DE2049755A1 - Crystalline Zeohthmassen and processes for their production - Google Patents

Description

DR.M. KÖHLER DIPL-ING. C GERNHARDT 2049755

phone: 55547 "8000 MÖNCHEN 15, 9 October 197o

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

W. 4o o53 / 7o

Mobil Oil Corporation New York, N.Y. (V.St.A.)

Crystalline zeolite masses and processes for their production

The invention relates to novel crystalline aluminosilicates and processes for their preparation. In particular, the invention relates to novel crystalline aluminosilicates with catalytic properties, to processes for their preparation and to their use for hydrocarbon conversions.

Zeolite materials, both natural and synthetic, have been shown to have catalytic capabilities for various types of hydrocarbon conversions. Certain zeolite materials are ordered, porous, crystalline aluminosilicates with a specific crystalline structure, within each of them one

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large number of small cavities are interconnected by a number of even smaller channels are. These cavities and channels are exactly uniform in size. Because the dimensions of these pores are such are to take up molecules of certain dimensions for adsorption, while those with larger dimensions are rejected These materials became known as "molecular sieves" and these materials come in a variety of ways applied to take advantage of these properties.

Such molecular sieves comprise a wide variety of positive ion containing crystalline ones Aluminosilicates both natural and synthetic. These aluminosilicates can be called rigid three-dimensional Lattice of SiO. and AlO. are described in which the tetraethers, by dividing them into common oxygen atoms are crosslinked or connected, the ratio being the sum of aluminum and silicon atoms Oxygen is 1: 2. The electrovalence of the aluminum-containing tetraethers is due to the inclusion of a cation balanced in the crystal, e.g. by the inclusion of an alkali or alkaline earth cation. This can be done through a Formula in which the ratio of Al to the number of different cations, e.g. Ca, Sr, Na, K or Li equals one unit. One type of cation was either totally or partially opposed another type of cations using ion exchange procedures exchanged in the usual way. By means of such a cation exchange it was possible the size of the pores of the given aluminosilicate to vary by appropriate selection of the particular cation. The spaces between the tetrahedra are

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before dehydration of water molecules "occupied.

The previously known procedures have resulted in the formation of a wide variety of synthetic crystallines Aluminosilicates. These aluminosilicates were designated by letters or other appropriate names Symbols such as those of Zeolite A (U.S. Patent 2,882,243), Zeolite X (U.S. Patent 2,882,244), Zeolite Y (U.S. Patent 3 13o oo7), zeolite K-G (US patent 3 o55 654), zeolite ZK-5 (US patent 3 247 195), zeolite beta (US patent 3 3o8 069), Zeolite ZK-4 (US Pat. No. 3,314,752) and Zeolite ZSM-5 (described in US Pat.

part registration of Serial No. 63o 993 (1967)), to name but a few to call, is illustrated.

The invention relates to novel stable synthetic crystalline aluminosilicate materials as follows may be referred to as "Zeolite ZSM-8" or simply "ZSM-8", and processes for their preparation and to hydrocarbon conversion processes carried out therewith. ZSM-8 has the characteristic X-ray diffraction diagram, as indicated in Table I below. ZSM-8 has the following composition, expressed in molar ratios of oxides as follows:

0.9 + 0.2 M ₂ O: Al ₂ O,: 5-loo SiO ₂ : ζ H ₂ O η

Here, M denotes at least one cation, η its valence and ζ a number from ο to 4o. In a preferred synthesized form, the zeolite has a composition, expressed in molar ratios of oxides, as follows:

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o.9 + o.2 M ₂ O: Al ₂ CU: lo-6o SiO ₂ : ζ H ₂ O η

Here, M is selected from a mixture of alkali cations, in particular sodium and tetraethylammonium cations

ZSM-8 has an exceptionally high degree of thermal stability, which makes it particularly effective and useful for use in procedures involving elevated temperatures. In this context it seems ZSM-8 to be one of the most stable zeolites currently available.

ZSM-8 has a certain distinguishable crystalline structure, essentially that shown in Table I. Has X-ray diffraction diagram. The exact position of the lines and their relative intensities can as a result of the special ion exchange and the heat treatment carried out vary somewhat. The most important characteristics are the lines listed in Table II below. The morphology of the particulars discussed below Examples are illustrated in FIG. 1.

