JPS6058164B2 - Crystalline silicates, their preparation and their use as adsorbents, extractants or desiccants, as ion exchangers or as molecular sieves - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel crystalline silicates and methods for producing these silicates.

The invention further relates to the use of these silicates, in particular as adsorbents and extractants, drying agents, ion exchangers and catalysts or catalyst supports for various catalytic processes, in particular for the catalytic production of aromatic hydrocarbons. The crystalline silicates of the present invention are SiO4 linked by covalent oxygen atoms.
-, FeO4- and optionally .AIO4-GaO4- and GeO4- are composed of a three-dimensional network of tetrahedra. The negative electric valence of the tetrahedron containing iron and optionally aluminum and gallium is in equilibrium due to the absorption in the crystal of monovalent and/or divalent cations.
Unlike atoms of silicon, iron, and optionally aluminum, gallium, and germanium, which exist in a non-exchangeable state, these cations can be exchanged, at least in part, with another cation when using a suitable exchange method. Can be replaced. The silicates of the invention are therefore suitable for use as ion exchangers. Apart from the iron and optionally aluminum and gallium present in the FeO4- and AIO4- and GaO4-tetrahedrons mentioned above, the silicates of the invention are further freed from iron which does not form part of the crystal structure of the silicate. , aluminum and/or gallium. This iron, aluminum and/or gallium present in and/or between the silicate crystals, for example in the form of precipitated hydroxides, does not contribute to the negative electric valence mentioned above. The crystal structure of the silicates of the present invention has molecular-sized voids that are normally filled with water of hydration.

After at least partial dehydration, the silicate can be used as an effective adsorbent and the adsorbed molecules are retained within the voids. These voids are accessible through pores in the crystal structure. The cross-sectional area of these pores limits the size and shape of molecules that can be adsorbed. This allows separation of certain molecules from a mixture based on their size, with some molecules being adsorbed onto the silicate while others are rejected. A material having this property is usually called a molecular sieve. This property of the silicates of the present invention results from the fact that only compounds with a specific structure can penetrate into the silicate or leave intact, respectively, resulting in the formation of a specific structure from a mixture of compounds of different structures. It is utilized when silicates are used as catalysts or catalyst supports for selective processes that convert only compounds having a specific structure or produce only compounds with a specific structure from a certain compound. The silicates of the present invention are a group of compounds characterized by their thermal stability, adsorption behavior and overall composition. The crystallinity of the various compounds is in accordance with the fact that they all exhibit distinct X-ray powder diffraction patterns. The silicates of the invention in the dehydrated state have the following total composition, expressed in moles of oxide:

where R=-species or more monovalent or divalent cation; a 0.1; b>0;c>O; a+b+c and n=
Valence of R.

The silicates of the present invention are thermally stable up to temperatures above 600°C and after dehydration at 400°C in vacuum
More than 3% by weight of water can be adsorbed at °C and saturated water vapor pressure.

In this patent application, a silicate is said to be thermally stable to temperatures above t° C. if heating the silicate to a temperature of t° C. does not substantially affect the X-ray powder diffraction pattern of the silicate. The present patent application therefore relates to new crystalline silicates having the overall composition, thermal stability and adsorption behavior described above.

Silicates that do not contain gallium and germanium, in other words, silicates in which c<5e are both O in all of the above compositions, are preferred. Furthermore, in all the above compositions, a is 0.
Silicates larger than 3 are preferred and especially when a is 0
．． A silicate greater than 5 is selected. Particular preference is given to silicates in which no aluminum is present, in other words silicates in which b is equal to 0 in all the above-mentioned compositions. Regarding y, it can be said that silicates in which y is less than 600 and especially less than 300 are preferred. Finally, preference is given to silicates according to the invention which have an X-ray powder diffractogram showing the reflections given in Table A below in particular. The values given in Table A were determined according to standard methods.

Irradiation: CU-Kα, wavelength: 0.15418r1m-A The letters used to indicate relative intensity in the table have the following meanings. ■S=extremely strong; S=strong; M=medium; W=weak; θ=angle according to Bratz's law. A complete X-ray powder diffraction diagram of a particularly preferred silicate of the invention is shown in B.
Shown in the table (irradiation: CU-Kα, wavelength: 0.15418n
m).

*Chi = intensity of the strongest isolated reflection appearing in the diagram B The letters used to describe reflections in the table have the following meanings: SP = sharp; SR = shoulder-like peak; NL = average. ; BD = wide; θ = angle according to Bratz's law.

The silicates of the present invention are prepared from an aqueous mixture containing the following compounds: - one or more containing a valent or divalent organic cation (R2) or generating such a cation during the preparation of the silicate; one or more silicon compounds, one or more iron compounds and optionally one or more compounds of alkali metals or alkaline earth metals (R1) and one or more aluminium, gallium and/or alkaline metals. Or germanium compounds.

