FR2485946A1 - NOVEL ZEOLITE, PREPARATION METHOD AND APPLICATION TO HYDROCARBON CONVERSION - Google Patents

Abstract

THE INVENTION RELATES TO A ZEOLITE. ACCORDING TO THE INVENTION, THE PRODUCT IS CHARACTERIZED BY A MOLAR RATIO OF AN OXIDE CHOSEN FROM THAT OF SILICON AND GERMANIUM AND THEIR MIXTURES TO AN OXIDE CHOSEN FROM THAT OF ALUMINUM AND GALLIUM AND THEIR MIXTURES THAT IS GREATER THAN ABOUT 5: 1 AND HAS SPECIAL X-RAY DIFFRACTION LINES. THIS ZEOLITE IS USED FOR THE IMPLEMENTATION OF VARIOUS HYDROCARBON CONVERSION REACTIONS.

Description

Until now, the known zeolites were alumino-silicates

  natural and synthetic, which constitute important and useful compositions

  possessing catalytic characteristics. These alumino-

  Silicates are porous and have well-defined and distinct crystalline structures, as determined by X-ray diffraction. In the crystals, there is a large number of cavities and pores whose sizes and shapes vary from zeolite to zeolite. Variations in pore size and shape result in changes in the absorbent and catalytic properties of the zeolites. Only molecules of certain sizes and shapes are able to enter the pores of a particular zeolite, while molecules of larger sizes or of different shapes are unable to penetrate the crystals.

zeolite.

  Because of their remarkable characteristics

  molecular sieves, as well as their potential

  acidic, the zeolites are particularly suitable

  to the treatment of hydrocarbons as adsorbents and, as catalysts, for cracking,

  reforming and other hydrotreating

  carbides. Although many different crystalline aluminosilicates have been prepared and tested, the search for new zeolites that can be

  use in the treatment of hydrocarbons and

chemical fuels is still going on.

  The Applicant has now discovered a new family of crystalline zeolites, hereinafter referred to as "C-HZ-5 zeolites" or, more simply, IICZH-5t, as well as a process for the preparation of these substances using compounds. choline type. (Choline is

  trimethyl (2-hydroxyethyl) ammonium hydroxide).

  In recent years, many crystalline aluminosilicates have been prepared with adsorption properties and catalytic properties.

  desirable. Typically, the zeolites are prepared

  from mixtures of reactions consisting of

  sources of alkali metal or alkali metal oxides

  earth, silica, alumina and, optionally, an organic species. However, depending on the reaction conditions and the composition of the reaction mixture, different zeolites can be formed even if the same organic species is used. For example, zeolites ZK-4, ZSlJa, faujasite and PHI have been prepared from tetramethylammonium compounds; and zeolites ZK-5 and ZS1M-10 were prepared from compounds

  N, N'-dimethyltriethylenediammonium.

  U.S. Patent No. 4,046,895

  Plank et al., of 6 September 1977, prescribes the preparation of

  A member of the ZS4-21 family, namely ZSM-38, is described as having a composition in terms of molar ratios of oxides, in the form of a novel family of crystalline zeolites. anhydrous, from (0.3 to 2.5) R 20: (0 to 0.8) Al 2 O 3 (greater than 8) SiO 2, o R is derived from trialkyl (2-hydroxyalkyl) ammonium compounds, such as choline and M represents an alkali metal cation US Patent No. 4,086,186

  Rubin et al., of 25 April 1978, and the United States Patent

  United States of America No. 4,166,813 to Rubin et al., Of September 26, 1978, discloses the preparation of a crystalline zeolite called ZSM-34 which has the composition, as synthesized and in anhydrous form, expressed in 30 molar ratios. of oxides as follows: (0.5 to 1.3) R20 (0 to 0.15) Na2O: (0.10 to 0.50) K20: Al2O3: xSiO2 o R is a cation containing organic nitrogen derivative

  choline and x ranges from 8 to 50.

