FR2538366A1 - FAUJASITE TYPE NAY WITH HIGH SILICA / ALUMINUM RATIO AND PROCESS FOR PREPARING THE SAME - Google Patents

Abstract

The invention relates to a process for the production of a Y zeolite. According to the invention, a reaction slurry is formed by mixing a source of alumina other than metakaolin or kaolin, a source of silica, a source of soda, a source of seeds or nucleation centers and another reagent which is either a controller of active soda or a combined source of silica and reactive alumina having a low content of active soda, in order to control the concentration of active soda and one heats the reaction slurry obtained to crystallize the Y zeolite. The accompanying drawing shows a comparison of a Y type zeolite at a high silica / alumina ratio and a zeolite according to the prior art. The invention applies in particular to the preparation of catalysts for catalytic cracking. (CF DRAWING IN BOPI)

Description

The present invention relates to the production of a zeolite

  type Y having a high ratio of silica to alumina and the resulting single zeolite obtained. US Patent No. 3,130,007 to Breck is the basic patent for zeolite Y, and defines the zeolite in terms of moles of oxides as 0.9 + 0.2 Na 2 O: A 1203: W Si O 2 xl H 20 o W is a value greater than 3 up to about 6 and

  x can be a value up to about 9.

  The disclosed use of zeolite Y is as an adsorbent.

  Breck describes two types of silica sources.

  When the major source of the silica is a source of relatively inexpensive silica such as sodium silicate, silica gel or silicic acid, the zeolite Y composition usually prepared has silica / alumina molar ratios (Si O 2 / A 1203) which range from more than 3 to about 3.9 Examples are given in Tables III and IV The lowest amount of soda used is in the range 5 By multiplying the lowest ratio of Na 2 O to At 1203 (which is 0.6) with the lowest ratio of Si O 2 / A 1203 of 8, the lowest possible Na content is 4.8 moles which is above the A line on

  Figure 1 which will be described below.

  If it is desired to have zeolite Y product compositions having silica / alumina mole ratios greater than about 3.9, then Breck employs, as a preferable major source of silica, more expensive sources of silica such as aqueous silica sols.

  colloidal and reactive amorphous solid silicas.

  As these soils of colloidal silica and solid silicas

  Amorphous-reactive materials are expensive in comparison

  sodium silicate, Breck offers no teaching on how to produce such a zeolite Y to

  strong silica from reagents at fairly low prices.

  Breck also requires a first digestion

  at room temperature The criticality of this aging-

  For example, British Patent No. 1,044,983 to Esso discloses the production of Y-type zeolites having a ratio of silica to alumina of 3 to 7, where the reactants have Low ratios of silica soda and silica water As the Breck patent, the preferred source of silica and the material used in all examples that are claimed to give a ratio of 5.5-6.8 Si O 2 / A 1203 in a well crystallized Na Y form is a silica sol which is a costly material. US Pat. No. 3,808,326 to McDaniel et al. Discloses the use of seeds or centers having a dimension average of less than about 0.1 to produce Y-type zeolites. In Example II, the resulting zeolite particles are reported to have a silica to alumina ratio of about 5.0 to 6.0, but no individual value is given Si O 2 ratios at Ai 203 range from 2 23 9.5 to 14.5 and the amount of Na 20 that is added is

  indicated with the quantity in each case which is sup-

  than the amount used in the present invention.

  U.S. Patent No. 3,671,191 to Maher et al. Discloses the preparation of high silica synthetic faujasite using seeds and a ratio of silica to alumina reactants of about 16: 1 to this preferred ratio. for the synthesis of silica to alumina of 16: 1, the ratio of Na 20 to alumina shown in Example 1 is 6.6 This is identified by the point G in FIG. 1. Among the products obtained, there is one

  at a ratio of 5.2 in Example 2 and 5.4 in Example 3.

  U.S. Patent No. 3,639,099 to Elliott et al. Discloses the production of a faujasite having a silica to alumina ratio greater than 4 using seeds. The improvement of this patent was to use a lower silica ratio. A range of 8-12 Si O 2 to 1A 1203 is disclosed with a preferred ratio of silica to alumina in the reaction slurry of about -9: 1. In this case, the reaction mixture The lowest level at the ratio of silica to alumina of 9: 1 would be 3.1 moles of Na.sub.2 O. This point is identified by the F-point. In the figure Among the products made from a ratio of 10 to 1 in Table 1, the smallest amount of free Na 2 O used was 3.5 and this produced a zeolite having an SiO 2 / A 1203 ratio.

only 5.47.

  U.S. Patent No. 4,016,246 to Whittam et al discloses the preparation of a zeolite Y having a molar ratio of silica to alumina of greater than 3 up to about 6.2. The process requires the use of a "active" hydrated sodium metasilicate which can be

  distinguish conventional sodium metasilicates.

  This unique hydrate is produced by three methods described in the patent. Since this raw material is difficult to obtain because it requires special manufacturing techniques, it seems that Whittam's method is also expensive to implement. U.S. Patent No. 4,178,352 to Vaughan et al. Discloses a Y-type zeolite synthesis using a minimum of excess reagents. There is a general indication that the resulting zeolites may have

  silica to alumina ratio of about 4 to 5.5.

  However, the highest ratio produced shown in the examples is in Example 6 at a ratio of 5.1. The final reactive mixtures have for each mole of A 1203 from 4 to 7.5 moles of SiO 2 and 1, 2 to 3 Na Most of the examples use solutions of the reactants where the ratio of silica to alumina is 6 to 1 with 1.8 or 1.9 moles of Na. The point E in the figure represents this technique. the molar ratio of silica to alumina is 6 and there are 1.8 moles of Na 2 O

1 mole of alumina.

  US Patent No. 3,574,538 to McDaniel discloses the use of kaolin and in the preferred embodiment, metakaolin and sodium silicate in the form of water glass to prepare faujasite materials having a ratio of silica to silica. In the examples, the products are made with the strongest ratios of silica to alumina of from 90 to 5.95. However, in industrial practice, it is difficult to obtain kaolin and / or metakaolin corresponding to the desired chemical and physical properties

optimizing this process.

  Wilson's British Patent NI 431,944 discloses the production of a crystalline alumino-silicate zeolite having a molar ratio of silica to alumina of 5.5 to 8.0. Sequential Steps for the Addition of the Reagents First, a solution of a faujasite precursor is formed and heated. Then, a solution of sodium silicate is added to increase the molar ratio Si O 2 / A 1203. critical step, an aqueous solution of aluminum chloride is added to

  to form a gel slurry Additional steps-

  require heating, removing gel from the slurry and adding additional water to the gel

  with further heating to promote crystallization.

  Wilson's method does not relate to a synthesis process where all reagents are essentially-mixed

at the same time.

  The present invention relates to the production of a type Y zeolite having a high silica ratio

with alumina of more than 5.0.

  Another object of the present invention is the production of a type Y zeolite having a high silica to alumina ratio, a high degree of crystallinity.

and an absence of occluded silica -

  Another object of the present invention is to obtain a Y-type zeolite with a high silica content made from a source of alumina other than metakaolin or kaolin. Another object of the present invention is to obtain a high silica Y-type zeolite which can be used for catalytic purposes by employing inexpensive sources of silica such as sodium silicate, silica gel or silica gel. silicic acid. Another object of the present invention is to lower the active sodium hydroxide content in the reaction mixture to obtain a type Y zeolite with a high

silica content.