Its preparation is carried out by maintaining the mixture at elevated temperature, preferably with stirring), until the silicate forms, and then separating the silicate crystals from the mother liquor. In the aqueous starting mixture from which the silicates of the present invention are prepared, the various compounds are present in the following molar ratios, expressed in moles of oxide.
/QO: (SjO2+GeO2)=0.01-1 and p and q are the valences of R and R2, respectively).

In addition to the novel silicates, the present patent application also discloses that starting from this aqueous mixture by maintaining the aqueous mixture having the above composition at elevated temperature until the silicate is formed and then liberating the silicate from the mother liquor. It also relates to a method of producing the novel silicates.

In the aqueous starting mixture from which the silicates of the invention are prepared, the various compounds are preferably present in the following molar ratios expressed in moles of oxide. The production of the silicates of the present invention may be carried out either under normal pressure or under elevated pressure. When using reaction temperatures above the boiling point of the mixture, it is preferred to work in an autoclave under autogenous pressure. The silicate is preferably heated at a temperature of 90 to 300°C, and especially 125 to 175°C, for at least 4 hours while stirring the mixture.
manufactured by maintaining the temperature at . After the silicate has formed, the crystals are separated from the mother liquor, for example by filtration, decantation or centrifugation. The crystal mass is then washed with water and finally dried at a temperature of 100 to 200°C. When the silicates of the present invention are obtained in the form of products of colloidal size, the anionic resin, cationic resin and anionic resin are in the form of particles of sufficiently large size to be easily separated from the suspension. in contact with an ion exchange resin selected from the group consisting of mixtures of ionic resins and cationic resins, or the other side is in contact with an aqueous treatment solution having a lower salt concentration than the aqueous colloidal silicate suspension. Excess siliceous components are removed from the aqueous suspension of colloidal silicate in the mother liquor remaining after crystallization of the silicate by contacting the aqueous suspension of the silicate with a semipermeable membrane that allows the excess silicate and soluble salt to pass through. Further processing of the silicate may be facilitated by removing soluble salts.
Suspensions of silicate can be prepared, for example, by alternatively cationic DOwex-50 (H+ form) and anionic DOw
ex-1 (0H-type) or may be contacted with demineralized water through a semipermeable membrane. The obstruction of silica pores that occurs in the production of the silicate of the present invention can be avoided by adding an alkali metal salt containing a monovalent anion to the basic mixture for producing the silicate. It may also be reduced by adding

Examples of suitable salts are NaCl, . KBr. ．． NaNO3 and LiCl. The quaternary ammonium compounds commonly used in the basic mixtures for producing the silicates of the invention may be replaced by a mixture of at least one compound j having the formulas a, R2, R3 and at least one compound j having the formula R4X. , where Rl, R2, and R3 are hydrocarbon groups or hydrogen, R, is a hydrocarbon group, and x is a negative group. Examples of such mixtures include (C2H,)3N+(C2H5)2S04,1(C,
)3N+(C2H5)2S04,(C3H7),N+
C3H7Br and NH3+ (C3H7)3N+C,H
There is 7OH. The quaternary ammonium compounds may also be substituted with primary amines having 2-107) carbon atoms in the molecule. Examples of suitable compounds used in the preparation of the silicates of the invention are listed below: alkali metal and alkaline earth metal nitrates, carbonates, hydroxides and oxides; primary, secondary and secondary. Tertiary alkylamines and quaternary alkylammonium compounds such as bromides and hydroxides; heterocyclic amines such as pyridine and piperidine; iron oxides, iron nitrates and ferrous ammonium sulphates; aluminum dihydroxide, sodium aluminate and activated amines; ) Luminas, such as gamma-alumina; sodium silicate, silica gel, silicic acid, aqueous colloidal silica sols and amorphous solid silicas, such as precipitated silica sols; gallium nitrate, gallium oxide and germanium oxide. For producing the silicate of the present invention. In the case of basic mixtures in which R1 is present in the alkali metal compound and R2 in the tetraalkylammonium compound and in particular in which R1 is present in the sodium compound and R2 is present in the tetrapropylammonium compound, selected. The silicates of the present invention are generally prepared from aqueous mixtures containing alkali metals or alkaline earth metals, but
They may also be prepared from aqueous mixtures free of such metals. As previously mentioned, the silicates of the present invention contain exchangeable cations.

In the silicates obtained by heating the aqueous mixtures described above, these exchangeable cations can be alkali and/or alkaline earth metal ions and monovalent and/or divalent organic cations. Please use the appropriate exchange method↓
Thus, alkali and alkaline earth metal ions can be replaced by other cations such as hydrogen ions, ammonium ions or rare earth metal ions. Monovalent and divalent organic cations can be converted to highly suitable hydrogen ions by baking the silicate. When the silicates of the present invention contain alkali metals and when these silicates are to be used as catalysts or catalyst carriers, the alkali metal content of these silicates is reduced in advance to 1% by weight or less, particularly 0.05% by weight or less. is preferable.