  U.S. Patent No. 4,187,283 to Kokotailo et al., February 5, 1980, discloses the

  preparation of a crystalline zeolite called ZSM-47.

  ZSM-47 is described as having been prepared from a compound of 2- (hydroxyalkyl) trialkylammonium,

like choline.

  Although ZSM-47, ZSM-34 and ZSM-38 are described in the technical literature as having been prepared from choline, it is recognized that they possess different crystalline structures as well.

  that catalytic possibilities also different.

  The novel zeolite according to the invention CZH-5 has a crystalline structure which still differs from that of ZSM-34, ZSM-38 and ZSM-47, as well as the

  reveals its different X-ray diffraction pattern.

  It also has a different catalytic ability.

  The present invention therefore has more particularly

  Zeolite which has a molar ratio of an oxide selected from silicon oxide, germanium oxide and mixtures thereof to a oxide selected from aluminum oxide, gallium oxide and their mixtures, greater than about 5: 1 and having the X-ray diffraction lines shown in Table I. The zeolite further has a composition, as synthesized and in the anhydrous state, expressed in terms of the molar ratios of the oxides as following: (0.5 to 1.4) R20: (O, O, 50) M20: W203: (greater than 5) YO2 where M is an alkali metal cation, W is selected from aluminum, gallium and. their mixtures, Y is selected from silicon, germanium and mixtures thereof and R represents a cation derived from a compound of the type

  choline as defined later in this memo.

  The CZH-5 zeolites may have a molar ratio YO2: W203 of greater than about 5: 1, preferably greater than about 40: 1. The range of molar ratios Y02: W203 preferably varies from about 8: 1 to 150: 1, more preferably from about 10: 1 to 100: 1 and more preferably from about 40: 1 to about 100 : l. Preferably, CZH-5 is an aluminosilicate wherein W is 4 -

  aluminum and Y represents silicon.

  The present invention relates to. also a process for preparing CZH-5 zeolites, characterized in that an aqueous mixture of sources of a compound containing organic nitrogen, an oxide selected from aluminum oxide, an gallium oxide and mixtures thereof and an oxide selected from silicon oxide, germanium oxide and mixtures thereof and having a composition, expressed in terms of molar ratios of oxides, which fluctuates between the following limits: YO2 / W203, 5: 1 to 350: 1; R20 / W203 -0.5: 1 to 40: 1 Y is selected from silicon, germanium and their mixtures, W is selected from aluminum, gallium and their

  mixtures and R represents a cation derived from a compound

  se choline type; in that the mixture is maintained at a temperature of at least 100 C until the crystals of said zeolite are formed; and in that

  the crystals in question are recovered.

  CZH-5 zeolites possess a crystalline structure whose X-ray powder diffraction pattern has the following characteristic lines:

TABLE I

d (A) has in Intensity

11.85 - 0.10 S

11.60 2-0.10 t

9.97- 0.05M

4.25 - 0.02 vs

3.87 0.01M

+ s M

3.83 - 0.01M

-e40,01

3.46 0.0 M

  In Table I and the following tables:

  S = Strong, M = Medium, VS = Very Strong and W = Low.

  A CZH-5 aluminosilicate zeolite typical of the X-ray diffraction grating presented

Table II.

-5 -

TABLE II

  7.46 7, 63 8.87 14.78, 25 18 74 18.95 19.15, 06, 92 21.32 21.77 21.87 21 98 22.47 22.96 23.19

23; 33

24.47 ;, 19, 77 26.30

26, 80

26.94 27X98 28.84

29; 30

  , 75, 93 d (A) 11.85 11.60 9.97, 99, 81 4.73 4 68 4 63 4.43 4 37 4 25 4.08 4, 8 4.06 4 04 3.96 3 , 87 3 83 3.73 3.64 3.54 3.46 3.39 3.33 3.31 3.19 3, 14 3.05 2.91 2.89 "6.

