 3 hours at 1500"F, higher than before. The final catalyst was 0.46% NaeO 345 with zeolite skew lattice dimensions to 24.40
It had a surface area of 112/g.

Throughout this specification, all percentages are by weight unless indicated to the contrary.

Example 2 The catalyst prepared in Example 1 was steamed for 4 hours at the specified concentration in 100% steam and then treated with a modified Engelhard microorganism as described in the above-mentioned U.S. patent (herein incorporated by reference). Subjected to activity test (MAT).

Table 1 7, 400 87.6 7, 450 82.5 7, 500 87, 3 7, 550 67.1 These results demonstrate the surprising activity of the catalyst of the invention.

Example 3 Since it is often advantageous to combine zeolite goldstone microspheres with additives of relatively low catalytic activity, a sample of the steam-treated catalyst was subjected to the steam treatment of teriyaki kaolin as described in U.S. Pat. No. 4,493,902. Additive microspheres (AM
) in a 1=1 ratio to reduce the activity over the normal microactivity test range, which was evaluated for selectivity by a separate microactivity test. Commercially available highly active catalysts (HACC), Ultrasive, treated with steam in the same manner (do not mix with additive microspheres)
260, and a sample of a commercially available competitive octane catalyst (COC) were used as control samples for comparison. The selectivity values shown in Table 2 clearly demonstrate the excellent performance of the catalyst of the invention, especially in coke and gasoline yields. Commercially available competitive octane catalysts appear to be made from smoked, reduced unit cell size Y-phasiasite distributed within a matrix of kaolin clay and a silica alumina hydrosyl binder.

! -2-Table 1 Selectivity conversion rate % of test octane catalyst, highly active commercial catalyst* (HACC) and competitive octane catalyst (COC) 1. Coke production rate Test catalyst/AM 3
゜22 3.63 4.21HACC3,744,
315,11 COC3,514,165,07 2, Ganlin Yield Test Catalyst/AM 4
9,8 53.1 55.8 (Cs-boiling point 421″
F) HACC49,852,855,2COC4
7,149,952,1 3, Gas Yield C9 - Test Catalyst/AM 12,0
13,3 15,0HACCIt,5 12.9
14,7COC14,415,917,8 4, LCO yield Test catalyst/AM 2
1,2 19.2 17,0 (boiling point 421-602
″F) HACC21°8 19,5 16.
9COC20,218,216,1 5, residual oil test ill/AM
13.8 10.8 7.97 (boiling point 602″F
+) HACC13,210,58,10CO
C14,811,88,91 B, i-C*/Cs= Trial M touch*/AM
7,18 1,48 7,90 molar ratio
HACC1, 321, 722, 30COC1,
451,882,50 The f-Cs/C4':'' molar ratio obtained using the test catalyst in combination with additive microspheres (AM) is higher than that obtained with either the highly active commercial catalyst or the competitive octane catalyst. It should be noted that the olefinicity of the gaseous product is also comfortably low, indicating a relatively high olefinicity in the gaseous product, which is consistent with the high olefinic content of the liquid product giving improved octane performance over the test catalyst.

In order to more clearly illustrate the surprising combination of good gasoline selectivity and high octane number of bulk gasoline obtained using the catalyst of the invention, the catalyst of the invention prepared as described above These three catalysts were further tested in a laboratory scale fluid catalytic cracking intermediate test rig using large samples of catalyst. Intermediate test equipment 17,0
It was operated at a catalyst dioilification of 7.9 seconds, a contact time of 7.9 seconds, a regenerative temperature of 1251'F, and a reactor temperature of 973'F.

This sample has a zeolite unit cell dimension of 24.37 and 0
．． It had a sodium content of 49%.

Approximately 70% catalyst in the steamer at 1450”F
The additive microspheres were mixed to give a nominal microactivity test conversion of . Table 3 shows the fluid catalytic cracking test results obtained using this catalyst, a highly active commercially available catalyst, and a competitive octane catalyst.

Table 3 Selectivity results of octane catalyst and fluid catalytic cracking equipment for HACC and COC, which were adjusted to 70%. 3 53.3 52
．． 5L CO18,719,018,4 Residual oil 11,3 11,0 1
1,6 gas, C*-12,814,415,3 coke 7,92 2,33 2°22R
ON 97, 3 88.8 90.8M0N
79,6 79,4 79.0 The fact that the catalyst of the present invention exhibits such superior performance is considered industrially unusual in terms of lower coke production and higher octane compared to the control catalyst. is dramatic, surprising and unexpected. The reasons for the excellent performance of this test catalyst are believed to be due, in part, to the size of the zeolite unit cell, the method of preparation, and the unique properties of the starting catalyst. The results shown in the table were obtained according to known methods.
Expected yield at 70% conversion as calculated by correlated results obtained at a number of conversions ranging from about 67.4% to about 69.7%.