  It is another object of this invention to provide a mother liquor with alum from a previous synthesis as a raw material when the active soda content is lowered to produce a zeolite Y.

high silica content.

  These and other objects will become better

  apparent from the description of the invention

following.

  High silica / alumina type Y-type sodium faujasite, HSAY, is produced by carefully controlling the active soda content to a level below the conventionally used amounts. Y-type faujasite is produced from one source. of alumina other than metakaolin or kaolin while the source of silica is an inexpensive source such as sodium silicate, silica gel, silicic acid or mixtures thereof The sodium content can be reduced by the one of two different techniques or a combination of the two The first is to add a controller of active sodium hydroxide as an acid and / or a solution of an aluminum salt that is obtained from aluminum and an acid which reduces the amount of active sodium in the porridge

$ 25 3 G 36;

  synthesis of zeoliteo The preferred materials are a

  dilute acid or a dilute solution of aluminum sulphate.

  The other technique is to use, as starting reagent, a combined source of reactive silica and alumina having a low active soda content.

  can be used in conjunction with the individual source

  dual silica and alumina source described above.

  A preferred combined source is a mother liquor previously

  lable which has been treated with an aluminum salt to obtain an aluminum salt gelled mother liquor having a low sodium content A preferred aluminum salt for this embodiment is sulphate

  aluminum which is also known as alum.

  By lowering the sodium hydroxide level, it is possible to produce unique and well crystallized Na 2 zeolites having a silica / alumina ratio of 5.0 and above and in particular at levels of 598 and higher. The silica / alumina may also be ion exchanged with rare earth or ammonium cations at even lower levels of Na to produce a more thermally stable, steamed zeolite promoter for the petroleum cracking catalysts.

  petroleum hydrocracking catalysts and others.

  Y-type faujasites obtained by this method have a high degree of crystallinity. When these materials are studied by magic-angle spinning nuclear magnetic resonance (MASNMR) as will be better described below, the peaks for Si Cl All and Si LO Ai are more acute than comparable commercial samples By expressing the sharpness with respect to the peak of Si l 2 A 1 1 and multiplying by ten, we obtain an index of acuity, SI The value of SI for the peak of Si 11 All is at least 6 and preferably at least 7 while SI for the Si 10 All peak is at least about 2.2.

and preferably at least 2.5.

  The invention will be better understood, and other purposes, features, details and advantages thereof

  will become clearer during the description

  explanatory text which will follow with reference to the accompanying schematic drawings given by way of example only, illustrating several embodiments of the invention and in which: FIG. 1 is a graph of slurry compositions for producing type Y faujasites in terms of Na 2 O and Si O 2 to A 120 ratios; FIG. 2 shows the deconvoluted MAS NMR spectra for high Y-type zeolite.

  silica according to the present invention and for commercial Na Y

  ized; and Fig. 3 is a graph of Si O 2 / Al ratio as a function of a unit cell length for high-ratio Na Y-type faujasite.

silica with alumina.

  High silica / alumina Y-type sodium faujasites are produced from sources of alumina, silica, soda, seeds or nucleation centers and another reagent which allows for reduced concentration.

  of active soda to be present in the reaction mixture.

  Preferred sources of alumina can be.

  either alumina trihydrate, alumina monohydrate, sodium aluminate solution or sodium sulphate (alum) solution Other possible sources of alumina may be alumina gel, hydroxide aluminum, aluminum chloride, aluminum nitrate or other aluminum and acid salts It is particularly desirable not to use kaolin or metakaolin because in industrial practice it is difficult to get these two materials

  in a form that meets the chemical and.

  desired physics optimizing this process.

  Preferred sources of silica are inexpensive sources such as sodium silicate,

  silica, silicic acid or mixtures of these materials.

  It is particularly desirable for an application

2538364;

  industrial, not to use the relatively expensive sources of silica such as aqueous sols of colloidal silica or the more expensive forms of reactive amorphous solid silica Another possible source of silica is a mother liquor gelled with alum which will be described

better below.

  The preferred source of soda is obtained from the sodium salt form of the compounds used to provide silica and alumina, ie sodium silicate and sodium aluminate. Other possible sources of soda are sodium hydroxide and sodium carbonate, although it should be remembered that the purpose of this invention is to reduce the amount of sodium hydroxide in the reaction mixture. Seeds or nucleation centers may be the seed material of conventional zeolite Y or the mother liquor of the production of zeolites A,

  X or Y or mother liquors gelled with alum.

  A preferred method of seed production is disclosed in McDaniel et al US Patent No. 3,808,326, and

  will be described hereinafter in Example 1.

  The other reagent that allows a reduced concentration of active sodium hydroxide to be present in the reaction mixture can be added in one of two forms or a combination of the two. In the first form, the material is considered as an active soda controller. because it will react with the active soda in excess to bind it so that it does not adversely affect

  the synthesis of zeolite Y with a high silica content.

  Examples of the materials controlling this active soda concentration are the acids, the salts obtained from the reaction of aluminum with an acid, and the mixtures of these two materials. The acid is preferably added in dilute form and a preferred acid. In the preferred embodiment, these added active soda controllers are added at the time of mixing the slurry or they are added approximately within 3 hours from the time the slurry has been heated. to get the results the

more effective.

  The other form of the other reagent is to provide a combined source of reactive silica and alumina having a low active soda content. This can be done by adding an aluminum salt to the mother liquor containing silica from from previous production to precipitate a hydrogel from

  silica / alumina having a low active sodium content.

  Examples of the aluminum salts include aluminum sulphate, aluminum chloride, aluminum nitrate or mixtures thereof Aluminum sulphate (alum) is the preferred salt A preferred example of this recycling technique is disclosed in U.S. Patent No. 4,164,551 to Elliott, alum, which is aluminum sulphate, is added to the filtered mother liquor to precipitate a silica / alumina hydrogel. This hydrogel is referred to as AGML or gelled mother liquor. Alum and its mother liquor or other mother liquors gelled with aluminum salt may be used directly as a raw material in the production of faujasite

  high silica content according to the present invention.

  According to the invention, the content of active sodium hydroxide

  should be reduced below the conventional

  With reference to FIG. 1, line A illustrates the conventional formulas which produce a faujasite having an SiO 2 to A 1203 ratio of 5.0 for a G-point reaction slurry with 16 moles of SiO 2. for each mole of A 1203 9 it was traditional to have an Na 0: Al O ratio of about 6.6 For a porridge

2 23

  reaction at point F with 9 moles of SiO 2 for each mole of A 1203, the ratio of Na 20: A 1203 has its lowest value at about 3.1 while for a reaction mixture at point E with 6 moles of If O 2 for each mole

  From A 1203 the ratio of Na 20: A 1203 is 1.7.

  Thus, the line A is based at least on the following points for ratios in the synthesis slurry. Ratio Report Si 02: Al 203 Na 20: Al 203

16: 1 6,6: 1

9: 1 3,1: 1

6: 1 1,8: 1

  In Figure 1, the moles of SiO 2 for 1.0 to 1203 in the slurry are indicated on the abscissa and the moles of Na 20: 1.0 to 1203 in the slurry on the ordinate a indicates the slurries according to Art. former giving Na Y having a ratio of Si O 21.0 to 1203 of 5.0 and b indicates the slurries of the present application which give

  HSAY having a ratio of Si O 2: 1.0 to 1203 of 5.8.