The alkali metal content of the silicate is very advantageously reduced by contacting it once or several times with a solution containing exchangeable cations. NH4+-silicates can be prepared in this way by treating the silicate with a solution containing, for example, ammonium ions. N.H.
H+ type silicate can be obtained by baking 4+-silicate. The H+ form of the crystalline silicate of the present invention is hereinafter referred to as HCS. It is called. (2) Calcining may be carried out in such a way as to convert at least a portion of the monovalent and/or divalent organic cations present in the silicate into hydrogen ions. The silicates of the present invention have catalytic activity and are used as catalysts themselves.

The silicates are also used as catalyst supports for one or more catalytically active metal components. Depending on the intended use of the catalyst, the metals deposited on the silicates of the invention are metals from groups IB, ■B, ■B, ■B, ■B and ■ of the periodic table. In this patent application, the periodic table is HandbOOkOfChemistryandPh
ysicsl 55th edition, page B2, refers to the periodic table of elements. Among these metals are copper, silver, zinc, cadmium, vanadium, chromium, molybdenum, tungsten, manganese, iron group metals, and platinum group metals. Metals may be deposited onto the silicate by conventional methods such as immersion, filtration, ion exchange, etc. Halogens, magnesium,
Accelerators such as phosphorus, boron, arsenic and antimony may be added. The silicates of the invention may be modified by incorporating therein at least 0.5% by weight of phosphorus, for example by reaction with a phosphorus compound. The catalytic activity of phosphorus-containing silicates can be increased by impregnating them with zinc compounds. Modification of the silicate with phosphorus makes the silicate less suitable as a catalyst for aromatization reactions, but improves its suitability as a catalyst for other reactions, such as alkylation. Very suitable catalysts for many types of processes are silicate-supported catalysts containing the following catalytically active metals or combinations of metals: nickel, copper, zinc, cadmium, chromium, platinum, Palladium, nickel-tungsten, cobalt-molybdenum, nickel-molybdenum, zinc-palladium, zinc-copper and zinc-rhenium. When using the silicates of the invention for catalytic purposes, the material should generally be utilized in the form of particles having a diameter of 0.5-57 m.

In the preparation method described above, the silicate is obtained in the form of a fine powder. The silicate is shaped into particles of larger size, for example by compression. The silicate may be mixed with an inorganic matrix or binder material if desired during molding. Examples of suitable matrix or binder materials are naturally occurring clays such as kaolin and bentonite. Other suitable matrix or binder materials are inorganic oxides such as alumina, silica, zirconia or combinations thereof, such as silica-alumina and silica-zirconia. In principle, any mixing ratio may be used when combining the silicates of the invention with matrix or binder materials. A matrix or binder material is selected that is free of alkali metals or has a very low alkali metal content. For the sake of simplicity, catalysts containing at least some of the silicates of the invention will be referred to hereinafter as "catalysts of the invention" in the present patent application. Catalysts of the invention used for hydrocarbon conversion processes are among them Generally exhibits higher stability if the silicates present in the silicates have a final particle size of 0.005-0.1 micron. Silicates with this small particle size use higher concentrations of organic components in the aqueous mixture to prepare the silicate. Although the catalyst of the present invention has an extremely long life, it is desirable to regenerate it from time to time.

This can be carried out very simply by burning out the catalyst). The catalyst of the present invention is particularly applicable to the following processes.

1 Catalytic cracking of heavy hydrocarbon mixtures to produce light hydrocarbon oil distillates; 72 Production of isoparaffins by isomerization of n-paraffins; 3 Hydrodesulfurization of hydrocarbon oil distillates; 4 Naphthenic aromas 5. Polymerization of olefins to produce polyolefins.

The silicates of the invention are further suitable for application in the following processes.

1. Hydrocracking of heavy hydrocarbon oils for the production of light hydrocarbon oil distillates, such as the conversion of gas oil to gasoline.

For this purpose, heavy hydrocarbon oils are prepared under hydrocracking conditions by a) a zeolite with a pore size larger than 7A;
a) a silicate of the invention and c) one or more metal components having hydrogenation/dehydrogenation activity in combination with at least one of the materials a) and b). Very suitable catalysts for hydrogenolyzing gas oil to produce gasoline are a mixture of HCS and rare earth-exchanged zeolite x impregnated with Ni-W and Ni/
W/SiO2-A]203. 2 Hydrocracking of heavy hydrocarbon oils to produce lubricating oils with high viscosity index.