Example 5 In this example, the tests were carried out at different temperatures,
It is illustrated that the main reduction in unit cell size is achieved in the second scrap calcination process, whereby different zeolite unit cell sizes can provide a range of catalysts with different catalytic properties. do. A series of such catalysts were prepared by varying only the second smoldering temperature, with other aspects of the synthetic procedure being identical to those previously described. Microactivity testing of these catalysts as a 1:1 combination with additive microspheres showed that the reduced zeolite unit cell size was at least partially responsible for the lower coke production observed in previous tests. suggests that it is contributing. The results are shown in Table 4.

Effect of zeolite unit cell size on coke formation of test octane catalyst
751000/2.469
3,36 4,09 5,12-(no second heating) 1000/1000 2.452 3,
25 3,72 4.391000/1200
2,444 3.32 3.89 4
,681000/1500 2.440
3,22 3.63 4.21 From this data,
It is clear that zeolite unit cell size is an important factor for the test octane catalyst selectivity and that reduced unit cell size is accompanied by lower coke formation.

Example 6 To further illustrate the effect of lattice size on the selectivity of the catalysts of the present invention, coke formation was investigated using various catalysts with different unit cell dimensions as shown in the figures. In Figure 1, the production of coke obtained using the unmixed catalyst of the present invention with unit cell dimensions of 2.444 nm and unit cell dimensions of 2.469 nm and 2.452 nm, respectively. The differences between the coke production obtained with other unmixed catalysts of the invention are plotted. These data were obtained using and correlated to results obtained for different conversions from 60% to 90%. Although the inclusion of data obtained at the highest conversions in this correlation appears to tend to somewhat exaggerate the propensity of the catalyst to coke formation at relatively low conversions, it is significant from the data presented here. Interpretations can still be obtained. The number shown in parentheses on each catalyst's curve is the percent coke production calculated for that catalyst at that conversion.

The coke production rate of a catalyst is usually related to the above formula: Coke % = A (activity) + 8 Conversion rate % Where activity = −−−−−−−−−−− 100 − Conversion rate % In the formula “ A +1 is generally catalytic coke (catalytic coke)
-1ytic coke), ((B II is generally catalyst/oil coke)
It is called. The data for this example were further analyzed to examine changes in "A" and "B 11 due to unit cell dimensions. The data are shown in FIG.

The procedure of Example 6 was repeated by combining the microspheres of the invention with different unit cell sizes as described above with additive microspheres in a 1:1 ratio. 2.469 nm and 2.45
The coke production rate of the catalyst containing Y-forager size 1- with a unit cell size of 2 nm and the Y-
The difference between the coke production rates of catalysts containing faujasite is shown in Figure 3, in which the numbers in parentheses are: - the coke production rate calculated for that conversion; %. Figure 4 shows the catalytic coke A'' by unit cell size for these catalyst compositions.
It shows the change in oil coke "B II".

Re-analyzing and correlating the above results, excluding results obtained at very high conversions, makes them more meaningful for the conversion range commonly encountered in normal industrial operations. I got what I thought was a relationship. The results are shown in FIG.

In Figures 3 and 5, when the catalyst is combined with additive microspheres, 2,444nml and 2°452n
It is particularly important to note the very low coke production obtained with the Y-Forshakate catalyst having a unit cell size of .

Figure 6 shows 2.440 nm, 2.444 nm, 2
．． Figure 3 shows the relative coke production rates of single (unmixed) catalysts with unit cell dimensions of 452 nm and 2.469 nm.

119-1 Catalysts as described above were tested for microactivity as described above after steaming for 4 hours in 100% steam at the indicated temperatures. The obtained activity is shown in FIG.

EXAMPLE 9 To illustrate that reduction in unit cell size alone in a Y-phasiasite catalyst does not necessarily provide the desired selectivity combination obtained by the present invention, a series of comparative catalysts were prepared as follows: It was prepared as follows.

As a control sample, a silica/alumina hydrosyl bonded Y-phasiasite-containing catalyst was prepared by incubating silica/alumina and a dorosol with a solution of sodium silicate.
T! J, but instead using a comparative solution of recycled mother liquor from the crystallization of Y-phasiasite.
Example 1 was prepared substantially as described in Examples 1 and 2 of U.S. Pat. No. 3,957,689. S! 02/Al
203 and Na e O/Si O! The final molar ratio of is l
The ratios stated in the patent were corrected by adding the appropriate liter of sulfuric acid during the preparation, which is necessary due to the relatively high Na5O content in the mother liquor. Silica alumina hydrosil, LZY-62 (Y-phasiasite in ammonium form marketed by Union Carbide Linde Branch) and kaolin in the following weight ratios (dry basis):
Mixed with: LZY-62 20% Si/AI Hydrosyl 25% Kaolin 55% The material thus obtained was spray dried to obtain microspheres with a diameter of approximately 65-70 microns.