  According to the present invention, sodium hydroxide levels are reduced to levels below line A by the addition of an active sodium controller such as an acid and / or an aluminum salt and an acid. The preferred forms of the acid or salt are dilute solutions and a preferred form of the salt is a dilute solution of aluminum sulphate (alum). Active soda is lowered to the levels indicated in line B of FIG. 0, for a reaction slurry having 16 moles of SiO 2 for each A 1203, the ratio Na 2 O: A 1203 will be about 0, and for a slurry of reaction with 9 moles of SiO 2 for each A 1203, the Na 2 u: A 1203 ratio will be about 2.4. Using this starting composition, Na Y faujasites having an SiO 2 to A ratio are obtained. 1203 from 5.8 to 6.0 Thus, line B is based on at least the following points for additions in the synthesis slurry Ratio Si O 2: A 1203 Ratio Na 20: A 1203

16: 1 5.0

9: 1 2,4

2538366;

  When adding materials to the reactor, care should be taken that gels do not form which are

  subsequently difficult to disperse or dissolve.

  When the materials are added sequentially, a preferred order is to first add the diluted sodium silicate, then slowly add the dilute acid with stirring, and then slowly add the dilute sodium aluminate with stirring and stirring. finally adding the seeds Another preferred method for accelerating the addition of the reagents is to bring the reactants in three streams to a fast mixer which forms a soft gel which can be directly fed to the crystallization reactor. A stream contains the sodium silicate and the seeds, the second stream is a dilute acid stream and the third stream is a

  diluted sodium aluminate stream.

  In another embodiment, after initial heating of the reagent mixture, the liquid volume of the slurry can be reduced by decantation so that subsequent crystallization, carried out for a relatively long period of time, can significantly reduced volume of reagents as a 2/3 volume reduction due to additional liquid removal The initial heating period can 'vary from a relatively short time like about 15 minutes to longer periods like a day Like the reaction is carried out in an all aqueous system, the mixture can be heated to temperatures of about 1000 C without requiring equipment

under pressure.

  Using a reaction slurry having a ratio of 16 Si O 2 to 1 Al 1203, Y-type sodium faujasites with SiO 2 / Al 2 O ratios of about 5.4 to about 6.0 are obtained according to the reduced amount of active sodium hydroxide present By using a reaction slurry having a ratio of 9 SiO 2 to 1 Al 2 O 3, sodium faujasites of type Y are obtained.

253866 ô

  with ratios of Sio 2 / A 1203 of between about 5.3 and about 5.8 depending on the reduced amount of active sodium hydroxide

present -

  HSAY zeolite, like conventional zeolites

  Na-type, may be ion-exchanged with solutions of rare earth salts or other metal salts or ammonium ion salts or combinations thereof to reduce the level of Na + ions in the zeolite to produce a thermally and hydrothermally stable promoter or activating agent for a catalyst for the treatment of petroleum fractions Such an ion exchange can be carried out by putting HSAY having a content of Na 2 O, as synthesized, of the order of 1015%, in contact with a solution in water of any salt mentioned above for 1 minute to 100 hours at temperatures of 0 to 1000 C, slipping the mass and washing the zeolite filter cake repeated exchanges with or Without calcination of the exchanged zeolite can be done to reduce the Na + ion content of the zeolite exchanged to a value of only 0.1-5% Na depending on the use of the activating agent. from HSAY echan These ions exchange processes are well

  known to those who are competent in the field of

  the ion exchange can be done after

  transformed the HSAY promoter into a catalyst.

  The high silica Y zeolites obtained by this process are considered unique and this is characterized by their high degree of crystallinity by measuring by the sharpness of their nuclear magnetic resonance (NMR) spectrum that one will describe hereinafter and by the absence of occluded silica While the SiO 2 / Al 2 O ratio increases, there is a change in the nature of the chemical bond involved S Ramdas and others in their article "Ordering of Aluminum and Silicon in Synthetic Faujasites, "Nature, Volume 292, July 16, 1981, at pages 228-230, reports that zeolites can have five types of silicon or aluminum silicon bonds. These five types of bond are expressed by a notation that gives the number of aluminum atoms to which silicon is bound by oxygen atoms Each silicon is bonded to four oxygen atoms, each of which is in turn bound to silicon or aluminum. five types of are Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al) and Si (O Al) o Thus, when silicon is bound by the four oxygen atoms to four atoms Aluminum, the notation is Si (4 Al). Klinowski et al. can also be seen in "A Revision of SI, Ordering in Zeolites Na X and Na Y" in J Chem Soc, Faraday Trans 2, 78, 1025-. 1050 (1982). The authors of Ramdas et al. Identified the five types of binding using nuclear magnetic resonance. Table 1 below gives the distribution of the five types of binding for a conventional Na Y having an Si O ratio. 2 / A 1203 of 4.8 and the theoretical distribution for a material of the HSAY type having an SiO 2 / A 1203 ratio of 6.0. For comparison, the table also gives the idealized bond possible for Na-type faujasite. X.

Table 1

  Type of Faujasite Nax Na Y HSAY Ratio Si O 2 / A 1203 2.4 4.8 6.0 Distribution of bonds (idealized) Si (4 Al) 16 OO Si (3 Al) 8 4 O Si (2 Al) O 16 16 If (1 Al) o 12 16 If (O Al) 2 2 4 The material of the type HSAY, when it is made according to the preservative 3 rdion, p 1 us of the airs Si (1 Al) and If (O Al) a conventional Na Y zeolite and less

$ 38366.

Si bonds (3 Al).

  To experimentally measure these five types of bonds, we obtain a high-resolution 29 Si nuclear magnetic resonance spectrum as shown in Figure 3 of the article by Ramdas et al. And a simulated curve to the calculator is produced based on the shapes of the Gauss peaks The area under the curves represents the relative populations

of the five possible modes.

  This new analytical technique was also used to determine the actual ratio of Si O 2 / A 1203 in the crystal lattice, to identify occluded silica if present, and to determine how the sample is crystallized. silicon-29 nuclear magnetic resonance, which is an isotope of silicon present at the extent of 4.70% of all silicon atoms. The spectra are obtained at 79.45 M Hz using an angle spinning. A two-sample HSAY labeled A and B produced by the present invention and a commercial NaY sample produced by the method taught by US Pat. 3,639,099 were studied by this NMR technique using MAS Sample A was produced by the method similar to that shown in Example 15 below and Sample B was produced by the method similar to that shown in Example 5. The NMR results showed that HSAY had an SiO 2 / A 1203 ratio in the 5.6 + 0.4 network, which there was no occlused silica and the crystallization was very good For this case, the ratio Si O 2 / Al 203 will be determined by the conventional wet chemical method The ratio determined by the nuclear magnetic resonance data was given because this value is strictly in terms of the amounts of silica and alumina in the crystal structure Si of silica

2538366.

  occluse is present, it can not be included in the

  -Resort determined by nuclear magnetic resonance.

  However, the NMR data is less precise as shown by the greater uncertainty for the values reported in Table 2. SAM spectra were obtained at 79.45 M Hz and referenced to tetramethyl silane using an external reference standard of HMDS. (hexamethyl disiloxane) and assuming HMDS = +6.7 ppm relative to TMS (tetramethyl silane). The spectra show five characteristic peaks of the five possible environments for tetrahedral framework silicon in zeolite structures as indicated by the spectra shown in Figure 2 The scale in Figure 2 is relative

  at TMS with the peak for TMS occurring at zero.