For this purpose, heavy hydrocarbon oils are subjected to hydrocracking conditions using a) an amorphous or crystalline wide-pore cracking catalyst, b) a silicate of the invention and c) a metal component having hydrogenation/dehydrogenation activity. one or more of the catalysts of the present invention. Very suitable catalysts for hydrocracking heavy hydrocarbon oils to produce low pour point, high viscosity index lubricating oils are Nl-W impregnated SiO2/ZrO2/clay catalysts and Zn/HCS. It is a catalyst consisting of a mixture of A very suitable catalyst for producing lubricating oil from underwax oil is Zn/
HCS and NI/HCS. 3. Improvement of the light and oxidative stability of lubricating oils produced by contacting the 2 oils with the silicates of the invention at elevated temperatures, either by conventional methods or by hydrolysis.

Improved results are obtained by contacting in the presence of small amounts of added n-paraffins, sulfur or sulfur compounds. 34 Improvement of Catalytic Cracking Gasoline by Contacting the Gasoline with the Catalyst of the Invention in the Presence or Absence of Hydrogen. In this method, for example, catalytic cracking gasoline is divided into a C6 top fraction and a C7+ bottom fraction, and only the C7+ bottom fraction is brought into contact with the catalyst of the present invention at elevated temperature and pressure. , and by combining the treated C7+ fraction with the untreated C6 fraction. Catalytic cracked gasolines which are highly suitable for quality improvement over the catalysts of the invention are gasolines produced in a catalytic cracking process carried out in such a way that a C6+gaso4r phosphorus containing less than 15% by weight of olefins is obtained. It is.
This C6+ gasoline can be upgraded very favorably in the absence of hydrogen on HCS or in the presence of hydrogen on Ni/HCS. 5 alcohols and/or ethers having up to 4 carbon atoms per alkyl group by contacting them with the catalyst of the invention at such low severity that the catalyst exhibits little aromatization activity. production of olefins from alcohols and/or ethers.

A product consisting essentially of C2-C4 olefins can be obtained by contacting methanol or dimethyl ether with HCS. A 6C2-q olefin or a mixture thereof with a C1-C5 paraffin is contacted at elevated temperature with a silicate of the invention whose alpha value (as defined in U.S. Pat. No. 3,960,978) has been reduced to 0.1-120. and thereby producing an olefinic gasoline containing less than 2% aromatics.

Reduction of the alpha value of the silicate of the present invention is achieved by first using it in a high temperature aromatization process or by steaming it. In this method propane or a C2-C3 paraffin/olefin mixture is converted into Zn/HCS, . Cr/HCS or N1/HCS
Excellent quality gasoline can be obtained by contacting with Improving the quality of naphtha by type-selective hydrogenolysis in which the naphtha is contacted with a catalyst of the invention, such as Ni/HCS, at elevated temperature and pressure and in the presence of hydrogen.

Catalytic hydrogenation dewaxing of a hydrocarbon oil by contacting the oil with a catalyst of the invention at elevated temperature and pressure and in the presence of hydrogen.

This method uses lubricating oils and shale oils such as Zn/HCS
Come in contact with it and remove it. Catalytic hydrodewaxing of the lubricating oil in this process may be carried out as the second stage of a two-stage dewaxing process in which the wax content of the lubricating oil is reduced by solvent winterization in the first stage.

The catalytic hydrogenation dewaxing of the present invention is also very suitably applied to lowering the freezing point of jet fuel. Separation of hydrocarbon mixtures, in particular from mixtures of xylene isomers by contacting the hydrocarbon mixture with the silicates of the invention
- Separating xylene.

Examples of mixtures of hydrocarbons separated by the silicates of the invention are: 2,2-dimethylbutane/2-methylpentane; iso-octane/3-methylpentane; iso-octane/2,5-dimethylhexane; Decalin/cyclohexane; 1,2-dimethylcyclohexane/methylcyclohexane-o-diethylbenzene/p-diethylbenzene; 2-ethyltoluene/4-ethyltoluene. In order to separate p-xylene from a mixture of xylene isomers, silicates of the present invention are preferably modified by reaction with a silane having an organic radical such as octadecyltrichlorosilane.

Transalkylation of an alkyl-substituted aromatic by contacting the alkyl-substituted aromatic with a catalyst of the invention under 10 transalkylation conditions.

This method is applied, for example, to the production of ethylbenzene from a mixture of benzene and diethylbenzene. 1
1 Alkylation of aromatics by contacting them with the catalyst of the invention together with an agent under alkylation conditions.

This method is applied, for example, to the production of ethylbenzene from benzene and ethylene. 12 Alkylation of olefins for the production of higher olefins by contacting olefins such as ethylene, propylene, butene-2 or isobutene and an alkylating agent such as dimethyl ether with the catalyst of the present invention at alkylation conditions.

13 A xylene mixture was heated with N in the presence of hydrogen at elevated pressure.
Conversion of ethylbenzene and aliphatic hydrocarbons present in a xylene mixture consisting of contacting with a catalyst of the invention such as i/HCS.