13 - -

  The above values were determined using standard techniques. The radiation was copper K-alpha / doublet and a scintillation counter spectrometer was used with a plumplurbandlet recorder. The heights of the I peaks and their positions, as a function of 2 O where O is the Bragg angle, were read from the spectrometer strip. From these measured values, the relative intensities were calculated, without I / I0, where I0 represents the intensity of the strongest line or peak, and d represents the interplanar spacing in Angstroms corresponding to the recorded lines. The X-ray diffraction grating shown in Table I is characteristic of all species of compositions of the CZH-5 family. The zeolite produced by exchange of the metal or other cations present in the zeolite for various other cations, generates substantially the same diffraction grating, although

  minor shifts can occur in the space-

  interplanar and variations in relative intensity. Minor variations in the diffraction pattern may also result from variations in the choline compound used for the preparation and variations in the silica to alumina mole ratio of a particular sample. Calcination can. also cause minor slips in the X-ray diffraction pattern. Despite these minor disturbances,

  the structure of the basic crystal lattice remains unchanged.

  CZH-5 zeolites can be prepared from

  appropriate way from a common aqueous solution

  sources of an alkali metal oxide, a compound of the choline type, an aluminum oxide or gallium oxide or mixtures of these two compounds and an oxide of silicon or germanium or a mixture of these two compounds. The reaction mixture must have a composition, expressed in terms of molar ratios of dioxides, which fluctuates between the following limits: Wide Preferred Y02 / w203 5-350 12-200

M20 / W203 0.5-20 1-17

R20 / W203 0.5-40 5-25

Cl / W203 20-200 50-150

H20 / W203 500-20000 1500-15000

  -7 - o R has the above meanings, Y represents silicon, germanium or mixtures thereof and W

  represents aluminum, gallium or their mixtures.

  M represents an alkali metal, preferably sodium.

  Typically, an alkali metal hydroxide or an alkali metal halide is used in the reaction mixture; however, these components can be

  omitted provided that an equilibrium alkalinity is maintained

  valente. The choline compound can provide the ion

hydroxide.

  By the term "cheline compound" is meant hereinafter an organic nitrogen compound having the formula R 1 R 2 R 3 NR 4 X. R 1, R 2 and R 3 have the same or different meanings and represent C 4 -C 4 lower alkyl radicals R 4 represents a C1-C5 hydroxyalkyl group and X is an anion The compounds of the choline type are generally trialkyl (2-hydroxyalkyl) ammonium compounds.

  cation choline (or trimethyl (2-hydroxyethanyl) ammonium).

  The compound of the choline type can be in the form of the hydroxide, for example choline hydroxide, the halide, for example fluoride, bromide or choline chloride, or it can be associated with other suitable anions, such as sulfate, acetate and nitrate anions. The reaction mixture which allows the synthesis of CZH-5 is typically carried out by the addition of water to choline chloride, choline fluoride, choline hydroxide, or mixtures thereof.

  these compounds and other compounds of the choline type.

  The reaction mixture is prepared using

  techniques for preparing conventional zeolites.

  Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, and aluminum compounds, such as AlCl 3 and Al 2 (SO 4) 3. Typical sources of silicon oxide include silicates, silica hydrogel, silicic acid, colloidal silica, and silica hydroxides. Gallium and germanium can be added in forms corresponding to their aluminum and silicon counterparts. Salts, particularly alkali metal halides, such as sodium chloride, may be added to the reaction mixture or formed therein. These salts facilitate the crystallization of the zeolite and prevent the occlusion of the silica in the network, as described in U.S. Patent No. 3,849,463 to Dwyer et al., November 19, 1974, whose

  the description is incorporated herein by reference

reference.

