JPS61209048A - High-octane and high-gasoline selectivity 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 is disclosed in patent application No. 107 filed on March 1, 1985.
This is a partial continuation of No. 362.

Lead is a cumulative poison. Government regulations prohibit its application, particularly its use in purines as an octane improver, since even small amounts can have serious adverse effects both on living organisms and on many common catalysts. It is restricted. Thus, refiners are eager for ways to produce high octane unleaded gasoline. Fluid catalytic pyrolysis is the mainstay of recent petroleum refining, but...
A naphtha book with high octane pudding in the shell! ! ! Construction φ-
A change in such conditions would sacrifice the gasoline selectivity due to its increased octane, i.e. as a result of such a change the amount of products that cannot be used in the gasoline would increase. One method for increasing octane in solin is to use Y-foujasite, which is commonly used in fluidized pyrolysis catalysts.
Ammonium exchange instead of rare earth exchange form
Grilled 1. and the use of Y-phosiasite. Unfortunately, the use of ammonium-exchanged, calcined Y-phasiasite is often limited due to the disadvantages it imposes on gasoline selectivity.

The present invention produces surprisingly high octane gasoline.
The present invention relates to a new fluidized pyrolysis catalyst for producing gas.

Furthermore, the catalyst of the present invention achieves this improvement in gasoline octa-7 without the substantial reduction in gasoline yield that typically results from octane improvement methods known in the art.

The invention also relates to the preparation and use of this catalyst for obtaining high octane gasoline in high yields. Moreover, these new catalysts and processes can achieve low coke, hydrogen and gas production while retaining satisfactory anti-layer resistance and excellent hydrothermal stability. The catalysts of the invention also find application in the upgrading of resid oils to give middle distillates of improved octane number. The catalyst of the present invention comprises Y-phasiasite with a reduced unit cell size of less than 1° that is crystallized in situ in a controlled microporous silica-alumina matrix and contains substantially rare earth oxides. include. The reduced lattice size Y-forujasite has a sodium content of less than 1.5% based on the catalyst casing. The catalytic microspheres of the present invention range from about 0.02 to about 0.25 ca/g in the size range of about 2.0 to about 10.00 nm.
pores and as described in U.S. Pat. No. 4,493,902 (
40% by weight in the macropores of Australian microspheres derived from a mixture of metakaolin clay and kaolin clay that is #M fired through at least its characteristic exotherm (included herein for reference). It is produced by crystallizing Y-phasiasite zeolite. After forming, crystallizing and washing the microspheres, the sodium content is reduced to less than about 1.5% and the microspheres are at least partially replaced with ammonium ions for the sodium ions in the Y-phasiasite. At least about 250 m
Hold 2/g BET table 11fliMt (Y while 2
- The most preferred catalyst of the present invention reduces the unit cell size of Y-forujasite by at least about 0.03 m'/g (approximately 300 to 425 m'/g (approximately % larger surface area); Y-phasiasite with a unit cell size of 24,35-24°55 people; approximately 0 based on the weight of the catalyst
．． 3~(). The present invention is prepared from microspheres containing Y-phasiasite in sodium form with a sodium content of 5% (assuming Na=0) and a silica:alumina molar ratio of at least about 4.8. The most preferred catalysts do not contain -a'ii catalytic transition positions, such as iron, cobalt, nilaur and platinum group metals. In most applications, zeolite-containing catalyst particles are used as catalysts. The catalyst as a combination of additive particles with low activity is introduced into the pyrolysis device. Additives such as calcined kaolin clay microspheres such as those described in U.S. Pat. No. 4,4533,902 or U.S. Pat. 1lISN691244.691245
and vanadium immobilization additives such as those shown in No. 69125°1 can be used. A particularly preferred additive for vanadium conversion is microspheres formed by smoldering a spray-dried mixture of hydrous kaolin and dolomitic limestone.

The zeolite-containing microspheres used as starting materials for the present invention are substantially as described in U.S. Pat.
Follow the teachings of No. 93,902! ! ! be left behind. It is preferable to form Y-phasiasite by a crystallization reaction occurring within macropores (60 nm or smaller) of microspheres. The formation of is referred to as "in-situ crystallization" and the resulting product will be referred to as "in-situ crystallized Y-phasiasite."

In situ crystallization leads to particles with the desired pore structure as described in this invention III and is prepared by the method of particle formation by incorporating a pre-synthesized zeolite into a silica alumina hydrosil/clay matrix. I did 2! This is highly advantageous because it provides particles with advantageous selectivity compared to similar catalysts. # According to the invention! llu catalysts generally have about 0
．． 2 to about 1. (), usually about 0.2 to about 0.5,
The Enderhard damage index is shown as described in U.S. Pat. No. 4,493,902. These values are strikingly low for any catalyst, but are particularly significant when compared to catalysts formed by incorporating zeolites into a silica alumina hydrosil/clay matrix. When the zeolite content approaches or exceeds 40%, it is difficult to achieve even a practical degree of lamination resistance in mixed catalysts. A typical Engel-Hado attrition index for an adulterated catalyst is substantially 1.
(), which is usually at least about 1.5-2. ().

A preferred starting composition is prepared according to Example 1 of the above-mentioned patent, except that the rare earth exchange is omitted, i.e., the starting material produced is the same as the first part (23) of Example 1 of the above-mentioned patent.
line) is substantially the same as that written therein. The size of the unit cell of zeolite in microspheres is approximately 2.464
2.473 nm to about 2.473 nm. The silica:alumina ratio of zeolite is approximately 2,464-2.47
The overall silica:alumina ratio of the catalyst is about 1, although from about 4.1 to about 5.2 for a unit cell size of 3 nm.
7 to about 3.4. It is important that the content of Y-phasiasite in the starting microspheres is greater than about 40% by weight, preferably in the range of about 50 to 10% Y-7 faujasite by weight. is preferred, thereby making it possible to obtain a desired combination of properties lα (activity, selectivity and octane-forming ability) of the final catalyst.

There is no reason why a zeolite content of more than 70% should not be used, as long as the resulting small M LII structures are acceptable. The corresponding surface area is approximately 30 +
It ranges from 1 to about 750 Tsuru2/g. The micropore structure of the final catalyst is not substantially different from that of the starting material, and therefore, in order to obtain the desired coke selectivity properties, particularly for the catalyst of the present invention, the pores of the starting microspheres must be Controlling structure is also important. In this regard, it is most important that the pore volume in the range 2-10n+a is from about 0.02 to about 0.25 cc/g. Furthermore, in a catalyst having a suitable pore structure, the volume of pores in the range of 2 to 10 nm is about 0.05 nm.
No Keisaku (), 20cc/g, while 60-2,0
The volume of pores in the 00 nm range is approximately 0.2 cc/
less than g.