This process makes the mixture more suitable as a feedstock for an isomerization plant for producing p-xylene.
This hydrotreatment obviates the need for the customary aromatic extraction of the feed mixture and fractional distillation of ethylbenzene. The catalyst of the invention is highly suitable for application in the following processes.

1. Catalytic dewaxing of light oil to improve its cloud point.

The process is carried out by contacting light oil at elevated temperature with the catalyst of the invention in the presence or absence of hydrogen and in the gas or liquid phase. Catalytic dewaxing of light oil is CO/MO/Al in the second stage.

Very suitable is the combination with catalytic hydrodesulphurization and hydrodenitrogenization of the dewaxed gas oil carried out over an O3 catalyst. A very suitable catalyst for the catalytic hydrogenation dewaxing of gas oil is Zn/Pd/
The catalyst of the present invention contains at least one polyvalent transition metal such as HCS and at least one Group I noble metal. N
When compared to other catalysts of the invention such as i/HCS, Z
n/Pd/HCS shows higher activity and stability in hydrodewaxing of gas oil. When catalytic dewaxing of gas oil is carried out in the presence of hydrogen, the gas oil is divided into a portion having a pour point below 1° C. and the remainder, and the dewaxing of the present invention, which consists of a silicate having a crystal size of about 0.05 microns, is obtained. Hydrogen consumption may be reduced by applying a catalyst in combination with low pressure, hydrodewaxing only the remainder, and blending the hydrodewaxed portion with the untreated portion. Production of p-xylene by another C8 monoaromatic isomerization. The process is carried out by contacting C8 aromatics with the catalyst of the invention (eg Ni/HCS) in the liquid or gas phase under isomerization conditions. 3 Production of p-xylene by methylation of toluene.

The process is carried out by contacting toluene and a methylating agent such as methanol, methyl chloride, methyl bromide, dimethyl ether or dimethyl sulfide with the catalyst of the invention under methylation conditions. For this application, an average crystalline size of more than 0.5 microns is used, the surface of which has been passivated by reaction with a nitrogen or silicon compound having a size sufficiently large that it cannot penetrate into the pore structure of the silicate. It is preferred to use silicate catalyst particles of . Examples of suitable silicon and nitrogen compounds are dimethyldichlorosilane and phenylcarbazole. The surface modification of the catalyst of the invention for the production of p-xylene by methylation of toluene is also such that it is composed of meta-carbonate units combined with siloxane units and is sufficient to prevent penetration into the pore structure of the silicate. This can also be achieved very advantageously by contacting polymers with large dimensions with a catalyst. Another method of modifying the surface of the catalyst of the invention for producing p-xylene by methylation of toluene is by treatment of depositing a 15 to 75% coke coating thereon. When toluene is methylated to produce p-xylene in the presence of the catalyst of the present invention, the alpha value (JournalOfCatalys
isl Volume ■, No. 4, 196 Cape August, 527-529
Preference is given to using catalysts consisting of silicates whose values (measured as described on page 1) have been reduced by steam treatment to a value below 500. At least 0.5% by weight of P to reduce the formation of m-xylene
、． Preferably, silicates doped with As or Sb are used. Methylation preferably at 575 to 700°C
carried out at a temperature of By methylation of toluene, p-
A very suitable catalyst for producing xylene has phosphorus added in an amount of at least 0.5% by weight and
The catalyst of the invention is activated by gas phase treatment with a mixture of methanol and water for a period of at least 1 hour at a temperature of 0°C. Another highly suitable catalyst for the methylation of toluene to produce p-xylene is the following catalyst according to the invention. a catalyst comprising at least 0.2% by weight of boron, b a catalyst comprising at least 0.5% by weight of magnesium, c a catalyst comprising an oxide of antimony.

4. Production of p-xylene by disproportionation of toluene with the catalyst of the invention under disproportionation conditions.

Catalysts highly suitable for this purpose are the following catalysts according to the invention: a catalyst containing at least 0.5% by weight of phosphorus, B
．． Catalyst comprising oxide of antimony, c at least 0.5
Catalyst containing wt% magnesium, d at least 0.2
% by weight of boron. A catalyst containing an oxide of phosphorus and an oxide of magnesium.

Although the catalysts of the present invention have been successfully used for each of the processes mentioned above, they are of further importance in other areas.

This is because these catalysts have been found to be particularly suitable for producing aromatic compounds from acyclic organic compounds. A wide variety of organic compounds are suitable as starting materials for the preparation of aromatics, such as alcohols, ethers, olefins, paraffins, aldehydes, ketones and esters. These catalysts not only have a predominantly aromatic nature from organic compounds with six or more carbon atoms in the molecule, such as hexadecane;
Surprisingly, it is also possible to produce aromatics in high yields from organic compounds having less than 6 carbon atoms in the molecule, such as methanol, ethanol and propane. Another surprising property of the catalyst of the invention is that when used for the preparation of the aromatics mentioned above, the organic compound used as starting material contains 6 or more or less carbon atoms. Regardless of whether the aromatic
The purpose is to produce a product containing from 1 to 10 carbon atoms. This latter property of the catalyst of the present invention is due to the fact that 6
Aromatic compounds having 1 w carbon atoms are considered to be of great importance as they are very suitable for use as gasoline components. In preparing aromatics using the catalysts of the present invention, the starting materials can be acyclic organic compounds such as methanol or propylene, as well as mixtures of substantially acyclic organic compounds.