  The reaction mixture is kept at a high temperature until the crystals of the zeolite are formed. The temperatures during the hydrothermal crystallization step are typically maintained at a value that ranges from about 1000 ° C to about 2350 ° C, preferably from about 120 ° C to about 2000 ° C, and more preferably from about 1350 ° C to about 1650 ° C. The crystallization period is typically greater than 3 days and preferably varies

  from about 7 days to about 50 days.

  Hydrothermal crystallization is carried out under pressure and usually in an autoclave of such material that the reaction mixture is subjected to autogenous pressure. Although the reaction mixture can be stirred during crystallization,

  is better not to do it.

  Once the zeolite crystals are formed, the solid product of the reaction mixture is prepared by using conventional mechanical preparation techniques, such as filtration. The crystals are washed with water and dried, for example, at a temperature of 90 to 1500 ° C. for 8 to 24 hours in order to obtain the CZH-5 zeolite crystals as synthesized. The drying step can be carried out at equal pressures or

  below atmospheric pressure.

  During the hydrophilic crystallization step

  Thermal, the crystals of CZH-5 can be allowed to nucleate spontaneously from the reaction mixture. The reaction mixture can also be inoculated with CZH-5 crystals both to direct and accelerate crystallization, as well as to minimize the formation of undesirable contaminant aluminosilicates. If the reaction mixture is inoculated with CZH-5 crystals, the concentration of the organic nitrogen compound of the choline type can be greatly reduced or eliminated, but it is preferable that a certain organic compound be present,

for example an alcohol.

  Synthetic CZH-5 zeolites can be used as synthesized, or they can be heat treated (calcined). Usually, it is desirable to remove the alkali metal cation by ion exchange and replace it with a hydrogen ion, ammonium ion or any other desired metal ion. We can

  use the zeolite in an intimate combination with

  Hydrogenation agents, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as palladium or platinum, for applications where a hydrogenation function dehydrogenation is desirable. Typical replacement cations may include metal cations, for example rare earths,

  Group II A and Group VIII, as well as their mixtures.

  Among the metal cations of replacement, it is preferred

  especially the cations-of metals like -

  rare earths, of Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, -

  C, Ti, Al, Sn, Fe and Co. -. The hydrogen, ammonium and metal components can be exchanged in the zeolite. We can also

  to impregnate the zeolite with metals, or one can physically

  intimately mix the metals with the zeolite

- 10 -

  conventional processes well known to the spe-

  specialists in the technical field. The metals may also be occluded in the crystal lattice, ensuring that the desired metals are present as ions in the reaction mixture, from which the CZH-5 zeolite is prepared. Typical ion exchange techniques involve contacting the synthetic zeolite with a solutin containing a salt of the desired replacement cation (s). Although a variety of salts may be used, chlorides and other halides, nitrates and sulphates are particularly preferred. Illustrative ion exchange techniques include those described in a variety of patents, including U.S. Patent Nos. 3,140,249, 3,140,251 and 3,140,253. Ion exchange can take place before or

  after calcination of the zeolite.

  After contact with the salt solution of the desired replacement cation, the zeolite is typically washed with water and dried at a temperature ranging from 3050C to about 3150C. After washing, the zeolite can be calcined in air or in an inert gas, at temperatures ranging from about 2000C to about 820C, for periods ranging from 1 to 48 hours and more, to generate a catalytically active product, particularly interesting

  for hydrocarbon conversion processes. independent

  In addition to the cations present in the synthesized form of the zeolite, the spatial arrangement of the atoms that form the basic crystal lattice of the zeolite remains substantially unchanged. The exchange of cations has only little

  or no effect on zeolite network structures.