The micropore volume of the zeolite-containing particles can be used to vary and control the silica retention. The silica retention can also be used to change other properties of the microsphere pore structure, if desired.

In the most preferred embodiment for the purposes of the present invention, the spherules are mixed with a transparent zeolite along with sodium silicate to serve as a binder throughout the mist-drying procedure and thereafter. Manufactured by 11.

For products prepared using external initiation, it is preferable to use a transparent initiator to avoid the formation of excessive fines during crystallization! 7.

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

After crystallizing the zeolite, retaining the silica (if desired), and collecting and drying the microspheres,
The sodium content of the zeolite must be reduced in one or more steps consisting of successive ammonium exchange and calcining treatments to produce microspheres containing reduced and lattice dimension Y-faujasite. , the overall sodium content must ultimately be reduced to less than about 1.5% (based on catalyst loading). In the laboratory, it has been found desirable to perform a two-part ammonia exchange on the dry catalyst before the first calcination treatment. These ammonia exchanges were carried out by slurrying the catalyst as about 30% to about 40% solids in a 2N ammonium nitrate solution at 180"F' maintained at about 3.0 LII by addition of sulfuric acid. After that, about 1
It is desirable to carry out this by stirring for 0 minutes to several hours.

After ammonia exchange, the microspheres are smoldered in the presence of hydrous vapor. In general, the lattice size of the zeolite should be reduced by at least about 00001-0.002 nm after the initial ion exchange and smoldering treatment.7 The sodium content after the initial ammonium exchange is usually about ! %. Final surface area is approximately 250+a2/g
or more, preferably 300 m2/g or more, more preferably 325+n7/g or less L1, most preferably 350 m2/g or more
However, after the first ammonium exchange, the activity of the final catalyst increases with respect to the ram level, as long as it is kept below Ifi2/g. . For maximum activity, the Na2O level should be between about 7% and about 2.5%. ()% is preferable. is the purine yield,
Optimal results for octane number and activity are 2.5-3.5% Na20 in the catalyst cake before first calcination.
It seems to be obtained depending on the content. Typical firing temperatures and times for the first smoldering are approximately 100 ml, with the important proviso that the zeolite is not so severely affected that the cage structure of the zeolite collapses during the smoldering process. '／
OO”F to about 1600°F1 preferably 900 to 15
00 DEG F.% more preferably in the range of about 1 to 10 hours at temperatures below 1000 DEG to 1500 DEG F., however, subsequent ammonium exchange will cause collapse of the cage structure of the zeolite. It is also an important condition that the smoldering be severe enough to be able to subsequently remove the residual sodium without causing any damage. Approximately 3 in 1000 ”l;
Time baking appears to adequately satisfy both of these conditions. The addition of approximately 15% water by weight appears to provide sufficient water vapor for the reduction of the lattice size in a closed system.1 After the first calcination treatment, the unit cell size of the zeolite is Approximately 2,460nmh to approximately 2,46nmh
It is preferably in the range of 9na+.

Paradoxically, the zeolite index (determined using X-ray diffraction compared to commercially available pure sodium form deaf Y-phasiasite standards) is often lower than it actually is during the ammonium exchange and annealing process. It is accepted that this suggests that much of the zeolite has been destroyed, thus indicating that the ammonium exchange and smoking have been too harsh. This apparent decrease in the zeolite index is presumed to be at least partially due to a shift in the peak position from that in the unexchanged, unfired product due to a new structural rearrangement of the zeolite cage structure. Ru.

Curiously, a significant reduction in the apparent zeolite index is actually desirable in intermediates and final products, even if the proportion of zeolite is reduced dramatically, perhaps down to a low proportion of 10 or 12% zeolite. , even if the apparent zeolite index shows a decrease.
In addition, excellent products can be obtained. Thus, using a starting material with a zeolite index in the range of 5% to 10%, the apparent zeolite index is reduced to 40.30 or less than 20 or less after the first ion exchange. It seems quite surprising that even so, it is possible to achieve excellent results. After the initial ion exchange treatment, the catalyst must be smoldered in the presence of water vapor, which is likely necessary to hydrolyze the aluminum in the zeolite lattice. Throughout this specification, the term "apparent zeolite index °" should be interpreted as a numerical value by the following procedure: First, the detector is adjusted to 20 increments of 0.()1. Measure the sample by X-ray diffraction over each region shown in the t5A table, holding it in increments for the indicated times. The ratio of these 10 ratios to the obtained counts is calculated, and then the W, operative mean of these 10 ratios expressed as a percentage is the apparent zeolite index.

1 Boyu 10 peaks 7 Otsuyasite apparent zeolite index 15.02 B, 50 0,502
14.60 1B, 09 0.503
18.00 19.00 1,0 (1419,
8020,800°50 5 23.00 24.20 0.50
6 2B, 20 2), 4
0 0.507 30.24
30.92 1゜OO830,9231,F2
0,7010 3:(,5034
,301,20X-ray M:fMK(1,(λ)=0.1
Following the 5418 nm first smoldering process, additional ammonia exchange treatments are performed in a manner substantially similar to those described above. Again, approximately 1.000″F'
Smoking at temperatures ranging from about 1600'F to about 1600'F is preferred. A separate smoldering process appears to further stabilize the catalyst against intermediate storage stages, and more importantly, moisture control during the smoldering process makes the zeolite 11
In addition to stabilizing in a controlled manner and reducing the dimensions of the unit cell, a suitable combination of temperature and moisture for 6 hours is preferred, in the presence of water preserved by washing after ammonia exchange. This is accomplished by steaming for 3 hours at 1500"F in a closed system.

The catalyst resulting from this smoking out is at least about 250 m 2
/ g, preferably 300 m”/g, usually Ha50
oIl12/Rio wo product-day t, /-IshiJuleho l/I+11? Convex t1. -2/, - to approximately 425m2
/g. Although the zeolite index, as commonly calculated for these catalysts, does not correlate reliably with zeolite content +E, a surface area of 350-425n+2/g roughly accounts for about 40% by weight. Corresponding to the zeolite content of Y-phasiasite with a reduced lattice size exceeding Get excellent results. Excellent results can be achieved with a final product exhibiting an apparent zeolite index of about 10-12%. After ammonium exchange, filter
The dried and smoked material exhibits a reduced unit cell size, a reduced sodium content of less than 1.5%, and a zeolite index of at least about 20% less than the starting material's zeolite index. Usually at least about 30. A despicably reduced zeolite index, often as much as 50 points lower (measured as described above)
often indicates. Preferred methods for reducing the unit cell size are by a combination of ammonium exchange and calcination, such as dealuminization with hydrochloric acid or chelation with ethylenenoaminetetraacetic acid, oxalic acid, reaction with tetrachlorosilane, etc. Reducing the lattice size by any known method is also within the scope of the invention. In many cases, these methods can also be used to further reduce the lattice size after a combination of ammonium exchange and annealing treatment. Ammonium exchange and annealing followed by <HCI leaching can produce catalysts of the invention with lattice sizes as small as 2,424 nm.
l! can do.