The aromatization process of the present invention is not only highly suitable for producing aromatics from methanol, but also for producing aromatics such as gasoline obtained in the hydrocracking, thermal cracking and catalytic cracking of straight-run gasoline and mineral oil fractions. It is also extremely suitable for increasing the octane number of gasoline. Aromatic hydrocarbons are produced from aliphatic and/or cycloaliphatic hydrocarbons by contacting the charge with the catalyst of the invention under aromatization conditions. Examples of suitable starting materials for the production of aromatics include ethylene, propylene, butylene, propane, butane, pentane, n-hexane, methylpentane, methylcyclopentane, Udex process raffinate, straight-run gasoline fraction, pyrolysis gasoline. There are distillates and products obtained in the Fischer-Tropschew hydrocarbon synthesis process.
Examples of suitable catalysts of the invention include HCS. ．． Zn/HCS.
．． Pt/HCS,. Ni/HCSlAu/HCS. ．． U
/HCS and Zn/Cu/HCS. When producing aromatics from olefins and paraffins, oxygen or air may be mixed into the charge to improve the aromatic yield. The yield of aromatics is achieved in two steps, i.e. first on a catalyst of the invention, e.g. The yield of aromatics may be increased by carrying out the process on a mixture with night. In addition to aromatics, gaseous products are also produced. The propane content of the gaseous product may be increased by carrying out the second stage of the process in the presence of hydrogen. When producing aromatics from aliphatics, the yield of alkyl-substituted aromatics is increased by carrying out the process in two steps, for example first on Zn/HCS and then on HCS. Zn-
The formation of naphthalene and coke during the aromatization reaction may be suppressed by applying the catalyst of the present invention comprising a metal in combination with Re. When producing aromatics from lower olefins, it is preferable to first oligomerize the olefin to a high molecular weight olefin over the catalyst of the present invention, and then aromatize this higher olefin again over the catalyst of the present invention. . In the first stage of the process considerably milder conditions are applied than in the second aromatization stage. The process involves contacting propylene with Ni/HCS, for example in a first stage at a relatively low temperature and high space velocity, and then contacting the product thus obtained in a second stage at a relatively high temperature and low space velocity. In Zn/HC
It may be converted to an aromatic mixture by contacting with S. An attractive embodiment of the aromatization process is to split the aromatization product into a gas phase and a liquid phase, hydrocrack the gas phase to increase its olefin content, and generate an olefin-rich fraction. This is an example of recycling to the reactor where aromatization occurs. When the aromatization reaction is used to improve the quality of naphtha, C3 and C
The production amount of 4 gases increases, and the production amount of C1 and C2 decreases. When using the aromatization reaction to improve the quality of naphtha, it is necessary to use aromatization reactions that contain Zn or Cd and group 1a (Na.
．． High liquid yields can be achieved by applying the catalyst of the invention with a modified activity corresponding to the addition of 0.1-3% by weight of elements of group K or Li) or of group a (PNSb or As). can get. Instead of incorporating these elements into the silicate, this modification may be achieved by steam treatment of the silicate. In addition to aliphatic and cycloaliphatic hydrocarbons,
Hydrocarbons containing heteroatoms such as oxygen, halogen, sulfur or nitrogen atoms may be used as a charge in the aromatization process of the present invention.

Examples of suitable compounds of this type are methanol, ethanol,
Isopropanol, 2-ethylhexanol, mixed oxo alcohols, mixed pentanol, methanol/propylene mixture, methyl mercaptan, dimethyl ether,
Tri-n-butylamine, methyl formate, acetic acid, acetone,
These are propionaldehyde, cyclopentanone, n-butyl formate, n-propyl acetate and hydrofuronic acid. The aromatization process of the present invention is also applied to the production of aromatic gasoline by converting carbohydrates into a mixture of water and alcohol and then converting this mixture to aromatic gasoline over the catalyst of the present invention. The aromatization process of the invention is also particularly suitable for application to hydrocarbons and/or oxygen-containing hydrogens obtained in the conversion of mixtures of carbon monoxide and hydrogen.