  Spectra were deconvolved into components

  separated by assuming that their nature was Gaussian.

  The full spectrum assignment is given in Table 2 below, with the peak areas corrected to account for the small differences in sideband corrections. These small differences in the offset values of the table, in comparison with those of the spectrum, are The areas of each peak were adjusted so that the sum of the areas of the five peaks was equal to 100 W, of each peak at half the height of the peak was also calculated. If L 1 All and Si L AIl of the HSAY sample of Figure 2 are more acute than comparable peaks of marketed Na Y this acuity can be mathematically defined as follows. If the peak area of Si l 2 Al J of each sample of Y is used as a reference, a dimensionless acuity factor, S, for each part is defined by S = Peak area = A (width at half-height) 2 W 2

  Then, the index of acuity, S I of each peak.

  other than the peak of Si l 2 Alj can be defined as S.I = 10 S Si N Ad Si l 2 Alj These values for n = 0 and 1 are given in Table 2 below.

Table 2

  Trade sample Si 02 / A 1203 ratio by NMR by chemical analysis Types of peaks Si (2 Al) Surface, A Width, w, at 1/2 height Sharpness, A / w 2 Si (1 Al) Surface, A Width, w, at 1/2 height Sharpness, A / w 2 Sharpness index * Si (o A) Surface, A Width, w, at 1/2 2 height Sharpness, A / w 2 Sharpness index *

, 2 + 0.4

, 0 + 0.1

  36.0 3.1 3.75 42.4, 1 1.63 4.3 9.0 3.6 0.69 1.8

, 5 + 0.4

, 9 + 0.1

  34.5 3.35 3.07 47.5 4.6 2.24 7.3 9.3 2.8 1.19 3.9 HSAY B

6.0 + 0.4

6.0 + 0.1

  33.7 3.2 3.29 47.1 4.0 2.94 8.9 13.6 4.0 0.85 2.6 * Acuity index = peak acuity of Si (1 Al) or

  If (O Al) x 10 / peak acuity of Si (2 Al).

  The data in Table 2 show that HSAY peaks of Si l 1 Al l and Si l OAil are much more acute than the same commercial Na Y peaks. The Si 1 Al J peak has a sharpness index, SI, at least 6 and preferably at least 7 while the peak of Si TO Alll has a

  S 1 index of about 2.2 and preferably at least 2.5.

  This sharpness of the Si I 1 All and Si IO AIJ peaks of HSAY according to the invention demonstrates the high SiO 2 / A 1203 ratio of the HSAY crystal lattice and the high degree of

crystallinity of HSAY.

  As described above, the magic angle NMR spectrum can indicate whether there is occluded silica because there will be a separate characteristic peak for silica that is characterized by silicon atoms that do not are related only to oxygen atoms where oxygen atoms are not linked to atoms other than the

silicon.

  The presence of occluded silica can also be determined from the length data of a unit cell E Dempsey et al; in the Journal of Physical Chemistry, 73 (2), 387-390, (1969) compared the chemical analysis as a function of the length of a unit cell of various Na X and Na Y faujasite samples. The smallest length of a unit cell among their Na Y samples was 2.466 nm for a Na Y having an Si O 2 / A 1203 ratio of 5.32 by chemical analysis. However, their length of a unit cell according to the number of aluminum atoms per unit cell (Figure 1 of their article) shows that the lowest number of aluminum atoms per unit cell is 53, which corresponds to a cell size or length of unit cell of 2.4665 nm Although they examined several other samples of Na Y o chemical analysis reported ratios up to 5.83, none of the samples of Na Y has a smaller unit cell, in length, that 2.4665 nm Therefore, they suggest that the Si O 2 / A 1203 high ratio ntillons contain

amorphous silica.

  If a sample of Na Y contains amorphous silica in an intimate mixture with crystalline Na Y, the apparent ratio by volume chemical analysis is more

  high than the actual ratio in the crystal lattice.

  Their data in Table I are shown in Figure 3 in the form of the size of a unit cell as a function of the ratio of Si O 2 / ba 203. The empty squares in Figure 3 show the data for well crystallized samples of Na Y; the length of a unit cell is inversely proportional to the ratio of Si O 2 / NA 203 The triangles in Figure 3 demonstrate that Na Y samples having a high ratio by

  chemical analysis do not show a progressive decrease

  sive the length of the cell with increasing ratio; these samples represented by triangles

  probably contain amorphous and occluded silica.

  For these high ratio samples, the cell length remains at 2.466-2.467 nm even though the ratio increases from 5.4 to 5.8 It can be concluded that the highest ratio in the crystal lattice of Na samples The y-squares they studied were 5.3 The solid squares in Figure 3 show the length of a unit cell as a function of the ratio of Si O 2 / A 1203 for a silica-type Na Y type faujasite. The solid squares appear to be generally an extension of the empty squares and demonstrate that the HSAY samples according to the invention have a unit cell length which is proportional to the ratio of Si O 2 / A 1203 obtained by chemical analysis. Solid squares continue to a cell length

  unit of 2.458 nm corresponding to a ratio of 6.0.

  Therefore, the HSAY samples of the present invention do not contain occlusive and amorphous silica intimately mixed with faujasite. Moreover, the ratio obtained by chemical analysis of each sample is the actual ratio of Si O 2 / Al 2 O 3 to crystal lattice. The unique high silica type Y zeolites produced by the present invention, with their high degree of crystallinity and absence of occluded silica

  are very useful as catalyst material Cescataly-

  The HSAY is ion exchanged to lower the alkali content and

  add catalytically active and stabilizing ions.

  Typically, HSAY is exchanged with rare earth ions and / or ammonium and hydrogen ions.

  be exchanged for ions either before or after the inclusion of

  In addition, the ion-exchanged HSAY can be calcined, i.e., heated to temperatures of about 200.degree. at 700 ° C either before or after inclusion in a catalyst matrix Preferably, HSAY, when it is used as a hydrocarbon cracking catalyst, has an alkali metal content, usually expressed

  by the sodium hydroxide content, Na 20, less than 6% by weight.

  The conversion of zeolite HSAY into a catalyst

  Useful particle size is obtained by dispersing the finely divided HSAY zeolite in a matrix of an inorganic oxide. The inorganic oxide matrix may comprise or include silica-alumina, alumina, silica salts or hydrogels in combination with additives. like clay, preferably kaolin

  and other zeolites such as zeolites of the ZSM type.

  The catalyst compositions can be prepared according to the teachings of US Patent No. 3,957,689 which is to combine a finely divided zeolite and clay with an aqueous slurry which is spray dried and ion exchanged to obtain a very active conversion catalyst. In addition, the method of preparing the catalyst may be as generally indicated in Canadian Patent No. 967,136 which is to combine zeolite and clay with a binder of an acidic alumina sol. it is desired to obtain a catalyst containing a silicone hydrogel binder, it is possible to use

  the treatment methods of US Patent No. 3,912,619.

  As indicated above, HSAY zeolite is particularly resistant to

2538366 '

  hydrothermal activation dams normally encountered

  during the regeneration of the cracking catalysts.