To form a Y-phasiasite catalyst with comparable reduced lattice serrations, reduced unit cell size was obtained from LZY-62 by calcination at 100F for 3 hours in the presence of 15 wt% water. Y-phasiasite was prepared. For smoldering, LZY-62 was oxidized in 2N N84 NO3 maintained at pH 3 by the addition of nitric acid.
Two changes were made by slurrying to 5% solids. The zeolite was then dissolved in 15% water vapor for 15 min.
This preparation was then comparable to that described above for the wA preparation of the catalyst of the present invention, except that the zeolite was not crystallized in situ. The material thus obtained was incorporated into the catalyst by mixing it with silica alumina hydrosil in the same manner as described above, except that in this case the relatively low activity expected from the presence of the ammonium form of the zeolite was reduced. The following ratios were used to compensate.

LZY-62 30% Silica Alumina Hydrosil 25% Kaolin with Reduced Lattice Size
45% of the material thus obtained was spray dried into microspheres as described above.

Both catalyst compositions were then heated to a pH of 4.0-4.5 for 180''
After slurrying the mixture separately in F water, it was filtered. −
The filter cake was then adjusted to pH 4.0~ by addition of HNOs.
After slurrying at 35% solids by weight in a 2N solution of ammonium nitrate maintained at 180″F,
) filtered. ) The filter cake is then adjusted to pH 4.0-4.5.
The reduced lattice size catalyst should have a sodium content of 0.27%. was recognized.

A reduced lattice size catalyst sample for this comparison was then prepared for testing. In order to give the control catalyst sample the necessary stability for subsequent use in an industrial fluid catalytic cracker, two rare earth exchanges were performed as follows: microspheres at pH 3.5-4. slurried at 35% by weight solids in a rare earth oxide-containing solution maintained at °O;
It was then washed and dried. The amount of rare earth oxide in the solution was about 3.5% of the weight of the catalyst, while the absorption rate was about 2.5% of the weight of the catalyst. The physical properties and compositions of the reduced lattice size comparative and control catalysts were found to be as shown in Table 5, while these It also summarizes the properties. Catalysts similar to those used as controls, which were not stabilized in any way, such as by lowering the unit cell size or by rare earth exchange, failed to provide industrially comparable stability.

Supervision - one loaf - reduced lattice contrast %Na of A' of the present invention! O00270,68' 0.47 Rare earth oxide, % 2.46
-Zeolite index, Y-Faujasite% fist 36 12
10-40 unit cell size (nm)
2,439 2,467 2,
440EA7, Decrease %/sec 1,5.7,7
1,4.7,5 0.2-1,2 Bulk density, a,
,'cc O,74,0,750,83,0,8
40,80-0,98 surface area, m! /g 18
9 153 336-345 Pore volume, cc/g 2-10 nm O,0550,031
0,18110-60nra 00052
0,042 0,08260-20
00 nm O, 3100, 2820, 21
Questionable correlation, see explanation in main text To compare the performance of these catalysts, four fists at the indicated temperatures were used.
After steam treatment for 6 hours, micro-activity test was carried out.
The results shown in Table 7 were obtained.

Clay/Vitrosol Matrix Water Vapor Lowering Lattice Control Catalyst of the Invention 1:1
Treatment salinity of the present invention Size catalyst Catalyst Test catalyst/AM Catalyst single weight 1400 73°7
77.3 78,9 87
,61450 65.8 70,0
70.9 82,51500 6
0.1 52.8 66.5 -
87,31550 53.115,9
53.5 67J Anonymous Microactivity Test Selectivity Comparison Test Results (Data corrected to 70% conversion) Reduced lattice size Control Catalyst of the Invention 1:1 Test
/AM coke - skewer 3.81
3.63 Gasoline selection rate 52.4
54,4 53.1C414,311,8
13,3 Light circulation oil 18,4 18,2
19.2'1'7,6
11.8 10.8 fist A number with questionable reliability. The measured value obtained was 3.29, which does not appear to the inventor to be reproducible.