  Zeolite CZH-5 can be manufactured in a wide variety of physical forms. In general, the zeolite may be in the form of a powder, granules or a molded product, such as a product

- he -

  extruded having sufficient size to pass through a 2 mesh screen (Tyler) and be retained on a 400 mesh screen (Tyler). In cases where the catalyst is molded, such as by extrusion with an organic binder, the zeolite may be extruded prior to drying, or it may be dried or partially dried and then extruded. The zeolite may be composed with other matrix materials resistant to the temperatures and other conditions used in organic conversion processes. Such matrix materials include active and inactive substances and synthetic and natural zeolites, as well as inorganic materials such as clays, silica and metal oxides. These may be natural or in the form of gelatinous precipitates, soils or gels, including mixtures of silica and

  of metal oxides. The use of a material in combination

  The combination with the synthetic zeolite, that is compounded with it, which is active, tends to improve the conversion and selectivity of the catalyst in certain organic conversion processes. The inactive materials suitably serve as diluents to control the extent of conversion in a given process so that the products can be obtained economically without resorting to other means of adjusting the speed of the conversion. the reaction. Frequently, zeolite materials have been incorporated into natural clays by

  example bentonite and kaolin. These materials, that is,

  say clays, oxides, etc., operation,

  partly as a binder for the catalyst. It is desirable

  to obtain a catalyst having good crush strength, since during the refining of the

  oil, the catalyst is subjected to a brutal treatment.

  This treatment tends to break the catalyst into materials

  powder that causes problems during treatment.

- 12 -

  Natural clays that can be made with zeolites. Synthetics according to the present invention include clays belonging to the families montmorillonite and kaolin, which families include sub-bentonites and kaolins. commonly known as Dixie, McNamee, Georgia and Florida et al., where the main mineral component is halloysite, kaolinite, dickite, nacrite or anauxite. Fibrous clays such as sepiolite and attapulgite can also be used as a support. Such clays can be used in the raw state, as they are at the outlet of the mine, or they may be initially subjected to

  calcination, acid treatment or modification of

chemical cation.

  In addition to the previous subjects, one can

  zeolites.CZH-5 with porous matrix materials and matrix material mixtures, such as. silica, alumina, titanium dioxide, magnesia, silica-alumina, silica-magnesia, silica-zirconium oxide, silica-thorium oxide, silica-beryllium oxide, silica-oxide titanium, titanium oxide-oxide. zirconium, as also ternary compositions, such as silica-thorium oxide, silica-alumina-zirconium oxide, silicalumin-magnesia and silica-magnesia-zirconium oxide. The matrix can be in the form

a co-gel.

  CZH-5 zeolites can also be compounded with other zeolites, such as mordenites, zerionites (eg X and Y) and synthetic and natural faujasites. They can also be composed with purely synbetic zeolites, such as those of the ZSM series. The combination of zeolites may also be composed in a porous inorganic matrix.

- 13 -

  The relative proportions of the zeolite

  crystalline aluminosilicate according to the present invention.

  The inorganic oxide gel matrix and matrix may vary within wide limits. The content of CZH-5 can vary from about 1 to about 90% by weight, but it usually fluctuates between about 2 and about

% by weight of the composite product.

  The following examples illustrate the preparation of

  CZH-5 zeolites by hydrothermal crystallization.

  Example 1 In a 500 ml Teflon bottle, 0.02902 g of sodium aluminate (48% Al 2 O 3,

  33% Na2O), 12.46 g of choline chloride and 50 g of water.

  To this mixture was added a second solution, prepared by dissolving 6.65 g of sodium chloride in 100 g of

distilled water.

  To the solutions thus prepared, a third solution consisting of 46.34 g of a solution of

  sodium silicate N (28% SiO 2) in 150 g of distilled water.

  The final reaction mixture was obtained by the addition of a hydrochloric acid solution prepared by the mixture of 2.68 g of concentrated hydrochloric acid (36%).

HC1) in 71.88 g of distilled water.

  The Teflon reaction bottle was sealed and the reaction mixture was autoclaved in an oven at 1500C for 15 days.

  until the crystalline precipitate formed.

  The crystals were allowed to settle, the clear supernatant liquid was decanted and the crystals were filtered, washed with distilled water to remove chloride ions and dried for 16 hours at 1200.degree.

  under a vacuum of 51 cm of mercury and under a nitrogen atmosphere.