  Regeneration includes high temperature oxidation (burning 3 to remove accumulated carbon deposits at temperatures up to about 1000 ° C). Furthermore, the catalysts that contain the HSAY described herein are found to be particularly resistant to contaminating metal deactivation assays. such as nickel and vanadium, which are rapidly deposited on the catalyst during the cracking of

residual type.

  While the precise reason why HSAY of the present invention and the catalysts containing HSAY described herein are particularly active and stable is not fully understood, it is believed that this particularly high degree of catalytic activity and stability after the vapor and in the presence of contaminating metals is due to the unique structure as described by S Ramdas et al. in the article "Ordering Of Alumin And Silicon In Synthetic Faujasites", Nature, Volume 292, July 16, 1981,

pages 228-230.

  In use, the catalytic cracking catalysts of the present invention are combined with a hydrocarbon feedstock which can typically include residual type hydrocarbon fractions containing up to about 1,000 parts per million. of nickel and vanadium and up to about 10% by weight of sulfur, 2% by weight of nitrogen. The cracking reaction is normally carried out at a temperature between about 200 and 6000 C using a ratio of catalyst to oil of the order of 1 to 30 During the cracking reaction, the catalyst typically accumulates about 0.5 to 10% carbon, which

  then oxidizes during regeneration of the catalyst.

  These catalysts are found to be capable of maintaining levels of activity even after accumulation up to

  about 4% of contaminating metals.

  The catalysts may advantageously be combined with additional additives or components such as platinum, which improves the CO / S Ox characteristics of the catalyst. Preferably, platinum is incorporated in the total catalyst composition in amounts of about 2 to 10 parts per million. Furthermore, the catalysts can advantageously be combined with S oxide getter components such as lanthanum / alumina compounds which contain

  20% by weight of lanthanum oxide.

  Having described the basic aspects of the invention ,.

  the following examples are given to illustrate

  specific embodiments.

EXAMPLE 1

  This example illustrates the preparation of nucleation centers or seeds, as revealed in

  McDaniel et al., U.S. Patent No. 3,808,326.

  A solution of 919 g of sodium hydroxide in 2000 ml of water was heated to dissolve 156 g of alumina trihydrate (A 1203 3H20) and the solution was then cooled to room temperature and evaporated. A second solution B was prepared by mixing 3 126 g of sodium silicate at 41.20 B.

  (Weight ratio 1.0 Na 20: 3.22 Si O 2) in 1 555 ml of water.

  Then, solution A was mixed in solution B with rapid stirring. The mixture was aged at room temperature for about 24 hours and then the slurry of the nucleation centers or seeds was ready.

for use.

EXAMPLES 2-5

  These examples illustrate the production of high silica / alumina type Y-type sodium faujasite where the seeded slurry has a silica / silica ratio.

alumina 16: 1.

  The solutions of the reagents were prepared as follows. A dilute acid solution was prepared by adding the various amounts of concentrated sulfuric acid having a density of 1.84 as shown in Table 1 to 100 ml of water and we waved

The mixture -

  A dilute solution of sodium aluminate was prepared by adding 91 g of a sodium aluminate solution containing 17.29% Na by weight and 21.896% by weight.

A 1203 by weight to 214 g of water.

  A dilute solution of sodium silicate was prepared by pouring 648 g of a silicate solution

  of sodium at 41.2 Bé having a ratio of 1.0 Na 20: 3.22 Si 02-

  in a Hamilton Beach blender cup of 10134 g and adding 200 ml of water and the water was totally mixed with sodium silicate in the blender While the blender was mixing, the diluted acid was added into the silicate diluted with the addition of the diluted aluminate Finally 47 g of seed slurry were added

in the mixture.

  The slurry was poured into tightly closed polypropylene bottles. The bottles were heated in a water bath until the slurry reached a temperature of 851 C, at which time the slurries were transferred to an oven. heated to 100 ° C. Samples of the slurry were taken from time to time while stirring the contents well and removing 50 ml of the slurry. The samples were filtered and washed at a pH of 10-10.5 and dried in a brine. oven at 1000 ° C, the percentage of crystallinity of each sample by X-ray powder diffraction techniques was compared to a commercially available sample and

  well crystallized Na-type faujasite The superficial

  The sample nitrogen was measured after degassing the sample at 538 ° C for 1 hour, by

  chromatographic method on a Perkin-

  Elmer-Shell 212 D or by the BET method on a

Adsorptomat Aminco.

  The dimension of a unit cell of a cubic cubic cell of HSAY o the three axes have

  an equal length (a = b = c) was measured as follows.

  About 1 g of HSAY powder which had been equilibrated in a desiccator was mixed overnight in an atmosphere at 33% relative humidity, with about 1 g of silicon metal powder. of X-ray powders made using filtered copper radiation through a nickel sheet The diffraction pattern was recorded from about 5212 e to 6002 e The position in degrees 2 e of the 997 plane reflection (h = 9, k = 9 and 1 = 7) and plane 999 was measured The first was published at about 54.0-54.202 G and the second at about 58.7-58.9 2 G The internal silicon standard had a reflection at 56.12 2 & theoretically The measured value of 26 for the two HSAY planes was corrected by the amount that the silicon peak varied from 56.12 Then the unit cell was calculated using the equation of the Bragg law: a = h 2 + k 2 + 12 2 sin G o A is the wavelength of copper K radiation of 0.154718 nm The unit cell was the average of

Plan 997 and Plan 999 -

  The resulting Na Y type faujasites produced, described in Table 3 below, which were crystallized from the slurries of Examples 2-3 had a ratio of

  If O 2 / A 1203 high and in particular to Examples 4 and 5.

Table 3

  Synthesis of, from Na Y faujasite at high boiled silica-alumina ratio seeded "16 Si 02: 1.0 A 1203"

Super area

  Nitrogen ratio m 2 / g Ratio Si O 2 / A 1203 by chemical analysis, 4, 7, 9 6.0 Unit cell size, nm 2.461

2,460.

2,459 2,458

Example

N Moles Na 2: 1.0

* To 1203

, 5, 4, 2, 0, Acid

sulfuric

America

concentrated

  tré (g) 16.7, 9 24.9 29.1 Hours in

1001 + C

crystal-

Us w w q

2538366 '

EXAMPLES 6-9

  These examples illustrate the production of high silica / alumina Y-type sodium faujasite where the seeded slurry had a silica: alumina ratio of 9: 1. The sodium silicate and sodium aluminate solutions had the same concentrations as in the Examples. Sodium silicate and half of the water were mixed in the blender cup of 1144 g of a Hamilton Beach mixer The seeds prepared according to Example 1 were added to the amounts shown in Table 4 and mixed. The sodium aluminate solution was mixed with the other half of the water. The mixture became very viscous, to the point where it has gelled, and the mixer has been stopped The gel has been scraped carefully and completely from the mixer cup, transferred to the bowl of a kitchen mixer

  Hobart After putting the Hobart mixer into operation

  The rest of the sodium aluminate solution was slowly added. Then the aluminum sulphate solution (alum), having 7.8% of A 1203 was slowly added while continuing the mixing. The thick gel and pasty was placed in 250 ml or 500 ml polypropylene bottles which were sealed in a non-watertight manner. The remaining heating and analysis process was as in Examples 2-5 The resulting Na-type resulting faujasites , described in Tables 4 and 5 were crystallized from the slurries of Examples 6-9 and had a high ratio Si O 2 // A 203, in particular

in Examples 8 and 9.