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■ 2043755

Table 1 _<

11.1 46 '2.97 4

10.0 42 2.94 3

9.7 10 -2.86. 2

9.0 -6 2.78 1

7.42 10 2.73 4 7.06. 7 2.68 1 6.69 5 2.61 '3

6.35 12 2.57 1 6.04 6. 2.55 1 5.97 12 2.5'l 1 5.69 9 2.49 6 5.56 13. 2.45 1

5.36 '3 2.47 2

5.12 4 2.39 * 3

5.01 7 2.35 1 4.60 7 2.32 1 4.45 3 2.28. 1 4.35 7 2.23 1 4.25 18 2.20 1 4.C7 20 2.17 1 4.00 10 2.12 1 3.85 100 2.11 1 3.82 57 2.08 1 3.75 25 2.06 1 3.71 30 2.01 6 3.64 26 1.99 6 3.59 2 1.95 2 3.47 6 1.91 2

3.43 9 1.87. 3 3.39 5 1.84 1 3.34 18 1.82 2 3.31 8

3.24 4

3.13 3 3.04 10 2.99 6

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Table II

Interplanar or Relative Intensity * '

Interfacial distance

d (A °) (1 / I ₀ )

11.1 ± 0.2 s

Ιο, ο ί 0.2 p

7.4 ί ο, 15 sch 7.1 - ο, 15 sch 6.4-0.1 sch

^ 'q8 ~ ° · ^ ^sc ^

5.57 ί ο, Ι sch

5, ol - o, l sch

4.26 - o, o8 in

4, o8 ± o, o8 m

3.85 ί o, o7 ss

3.71 - o, o5 m

3.47 i o, o4 sch

3.05 - o, o3 sch

(1) ss = very strong, s = strong, m = medium, sch = weak

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These values were determined using standard procedures. The radiation consisted of the K-alpha doublet of copper using a scintillator counter spectrometer with a pen pen. The "peak" heights, I, and the locations as a puncture of 2 theta, where theta is the Bragg's angle, were read from the spectrometer card. From this the relative intensities, 100 I / I _Q »where I _{Q is} the intensity of the strongest line or peak, and d (observed), the interplanar or interfacial distance, corresponding to the recorded lines were calculated. It can be seen that this X-ray diffraction pattern is characteristic of all types of ZSM-8 compositions. The ion exchange of the sodium ions for cations shows essentially the same diagram with some small shifts in the interplanar distance and with a change in the relative intensity. Other minor changes may depend on the silicon: aluminum ratio of the particular sample as well as when the sample has been subjected to a heat treatment.

ZSM-8 is useful for cracking and hydrocracking processes. However, it is particularly useful with many others Petroleum Refining Practices. The latter working methods include the isomerization of η-paraffins and naphthenes, the polymerization of compounds containing olefinic or acetylenic carbon-carbon bonds, e.g. isobutylene and butene-1, reforming, alkylation, Isomerization of polyalkyl substituted aromatics, e.g. o-xylene, and the disproportionation of aromatics, e.g. toluene, being a mixture of benzene, xylenes and higher Methylbenzenes is obtained. ZSM-8 has an exceptionally high selectivity and under the conditions of Hydrocarbon conversion, it provides a high percentage

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rate of desired products based on total products compared to known zeolitic hydrocarbon conversion catalyst ^

As noted above, ZSM-8 is on several catalytic processes such as hydrocarbon catalytic cracking and hydrocracking are useful. Additionally for its thermal stability, ZSM-8 provides conversion of the cracked oil to materials of minor value Molecular weights and boiling points that are of greater are economic value. It is common knowledge that the property or ability to be stable under high temperatures and / or in the presence of high temperature water vapor is extremely important for a cracking catalyst. ZSM-8 can either be in the alkali metal form, e.g. the sodium form, the ammonium form, the hydrogen form or another monovalent or polyvalent cationic Form to apply. One or the other of the last two forms (or a mixture of which) used. ZSM-8 can also be used in intimate combination with a hydrogenation component, e.g. tungsten, Vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a noble metal such as platinum or palladium are used when a hydrogenation-dehydrogenation function is to be performed. Such a component can by replacement or impregnation in the composition be introduced or it can be intimately mixed with it physically. Such a component can be in or on ZSM-8, e.g. in the case of platinum the zeolite with an ion containing platinum metal is treated. Thus, suitable platinum compounds include chloroplatinic acid, platinum dichloride and various compounds, containing the platinum amine complex.