  The X-ray diffraction pattern of the product was determined and found to be that shown in Table III, this pattern being characteristic of

CZH-5.

- 14 -

TABLE III

d (A) Intensity il, 79 S

11.56M

9.94M

, 97 W

, 79 W

4.72 W

4.67 W

4.62 W

4.42 W

4.24 VS

4.07 VS

4.04 S

3.96 W

3.87 M

3.82M

3.72 W

3.63 W

3.53 W

3.45 M

3.38 W

3.32 W

3.18 W

3.13 W

3.04 W

2.91 W

2.88 W.

Example 2

  In a 500 ml Teflon bottle, 0.5743 g of sodium aluminate (48% Al 2 O 3, 33% Na 2 O), 12.33 g of choline chloride and 1 g of water were mixed. To this mixture was added a second solution prepared by dissolving 6.54 g of sodium chloride in

100 g of distilled water.

- 15 -

  To the thus prepared solution was added a third solution consisting of 45.86 g of a solution of N sodium silicate (28% SiO 2) in 150 g of distilled water. The final reaction mixture was obtained by adding a solution of hydrochloric acid prepared by the mixture of 2.96 g of concentrated hydrochloric acid.

  (36% HCl) in 72.0 g of distilled water.

  The Teflon reaction bottle was sealed and the reaction mixture was autoclaved in an oven at 150 ° C. for 15 days.

  until the crystalline precipitate forms.

  The crystals were allowed to settle, the clear supernatant liquid was decanted and the crystals were filtered, washed with distilled water to remove chloride ions and dried for 16 hours at 120 ° C. under a vacuum. 51 cm and under a nitrogen atmosphere. The X-ray diffraction grating was determined and found to be that shown in Table IV.

typical of CZH-5 zeolite.

TABLE IV

d (A) Intensity

$ 11.79

11.56M

9.9.4 M

, 97 W

, 79 W

4.72 e-W

4.67 W

4; 62W

4.42 W

4724 S

4; 07 M

4.04M

3.96 W

3.87 S

3182 S

3.72 W

3.63 W

3.53 W

> 2485946

  - 16- TABLE IV (continued) dMA) Intensity

3.45M

3.38 M

3.32M

3; 18W

3.13 W

3.04 W

2.91 W

2, 88 W

Examples 3-7

  Examples 3-7 illustrate the preparation of CZH-5 and the effect of the time during which the reaction mixture is maintained at elevated temperature and under autogenous pressure, on the formation

zeolite crystals.

  The reaction mixtures of Examples 3-7 were prepared so that they had the following molar ratios of ingredients: SiO 2 / Al 2 O 3 80: 1 R 2 O / Al 2 O 3 · 16: 1 (R = choline) Na 2 O / Al 2 O 3 4.0: 1

H20 / A1203 8328: 1

  NaCl / Al 2 O 3 84: 1 weight% Al 2 O 3 and SiO 2 3 wt% NaCl 3 In each of the experiments of Examples 3 to 7, the reaction mixture was maintained at 150 ° C. under autogenous pressure, without stirring during

crystallization.

  Table V shows the crystallization time

  and the results of the analysis of the products obtained.

TABLE V

*Example

Crystallization time

  (days) Analyzes Prod .: Structure (RDX) amor

CZH-5%

% CZH-5

% CZH-5

% CZH-5

Composition PALm SiO2 / A1203

R20 / A1203

Na20 / A1203

  * Ignition loss - 540 C, 10 hours, in the air.

  Cr A \ .O CP% 6.68 37.5 1.02 0.28 8.05 42.5 1.08 0.23 3.03 53.7 1.33 0, o7 4.33 64.2 1 , 38 0.20 8.96 54.2 1.33 0.23 I j I

- 18 -

  CZH-5 zeolites are suitable for

  implementation of hydrocarbon conversion reactions.