Table 4

  Synthesis of Na Y faujasite with a high silica-to-alumina ratio from seeded slurries "9 Si O 2: 1.0 to 1203 Reagents Moles Na 20: 1.0

A 1203

  3.0 2.8 2.6 Seeds g. Sodium aluminate solution g Water Sodium silicate g Solution

A 12 (504) 3

g

9 2.4 175

Example

NOT

96,169

774,289

Table 5

  Synthesis of Na Y faujasite with a high silica-to-alumina ratio from seeded slurries "9 Si O 2: 1.0 to 1203" Reaction time and product analysis Example Hours

N 100 + 1 C

%

crystal-

Linite

Superficial area

  Nitrogen ratio 2 / g m / g Ratio Si O 2 / A 203 by chemical analysis, 3, 4, 6, 8 Dimension of a unit cell, nm 2,464 2,462 2,461 2,460 rla seen Co Cr% i 0%.

2538366 '

EXAMPLE 10

  This example illustrates the synthesis using a reduced volume of the slurry after an initial heated reaction so that the crystallization step performed over a relatively long period of time can be done with a substantial reduction in the required volume. A 16: 1 slurry of silica with alumina was prepared having the composition according to Example 5. The slurry was heated in a bottle without stirring for 24 hours at 1000 C. During this period,

  solids settled at the bottom of the bottle After -

  During the 24 hour heating period, the mother liquor was removed by decantation, so there was about 2/3 reduction in volume. The remaining solids surrounded by the mother liquor were then heated at 1000 C for 131 hours to obtain a good product having a surface area of 897 m 2 / g, a crystallinity of 94% with a unit cell size of 2.459 nm This corresponds to a ratio of Si O 2 / Al 2 O 3 of 5.9 as

can see it in Table 5.

EXAMPLE 11

  This example illustrates the production of Y zeolite using a reduced volume of slurry with

  a shorter period of initial heating.

  A procedure similar to that used in Example 10 was followed except that instead of heating the slurry for 24 hours at 1000 ° C., it was heated at 1000 ° C. for 15 minutes. The solids were then returned to the bottle and a quantity of mother liquor just sufficient to cover the solids was added there. As these solids were more fluffy than those produced in Example 10, took a larger amount of liquor The volume reduction was about 55-60%, which is slightly lower than

  the volume reduction obtained in Example 10.

  After crystallization of the mixture at 1000 C for 144 hours, the product had a crystallinity of 107%, the unit cell α-dimension was 2.461 nm and the wet-chemical analysis of SiO 2 / A 1203 was 5.8. This example also shows obtaining a good product at reduced volumes of crystallization with the recovery of excess mother liquor which can be

  recycled or used for other purposes.

EXAMPLE 12

  This example also illustrates the synthesis using a reduced volume of slurry with a period

  initial slightly longer heating.

  In this example, the exact procedure of Example 11 was followed except that instead of initially heating the slurry to 1000 C for 15 minutes, it was heated for 1 hour. The solids were filtered as in example 11 process and we just added

  enough mother liquor to cover the solids.

  After heating at 1000 ° C for 93 hours, the percent crystallinity was 109%, the unit cell α-dimension was 2.460 nm and the SiO 2 / A 1203 ratio by wet chemical analysis was

of 5.8.

EXAMPLE 13

  This example illustrates the use of an alum AGML gel mother liquor to provide some of the silica and alumina reactive materials when using a silica / silica slurry.

alumina 16: 1.

  From a previous production of a type Y sodium zeolite made by the method of US Pat. No. 3,639,099 to McDaniel et al., The filtrate typical of the mother liquor filtered from the fully crystallized Na Y batch contains 4.9 g. % If O 2 and 4.0% Na 2 O

S 58366

  A solution of aluminum sulphate (alum) is added and the silica-alumina gel, AGML precipitates and is recovered by filtration The gel contains: 12.6% Si O 2 3.4% Na 20

2.8% to 1203

2.6% SO 3, and

the rest being water.

  A slurry for the synthesis of a high silica faujasite according to the present invention was made by mixing, in a mixer, 300 g of AGML with 200 g of water and 510 g of a sodium silicate solution ( 41.2 Be, containing silica and sodium hydroxide at a ratio of 3.22 Si O 2: 1.0 Na 20). Then 54 g of sodium aluminate solution (18.2) were added. % Na 20;

  21.4% to 1203), diluted with 185 g of water and mixed well.

  Finally, 47 g of a mixture were mixed in the mixer.

  seeded slurry as produced in Example 1.

  The effective ratio of the slurry was 5.2 Na 20: 1.0 to 1203:

16 If O 2: 280H 20.

  The fully mixed slurry was placed in a 1.0 liter polypropylene bottle, which was placed in an oven at 100 + 1 C. After 61 hours, the slurry produced a well crystallized faujasite of Na Y, of the high silica type of the present invention having a nitrogen surface area of 952 m 2 / g This was measured on a Digisorb instrument manufactured by Micromeritics Inc, Norcross, GA. HSAY faujasite had chemical analysis following: 10.7% Na 20 19.8% A 1203 69.5% Si O 2 with a ratio Si 02 / A 1203 = 6.0 and crystallinity

102%.

  It is an efficient use of a residual current.

EXAMPLE 14

  This example illustrates the use of an alum gelled mother liquor to provide a portion of the silica and alumina reactive materials when using a

  boiled to a ratio of silica to alumina of 9: 1.

  1080 g of AGML produced as described in Example 13 were placed in a mixer tank and 319 g of 41, -20 Be silicate was added and blended into the blender. 69 grams of a sodium aluminate solution were then slowly added and mixed. The slurry became stiff, but softened after mixing for 1 to 2 minutes. Finally, 93 grams of a slurry of seeds were added. according to Example 1 The slurry was transferred to a 1.0 liter polypropylene bottle and heated in a 100 + 10 C oven. The effective ratio of oxides in the

  slurry was 2.4 Na 2 O: 1.0 AI 203: 9 Si O 2: 140H 20.

  After 44 hours, a high silica Y-faujasite crystallized, having a nitrogen surface area of 937 m 2 / g and good crystallinity measured as 101% in comparison with Standard Na Y Marketed The chemical analysis of the composition on a dry basis was as follows

  10.9% Na 2 O 20.4% A 1203 68.7% Si O 2-

  The SiO 2 / AM 203 ratio was 5.7.

EXAMPLE 15

  This example demonstrates the amplification of the 56.77 liter batch process which yields almost 6.0 kg of

dry product.

  40.0 kg of commercial sodium silicate (Philadelphia Quartz brand "N", density, 80 Bé) were placed in a mixing tank and diluted with 11.5 kg of water. The mixer was started and continued to run throughout the addition of the chemicals A solution of 1531 grams of concentrated sulfuric acid (density 1.84) diluted with 11.4 kg d was added very slowly over a period of 15 minutes. The mixture was continued for half an hour

Furthermore.

  Then, a dilute sodium aluminate solution of 526 grams of a concentrated solution of sodium aluminate (18.2% Na, 21.4% to 1203) mixed with 5.9 kg. of water was slowly added on

a half hour.

  Finally, 2631 grams of seeds or nucleation centers (described in Example 1) were added. The slurry was pumped to a 75.7 liter steam jacketed reaction tank and heated to 100 + 1 C to crystallize Na.sub.2. The slurry was sampled from time to time to monitor the progress of crystallization after 105 hours. at the temperature, the test was stopped The slurry was filtered and the filter cake washed to rid it of

mother liquor in excess.