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The compounds of the useful platinum or others Metals useful in compounds in which the metal is present in the cation of the compound and divided into compounds in which the metal is present in the anion of the compound. Both Types of compounds containing the metal in the ionic state can be used. A solution, in which the platinum metals in the form of a cation or a cationic complex / e.g. Pt (NEz) Z-Cl. exist, is particularly useful. Me some hydrocarbon conversion processes this precious metal form of the ZSM-8 catalyst is not necessary, e.g. for o-xylene isomerization at low temperature and in the liquid phase.

ZSM-8 should be dewatered or at least partially dehydrated when used as an adsorbent or as a catalyst in one of the processes described above. This can be achieved by adding or the like to a temperature in the range from 2oo to 600 ⁰ C in an inert atmosphere, such as air, nitrogen., -And heated at atmospheric or subatmospheric pressures from 1 to 48 hours. The dehydration can also be carried out at lower temperatures using only a vacuum, but a longer period of time is required to achieve a sufficient degree of dehydration.

Zeolite ZSM-8 can be prepared in a suitable 7 / iron, by making a solution containing a tetraethylammonium salt together with sodium oxide, aluminum oxide and an oxide of Contains silica and water, brings to implementation.

The relative applicable proportions or proportions of the various components are in a very complex

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xen Y / eise interrelated with each other, and it is without further apparent that not any and all ratios of the reactants to form the desired zeolite are effective. Indeed, completely different zeolites can be made using the same Starting materials prepared depending on their relative concentration and the reaction conditions as described in U.S. Patent No. 3,380,069. However, it has generally been found that when used of Tetraäthylammoniumhydroxyd ZSM-8 from the said Hydroxide, sodium oxide, aluminum oxide, silica and water by converting the mentioned materials into such Ratios that the formation solution has a composition, expressed in molar ratios of the oxides, within of the range given below, can be produced:

SiO ₂ / Al 0, about Io to 2oo

Na ₂ O / Tetraäthylammonium- about 0.05 to 0.02 hydroxide

Tetraethylammonium hydroxide / SiOp about 0.08 to 1.0 HpO / tetraethylammonium hydroxide about 80 to 2oo

The crystals are then separated from the liquid and recovered. Typical reaction conditions include heating the above reaction mixture to a temperature of about 149 to 204 ° C (300 to 400 ° F) for a period of about 6 hours to 60 days. A more preferred temperature range is at about 171-188 ⁰ C (34o to 37o ⁰ P), wherein the time period is bi3 8 days at a temperature in this range for about 12 hours.

It can be seen that instead of Tetraäthylamiaonium-

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hydroxyd other. Tetraethylammonium salts, e.g. tetraethylammonium bromide, can be used.

The digestion or maturation of the gel particles is up to executed to form crystals. The solid product is removed from the reaction media, for example by cooling Separate all of the material to room temperature, filter and v-wash with water.

The product described above is dried, for example, at Ho ⁰ O (23o ° P) for about 8 to 24 hours. If desired, milder conditions, for example room temperature under vacuum, can of course also be used.

ZSM-8 is manufactured using materials that comply with the provide suitable oxide. Such compositions include sodium aluminate, aluminum oxide, sodium silicate, Silica hydrosol, silica gel, silicic acid, sodium hydroxide and tetraethylammonium salts. Ss is It can be seen that each oxide component used in the reaction mixture is derived from one or more starting reactants can be supplied, and these can be mixed with one another in any order. For example can be sodium oxide by means of an aqueous solution of sodium hydroxide or an aqueous solution of sodium silicate are fed. The tetraethylammonium cation can supplied by the bromide salt. The reaction mixture can be prepared either batchwise or continuously will.