  The hydrocarbon conversion reactions are chemical and catalytic processes in which carbon-containing compounds are exchanged for different carbon-containing compounds. Examples of hydrocarbon conversion reactions are catalytic cracking, hydrocracking, and olefin and aromatic compound formation reactions. The catalysts are of interest in other reactions of hydrocarbon conversions and petroleum refining, such as

  the isomerization of n-paraffins and naphthenes, the poly-

  merification and oligomerization of olefinic or acetylenic compounds, such as isobutylene and butene-1, reforming, alkylation, isomerization of polyalkylaromatic compounds (eg orthoxylene) and disproportionation of aromatic compounds (eg toluene), so as to obtain a mixture of benzene, xylene and higher methylbenzenes. CZH-5 type catalysts have a high selectivity and, under hydrocarbon conversion conditions, can give a high percentage of desired products

compared to total products. -

  CZH-5 zeolites can be used for

  treatment of hydrocarbon feedstocks. Hydro loads

  Carbon compounds contain carbon compounds and can come from many different sources, such as virgin oil fractions, recycle oil fractions, oil shale, liquefied coal, asphalt sand oil and, in general, any carbon-containing liquid susceptible to zeolitic catalytic reactions. Depending on the type of treatment that the hydrocarbon feedstock must undergo, the feedstock may contain metals or be free of metals or it may also contain high or low amounts of nitrogen-containing impurities or

- 19 -

  sulfur. It should be understood, however, that the treatment will be all the more effective and the catalyst even more active than the metal content,

  nitrogen or sulfur load will be lower.

  The conversion of hydrocarbon feedstocks may take place in accordance with any mode of operation, for example, in fluidized bed, moving bed or fixed bed reactors, depending on the types of treatment

that we want to implement.

  The composition of the catalyst particles will vary depending on the conversion process and procedure. By the use of catalysts of the CZH-5 type

  containing hydrogenation components, it is possible to

  crack residual heavy oil products, cyclic products and other hydrocrackable feedstocks at temperatures ranging from 175 to 4850C, using hydrogen to hydrocarbon feedstock molar ratios that range from 1 to 100. The pressure may vary from 0, 5 to 350 bar and the liquid hourly space velocity ranges from 0.1 to 30. For these purposes, the CZH-5 type catalyst can be mixed with mixtures of inorganic oxide supports, also with faujasites, such as X and Y. Hydrocarbon cracking feeds can be catalytically cracked using CZH-5 at hourly liquid space velocities ranging from 0.5 to 50, at temperatures ranging from 2600C to 6250C and pressures which vary from a pressure below atmospheric pressure to several

hundreds of atmospheres.

  CZH-5 can be used to dewax hydrocarbon feeds by selectively removing

  chain paraffins - straight and slightly branched chain.

  The operating conditions can be those of hydrodewaxing-moderate hydrocracking, or they can use low pressures in

- 20 -

  the absence of hydrogen. Dewaxing in the absence of hydrogen at pressures below 30 bar and,

  preferably less than 15 bar, is by far preferred

  because large amounts of olefins can be obtained from cracked paraffins. CZH-5 can also be used for carrying out reforming reactions using temperatures ranging from 300 ° C. to 6000 ° C., pressures ranging from 35 to 110 bars and speeds.

  hourly liquid spaces that fluctuate from Ol to 20.

  The molar ratio of hydrogen to hydrocarbon can in

the whole range from I to 20.

  The catalyst according to the invention can also be used for the hydroisomerization of normal paraffins, when the catalyst in question is provided with a hydrogenation component, for example

  platinum. The hydroisomerization is carried out at temperatures

  90 to 375 ° C and at liquid hourly space velocities ranging from 0.01 to 5. The molar ratio

  Hydrocarbon hydrogen typically ranges from 1: 1 to 5: 1.