The results shown in Tables 6 and 7 show that the comparison catalyst with reduced lattice size exhibits a lower gasoline selectivity than either the control or the inventive catalyst, whereas the activity of the inventive catalyst is
It shows superiority over either the control catalyst or the reduced lattice size comparison catalyst. Thus, an unexpectedly high gasoline selectivity and improved octane number are achieved with a concomitant reduction in residual oil and increased activity.

Example 10 The selectivity and activity of the catalytic microspheres of the present invention were demonstrated in U.S. Pat.
493.902, 0.27% according to the procedure of Example 1 of that patent.
Microspheres with a NazO content of 8.72% and a rare earth oxide content of 8.72% were prepared. One part by weight of these catalytic microspheres prepared as described in that patent were used to reduce the activity to a range generally acceptable for industrial operations and standard microactivity tests. in combination with 3 parts of additive microspheres. The results of the microactivity tests for the combined compositions are shown in Table 8.

Table 8 Part 1 H2C (Na t O0, 27%); Re O8
,72%+AM 3-Part Microactivity Test Selectivity Pot Selectivity, % Coke 2.52 2,98 3,58
4,43 5.70 Gasoline 47.2
50.3 53.0 55.0 55.8 Gas, C4-10,311,713,415,618,5
LGO23,221,519,417,214,a residual oil 16.8 13,5 10.6 7.76 5.
On the 16th, 27, 89-rim-ni 1
Conversion Range 39-76% A comparison of Tables 8 and 2 shows that the substantial increase in octane obtained with the catalyst of the present invention is obtained without the cost of a substantial decrease in gasoline selectivity. is clear. For example, at 7° and 75% conversion, the gasoline yield obtained with the catalyst of the present invention slightly exceeds that of the rare earth exchanged high zeolite catalyst (H2C), while at 65% conversion. The decrease in is not excessive. The isobutane to C4 olefin ratios obtained in both examples are consistent with the increased octane obtained with the reduced lattice size high zeolite catalyst, as demonstrated in the other examples.

picture ! J11 To demonstrate the influence of rare earth oxides on the activity of the catalyst of the invention, a sample of the catalyst prepared as in Example 1 was exchanged with rare earth to a content of 0.67%. The results of a microactivity comparison test to show a comparison of the stability of both catalysts after 4 hours of steam treatment at the indicated temperatures are shown in Table 9.

1st - surface touch 17, UC82,440nm touch 12. UC82
, 441nm water vapor Na t O 0, 46%,
Na, Q 0.40%.

Processing temperature Re00.0% REOo,
67% 1400 87.6
84.71450 82.5
87, 81500
87, 3 77.41
550 67, 1
70.5 Note that small amounts of rare earth exchange improve activity only at very high steaming temperatures (1550'F), whereas at low steaming temperatures rare earth exchange actually reduces activity. It is important to do so. This is unusual since rare earth exchange usually provides improved catalytic activity and hydrothermal stability.

Example 12 To illustrate the effect of rare earth oxides on selectivity,
Samples of Catalysts 1 and 2 from Example 11 above were combined with equiply of additive microspheres to evaluate microactivity test selectivity at 70% conversion. The results are shown in Table 10.

Thus, although the selectivities are very similar, there is a slight improvement in gasoline yield for the rare earth exchange catalyst (which is expected for the rare earth exchange catalyst) and a reduced coke coke production rate (which is unexpected). It is acknowledged that there are some indications. The most surprising thing is! C4/
Although the C4= ratio does not increase by rare earth exchange,
The increase is generally expected because promotion of hydrogen transfer reactions by rare earth ions results in a decrease in the olefinic character of the gas and liquid products. Octane number measurements on actual liquid synthetic crude oils are believed to be necessary to determine whether there is in fact a slight negative effect on octane by the exchanged rare earth ions.

Example 13 Variation in Gasoline Yield and Olefinicity of the C4 Fraction To illustrate H, a conventional high zeolite catalyst (H2C) as described above and a competitive octa-C catalyst (H2C) as described above were used.
COC) and the catalyst of the invention were comparatively measured for the ratio of isobutyne to C4 olefin. The results are summarized in Table 11.

1L1 Unit cell size for a reduced lattice size high zeolite catalyst (
Gasoline yield and i-C+/C as a function of UO3)
4” molar ratio (as compared to COC and H2C controls) 1
Gasoline UO3 (^) used for selectivity correlation with 0% conversion Conversion range Yield 1-0
4/C4” invention 24.40 52-7
2 53.1 7, 48 German medium
24.44 49-78 53.0
7, 6024.52 54-76
52.4 7, 4724.69
55-81 52.1 7,
65zC approx. 24.72 39-76
53.0 1,89 QC---57-7749,91,8847-8051
, 11, 69 H2C of the reduced lattice size (ts of the present invention) is H2C
It is important to note that it has a gasoline yield substantially similar to the control, but with a significantly reduced i-C4/C4= ratio. This data also shows that there is a 0.5-1% (absolute) increase in gasoline yield when lowering UO3 from 24.69 to 24.408. Both high zeolite catalysts produced significantly more layered gasoline than the competing octane catalysts.