ZSM-8 can replace the original cations associated with it through a wide variety of other cations according to the working

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-12- 2 O Λ 9 7 5 5

have replaced ways. Typical replacing or exchange cations include pulp, ammonium and metal cations including mixtures thereof. The metallic exchange cations include, in particular, cations of metals, such as rare earths, manganese, calcium, and metals from group II of the periodic table, e.g. zinc, and of Group VIII of the Periodic Table, e.g., nickel, are preferred. The exchange process can apply to the freshly made Form, the dried form or applied after calcination. Can be calcined before replacement can be used to facilitate alkali removal down to a very low concentration.

Typical ion exchange procedures are to mix ZSM-8 with a salt of the desired exchange cation or to bring the desired exchange cations into contact. Though a great variety of salts have been used can be, especially the chlorides, hitrate and ground Sulfates preferred.

Typical ion exchange procedures are described in a wide variety of patents, such as U.S. Patents 3,140,249, 3,140,251, and 3 Uo,253.

After contacting with the salt solution of the desired replacing cation, the zeolite is then preferably with \ 7asser washed and dried at a temperature in the range of 65.6 to about 316 ⁰ C (I5o to 6oo ° P) dried, and then in air or other inert gas calcined at temperatures in the range of about 26o to 816 C (50 to 150 P) for a period of time in the range of 1 to 3 48 hours or more. According to the invention it has also been found that catalysts with improved selectivity and with other advantageous

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Properties in some hydrocarbon conversion processes, e.g. catalytic cracking, can be obtained by subjecting the zeolite to a treatment with steam at elevated temperatures in the range of 427 to 816 ⁰ G (800 to 15oo ° P) and preferably in the range of 538 to 76o ° C ( looo to 1400 ⁰ P). The treatment can be carried out in atmospheres of 100% water vapor or in an atmosphere consisting of water vapor and a gas which is essentially inert to the zeolite materials.

A similar treatment can be at lower temperatures and elevated pressures, be carried out at 177-371 ⁰ C (35o to 7oo ° P) in Io to about 2oo atmospheres for example.

Regardless of the cations that replace the sodium in the synthesized form of ZSM-8, the spatial arrangement of the aluminum, silicon and oxygen atoms that form the basic crystal lattice through the described replacement of sodium or another alkali metal essentially unchanged, as this by inclusion from X-ray powder diagrams of the ion-exchanged material were determined. Such an X-ray diffraction diagram of the ion-exchanged ZSI.1-8 shows a diagram, which is essentially the same as the graph set forth in Table I above. The most important Characteristic curves are the lines listed in Table II above.

The aluminosilicates made according to the invention come in a wide variety of particle sizes manufactured. In general, the particles can be in the form of

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a powder, granules or granules or a shaped product, e.g. an extrudate with a sufficient Particle size to pass through a sieve with a mesh size of about 8 mm or more (2 mesh Tyler screen) and to go through a sieve with a mesh size of about 0.045 mm (4oo mesh Tyler screen) to be held back. In the cases where the catalyst is shaped, for example by Pressing or extruding, the aluminosilicate can be before drying or in dried or partially dried State to be extruded.

For many catalysts it is desirable to give the ZSM-8 a further advantage over the temperatures and other conditions which are used in organic conversion processes to incorporate permanent material. Such Materials include active and inactive materials and synthetic or naturally occurring zeolites as well inorganic materials, e.g. clays, silicon dioxide and / or metal oxides. The latter can either be in naturally occurring forms or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides can be used. The usage of a material in conjunction with ZSM-8, i.e. combined with it, which is active, tends to improve conversion and / or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the extent of conversion in a given process or to control so that products in more economical and can properly be obtained without the use of other means of controlling the extent of the reaction. Often times, zeolite materials were naturally occurring

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Clays, e.g. bentonite and kaolin, incorporated in order to increase the breaking strength of the catalyst under technical operating conditions to improve. These materials, namely clays, oxides or the like., Act as binders for the Catalyst. These materials can also contribute to the catalytic activity on their own, this being shown in can take place in a synergistic manner. It is also desirable to have a catalyst with good breaking or breaking strength At a petroleum refinery, the catalyst is often subjected to rough handling which can break the catalyst into powdery materials, creating problems caused during processing or handling. These clay binders were used to improve breakage or Attrition resistance of the catalyst as well as used due to its own catalytic activity.