  In addition, the catalysts can be used to isomerize and polymerize olefins using

  temperatures ranging from 0 C to 2600C ..

  Other reactions which can be carried out using the catalyst according to the invention containing a metal, for example platinum, include the hydrogenation-dehydrogenation reactions and the reaction reactions.

denitrogenation and desulphurization.

  CZH-5 can be used for carrying out hydrocarbon conversion reactions with active or inactive carriers, with organic or inorganic binders and with or without additional metals. These reactions are well known to specialists in

  as are the reaction conditions.

  to use for their implementation. We can also

  use CZH-5 as an adsorbent for hydro-

carbon.

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Claims (12)

  A zeolite characterized in that it has a molar ratio of an oxide selected from silicon oxide, germanium oxide and mixtures thereof, to a   oxide selected from aluminum oxide,   lium and mixtures thereof, greater than about 5: 1 and having the following X-ray diffraction lines: d (nm) Intensity 1.185 + 0.010 strong 1.160 + 0.010 average 0.997 + 0.005 average 0.425 + 0.002 very strong 0.387 + 0.001 average 0.383 + 0.001 average 0.346 + 0.001 average 2. Zeolite characterized in that it has a composition, as synthesized and in the anhydrous state, expressed in terms of molar ratios of oxides, which follows: (0.5 to 1.0) R20: (O at 0.50) M20: W203: (greater than about) Y02, where M represents an alkali metal cation, W is selected from aluminum, gallium and mixtures thereof, Y is selected from silicon, germanium and mixtures thereof and   R is a cation derived from a choline compound.   Zeolite according to Claim 2, characterized in that W represents aluminum and Y represents silicon. Zeolite characterized in that it is prepared   by the heat treatment of the zeolite according to any one   of the preceding claims, at a temperature from about 200 ° C to 820 ° C. * -o / - * - 22 -   5. A zeolite according to any one of the claims   tions, characterized in that the said   molar port greater than about 5 ranges from about 8: 1 to 150: 1, preferably from about 10: 1 to 100: 1, especially about 40: 1.   6. A zeolite according to any one of claims   characterized in that it has undergone ion exchange with hydrogen, ammonium, rare earth metal, group IIA metal or group VIII metal, rare earth metals, metals   group IIA where the metals of group VIII are preferably   occluded in the zeolite in question.   7. Composition of matter, characterized in that it comprises a zeolite according to any one of   preceding claims, and an inorganic matrix.   8. Process for preparing a following zeolite   any one of claims $ to 6, characterized   in that it comprises the steps of: (a) preparing an aqueous mixture containing sources of a choline-type compound, an oxide selected from aluminum oxide, gallium oxide and mixtures thereof and an oxide selected from silicon oxide, germanium oxide and mixtures thereof, (b) maintaining the mixture at a temperature of at least 100C until the crystals of said zeolite are formed and (c) recovering said crystals.   9. Process according to claim 8, characterized in that the aqueous mixture has a composition, expressed in terms of molar ratios of oxides which is within the following limits: Y02 / W203, 5: 1 to 350: 1, R20 / W203, 0.5: 1 to 40: 1; Y is selected from silicon, germanium and mixtures thereof, W is selected from aluminum, gallium and mixtures thereof and R represents a cation derived from a choline compound. - 23 -   10. Process according to any one of the claims   8 and 9, characterized in that the temperature of step (b) ranges from about 135 ° C to about 175 ° C and that the mixture is maintained at said temperature under the autogenous pressure. A hydrocarbon conversion process, characterized in that a hydrocarbon feedstock is contacted with a zeolite-containing composition according to any one of claims 1 to 6 under conversion conditions. hydrocarbons.   12. The process for the conversion of hydrocarbons according to claim 11, characterized in that the process in question is hydrocracking, dewaxing, reforming,   oligomerization or polymerization of olefins, isomerism   cation, dismutation, alkylation or catalytic cracking