In order to briefly examine the performance comparison of conventional high zeolite catalysts with normal lattice dimensions, 25% H2C and 75% AM
samples were evaluated in an intermediate test unit using the feedstocks shown in Table 13, with a catalyst: oil conversion of 9.11, a reactor temperature of 962″F, and a regenerator temperature of 125°F.
The procedure was essentially as shown in Example 4, except that the temperature was 7″F.Obtained results (adjusted to 70% conversion)
are shown in Table 12. It is quite surprising that a high zeolite catalyst with reduced lattice size produces more gasoline but substantially less coke than a comparative high zeolite catalyst with a normal lattice size stabilized with rare earth oxides. . Furthermore, these advantages are due to the extremely high gasoline Research Octane Number (RON) of 97.3.
It is also achieved with See Table 3. Based on our experience with rare earth oxide stabilized high zeolite catalysts, this research method octane number is significantly lower than that obtained with the catalyst of the present invention.

Table 12 Carbon on Regenerated Catalyst, % 0.04 Delta Carbon, % O, 27 Yield, % 7 Lent'75%'AM/
25%HZ C conversion rate
70.0 (active)
2.33 gasoline (Cs-421F)
54.77LCO (421~602'F +
) 18.63 residual oil (602F+)
17, 37C4 minus
12.63 coke
2.60 total
100.00 IC42,70 n C40,47 C4= 4.27
Total Co 7.44Cs
O,50Cs”
3.43 total C
s 3.93 yield, %
Blend 75% AM/25% H2cC!
0.26CI
-0,32 Cz O,43
HsSO, 17
HtO,02
C2 and below total 7,261-
Engineering 1-1 Mid-Continent Gas Oil Feedstock Microactivity Intermediate Test Test Feedstock Feedstock API Specific Gravity (@60″F) 28°0 28.6
0.26 0.22 Simulated distillation I B P 415'
l"322"F10%550"7:
485′F20% 609″F
560'F3G% 659'F
620"F40% 7077' 665
F50% 756"F 702'F60
% 807”F 739’F10%
864 777 80% 932
'F 820'F90% 1030π
817π92% 1066F 8
91F99% 992”F total sulfur 0.59 0.52Fe
1 ppa+ 0,76
Cu 3pol
O, INt
IEIDI t. less than OV
1 ppm 7
, less than 0 total nitrogen 903 DI) 11 67
51) I11 basic nitrogen 1
391) l) II 2331) l) 1 pour point
90″F 58″F Bromine number 2
2-large 15 To investigate the effect of unit cell size on selectivity, 2,440 nm, 2,444 nm, 2.4
Microactivity testing was performed on samples of catalyst microspheres prepared as in Example 5 with unit cell dimensions of 52n<11> and 2.469 nm. In each test, catalyst microspheres were combined with an equal weight of additive microspheres as described above. Table 14 summarizes the variation in gasoline yield obtained at various unit cell sizes. Section 15.1
Tables 6.17.18 and 19 summarize the coke production rate, gas yield (C4-), isobutane to C4 olefin molar ratio, CO yield and resid yield, respectively.