  The product was a well crystallized HSAY at

  a ratio Si O 2 / A 1203 of 6.0 and a crystallinity of 96%.

EXAMPLE 16

  This example demonstrates both amplification at a batch of 56.77 liters and the use of another type of sodium silicate. Mixing processes

  and crystallization were the same as in Example 13.

  41.5 kg of Diamond Shamrock DS 34 sodium silicate (25.6% SiO 2, 6.6% Na 20) and 14.6 kg of water were mixed together A solution of 696 grams was added

  of concentrated sulfuric acid diluted with 4.5 kg of water.

  5253 grams of sodium aluminate at the same concentration as in Example 13 diluted with 4.5 kg of water were added. Finally, 2 192 grams of

  seeds of the type described in Example 1. Crystallization at 100 + 10 C gave HSAY at a ratio of SiO 2 / A 1203

of 5.8 and a crystallinity

104% in 72 hours.

EXAMPLE 17

  This example illustrates the production of a batch

  important by using simultaneous addition of reagents.

  Three solutions were prepared. In a first tank were added 36.7 kg of sodium silicate at 41.0 Bé, 12.2 kg of water and 2633 g of sodium seeds.

2538366 '

  type described in Example 1 The materials were mixed

and heated to 60 C.

  In a second tank, a dilute acid solution was prepared by mixing 1537 g of concentrated sulfuric acid with 9100 g of water. In a third tank, dilute sodium aluminate solution was prepared by mixing 5,232 grams of sodium aluminate (18.2% Na 2 O and 21.4%

A 1203) to 6,800 g of water.

  The three tanks were connected by lines to a reactor having a quick mix pump

  and the line of the first tank was opened first.

  After mixing the three streams with the fast mixing pump, they formed a soft gel which was fed to a reactor while stirring. The reactor was closed and the gel heated gradually to 100 ° C while continuing to agitate it. When the temperature of 100 ° C. was reached, the stirrer was stopped and the mixture held at this temperature for 70-80 hours to crystallize HSAY The slurry was then quenched with cold water and filtered with subsequent washings with hot water The material was dried and gave 6 kg of well crystallized HSAY having an Si O 2 / A 1203 ratio of 5.9 and a crystallinity percentage of 103%. The size of a unit cell was 2,460 nm and the nitrogen surface area measured by the BET method using a Micromeritics Digisorb apparatus was 875 m 2 / g Chemical analysis was 11.0% Na 20,

19.6% to 1203 and 68.4% if O 2.

EXAMPLE 18

  A HSAY zeolite was exchanged for rare earths and calcined to obtain a "CREHSAY" comprising 14.0% RE 203, 2.45% Na 2 O and a silica to alumina ratio of 5.9: 1. , 0 by the following process (RE

means rare earths).

  A 444 g portion of the HSAY filter cake (45% solids) obtained in Example 17 was slurried in 9 liters of deionized e-liquor. The HSAY slurry was then mixed into a solution. of 4,444 ml of a mixed market solution of rare earth chlorides (61% RE C 13 6 H 20 by weight) diluted with 7.5 l of deionized water. The mixture was heated

  90-100 ° C and was maintained at this temperature.

  The slurry was filtered and the filter cake was washed twice with 3 liters of deionized boiling water. The washed filter cake was slurried in a solution of 4444 ml of a commercially available solution. rare earth diluted with 16.5 liters of deionized water where it was heated again

  the mixture at 90-100 ° C and kept at this temperature.

  For one hour, the slurry was filtered and the resulting filter cake was washed three times with 3 liters of deionized and boiling water. The filter cake was then oven dried at 150 ° C for 4-8 hours. the dry zeolite was calcined at 538 ° C. for 3 hours. The CREFSAY product had the following properties: Ignition loss 2.1% by weight RE 203 14.90% by weight Na O 2.5% by weight Si O 2 / A ratio 3203 5.9 + 0.1 Nitrogen surface area (by BET method) 768 m 2 / g

EXAMPLE 19

  (a) CREHSAY of Example 18 was used to prepare an FCC catalyst (fluid catalytic cracking) according to the teachings of US Patent No. 3,957,689. An acid-alum-silica sol was produced by mixing two solutions A and The solution A consisted of 11.5 kg of 12.5% sodium silicate of SiO 2 (Na 2 O: 3.2 Si O 2). Solution B consisted of 3.60 liters of sodium silicate. a solution formed of 20% by weight of acid

2538366;

  sulfuric acid (2.2 l) and diluted aluminum sulphate solution, 77 g to 1203 per liter (1.4 liters) The ratio of the flows of solutions A and B through the mixer is about 1, 5 liters of solution A for 0.5 liter of solution B The ratio of the flows is adjusted to produce an acid-alum-silica sol having a pH of 2.9 to 3.2 at 14.4 kg of a acid-alum-silica sol, a slurry composed of 2860 g of kaolin clay and 2145 g of CREHSAY of Example 18 mixed in 6 liters of water was added. The mixture of the acid sol -alum-silica and CREHSAY slurry and kaolin in water was mixed and spray-dried using an inlet temperature of 316 C and an outlet temperature of 149 C. A 3000 g portion of the product spray dried was slurried in 11.3 liters of water at 60-71 ° C. and filtered. The filter cake was washed three times with 3 liters of a 3% solution of ammonium sulfate. Onium Then the cake was boiled in 9 liters of hot water, filtered and finally rinsed three times with 3 liters of hot water The catalyst

  was then oven dried at 149 C.

  (b) A catalyst having the same proportions of ingredients was similarly formed from conventional rare earth-exchanged Na Y and calcined having a silica to alumina ratio of about

4.9 + 0.1.

  The results of the comparison tests are

  shown in Table 6 below.

  activity, a modification of the test process published by FG Ciapetta and DS Henderson entitled "Microactivity Test For Cracking Catalysts", Oil And Gas Journal, Volume 65, pages 88-93, October 16, 1967. are used routinely in the petroleum industry to evaluate cracking catalysts in the laboratory The fraction of petroleum that was cracked on these catalysts was a heavy diesel from West Texas (WTHGO) using

2538366 7;

the following test conditions:

Temperature 499 C; -

  Hourly space velocity by weight (HSV) 16; Oil Catalyst Ratio WTHGO (1.67 g) was passed through 5.0 g of catalyst in 1.3 minutes The products were collected and the percentage conversion of gas oil to hydrogen, light gases, hydrocarbons of the range of gasoline and others are determined by chromatography

in the gas phase.

  The catalysts were impregnated with Ni and V as naphthenates dissolved in WTHGO; then the hydrocarbons were burned slowly raising the temperature to 677 ° C. Then, the metal impregnated catalysts were steam deactivated by the process.

  S-13.5 before the microactivity-cracking test.

Table 6

  Catalyst Composition Example 19 (b) Example 19 (a) (wt%) Zeolite 35 Si O 2 24 24 Clay 41 41 Na 2 0.49 0.37

-2 RE 203 -4.94 5.08

RE 203

A 203 26.5 26.0

  Microactivity (volume% conversion) after indicated deactivation

S-13.5 (1)

  0% Metals 82 86 1% (Ni + V) (2) 53 74

1500 (3) 81 80

1550 (4) -20 64

/

2538366 -

  Table 6 (continued) Partial chemical analysis of zeolite Si O 2 / A 1203 (ratio) RE 203 (wt%) Na 20 (wt%) CREY

4.9 + 0.1

, 0 + 1

3.2 + 0.2

  (1) (2) Steam deactivation: 8% steam at 1.08 bar Ni = V (3) Steam deactivation: 5

% of steam at 0 bar.