As mentioned above, the final catalyst microspheres should be substantially free of rare earth oxides and contain, for example, iron, cobalt,
Preferably, it also substantially does not contain compounds of transition metals such as nickel and platinum group metals. Substantially free of these metals shall mean that the amount present must not significantly exceed the amount generally accepted as an impurity in the raw material. For transition metals other than iron group metals, rare earth oxides, and platinum group metals, ``substantially free of'' means
This should be taken to correspond to a content of these impurities of less than about 1.0%. Increased use of rare earth oxides usually results in decreased gasoline octane yield from the product.

Since platinum group metals and their sulfides and oxides are more catalytically active than other metals, the expression "substantially free" in this case is approximately 0.01
It should be interpreted as corresponding to a content of less than %. As mentioned earlier, the pore structure of these catalysts is particularly important insofar as it relates to selectivity, especially coke,
Hydrogen, drying gas and purine selectivity are an important part of this invention. 2-Io in the catalyst of the present invention
The volume of pores in the nanometer range ranges from about 0.02 to about 0.25 cc/g. In a preferred embodiment of the invention, the volume of the pores (micropore volume) of 2 to 10 r++e is about 0.05 to 0.20Ce, 7g, and the volume of pores in the range of 60 to 2,000n+* In preferred embodiments within the range, the micropore volume is from about 0.08 to about 0.15 ec/g; even more preferred;
In specific examples, the micropore volume is about 0.08 to about 0.10 cc/g, while the total porosity (2 nm or greater) is less than about 0.5 cc/g.

In the catalysts of the present invention, the unit cell size of the Y-phasiasite is at least about (),003 nm, preferably at least about 0,005 nm, smaller than the initial lattice of Y--/oasiasite in the starting material.

More preferably it is reduced by at least about 0.10 nm. In another preferred embodiment, the unit cell size is less than 2,460 nm, more preferably 2,455 nm.
less than m. In this regard, although there is no known lower limit on lattice size, based on existing data, the most preferred catalysts have -Q1 lattice sizes of about 2,435 nm to about 2,455 nm. However, from a practical point of view, 70%
Considering that the selectivity in conversion is still adequate, the cost of reducing the unit cell size increases dramatically with the increase of the reduction ratio, so about 2.450 to 2.4
It appears highly advantageous to use catalysts with a unit cell size of 60 nm.

The sodium content of the catalyst of the present invention is less than 1.5% by weight, based on the total weight of the catalyst, including both zeolite and matrix. In preferred embodiments, the sodium content is less than 0%, more preferably less than 0.8%. Catalysts according to the invention are often fired only once, since the final firing is accomplished when the catalyst is added to the regenerator. In that case, the grid size is primarily the final N
Controlled by the a2O content, which is heavy, vague and about 0
．． 2 to about 0.8%, more preferably about 0.2% by weight
Optimally, the fIA ranges from 5% to about 0.005%.

In a most preferred embodiment, the sodium content is
From about 0.3 to about 0 by weight, again based on the total weight of the catalyst.
Preferred catalysts of the present invention in the range of 5% are prepared from starting materials containing Y-phasiasite with a molar ratio of silica to alumina greater than 4.5, more preferably greater than 4.8. prepared.

Figure 1 shows the sample conversion rate. Single catalyst Total conversion rate range data (60-90) shows.

The tlS2 diagram shows catalyst/oil and catalytic reaction coke production rates as a function of unit cell size for ultra-stabilized high zeolite catalysts.

The Pt53 diagram shows the relationship between the coke production rate (difference between samples with 24 and 44 lattice sizes) and 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- 90) is shown.

The fjS4 diagram shows the variation of unit cell dimensions and catalytic reaction coke "A" and catalyst/oil coke "B" for catalyst composition.

Figure 5 shows the coke production rate of the ultra-stabilized high zeolite catalyst (
The range data of the catalyst stabilization conversion rate in combination with AM is shown in the relationship between the lattice size sample of 24 and 44 people) and the conversion rate of 1:1.

Figure 6 shows the relationship between Δ coke production rate and conversion rate and unit cell size compared to the unit cell size of 24.40 single catalysts, the entire data range was used for calculations (60-90
% 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 5, the numbers in parentheses are the calculated coke yields at each corresponding conversion.

Example 1 A sample of high zeolite catalyst in sodium form prepared as in Example 1 of US Patent fJS 4,493.902 was used in this example. HN each time
2 N N H= pH kept at 3 by addition of O3
Slurry the catalyst at 35% solids in N Osm liquid;
Ammonium exchange was performed by heating at 180"F' for 1 hour with stirring followed by filtration. After drying in a drying oven, this sample had a sodium content of 2.78% Na2O, a zeolite index of 51, and It had a zeolite unit cell size of 24.72 angstroms.

A 600 g sample of the catalyst containing 2.78% Na2O obtained in this way was packed into a covered cordierite smoking tray and the water vapor required during smoking (this was equal to the size of the unit cell) 100 mj! moistened with H,O. The samples were then smoked at 1000"F' for 3 hours. ■ For burning out, the catalyst was again ammonium exchanged twice by the same procedure as before. After filtration, the wet catalyst cake was placed in a covered cordierite tray. A second firing was carried out for 3 hours at a higher temperature of 1500"F' than before. ! The final catalyst is 0.46% Na20
It had a surface area of 45 m2/H, with a zeolite unit cell size of 24.40 people.

Throughout this specification, all percentages are percent heavy plasma unless stated to the contrary.

Example 2 The catalyst prepared in Example 2 was treated with an enzymatic compound as described in the aforementioned U.S. patent (herein incorporated by reference) after steaming for 4 hours in 10% steam at the temperature indicated. was subjected to a modified microactivity test (MAT).

Table L Test Hydrothermal Stability of Octane Catalyst Water - Burning Rate ~ Burning Rate %
Yu 1.400
87.61, 450 8
2.51.500 81.31.
550 67°1 These results demonstrate the surprising activity of the catalyst of the invention.

Example 3 Since it is often advantageous to introduce zeolite-containing microspheres with catalytically less active additives,
A sample of the steam-treated catalyst was prepared in U.S. Pat.
By mixing #M calcined kaolin hydrous steam-treated microspheres (AM) as described in No. 902 in a 1=1 ratio, the activity was lowered to the normal microactivity test range, and then these were further mixed with microspheres (AM) containing microspheres containing microspheres. The selectivity was evaluated by experiment. A commercially active commercially active catalyst (IIACC), tt, trasyl 260. and commercially available competitive octane catalyst (COC) were used as control samples for comparison. The selectivity data shown in Table 2 demonstrate the superiority of the catalyst of the present invention, particularly in coke and gasoline trucks Commercially available competitive octane catalysts are smoky, dispersed within a matrix of kaolin clay and silica-alumina hydrosil binder.
It is believed that the material was prepared from Y-phasiasite with a reduced unit cell size.