Naturally occurring clays that can be compounded with ZSM-8 include the montmorillonite and Type of kaolin, these types being the sub-bentonites and the kaolins, commonly called Dixie, McNamee-Georgia and Florida clays are known, or include others in which the main mineral constituent halloysite, kaolinite, Is dickite, nacrite or anauxite. Such clays can be used in the raw state, as they were originally mined or mined may be used, or they may initially be calcination, acid treatment or chemical Subject to modification.

In addition to the materials described above, ZSIvI-8 can be composed of a porous matrix material e.g. silica-alumina, silica-llagnesium oxide, Silicon dioxide-zirconium oxide, silicon

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dioxide-thoroxide, silicon dioxide-beryllium oxide, silicon dioxide-titanium oxide, as well as ternary compositions, e.g. silicon dioxide-aluminum oxide-thoroxide, silicon dioxide-aluminum oxide-zirconium oxide, Silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a mixed gel. The relative proportions or proportions of finely divided crystalline Aluminosilicate ZSM-8 and inorganic oxide gel matrix vary widely with crystalline aluminosilicate levels ranging from about 1 to about 9o wt. ^ And usually especially when the composition is made in the form of beads, in the range of about 2 to about 50 weight percent of the composition.

When using the ZSM-8 catalytic converter according to the

Finding that contains a hydrogenation component, residues of heavy petroleum, circulating or circulating masses and other hydrocrackable feedstocks from hydrocracking at temperatures between about 2-4 and 44o ° C (400 F and 825 F) using molar ratios of hydrogen to hydrocarbon feed subject to ground in the range between 2 and 8o. The pressure used varies between 0, 7o and 176 atmospheres (Io and 2500 psig) and the liquid hourly space flow rate varies between o, l and io.

When using the catalyst according to the invention for catalytic cracking, hydrocarbon cracking masses can be produced at an hourly space velocity between about 0.5 and 50, a temperature between about 288 and 593 ° C (55o and 100o ° F) and a pressure between about subatmospheric pressure and several loo atmospheres be cracked.

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When using a catalytically active, containing a hydrogenation form of ZSM-8 reforming compositions can be reformed employing a temperature between about 371 and 538 ⁰ C (7oo and looo ° F). The pressure can be between about 7.03 and 70.3 atmospheres, but is preferably between about 14.1 and 49.2 atmospheres. The liquid hourly space flow rate is generally between 0.1 and Io, preferably between 0.5 and 4, and the hydrogen to hydrocarbon molar ratio is usually between 1 and 2o, preferably between 4 and 12.

The catalyst may also be used for hydroisomerization of normal paraffins, when provided with a hydrogenation component, eg, platinum. The hydroisomerization is carried out at a temperature between about 93.3 and 371 ⁰ G (2oo and 700 ° F), preferably 149 and 288 ⁰ C (3oo and 55o ° F) at an hourly liquid space flow rate between 0.1 and 2, preferably between 0 , 25 and 0.50 using hydrogen in such a way that the molar ratio of hydrogen to hydrocarbon is between Ιίΐ and 5: 1. In addition, the catalyst for olefin isomerization employing temperatures between about ⁰ C and 26o -1.11 ° C (3o and 5oo ° F) may be used ground v /.

Y / eitore reactions made using the catalyst according to the invention containing a metal, e.g., platinum, carried out include: hydrogenation-dehydrogenation reactions and desulfurization reactions.

The invention is illustrated below by way of examples explained in more detail.