(4) Steam deactivation: 5

% of steam at 0 bar.

  hours at 732 C, pressure. hours at 816 C, hours at 843 C,

EXAMPLE 20

  (a) A 2576 g slurry of a HSAY filter cake (45% solids) was formed from a batch of HSAY synthesized as in Example 17 and 4.186 g of kaolin in 8.0 liters of water This porridge has

  was completely mixed with 13.8 kg of an acid-alum

  silica, the preparation of which has been described in Example 19.

  The mixture was spray-dried using the conditions described in Example 19. The material thus spray dried was washed with water and ion exchanged with a mixed solution of rare earth chloride as follows: 3000 g of the spray-dried material was slurried in 11.3 liters of deionized hot water at 60-71 ° C and filtered. The filter cake was rinsed three times with 3 liters of hot water. the cake was re-slurried in 9 liters of hot water and again filtered The cake was rinsed three times with 3-liter portions of hot water. The filter cake was then slurried in 10 liters of water. hot water and we have

HSACREY

, 8 + 0.1

14.0 + 1

2.4 + 0.2

2538366 '

  215 ml of a mixed rare earth chloride solution (60% by weight of RE C 13 6 H 20) were mixed into the slurry. The slurry was gently stirred for minutes and maintained at a temperature of 60.degree. 71 C and p H was maintained at 4.7-5.2 Finally, the slurry was again filtered and rinsed with three

3-liter portions of hot water.

  (b) A similar catalyst was prepared using a conventional Na 2 zeolite having an Si O 2 / A 203 ratio of about 4.9 + 0.1. The finished catalyst was then oven dried at 149 ° C. The final catalyst formed from HSAY was compared in the tests given below in Table 7, with the catalyst

  produced in a similar way from Na Y convention-

  A heavy diesel from West Texas was cracked in the microactivity test using the conditions

test example given in Example 19.

Table 7

  Catalyst Composition Example 20 (b) Example 20 (a) (wt%) Zeolite 17 17 Si O 23 23 23 Clay 60 60 Na 20 0.74 0.70

RE 20 3.68 3.83

  Si 02 / A 1203 ratio in zeolite 4.9 + 0.1 5.8 + 0.1 Microactivity (volume% conversion) S-13.5 Deactivation As-is 73 82 0% metals 68 72 0.5% ( Ni + V) 28 54 1500 Deactivation (1) 48 62 (1) Steam deactivation: 5 hours at 816 C,

% of steam at 0 bar.

  For each of the catalysts described above in Examples 19 and 20, the catalyst produced with the HSAY type zeolite showed better resistance to hydrothermal deactivation than the same catalyst formula with an equal amount of conventional zeolite of the type. The two catalysts of Examples 19 and produced with HSAY also show greater resistance to deactivation by contamination of vanadium and nickel (highly poisonous metals) than equivalent catalysts made with a conventional Y-type zeolite. Examples of catalysts above clearly indicate that valid catalysts can be obtained.

  cracking using HSAY according to the present invention.

Claims (15)

R E V E N D I C A T IO N S   A process for producing zeolite Y having the formula, in terms of moles of oxides 0.9 + 0.2 Na 2 OA 12: 3 W Mi O 2 × H 20 o W is greater than 5.0 and x may have a value up to about 9, characterized in that it consists in (a) forming a reaction slurry by mixing a source of alumina other than metakaolin or kaolin;   a silica source selected from the group   consisting of sodium silicate, silica gel, silicic acid and mixtures thereof; a source of soda; a source of seeds or nucleation centers; and another reagent which is either (I) an active sodium controller selected from the group consisting of an acid, a solution of a salt obtained from aluminum and an acid, and mixtures thereof; (II) a combined source of reactive silica and alumina having a low active soda content; or (III) a mixture of (I) and (II); said sources and said other reagent being chosen to control the concentration of active sodium hydroxide in the reaction slurry, by measuring the ratio of moles of Na 2 O to one mole of A 1203, below the value given by the line A of the FIG. 1 for the corresponding ratio of moles of silica to one mole of alumina in the reaction slurry, said line A being based on at least the following points for ratios in the synthesis slurry. 1203 16; 1 9: 1 6: 1 Ratio Na 20: A 1203 6.6: 1 3.1: 1 1.8: 1 and (b) heating the reaction slurry produced in step (a) to crystallize zeolite Y . Process according to claim 1, characterized in that W in the formula has a value equal to or greater than about 5.8 by maintaining the active sodium concentration in the reaction slurry at or below the value given by the line B of Figure 1 for the corresponding ratio of moles of silica to moles of alumina in the reaction slurry, said line B being based on at least the following points for ratios in the synthesis slurry. S10 ratio 2: A 1203 16: 1 9: 1 3. Process characterized in that active is acid 4. Process characterized in that and an acid in the aluminum sulphate.   5. Process characterized in that Na O ratio; Al O O 2 23   , 0 2,4 according to claim 1, the acid in the sulfuric acid controller. according to claim 1, -   the salt obtained from active soda control aluminum is according to claim 1, the combined source of silica and   Alumina is a mother liquor gelled with aluminum salt.   6. The process according to claim 5, wherein the aluminum salt which gels the mother liquor is selected from the group consisting of Ealiiuilium sulfate, uxiloride   of aluminum, aluminum nitrate and mixtures thereof.   7. Process according to claim 6, characterized in that the aluminum salt is aluminum sulphate. 8. Process according to claim 1, characterized in that the reaction slurry is heated and the excess mother liquor is decanted before   that the reaction product is crystallized.   9. Process according to claim 1, characterized in that the source of alumina, the source of silica, and the active sodium hydroxide controller are supplied by separate streams in a mixer, the source of the seeds or nucleation centers being added to one of the currents to form the reaction slurry that   is then heated in step (b).   Process according to claim 9, characterized in that the separated streams are fed simultaneously to the mixer.   11. Zeolite Y with a high silica content, characterized in that it is obtained by the process   according to any one of claims 1 to 10.   12. Zeolite Y with a high content of well-crystallized silica with little occluded amorphous silica, characterized in that it has the formula, as crystallized, in terms of moles of oxides 0.9 + 0.2 Na 20: A 1203: w If O 2 x H 20 o W has a value greater than 5.0 in the crystal lattice of zeolite Y, x has a value of up to about 9 and has a sharpness index, SI> of at least 6 for the peak of si E 1 M and at least about 2.2 for the peak of Si LO Aj based on the formula of the index of acuity SI = 10 S Si tn All Si r 2 A 13 o N is O or 1 and where the sharpness, S, is defined as S = area of the width 2ic to 1/2 height) the peak area and the width are measured on the spectrum of nuclear magnetic resonance peaks   to deconvolute magic angle spinning of silicon-29 -   13. Y zeolite according to claim 12, characterized in that the acuity index is at least 7 for the peak of Si l 1 Al and at least 2.5 for the peak of Si l O All Zeolite according to Claim 12, characterized in that W has a value greater than 5.4.   Zeolite according to claim 12,   characterized in that W has a value greater than 5.8.