Comparison of selectivity between test octane catalyst and high activity (COC) 1, coke production rate Test catalyst/AMHA
CC COC 2,7y Sorin Yield Test Catalyst/AM (
Cs 421F boiling point) HACCOC 3.S yield C4-Test catalyst/AM ACC COC 4, LCO yield Test catalyst/AM(4
21-602'F boiling point) HACCOC 5, residual oil test catalyst/AM (
602″F′ ten boiling, σ) HACCO
C 6゜i C-/C4 Test Catalyst/AM Molar Ratio HA CCOC Table 2 Commercial Catalyst (HACC) and Competitive Octane Catalyst Conversion, % 3.74 4.31 5,1
13.51 4.16
5,0 fu 49.8
53,1 55,849.8
52.8 55.24f, 1
49.9
52.112.0 13,3
15,011.5 12.9
14,714.4 15.9
17.821.2 19.2
17,021.8 19,5
16°920.2 18.
2 16°113.8 10
．． 8 7.97m, z i
o, s a, t.

14.8 11.8 8゜9
11.18 1.48 1,
901.32 1,72 2
．． 301.45 1,88
The i-C4/C, = molar ratio obtained using the test catalyst in combination with 2.50 additive microspheres was 11 times lower than that obtained with either the highly active commercial catalyst or the competitive octane catalyst; It should be noted that this indicates a relatively high olefinicity in the gaseous product, consistent with a high olefinic content of the liquid product giving improved octane performance.

Example 4 To illustrate even more dramatically the surprising combination of good solin selectivity and high octane numbers of the large amounts of purine obtained using the catalyst of the invention, These three catalysts were further tested in a laboratory scale fluid catalytic pyrolysis (FCC) intermediate test apparatus using large samples of prepared catalysts of the invention. The intermediate test unit was operated at a catalyst:oilification of 11.07, a contact time of 19 seconds, a regenerator temperature of 1251"F' and a reactor temperature of <7973. This sample had a zeolite unit cell of 24.37 Dimensions and ()84
It had a sodium content of 9%. After steaming at 145°, the catalyst was combined with additive microspheres to give a nominal microactivity test conversion of about 70%. 1·'C(:.

The results of the midterm exam are shown in Table 3.

PI3Ue FCC Intermediate Test i Setting μB Test Octane Catalyst and f(A
Comparison of selectivity results of CC and COC〃Purine
55.3 53.3 52゜5], CO18
,719,018,4 Residual oil 11,3 11,0 11
,8gas,C,-12,814,4'15.3 Coke 1.92 2,33 2,22R
OM 91.3 88.8 90
．． 8NON 79.6 79.4
79.0 The fact that the catalyst of the present invention shows good performance in terms of low coke production and high octane compared to control catalysts, which is considered exceptional throughout the industry, means that:
This is completely surprising and unexpected. The reasons for the superior performance of the test catalysts may be due in part to the size of the zeolite unit cell dimensions, the method of preparation, and the unique properties of the starting catalyst.

The results shown in the table are at 70% conversion, calculated according to known procedures and by correlating results obtained at a number of conversions ranging from about 67.4% to about 69.7%. This is the predicted yield.

Example 5 In this example, the main reduction in the unit cell size is carried out in the second smoldering process, which can be carried out at different temperatures, so that the zeolite unit cell sizes are different and common. have different catalytic activities,
Demonstrate that a range of catalysts is provided. A series of such catalysts were prepared by varying the second fii calcination temperature, keeping other aspects of the synthetic procedure the same as described above. , microactivity testing of these catalysts in combination with additive amount spherules in a 1:1 ratio showed reduced zeolite l
It is suggested that the lit lattice size is at least partially responsible for the low coke production rates observed in previous tests. This data is shown in the tjSA table.

Person 21 - Effect of zeolite unit cell size (UO3) on coke formation of test octane catalyst Coke formation rate at the following conversion % Smoldering temperature LICSnm 65 70
75LLfflL[g-what-r3i
, --=1000/1000 2.4
52 3゜25 3.72 4.391000/120
0 2,444 3,32 3.89 4.68
1000/1500 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 selectivity of the tested octane catalysts and that reduced unit cell size is associated with lower coke production rates.

Example 6 In order to further examine the influence of lattice size on the selectivity of the catalyst of the present invention, the coke production rate was measured using various catalysts with different +1 position lattice and r method as shown in the figure. In Figure 1, the coke production rates obtained with the non-mixed catalyst of the present invention having a unit cell size of 2.414 nm and 2.469 nm and 2.
, 452n, the difference in coke production rate difference obtained with the non-mixed catalyst of the present invention having a unit cell size of 452n is plotted.

Please note that these data are obtained using results obtained for different addition rates of 60-90% and are correlated! II should be adjusted. The inclusion of data obtained at the highest addition rates in this correlation appears to tend to somewhat exaggerate the propensity of the catalyst to coke formation at relatively low conversions, but still the data presented It is possible to obtain a meaningful interpretation from

For each catalyst, the number shown in parentheses is the % coke production calculated for the catalyst at that conversion.

The coke production rate of a catalyst is usually related to the following formula: Coke % = A (activity) + B In the formula, "A" is generally called catalytic coke, and "I
3" is generally called catalyst/oil coke. The data shown in this example was further analyzed to determine the changes in catalytic coke and catalyst/oil coke depending on the unit cell size. The data are shown in Figure 2. show.

Example 7 Using microspheres of the invention of different unit cell dimensions as described above in combination with additive microspheres in a 1:1 ratio:
The procedure of Example 6 was repeated. 2゜469na+ and 2.4
The coke production rate of the catalyst containing Y-phasiasite with a unit cell size of 52 nm and the Y-
The difference in coke production rate of catalysts containing faujasite is shown in FIG. The numerical value shown in parentheses in the same figure is the coke production rate % calculated for the conversion rate. FIG. 4 shows the variation of unit cell dimensions and catalytic reaction coke "A" and catalyst/oil coke "B' for these catalyst compositions.

We excluded the results obtained at very high conversion rates in order to obtain a correlation that appears to be more meaningful over the range of conversion rates commonly encountered in normal industrial operations. Reanalyze the data of j, l;iM: L 11. I made a correlation. The results are shown in figure fjS5.