Year-1 soil gasoline yield % Conversion rate % Unit cell size, nm Correlation range 60 65
70 75 802.440 52
-79 46.4 49,6 52.4 54,6
55,752-72 46.3 49.8 53
,1 55.8 57.82.444 6
2-81 46.6 49,9 52,8 55,
3 56°662-78 46.5 49,9 5
2,9 55.3 56,949-81 46.9
50,2 53.0 55,3 56,449-78
46.9 50.2 53.0 55.3 5B
, 42.452 54-82 46.
1 49,6 52,5 55,1 56.654-7
6 48.1 49,5 52,4 54,7 5
6,02.469 49-83 48
．． 1 49.4 52.2 54,5 55,755-
81 46.2 49.3 52.1 54.2
55.248-83 46.4 49,7 52,
5 54,9 56,148-81 46.3 4
9,6 52.4 54.5 55.7 Table 15 Coke production rate Conversion rate % Unit cell size nm Correlation range 60 65
70 75 802.440
52-79 2,83 3.28 3,89
4,74 6.0252-72 2,91
3,22 3,63 4,21 5,082.
444 62-81 2.95 3,
35 3,88 4,63 5.7662-78
2.89 3゜32 3.89 4,68
5.8749-81 2.94 3,34
3,88 4,63 5.7649-78
2.93 3,35 3゜90 4,68 5
,842.452 54-82 2.8
6 3゜25 3,77 4,49 5.58
54-76 2,89 3,25 3.72
4,39 5,392.4f39 49
-83 2,90 3゜40 4,08 5
,01 6,4255-81 2,81 3.
36 4,09 5゜12 6.6748-83
2.97 3,46 4.12 5.03
6,4148-81 2.97 3.49
4,17 5. t3 6.57 Table 16 Gas (C4-) Yield % Conversion rate % Unit cell size nm Correlation range 60 65
70 75 802.440 52-7
9 10.8 12,1 13,7 15,7 1
8,352-72 10.8 12,0 13,3
15,0 17.12゜444 62-8
1 10.5 11,8 13,3 15,1 1
7,662-78 10.6 11,8 13.2
15.0 17,249-81 10.2 11
,5 13,1 15,1 17,849-78
10.2 17,5 13.1 15,0 17.62
．． 452 54-82 17, 0 12
．． 2 13,7 15,4 17,854-76
17,0 12,3 13.9 15.9 18,62
．． 469 49-83 17, 0 12
．． 2 13,7 15,5 17.955-81
17,0 12,3 13,8 15,7 18.14
8-83 10.7 12,0 13,6 15,
5 18,148-81 10.8 12.1 1
3,7 15.8 18.5 Table Isobutane/C4 olefin molar ratio Conversion rate % Unit cell size nm Correlation range 60 65
70 75 802.440
52-79 0,95 7,21 7,57
2.08 2.8952-72 0.95
1,18 1,48 1,90 2,542.
444 62-81 7, 01 1,
25 1,56 1,99 2.6262-78
1,03 1,26 7,55 1,96
2.5549-81 1,14 1゜35
1,62 1,99 2.5149-78
1,13 7,34 1,60 1,94 2
,422.452 54-82 7,0
1 1,23 1,52 1,92 2.44
54-76 7,02 1,21 7,47
1,81 2.292.469 49-
83 7,09 1,34 1°67 2.
13 2.8155-81 1,00 1,2
7 7, 65 2, 19 3.0348-83
1,09 1,34 1,67 2.13
2.8148-81 7,09 1,34
1,67 2,13 2.81 Table 18 LCO yield conversion rate % Unit cell size capability Correlation range 60 65 70
75 802.440 52-79
22.9 21.1 19.1 16.8 14.
352-72 22.9 27, 2 19.2 1
7.0 14.62.444 62-81
22.8 21.1 19.1 17.0 14.
662-78 22.7 21,0 19,2 1
7,1 14.849-81 22.8 21,1
19.1 17.0 14.649-78 22
．． 8 21,1 19.2 17,1 14,72.4
52 54-82 22.6 21,0
19,2 17,1 14,954-76 22
．． 6 21,2 19,5 17,6 15.62゜4
69 49-83 22.2 20,6
18,7 16.7 14,455-81 22
．． 4 20,8 18,9 16,8 14,548-
83 22.2 20,5 18,7 16,6
14.348-81 22.2 20.6 13,
7 16,7 14.4m-works-residue Oil % Conversion rate % Unit cell size nm Correlation range 60 65
70 75 802.440 52-
79 17.1 13.9 17.0 8.21
5.6652-72 17.1 13,8 10
．． 8 7,97 5,392.444 6
2-81 17.2 13,9 10,9 8,0
2 5.3662-78 17.3 14.0
10.8 7,91 5.1949-81 17
．． 2 13.9 10.9 8.02 5.3749
-78 17.2 13.9 10,8 7,94
5,272.452 54-82
17.4 14.0 10.8 7,87 5.09
54-76 17.4 13.8 10.5 7.
39 4,452.469 49-83
17.8 14,4 11,3 8,34 5.
6155-81 17.6 14,2 17,1
8,19 5.4748-83 17,8 14
,5 11,3 8,44 5.7348-81
17.8 14.4 17.3 8.34 5.8
1 The results summarized in Tables 14 to 19 are 0.0030
We demonstrate that even small amounts such as m can yield desirable results by lowering the unit cell size of high zeolite catalysts, and by further reducing the unit cell size to less than 2°460 nm. -C It has been proven that improved properties can be obtained. The summarized results demonstrate that desirable selectivity combinations are obtained when the unit cell dimensions are in the range of about 2.440-2.455 nm.