The mixture of carbon monoxide and hydrogen is converted into an aromatic hydrocarbon mixture in one or two stages. In this two-step process, a mixture of carbon monoxide and hydrogen is introduced into a catalyst containing one or more metal components having catalytic activity to convert the H2/CO mixture into hydrocarbons and/or oxygen-containing hydrocarbons in the first step. come into contact with. The product thus obtained is converted in a second stage into an aromatic hydrocarbon mixture in contact with the catalyst of the invention under aromatization conditions.
In the one-step process, a bifunctional catalyst comprising, in addition to the crystalline silicate of the invention, one or more metal components with catalytic activity for converting the H2/CO mixture into hydrocarbons and/or oxygen-containing hydrocarbons. is contacted with a mixture of carbon monoxide and hydrogen. This method is preferably carried out as a one-step method. A mixture of carbon oxide and hydrogen suitable as a charge for the process described above is produced by steam gasification of a carbon-containing material at high temperatures. Examples of such materials are lignite, anthracite, coke, crude oil and its fractions, and oils produced from tar sands and bituminous shales. During steam gasification, the charge in a finely dispersed state contains, inter alia, hydrogen, carbon monoxide, carbon dioxide, nitrogen and water, by means of steam and oxygen or, if desired, oxygen-enriched air. It is converted into a gas mixture. Steam gasification is preferably carried out at a temperature of 1000 to 20000C and a pressure of 10 to 50 bar. In order to be able to remove impurities such as ash, carbonaceous matter and hydrogen sulfide from the gas obtained in steam gasification and having a temperature of more than 1000 °C, this gas is first
It must be cooled to a temperature between 'C and 200C. This cooling is very well accomplished in boilers that generate steam using waste heat. The cooled gas is flushed with water to remove virtually all solids. After this washing, where the temperature of the gas has decreased to 20-80°C, the gas is further purified to remove hydrogen sulfide and carbon dioxide. This is AD
This is very suitably carried out by the IP method or the SULFINOL method. 1.0 to 3.0 for producing aromatic hydrocarbons starting from a mixture of carbon monoxide and hydrogen.
Gas mixtures with a H2/CO molar ratio of 1.5 to 2.5 are particularly preferred. If the mixture of hydrogen and carbon monoxide utilized does not have the desired molar ratio, this may be adjusted by addition of hydrogen or carbon monoxide.
Increasing the hydrogen content of the mixture at the expense of the carbon monoxide content is also very advantageously achieved by subjecting the mixture to the well-known water gas conversion reaction. The mixture of carbon monoxide and hydrogen is preferably heated to 200-500°C.
and especially at a temperature of 300-450°C, a pressure of 1-150 bar and especially a pressure of 5-100 bar and a temperature of 50-50
00 and especially at a space velocity of 300-3000 N1 gas/I catalyst/hour to aromatic hydrocarbon mixtures. The catalyst having the activity of substantially converting the H2/CO mixture into oxygen-containing hydrocarbons preferably contains one or more of the following metals: zinc, chromium and copper. Contains.

Furthermore, a combination of at least two of these metals,
For example, a zinc-copper, zinc-chromium or zinc-copper-chromium combination catalyst is selected. Catalysts consisting of a zinc-chromium combination are dynamically preferred. If a catalyst capable of substantially converting the B2/CQ mixture to oxygen-containing ζ hydrocarbons is used, a catalyst capable of substantially converting the H2/CO mixture to methanol is selected; The combination is extremely suitable. Combinations of the above metals may be applied to the carrier material if desired. By introducing acid functionality into these catalysts, for example by applying metal combinations to acidic supports, H2/CCB. The compound can be converted not only to methanol but also to a considerable extent to dimethyl ether. Catalysts having the activity of substantially converting H2/CO mixtures into hydrocarbons are known as Fischer-Tropsch catalysts.