In Figures 3 and 5, 2.444 nm and 2°452
It is particularly important to note that very low coke production rates are achieved when a Y-phasiasite catalyst with a size of n+n units is combined with additive microspheres.

f56 diagram is 2. 440nm, 2. 444nm,
2. For 452 nm and 2.469 nm unit cell sparsity catalysts, 60-9
The relative coke production rates obtained using a correlation over a wide conversion range of 0% are shown.

Example 8 Catalysts as described above were treated with water #F in 100% steam at the indicated temperature for 4 hours and then tested in the microactivity test described above. The obtained activity was measured at No. 7 t! Shown in 1.

Example 9 To illustrate that reducing the unit cell size of a Y-phasiasite catalyst alone does not necessarily provide the desired combination of selectivities obtained by the present invention, a series of comparisons were performed as follows. A catalyst was prepared.

As a control, silica alumina hydrosil was prepared essentially using a comparable solution of recycled mother liquor from the crystallization of Y-phasiasite, but instead of using a solution of sodium silicate. A silica/alumina hydrosil bonded Y-phasiasite-containing catalyst was prepared as described in Examples 1 and 72 of No. 3,957,689.
The 20y and Na-0/52Oz molar ratios were adjusted to the ratios specified in the patent by adding the appropriate amount of sulfuric acid required during the preparation due to the relatively high Na2O content in the mother liquor. Silica alumina hydrosil, L7
．． Y-62 (Y-phasiasite in ammonium form marketed by Union Carbide's Linte Division) and kaolin were combined in the following weight ratios (dry basis): L, Z Y -6220% S i / Al Hydrosyl 25% Kaolin 55% The material thus obtained was spray dried to about 65~'? (1
Microspheres with a diameter of microns were obtained.

To form a comparative reduced lattice size Y-phasiasite catalyst, a reduced 1st lattice size Y-
1 in the presence of 15% precious water.
By smoking at 000″F′ for 3 hours, LZY-
Prepared from 62. After all, the LZY-62 was slurried at 35% solids in a solution of 2N NH,NO kept at 3 p) by the addition of nitric acid.
The zeolite was exchanged with ammonium twice, then the zeolite was exchanged with 15
Bake for 3 hours at 1500°F in the presence of 1% water vapor
It was. The g4gJl product is thus similar to that described above for the preparation of the catalyst of the present invention, except that the zeolite was not crystallized in situ. The material thus obtained was prepared as a catalyst by mixing with silica alumina hydrosil as described above, except that the following proportions were used to compensate for the lower activity exhibited by catalysts containing zeolites in the ammonium form. It got mixed in.

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

Both catalyst compositions were then slurried separately in water at 180''F' at 460-4.5 pi (pi) and the filter cake was then adjusted to pH by addition of HN O2.
It was also filtered by keeping it as a slurry for 20 minutes at 35% solids in 180T of 2N ammonium nitrate solution maintained at 4° θ to 4.5°. The filter cake was then washed two more times by slurrying in 180"F water at p [-140 to 4.5 and then filtering, dried in dryer 4 and analyzed for sodium. Reduced lattice. The sodium content of the sized catalyst was found to be 0.27%.

A comparative reduced lattice size catalyst sample was then prepared for testing. The control catalyst was then exchanged twice with rare earth to give it the necessary stability for use in an industrial F' CC device as follows: Microspheres were 3.
It was slurried with 35% by weight solids for about 1 hour in a rare earth oxide containing solution maintained at a temperature of 5 to 4.0, then washed and dried. The amount of rare earth oxide in solution was about 3.5%, while the absorption rate was about 2.5% by weight of catalyst. The physical properties and compositions of the reduced lattice size comparison and control catalysts were found to be as shown in Table 5, which also summarizes these properties for the inventive catalysts. ing. Catalysts similar to those used as controls that were not stabilized in any way, such as by lowering the lattice size or by rare earth exchange, did not have industrially comparable stability. .

Na10% 0.27 0,
68 0,4),1On+a
O, 0550, 0310, 18110-60nm+
0.052 0', 042 0,
08260-2000nm 00310 0
,282 Some correlation between 0.214 trillion and The results shown are obtained.

1 [Micro activity after steam treatment 1400 73.7 77.3 78゜9
87.81450 65.8 70,0
70.9 82.51500 Bo,
1 52°8 86.5 81.3155
0 53.1 15.9 53.5
67.1th! Coating - Micro activity selectivity test results (data supplemented with 70% conversion +1') Wood coke 3,29 3,59 3,81 3
．． 6: (Gasoline selectivity 52.4 51.1 54.4 5
3. IC4-14, 315, 311, 813, :) Light circulating oil 18.4 18,2 18,2 19°2 residual oil 11.6 11.8 11.8
10.8 Data with questionable reliability. The first measurement of coke production rate obtained was 3.29, which appears to the inventors to be an alarmingly low value. Reexamination of the results from another point on the same comparative catalyst gave the results shown in the rebreath test column of Table 7, which appear to be relatively reliable.

The results shown in Tables $6 and 7 show that while the comparison catalyst with reduced lattice size shows a lower gasoline selectivity than both the control catalyst and the inventive catalyst, the activity of the inventive catalyst is lower than that of the control catalyst or the inventive catalyst. This shows that the lattice size is superior to any of the comparative catalysts. The improvements obtained in octane number are thus accompanied by unexpectedly high gasoline selectivity and reduced residual oil and improved activity.

Example 10 To compare the selectivity and activity of catalyst microspheres of the present invention with microspheres prepared according to U.S. Pat. No. 4,493,902, 0.27% N was added according to Example 1 of that patent.
Microspheres with a2O content and rare earth oxide (REO) content of 8.72% were prepared.

One part by weight of these catalyst microspheres was added as described in the patent to reduce the activity to a range that is generally acceptable for industrial operations and standard microactivity tests. The prepared heavy liquid was combined with 3 parts of additive microspheres. The results of the microactivity tests for the combined catalyst compositions are shown in Table 8.

8L Part 1 H2C (0°27%N +120); 8,
Selectivity conversion by microactivity test of 72% ReO + 3 parts AM, % coke 2.52 2.98 3.58 4.4:
l 5. '70〃Sorin 47.2 50.3 5
3.0 55.0 55.8 parts%C4″″ 10.3
11.7 13,4 15,6 18,5LCO23
,221,519,417,214°8 Residual Oil 16
．． 8 13,5 10.6 7.76 5.16i-
C, /C41,311,581,892,342,98
A comparison of Tables 8 and 2 shows that the substantial increase in octane obtained with the catalyst of the present invention is achieved at the cost of a substantial reduction in gasoline selectivity. Make it clear that this is not the case. For example, at conversion levels of 70 and 75%, the gasoline yield obtained with the catalyst of the present invention is slightly higher than that of the rare earth-exchanged high zeolite catalyst (II Z C). , the drop in conversion of 65% is not excessive. The isobutane to C4 olefin ratio obtained in both examples is consistent with the improved octane number obtained with the reduced lattice size high zeolite catalyst as demonstrated in the other examples.