The example in Example 1 shows that when the catalyst of the present invention is combined with form-selective zeolite retention particles other than faujasite, such as ZSM-5, a substantial increase in octane is achieved but a decrease in gasoline yield is achieved. Although accompanied by a substantial decline,
However, the reduction is demonstrated to be commercially acceptable in view of the excellent gasoline yields obtained with the microsphere-incorporated catalysts of the present invention.

To demonstrate the effectiveness of the combination of ZSM-5-containing microspheres and the catalyst composition of the present invention, approximately 1% ZSM by weight was added by adding microspheres containing 20% ZSM-5 in kaolin. The procedure of Example 4 was repeated except to provide an overall catalyst composition containing -5. The catalyst to oil ratio was 9.31. The results are shown in Table 20.

Table 20 FCC Intermediate Test Selectivity Yield Adjusted to 70% Conversion, Weight % Test Catalyst/AM+ZSM-5 Gasoline 53.2LCO18.7 Residual Oil 11,
4 gas, C4-14,7 coke 2.10RON
92.2M0N
The Research Method Octane Number (RON) of 79.292.2 is considered particularly excellent when considered in combination with the gasoline yield of 53.2. While unleaded regular gasoline is usually specified as having (RON + MON)/2-87, the (RON + MON>/2 for naphtha in Example 16) generally indicates the octane number of naphtha in real terms. It is 85.7 before modification to improve the performance.

Example 17 The procedure of Example 1 was repeated except that the initial smoldering was carried out at 1500'F and after the fourth ammonia exchange (second after scrap burning) the batch of microspheres was divided into three parts: One part was dried in a drying mold and then subjected to no further heat treatment before microactivity testing. The second part was smoked at 1000'F for 3 hours as described in Example 1, while the third part was fired at 1500"F, so that the grid sizes were 2. 454; 2.446
and 2.441no+. Tables 21 and 22 also show the activity and selectivity obtained after 4 hours of steaming in 100% steam at the indicated conductivity, as well as the sodium content and grid dimensions.

For ease of comparison, results obtained using the catalyst prepared as described in Example 5 are also included in Table 21.

Table 21 Explosion Wetness USC conversion rate %/Steam treatment humidity 1 time/2 times nm %Na O14001450
150015501000/1500 2,44
0 0,46 87,6 82.5 81
゜3 67.11500/1500 2,44
1 7,01 g5.4 82,8 7
4,0 60.71000/1000 2.4
52 0.37 88.8 86,7 7
5,9 69.21500/-2,4540,82
88,683,176,259,61000/1200
2゜4440゜36 87,1 85
,2 77.5 70.21500/1000
2,446 1,00 84.5 83
, 2 78.2 60.4 Although these activities are somewhat lower than those obtained previously, they are still quite acceptable, which is quite surprising given the high sodium content. It will be done. Since these catalyst microspheres are often used in combination with additive microspheres, the activity levels shown in Table 21 are industrially acceptable.

Comparison of product selectivity results (data adjusted to 70% conversion) Fish grilling temperature LIC8nm 2,440 2,441 2
,452 2.454 2,444 2.446 Coke 3,63 4,26 3,72 4
,40 3,89 3.89 gasoline 5
3,1 52,4 52,4 51,7 52
．． 9 53,704- 13.3 13
,3 13,9 13,9 13.2 12,
4LCO19, 219, 219, 518, 619, 22
0.0 residual oil 10.8 10.8 10.5 17
,4 10,8 10,0i-C+/C*-1,481
, 621, 471, 691, 551, 55 These results indicate that if the second smoking is to be carried out in the range of 1200-1600"F, preferably 1400-1600"F, the initial Smoked 800-1200
The first explosion should be within the range of 1300-1600'F, preferably 1400-1'F.
6007", and the subsequent explosion was carried out at 800"
It has been demonstrated that surprisingly good results can be obtained when run at ~1200''F, preferably 900-1100''F.

Example 18 A second example of the rare earth form of the catalyst of the present invention was prepared as follows: the starting material was converted to 0.26% NaeO by a continuous exchange procedure with hot nitric acid solution before calcination. Starting material was similar to Example 1 except for ammonium exchange to lower sodium content. After water washing and drying, 600 ml of this catalyst was exploded in a fluidized bed under an atmosphere of 100% steam at 1150''F for 2 hours.

The recovered product of 4149 was slurried in 550 ml of deionized water and then 124 g of 25% rare earth oxide solution was added. pH was 3.4.

The exchange reaction was carried out at 175"F for 2 hours, during which time the product was filtered, washed with 2.5% deionized water, and dried. The final product contained 0.21% on a volatile free basis. Na
It contained 5O and 7.46% REO. The apparent zeolite index is 40 and the unit cell size is 2.4.
It was 41 nm.