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Whenever adsorption values are given in the following examples, these were determined as follows:

A weighed sample of the zeolite material was mixed with the desired pure adsorbate vapor in an adsorption chamber at a pressure lower than the vapor-liquid equilibrium pressure of the adsorbate brought into contact at room temperature. This pressure was increased during the adsorption period maintained constant, this duration not exceeding about 8 hours. The adsorption was stopped, when a constant pressure had been reached in the adsorption chamber, namely 12 mm mercury for water and 20 mm Mercury in η-hexane and cyclohexane. The weight increase was calculated as the adsorption capacity of the sample.

example 1

2.8 g of sodium aluminate (41.8 wt $ Al ₂ O, -.. 31.6 wt # Na ₂ O) were added to a 3o g ^ 4o wt aqueous solution of Tetraäthylammoniumhydroxyd preset at about 37.8 ⁰ C. (loo ° P) was heated, given. 150 grams of Ludox (30 wt. $ SiOp) was then added and the entire mixture was subjected to mixing in a high shear mixer. This mixture was then placed in a 25o ml autoclave equipped with a Pyrex liner and maintained at about 178 ⁰ C (352 ⁰ P) for 7 days. The autoclave was then allowed to cool to room temperature and the resulting product was separated from the reaction sludge by decantation, followed by washing with water. The dried product had the X-ray diffraction pattern of Z8M-8 as shown in Table I.

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Example 2

1.2 g of sodium aluminate (41.8% by weight Al ₂ O, _{-31.6 2} O) in 3o g of water were added to 25.8 g of a 40% by weight aqueous solution of tetraethylaminonium hydroxide, which was diluted to about 37% by weight. , 8 ⁰ C (loo ° P) was heated given loo g Ludox (3o wt. $ SiO ₂₎ were then added and the entire mixture was then subjected to mixing in a mixer of high shear force. This mixture was then placed in a 25o ml autoclave equipped with a Pyrex liner and maintained at about 182 to 188 of ⁰ G (36o to 37o ⁰ F) for 9 days. The autoclave was then allowed to cool to room temperature and the resulting product was separated from the reaction sludge by decantation, followed by washing with water. The dried product had the X-ray diffraction pattern of ZSM-8 _o

Example 3

L, above sodium aluminate (41.8 wt. ^ S AlpO, - 31.6 wt. $ Na ₂ O) in 30 g of water were added to 21.5 g of a 40 wt , 8 ⁰ C (loo ° P) was heated given loo g Ludox (3o wt. $ siop) WUR the then added and the entire mixture was then subjected to mixing in a mixer of high shear force. This mixture was then placed in an autoclave with a Pyrex liner and maintained at about 171 ⁰ C (34o ° F) for 6 days. The autoclave was then allowed to cool to room temperature and the resulting product was separated from the reaction sludge by decantation, followed by washing with water. The dried product had the X-ray diffraction pattern of Z8M-8.

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Example 4

0.8 g of sodium aluminate (41.8 Gevr.fo) Al ₃ O ₅ -. 31.6 wt ^ ₂ O) in 3o g water were added to 17.2 g of a 4o wt strength ^.
aqueous solution of Tetraäthylanunoniumliydroxyd, which on
about 37.8 ⁰ C (100 ⁰ P) was heated, given 100 g of Ludox
(3o wt. ^ SiOp) was then added and the entire mixture was then subjected to mixing in a high shear mixer. This mixture was then placed in an autoclave with a Pyrex liner and maintained at about 182 to 188 of ⁰ G (360 to 37o ° F) for 9 days. The autoclave was then allowed to cool to room temperature and the resulting product was separated from the reaction sludge by decantation followed by washing with water. The dried product had the X-ray diffraction pattern of ZSM-8.

Example 5

A mixture of 1.2 g sodium aluminate, (41.8 wt
Al ₂ O ₃ - 31.6 wt. # Wa ₂ O), 3.5 g sodium hydroxide and 70 g
V / ater was added to 20 g of tetraethylammonium bromide.
100 grams of Ludox (30 wt % SiO ₂ ) was then added and the entire mixture was subjected to mixing in a high shear mixer. This I.iischung was then placed in a 25o ml autoclave equipped with a Pyrex liner and maintained at about 178 ⁰ C (352 ⁰ P) during 9 days. The autoclave was then allowed to cool to room temperature and the resulting product was separated from the reaction sludge by decantation followed by water
was washed. The dried product had the X-ray diffraction pattern of ZSM-8.