Example 11 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 rare earth exchanged to a content of 0.67%. The results of the microactivity test after 4 o'clock steam treatment at supporting temperature are shown in Table 9 for comparison of the stability of both catalysts.

”1 Table 14Q0 87,6
84. F1450 82.5 8
1.8+500 81.3 77.
41550 6f. 1
70.5 Note that exchange of a small amount of rare earth only decreased activity at very high steaming temperatures (1550″F), and at relatively low steaming temperatures rare earth exchange actually decreased activity. This is particularly important since rare earth exchange usually compromises improved catalytic activity and hydrothermal stability.
This is unusual.

"X, Example 1? To demonstrate the effect of rare earth oxides on selectivity, samples of catalysts 1 and 2 from Example 11 above were combined with equal weights of additive microspheres to achieve a conversion of 70%. The selectivity was evaluated by microactivity test at
Shown in Table 0.

Tsume Yuko L (Selectivity of REO-containing and ratio-containing catalysts) Final production rate 3,633.54 Gasoline yield 53゜1 53.3 Gas, C
, -13゜3 13.2 Residual oil 1
0,8 10.8LCO19,219,2 i-C,/C< 1°48
1.36 bottles correlated over a conversion of 52-72%.

The conversion rates of woody plants were correlated over 60-76%.

Thus, although the selectivities are very similar, there is a much lower gasoline yield (as expected for a rare earth exchange catalyst) and a lower coke production rate (as expected for a rare earth exchange catalyst) for rare earth exchange systems.
There are slight indications (unexpected).

Even more surprisingly, the increase in the i-C4/C- ratio due to rare earth exchange is commonly predicted by the promotion of hydrogen transfer reactions by rare earth ions, resulting in a decrease in the olefinicity of the gaseous and liquid products. is not recognized,
Octane number measurements on actual liquid synthetic crude oils are believed to be necessary to determine whether there is an adverse effect on octane due to the small exchanged rare earth ion content.

Example 13 To illustrate the variation in gasoline yield and olefinicity of the 04 fraction, the gasoline yield and isobutane to 04 olefin ratio were compared with conventional high zeolite catalysts (as described above).
H2C) and a competitive octane catalyst (C
OC) was measured as a comparison.

Gasoline yield and i-C4/C4 ratio (
Comparison with COC and cytoizc controls) Selectivity was adjusted to 70% conversion 24.44 49-78 53.0 1°60
24.52 54-76 52.4 1.47
24.69 55-81 52.1 1.65
12c Control 24.72 39-76 53.0
1,89COC---57-7749,91,8847
-8051,11,89 The reduced lattice size H2C (catalyst of the invention) is 1-
It is important to note that although the IZC control has substantially the same gasoline yield, the i-C,/C, ratio is significantly reduced. This data sets UC8 to 2
It also indicates that there is a 0.5-1% (absolute value) increase in gasoline yield when decreasing from 4.69 to 24.40 nme. Both high zeolite catalysts showed significantly higher gasoline yields than competing octane catalysts.

Example 14 To further compare the performance of conventional high zeolite catalysts with standard lattice dimensions, 25% 1-I Z C
and 75% AM were evaluated in an intermediate test unit using the feedstocks shown in Table 13. The intermediate test apparatus was substantially as described in Example 4, except that the catalyst to oil ratio was 9°11, the reaction bed temperature was 962°F, and the regeneration cooling temperature was 1257″F'. It was operated in the same way.

The results (adjusted to 70% conversion) are shown in Table 12. It is quite surprising that a reduced lattice size high zeolite catalyst produces more gasoline but substantially less coke than a standard lattice size comparison high zeolite catalyst stabilized with rare earth oxides. It is the right thing to do. Furthermore, these advantages are extremely high at 91.3.
This is accomplished while also obtaining Sorin Research Octane Number (see Table 3).

Research method octane numbers with high zeolite catalysts stabilized with rare earth oxides are, based on the inventor's experience, significantly lower than those obtained by the present invention.

Intermediate test depleted catalyst for high zeolite catalyst of standard lattice size with stop and flame] 2 carbon, % 0.31 carbon on regenerated catalyst, % 0.04 Δ carbon, %
0.27 Yield, % Blend 75% AM725% HZ C Conversion 70.0 (Activity)
2.33 gasoline ((:, -4
21″[:') 54. Fu LCO (42
1-602'F+) 18.63 residual oil (602"F+) 11.37C4
minus 12.63 coke
2.60 total
ioo, o.

iC, 2, F O NC, 0, 47 C4 = 4, 2 F 04 total 7.44Cs
0050C,=
3.43C1 total 3.93C20,26 C,= 0.3
2C, 0, 43 +1. s
0.17] 120゜02 02 or less Total 1.26 eaves L1 Table Midcontinent light oil feedstock analysis micro activity test
Intermediate test feed material Feed material ＾P■ Specific gravity (@60″F) 28,0
28.6 Ram Spottom Carbon 0.26
0.22 Simulated Distillation 1 [IP 415″
)'322'F10% 550 below 4
85"F'20% 609 lower 560"F30
% 659°F 620 below 40% 707″F 665″F 50%
758”F 702”F60% 80
7″l:' 7:+9 lower 70% 864 lower
777”F80% 932 lower 820・
〒90% 10 pieces (0°F 877°
F92% 108B'F 893″F99
% 992T total sulfur (wt%)
0,59 0,52Fc
lppm
O, FloCu
3pp-〇, INi
lppm less than 1.0V
tpp Shizuku
Total nitrogen less than 1°0 903pp ring
6f511p mt8 basic nitrogen
139ppm 23mm - Pour point
90°F 58”T' odor value
22 Example 15 To illustrate the influence of medium lattice size on selectivity, 2, 4 were @at as in Example 5.
4 On+a, 2°444nm, 2. 452
Microactivity tests were performed on samples of catalyst microspheres with unit cell dimensions of 2.469 nm and 2.469 nm. In each failure, catalyst microspheres were combined with an equal weight of additive microspheres as described above. Table 14 summarizes the changes in purine yield obtained at different unit cell dimensions. Tables fIS 15.16.17.18 and 19 summarize coke production, carbon yield (C4-), isobutane to C, molar ratio of isobutane to olefins, LCO yield and residual oil, respectively.

? "T~'"
? ″〜G″′G%J? ~ ′ ~
The results summarized in Tables 14-19 illustrate the desirable results obtained by reducing the unit cell size of high zeolite catalysts by even as little as 0.003 nm, and demonstrates the improved properties obtained by reducing the The summarized results also demonstrate the desirable selectivity combination obtained when the unit cell size is in the range of about 2,440 to 2°455 nm.