The catalytic performance of this example on a blend of 150% catalyst and 50% additive microspheres was investigated by microactivity testing. The results are shown in Tables 23 and 24.

A comparison of the catalyst activity in Table 23 with the data in Table 6 (for the 1:1 blend) shows that this rare earth form of the catalyst of the invention is more effective after steam treatment, especially at relatively high conductivities. This suggests that it has great activity. A comparison of the selectivities shown in Table 24 and those in Table 10 shows that the selectivities are comparable. In this case, a relatively high fc+/C4= ratio would appear to indicate a loss of octane.

Table 23 Micro-activated steam treatment after steam treatment Catalyst temperature of the present invention F 1:1 test catalyst/AM1450
73.0 1500 70.5 1550 63.0 Table 24 Microactivity Test Selectivity Coke Formation 3.84 Gasoline Yield 53.2 Gas, Ca-13.0 Residual Oil 10.3 LGO1
9,7! -04/C4-1,57

[Brief explanation of the drawing]

Figures 1 and 6 show the variation in total coke production rate obtained with the simple catalyst of the present invention with different unit cell sizes. FIGS. 2 and 4 show the variation with unit cell size of the catalytic reaction coke and catalyst/oil coke of the single and combined catalysts of the present invention. Figures 3 and 5 show the variation in total coke production rate obtained with the combined catalyst of the present invention with different unit cell sizes. FIG. 7 shows the variation in activity obtained by the present invention as a function of steaming temperature and unit cell size. Patent applicant Engelhard Corp. FIG.
l. Conversion key FIG. 2゜FIG, 3゜FIG, 5゜FIG, 6゜Ilζヰ% FIG, 7゜

Claims (1)

Claims: 1. (a) at least about 40% Y-phase by weight crystallized in situ in a silica-alumina matrix having a micropore volume of about 0.02-0.25 cc/g; providing microspheres containing diacite; and (b) ammonium exchange treatment and subsequent treatment in the presence of water vapor;
1. A method for producing Y-fouriasite-containing catalyst microspheres, comprising the step of reducing the unit cell size of the Y-fouriasite by at least about 0.010 nm by calcination. 2. The method according to claim 1, wherein the size of the unit cell is reduced to less than 2.460 nm. 3. The method according to claim 1, wherein the size of the unit cell is reduced to 2.435 to 2.455 nm. 4. The final surface area of the catalyst is more than 300 m^2/g, and the initial Y-phasiasite content of the prepared microspheres is about 5.
2. The method of claim 1, in the range of 0 to about 70%. 5. The final surface area of the catalyst exceeds 300 m^2/g and Y
-The size of the unit cell of faugiasite is 2.455n
2. A method according to claim 1, wherein the method is less than m. 6. The method according to claim 1, wherein the final surface area is in the range of 300 to 425 m^2/g. 7. The volume of pores in the range of 2-10 nm is 0.05-
0.20 cc/g, the volume of pores in the range of 10-60 nm is about 0.02-0.3 cc/g, and the volume of pores in the range of 60-2,000 nm is about 0. ．．
2. The method of claim 1, wherein the amount is less than 3 g/cc. 8. Sodium content of Y-phasiasite is 0.8%
2. The method of claim 1, wherein: 9. Sodium content of Y-phasiasite is 1.5%
2. The method of claim 1, wherein the unit cell size of the Y-phasiasite is reduced to less than 2.445 nm. 10. Sodium content of Y-phasiasite is 0.3
5. The method of claim 1, wherein the reduction is in the range of -5%. 11. essentially a unit cell size of less than 2.460 nm, a sodium content of less than about 2% by weight, a micropore volume of about 0.02 to about 0.25 cc/g, and 250 m^
A fluid pyrolysis catalyst consisting of in situ crystallized Y-phasiasite microspheres with a surface area greater than 2/g. 12. The catalyst of claim 11, wherein the unit cell size is less than 2.460 nm and the total porosity is less than about 0.25 cc/g. 13. The size of the unit cell is approximately 2.435-2.455n
The catalyst according to claim 11, which is m. 14. The catalyst according to claim 11, wherein the surface area of the catalyst is more than 300 m^2/g. 15. The catalyst according to claim 11, wherein the surface area of the catalyst is more than 350 m^2/g. 16. The method according to claim 11, wherein the surface area is in the range of 300 to 425 m^2/g. 17. The volume of pores in the range of 2-10 nm is 0.05
~0.20 cc/g, the volume of pores in the range 10-60 nm is approximately 0.02-0.3 cc/g, and the volume of pores in the range 60-2000 nm is approximately 0.
12. The catalyst of claim 11, wherein the amount is less than 3 g/cc.