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Example 6

l, og sodium aluminate (41.8 wt. $ AIpO, -31.6 PO), 3.5 g sodium hydroxide and 80 g water / water were added to 2 o g tetraethylammonium bromide, loo g Ludox (3o SiOp) were then added and the entire mixture was subjected to mixing in a high shear mixer. This mixture was then placed in a 25o ml autoclave equipped with a Pyrex liner and maintained at about 178 G ⁰ (352 ⁰ F) for 12 'hunting. The autoclave was then allowed to cool to room temperature and the resulting product was separated from the reaction sludge by decantation, followed by washing with water. The dried product had the X-ray diffraction pattern of ZSM-8.

The compositions of Examples 1 to 6 were evaluated for sorption properties. The results this evaluation, as well as a summary of its manufacturing process, is given in Table III below reproduced.

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Table III

Example 1 2 3 4 5

^NaA10 2 2.8 1.2 l, oo, 8 1.2 l, o

NaOH - - - - 3.5 3.5

H ₂ O - 3o 3o 5o 7o 8o

Tetraethylammonium hydroxide

(40 # aqueous solution) 3o 25.8 21.5 17.2

Tetraethylammonium bromide - - - - 2o 2o

Ludox (3o wt. ^ SiO ₂ ) 15o loo loo loo loo loo

Composition. Molar ratio

(TAA) ₉ O *) 3.55 7.14 7.14 7.14 - - '

_ TÄA Br - - - - 19.4 23.2

ο Na ₂ O 1.24 1.24 1.24 1.24 lo, 2 11.9

co Al ₉ O, l, oo l, oo l, oo l, oo l, oo l, oo

a> SiO ₉ 64 loo 12o 15o loo loo

- * H ₉ O ^ 6oo 1265 152o 22oo 16oo 21oo

> * Crystallization, temp. ⁰ C

- * ( ⁰ P) 352 34ο 34ο 34ο 352 352

• Time, days 7 9 6 9 9 12

*) (TAA) = tetraethy ammonium

Adsorption,

Cy-C, - o, 9 o, 6 o, 4 ο, 7 1.6 1.6

nC £ ^D 5.1 6.4 4, o 9, ο 7.6 8, ο

H ₂ O ⁰ 6.3 4.6 2.9 3.8 5.7 5, ο

Product composition, molar ratio

(TAA) ₉ O o, 69 o, 57 ο, 67 Ι, οο ο, 45

Ha ₉ O ^c ■ ο, 4ο ο, 14 ο, 13 ο, 59 ο, 33

Al ₉ O, Ι, οο Ι, οο Ι, οο Ι, οο Ι, οο

⁵ 82.1 43.2 56.1 81.3 4 &> 8

CD -O-

CO »

cn cn

Example 7

A crystalline aluminosilicate ZSM-8 in Example 1 beschriebenenArtwurde by 7 / echselwirkung of .Natriumaluminat, Tetraäthylammoniumhydroxyd, colloidal silica and water at 163 ° to 177 ⁰ C (325 to 35o ° P) and 38.7 to 4o, 8 atm (55o to 58o psig) for 6 days and was used to prepare a pour point depressant catalyst for a high pour point Amal Gas Oil.

In the synthesized state, the highly crystalline product had the following adsorption properties: for cyclohexane 0.7% by weight; $ n-hexane 7.7 wt, $> and V / ater 3 »5 wt.. In addition, the calculated molar composition on a dry basis was as follows

0.35 (TAA) ₂ O: 0.23 Na ₂ O: Al ₂ O ₃ : 32.2 SiO ₂

In the preparation of the activated catalyst were 18.8 g of the dried Na-ZSM-8-ECO Porm a base exchange for four contacts of 1 hour at about 92 ⁰ C (198 ⁰ P) with 185 cm ⁵ of 5 wt. ^ Subjected igen NH «C1 solution, whereupon it was washed with water, dried and calcined for 10 hours at 538 ° C. (100 ° C.). In addition, two 1-hour contacts with a 5 wt. Consecutive NH.Cl solution were used in order to reduce the remaining ilodium content to 0.19 wt. This exchanged ZSM-8-I material was then washed essentially free of residual chlorine ions with Y / water, dried in air at Ho ⁰ C (23o ° P), pelletized and cut to a size corresponding to a sieve

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brought a mesh size of about 1.168 to 0.68 mm (14 to 25 mesh) and finally ^{calcined again at 538 0} C (1000 ⁰ F) for 10 hours.