Although the examples in Example 1 show that substantial increases in octane can also be achieved when the catalyst of the invention is combined with form-selective zeolite retention particles other than 7-Osiasite, such as ZSM-5. , which is accompanied by a reduction in gasoline yield, but which is industrially acceptable in view of the excellent gasoline yield obtained with the catalysts comprising the microspheres of the present invention.

To demonstrate the effectiveness of the combination of ZSM-5-containing whole-vehicle spheres and the catalyst composition of the present invention, approximately 1% ZSM-5 by weight was added.
The procedure of Example 4 was repeated except that microspheres containing 20% ZSM-5 in kaolin were added so that the total catalyst composition containing ZSM-5 was quaternary. The catalyst to oil ratio was 9.31. The results are shown in the PIS20 table.

Selectivity results from 1 friend FCC intermediate V, experiment (data adjusted to 70% conversion) Supervisor 11 Senkou So 10L Gourd M+7-Shimomizo Nishi gasoline 53.2L (:0
18°7 residual oil
11.4 Soce, C, -14,7 Coke 2. lOR0M
92.2M0N
79.292.2 Research Method Octane number (1' (ON) is considered particularly good as it is associated with a gasoline yield of 53.2%, regular unleaded gasoline is usually (RON+MON)/
2=87, but in NL, (RON+MON)/2 for the naphtha of Example 14 is:
Prior to reforming, which substantially increases the octane number of the naphtha, it is typically 85.7.

Example 17 The procedure of Example 1 was repeated except that the first smoldering was performed at 15001 F' and the batch of microspheres was divided into three parts after the fourth ammonium exchange (second smoldering). After drying in an oven, the first part was not subjected to any further heat treatment before testing for microactivity.

The second part was smoked for 3 hours at 1ooo as described in Example 1, while the third part was smoked at 1500°F for 3 hours.
Baked. The sizes of the grids thus obtained were 2°454; 2.446 and 2.441 nw+, respectively.

Tables tj & 21 and 22 include sodium content and lattice dimensions for 4 in 100% steam at the indicated temperatures.
The activity obtained after steam treatment between vf and 1! ! The selection rate was also shown. For ease of comparison, results obtained with the catalyst prepared as described in Example 5 are also included in Table 21.

Although these activities are somewhat lower than those obtained previously, they are still acceptable for 1,5λ, which seems quite surprising in view of the high sodium content. Since these catalyst microspheres are often combined with additive microspheres, the activity levels shown in WS21f are industrially acceptable.

These results indicate that the second smokiness is 1200-16001'
, preferably in the range of 1400 to 3600, the first firing of the catalytic amount small spheres is 800 to 120.
0"F, preferably in the range of 900 to 1100"F', but the first roasting temperature is 1300 to 1600"F, preferably 1400 to 16
It has been demonstrated that surprisingly good results can also be obtained when calcining at 800-1200"F1, preferably 900-1100"F'.

[Brief explanation of the drawing]

Figures 1 and 6 show the variation in total coke production obtained with plain inventive catalysts of different unit cell dimensions. Figures 2 and 4 show the variation of catalytic coke and catalyst/oil coke with unit cell size of single and combined dead catalysts of the present invention. 3 and 5 show the variation of the total coke production rate obtained with the combined catalyst of the invention with different unit cell dimensions. FIG. 7 shows the steam path Pl! Figure 2 shows the variation in activity obtained with the catalyst of the invention as a function of temperature and unit cell size. FIG. l. Me? , rate FIG, 2゜FIG, 3゜FIG, 5゜FIG, 6゜AI-f'/-

Claims (1)

[Claims] 1. (a) In-situ production of Y-forujasite within the macropores of calcined microspheres formed by spray drying of an aqueous slurry of hydrous kaolin, sodium silicate, and calcined kaolin. crystallization to form microspheres containing the sodium form of Y-phasiasite;
The weight of Y-phosiasite is about 5% of the total weight of the microspheres.
and (b) increasing the lattice size of the Y-phasiasite in the microspheres by at least one ammonium exchange, followed by calcination in the presence of water vapor, and then another ammonium exchange. A method for producing fluidized pyrolysis catalyst microspheres containing Y-forujasite with a step of reducing the particle size to within the range of about 2.435 to about 2.455 nm; the surface area of the resulting catalyst is about 300 m^
2/g to about 425 m^2/g, and the sodium content (as Na_2O) ranges from about 0.3 to about 0 by weight.
．． 5%, and the apparent zeolite index of the catalyst is approximately 2.45
0 nm to about 2.460 nm, the catalyst is substantially free of rare earth oxides, and has pores in the range of 2 to 10 nm in size. The manufacturing method, wherein the volume is about 0.02 to about 0.25 cc/g. 2. The molar ratio of silica to alumina of the sodium form of Y-phasiasite is at least about 4.5;
A method according to claim 1. 3. The method of claim 2, wherein the molar ratio of silica to alumina of Y-phasiasite in the sodium form is from about 4.8 to about 5.2. 4. The method according to claim 2, wherein another calcination is performed after said another ammonium exchange. 5. The method of claim 4, wherein the sodium content (as Na_2O) of the catalyst is reduced to less than 2.0% by weight of total catalyst before calcination in step (b). 6. The method according to claim 4, wherein the size of the unit cell of Y-phasiasite after the first firing is about 2.460 to about 2.469 nm. 7. further comprising the step of mixing the produced catalyst microspheres with additive microspheres that are relatively catalytically inert to thermal decomposition, such that the weight of the additive microspheres is less than the weight of the total mixture; 2. The method of claim 1, wherein both amounts are about 35%. 8. The method according to claim 1, wherein the spray-dried catalyst microspheres are internally calcined. 9. The method according to claim 1, wherein the spray-dried catalyst microspheres are externally calcined. 10. Catalyst microspheres produced by any of the methods of claims 1 to 9. 11. (a) a microorganism containing at least about 40% by weight Y-phasiasite crystallized in situ in a silica-alumina matrix having a micropore volume of about 0.02-0.25 cc/g; Provide spheres; (b) sodium content of about 7-2.0% by weight of total catalyst (Na_2O
), followed by calcination, and then another ammonium exchange to reduce the unit cell size of the Y-forujasite by at least about 0.010 nm. A method for producing catalyst microspheres. 12. The method of claim 11, wherein the unit cell size is reduced to less than 2.460 nm and the final Na_2O content is reduced to about 0.3 to about 0.5% by weight of total catalyst. 13. Set the unit cell size to approximately 2.450 to 2.460n.
12. The method according to claim 11, wherein the method is reduced to m. 14. The final surface area of the catalyst is greater than 300 m^2/g, and the initial Y-phasiasite content of the provided microspheres is in the range of about 50 to about 70%, Claim 1
The method described in Section 1. 15. The final surface area of the catalyst is more than 300 m^2/g, and the unit cell size of Y-forujasite is 2.455.
12. The method of claim 11, which is less than nm. 16. The method of claim 11, wherein the final surface area is in the range of 300 to 425 m^2/g. The volume of pores in the range of 17.2 to 10 nm is 0.0
5 to 0.20 cc/g, and the volume of pores in the range of 10 to 60 nm is about 0.02 to 0.3 cc/g;
12. The method of claim 11, wherein the pore volume in the range 60-2,000 nm is less than about 0.3 g/cc. 18. The sodium content of the catalyst (as Na_2O) is 0.
．． 12. The method of claim 11, wherein the reduction is below 8%. 19, the sodium content (as Na_2O) of the catalyst is 1
．． 12. The method of claim 11, wherein the unit cell size of the Y-phasiasite is reduced to less than 5% and the unit cell size of the Y-phasiasite is reduced to less than 2.445 nm. 20, the sodium content of the catalyst (as Na_2O) is 0
．． 12. The method of claim 11, wherein the reduction is in the range of 3 to 0.5%. 21. For a fluidized pyrolysis catalyst consisting essentially of microspheres of substantially rare earth oxide-free crystallized Y-phasiasite with a unit cell size of less than 2.460 nm. , from about 0.2 to about 0 by weight of catalyst
．． 8% sodium (as Na_2O) content, approx. 0.
02 to about 0.25 cc/g and a micropore volume of 25
The catalyst is characterized in that it has a surface area of more than 0 m^2/g. 22. The catalyst of claim 21, wherein the unit cell size is less than 2.460 nm and the total porosity is less than about 0.25 cc/g. 23. The catalyst of claim 21, wherein the unit cell size is about 2.435-2.455 nm. 24. The catalyst according to claim 21, wherein the surface area of the catalyst is more than 300 m^2/g. 25. The catalyst according to claim 21, wherein the surface area of the catalyst is more than 350 m^2/g. 26. The catalyst according to claim 21, wherein the surface area is in the range of 300 to 425 m^2/g. 27, 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.
22. A catalyst according to claim 21, which is less than 3 cc/g. 28. The catalyst of claim 21, wherein the sodium (as Na_2O) content of the catalyst is from about 0.25 to about 0.5% by weight. 29. The catalyst of claim 21, wherein the sodium (as Na_2O) content of the catalyst is from about 0.3 to about 0.5% by weight. 30, the sodium (as Na_2O) content of the catalyst is 0
．． 22. The catalyst of claim 21, wherein the Y-phasiasite lattice size is in the range of 3 to 0.5% and the lattice size of the Y-phasiasite is from about 2.450 to about 2.460 nm. 31. Petroleum feedstock in a fluidized bed from about 900 to about 1
contacting a reduced lattice size, controlled micropore volume Y-fouriasite-containing catalyst at a temperature of 100°F, the catalyst having a surface area of about 250 m^2.
/g and the micropore volume is from about 0.02 to about 0.2
5 cc/g, and the sodium content of the catalyst (Na_2
O) is less than about 1% by weight, the lattice size of the Y-phasiasite is less than about 2.460 nm, and the Y-phosiasite is formed by in situ crystallization and substantially A process for fluid catalytic pyrolysis of petroleum feedstocks, characterized in that it is free of rare earth oxides and catalytically active transition metals. 32, the size of the unit cell of the Y-phasiasite is 2
．． less than 455 nm and the total pore volume of the catalyst is 0.2
32. The method of claim 31, wherein the cc/g is less than cc/g. 33. The method of claim 31, wherein the unit cell size of the Y-phasiasite is about 2.435 to about 2.455 nm. 34. The method of claim 31, wherein the surface area of the catalyst is greater than 300 m^2/g. 35. The method of claim 31, wherein the surface area of the catalyst is greater than 350 m^2/g. 36. The method of claim 31, wherein the surface area of the catalyst is in the range of 300 to 425 m^2/g. The volume of pores in the range of 37.2-10 nm is 0.05
~0.20 cc/g, the volume of pores in the range of 10 to 60 nm is approximately 0.02 to 0.3 cc/■, and the volume of pores in the range of 60 to 2,000 nm is approximately 0
．． 32. The method of claim 31, wherein the amount is less than 3 g/cc. 38.The sodium content of Y-phasiasite is 1.0
32. The method of claim 31, wherein the method is less than %. 39.The sodium content of Y-phasiasite is 0.8
32. The method of claim 31, wherein the method is less than %. 40.The sodium content of Y-phasiasite is 0.3
32. The method of claim 31, in the range of -0.5%. 41, (a) Formed by spray drying of an aqueous slurry of aqueous kaolin, sodium silicate and calcined kaolin.
In situ crystallization of Y-phasiasite within the macropores of calcined microspheres, (b) sodium content (N
(c) a first ammonium exchange of the sodium in the microspheres to reduce the amount (as a_2O) from about 2.0 to about 7% by weight of the catalyst, followed by a first calcination in the presence of water vapor; Y-forujasite-containing fluidized pyrolysis catalyst microspheres made by a step consisting of a second ammonium exchange to further reduce the sodium content (as Na_2O) to about 0.2 to about 0.8% by weight of the catalyst. , exhibiting a surface area of more than 250 m^2/g and a micropore volume of 0.02 to about 0.25 cc/g, and being substantially free of rare earth oxides. - catalytic microspheres containing faujasite. 42. The size of the unit cell of Y-fauziasite is 2.
42. The catalyst of claim 41, which has a particle diameter of less than 460 nm. 43. The unit cell size of Y-fauziasite is approximately 2
．． Claim 4, which is 435 to 2.455 nm.
Catalyst according to item 1. 44. The catalyst according to claim 41, wherein the surface area of the catalyst microspheres exceeds 300 m^2/g. 45. The catalyst according to claim 41, wherein the surface area of the catalyst microspheres exceeds 350 m^2/g. 46. The surface area of catalyst microspheres is 300-425 m^2/
42. The catalyst of claim 41 in the range g. The volume of pores in the range of 47.2 to 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
．． 42. The catalyst of claim 41, having less than 3 g/cc. 48. The catalyst of claim 41, wherein the sodium content (as Na_2O) of the catalyst is from about 0.25 to about 0.5% by weight. 49. Before the first firing, the sodium content of the catalyst (Na_
42. The catalyst of claim 41, wherein the catalyst reduces the amount of carbon dioxide (as 2O) to within the range of about 2.5 to about 3.5% by weight of the catalyst. 50, the sodium content of the catalyst (as Na_2O) is 0
．． 42. Catalyst according to claim 41, in the range 3-0.5%. 51. The fluid pyrolysis catalyst microspheres containing Y-phasiasite according to claim 41, wherein the Y-phosiasite within the microspheres does not substantially contain a transition metal.