This calcined Katalysa.tor was a .343 for cracking to 538 ⁰ C (65o to looo ° F) -Amal Gas Oil of high pour point (37.8 C ⁰ - loo ° F) used, the properties in Table IV below at about ⁰ C (921 ⁰

493 ⁰ C (921 ⁰ F) 4p LHSY undciij 15-Θ / Θ-are listed » *

/ '£ /' - * «- *" t- Ka-la.hitd.Hr '. Gl - I ^ / Vt eiltη / 1 vcvl_} Γ <# /

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Table IV Properties of Amal gas oil

Aniline Pt. about lol ° 0 (214.8 ⁰ P)

specific gravity o, 3676

Pour point. 37.8 ⁰ C (loo ° F)

distillation

Vacuum distillation, corrected to 76o mm ( ⁰ O) ( ⁰ P)

Initial boiling point (IBP)

Io 2o 3o 4o 5o 6o 7o 8o 9o 95

The product distribution, based on the load, after this contact was as follows:

334.4 634 368.5 695 378, o 712 389.9 733 4ol, o 754 414.0 777 425, o 797 44o, 5th 825 455.2 852 473.4 884 493, o 92o 5o6.4 944

9 8 17/1870

Conversion, Vol. # 28.4

C ₅ +, gasoline (gasoline), vol.fo 8.8

Total G ₅ ¹ S Vol. # Lo, 9

Dry gas, wt. ^ H »5

Coca, wt. ^ O, 3

(? Loo ⁰⁾ In this method, the pour point of 37.8 ⁰ C Amal Gas Oil of 37.8 ⁰ C (loo ° P) was reduced to:

41o ⁺ product 3.89 ⁰ C

4I0-650 product

65o ⁺ product

Weight

6.7

-37.2 ⁰ C pour point (<-35 F)

Gew. ^ 9o, 4

-1.11 ⁰ C pour point (30 ⁰ P)

109817/1870

Claims (1)

Claims 2. Crystalline zeolite masses according to claim 1, having a composition expressed in molar ratios of oxides, as follows: o.9 ± ° » ^{2 K} 2 °: Al ₉ O-,: 5-loo SiO ₉ : ζ H ₉ O η ^ά * da where M is at least one cation with a valence η and ζ a number between ο and 4o. 3 · Crystalline zeolite compositions according to one of the claims 1 to 2, characterized in that M is a mixture of tetraethylammonium ions and alkali cations represents. 4. Crystalline zeolite compositions according to claim 1 or 2, characterized in that LI Alky! Ammonium, metal, Means ammonium and / or hydrogen. 5. Crystalline zeolite compositions according to one of claims 1 to 4, characterized in that the silicon dioxide / aluminum oxide-IIol ratio in area between 3o and 9o. 6. Crystalline zeolite compositions according to one of claims 1 to 5, characterized in that they are rare Contain earth, zinc, nickel or hydrogen cations. 10981 7/1870 7. A process for the production of crystalline zeolite compositions according to any one of claims 1 to 6, characterized in that characterized in that a reaction mixture is formed which contains a tetraethylammonium salt, sodium oxide, Contains aluminum oxide, an oxide of silicon and water, -and said mixture to the formation of Aluminosilicate crystals with an X-ray powder diffraction pattern, which is essentially the same as that given in Table I, converts 8. The method according to claim 7, characterized in that the reaction mixture has the following composition having: O ₃ - Io to 2o NapO / tetraethylammonium hydroxide 0.05 to 0.22 Tetraethylammonium hydroxide / SiOo 0.08 to 1.0 HpO / tetraethylammonium hydroxide 80 to 2oo 9. Use of the crystalline zeolite compositions according to one of claims 1 to 6 for converting hydrocarbons, these in contact with the zeolite ZSM-8 containing catalyst under conversion conditions to be brought. 109817/1870