Generally these catalysts contain one or more of the iron group metals or ruthenium together with one or more promoters and sometimes a support material such as diatomaceous earth to improve activity and/or selectivity. The catalyst may be prepared by precipitation, melting or soaking. When using Fischer-Tropsch catalysts in the aromatization process of the invention starting from H2/JCO mixtures, iron or cobalt catalysts are chosen, especially such catalysts prepared by immersion. Fischer extremely suitable for application in aromatization processes starting from H2/Cq compounds
The Tropschü catalyst is our Dutch patent application No. 76124.
It is described in No. 60. In the aromatization process of the present invention starting from a H2/CO mixture, a single catalyst is active to convert the H2/CO mixture into a mixture containing not only hydrocarbons but also a comparable amount of oxygen-containing hydrocarbons. or one catalyst exhibits catalytic activity that substantially converts the H2/CO mixture to hydrocarbons while the other catalyst
Any of two catalysts that exhibit catalytic activity to substantially convert the 2/Cq mixture to oxygen-containing hydrocarbons may also be used. Single-stage processes are highly preferred for producing aromatic hydrocarbon mixtures starting from H2/CO mixtures. In this process, a bifunctional catalyst is used, consisting of two separate catalysts, conveniently designated as catalysts X and Y. Catalyst X is a catalyst containing a metal component with catalytic activity to convert the H2/CO mixture into hydrocarbons and/or oxygen-containing hydrocarbons, and catalyst Y is a crystalline silicate of the invention. In bifunctional catalysts, catalysts X and Y can in principle be present as a mixture in which each particle of catalyst X is surrounded by a number of particles of catalyst Y, or vice versa. When carrying out the process with a fixed catalyst bed, this bed may consist of alternating layers of catalyst x and catalyst Y particles. If both catalysts are used as a mixture, this mixture can be a macromixture or a micromixture. In the first case, the bifunctional catalyst consists of two macroparticles, one consisting entirely of catalyst X and the other consisting entirely of catalyst Y. In the second case, the bifunctional catalyst consists of one type of macroparticles, each macroparticle being composed of a large number of microparticles each of catalysts x and Y. The bifunctional catalyst of the present invention in the state of a micromixture is
For example, it may be prepared by intimately mixing a fine powder of catalyst X with a fine powder of catalyst Y and shaping the mixture into larger particles by extrusion or squeezing. The bifunctional catalysts are preferably applied in the form of micromixtures. Bifunctional catalysts can also be prepared by incorporating into crystalline silicates, for example by soaking or ion exchange, a metal component with catalytic activity that converts H2/CO mixtures into hydrocarbons and/or oxygen-containing hydrocarbons. Good too. The most important applications of the catalyst of the invention are a) the steam gasification of coal, b) the conversion of the H2/CO mixture thus obtained into a mixture consisting essentially of hydrocarbons, preferably over a Fischer-Tropsch catalyst. or preferably over a methanol synthesis catalyst into a mixture consisting essentially of oxygen-containing hydrocarbons; and c) converting the product obtained in reaction b) to an aromatic gasoline over the catalyst of the invention. It is found in the field of producing synthetic gasoline from coal by converting it.

Preferably reactions b) and c) are carried out together in one step over the previously discussed bifunctional catalyst. The aromatization process of the invention is also particularly suitable for producing p-xylene from lower hydrocarbons such as propane, propylene, imbutane, butane, butylene, hexane, cyclopentane and methylcyclopentane.

Because the catalyst of the present invention has the surprising property of converting these compounds into highly aromatic products, the C
This is because it has been found that the C8 monoaromatic fraction has a much higher p-xylene content than the C8 monoaromatic fraction obtained in conventional methods of producing p-xylene. A similar phenomenon is observed when using the catalyst of the invention in the production of p-xylene by methylation of toluene. Here again we see products in which the C8 monoaromatic fraction has a surprisingly high p-xylene content. The following catalysts according to the invention are highly suitable for aromatizing lower hydrocarbons to produce p-xylene. a at least 0.2
Catalyst containing % by weight of boric acid, b at least 0.5% by weight
Catalyst containing magnesium, c Catalyst containing antimony oxide.

p-xylene can also be prepared very suitably by contacting C1-C4 alcohols, ethers derived therefrom or mixtures thereof with the catalyst of the invention consisting of a silicate having a crystalline size of at least i micron in aromatization conditions. Manufactured.

A very suitable charge for this process is methanol. Besides being used as catalysts or catalyst supports, the silicates of the invention are also suitable for many other applications such as use as adsorbents and extractants, desiccants, ion exchangers and molecular sieves.

The present invention will now be explained with reference to the following examples.

Example 1 Six types of silicates (1-6) were produced as follows.

Silicate 1 Na204.5 [(C3H7)4N]20Fe2032
Fe with molar composition of 9.1Si02.468H20
(NO3)3, SlO2, NaNO3 and [(C3H
7) A mixture of 4N')0H in water was heated to 150 DEG C. with stirring for 48 hours in an autoclave under autogenous pressure.

After the reaction mixture was cooled, the produced silicate was separated, washed with water until the pH of the washing water was about 8, and then
Dry at ℃ for 2 hours. The silicate thus produced had the following chemical composition. 0.67 [(
C3H7)4N]20・0.23Na20・Fe2O3
・30S102・91-[20. Silicate 2 This silicate was prepared in substantially the same manner as Silicate 1, except that the starting material was Na2O4.5 [(C
3H,)4N,1200.5Fe20329.1Si0
The difference was that it was an aqueous mixture with a molar composition of 2.468H20.

Silicate 2 produced in this manner had the following chemical composition. 0.80 [(C3H7)4N] 20.0
．． 30Na20-Fe2O345SiO2・13H20
．． Silicate 3 This silicate was prepared in substantially the same way as Silicate 1, except that the starting material was an aqueous mixture containing A1(NO3)3 in addition to Fe(NO3)3 and having the following molar composition: were different.

Na2O・4.5 [(C3H7)4N]20・0.33
A12030.67Fe203・29.1S102・4
28H20. Silicate 3 thus produced had the following chemical composition. Silicate 4 This silicate was prepared in substantially the same manner as Silicate 3, with the difference that in this case the starting materials were an aqueous mixture having the molar composition:

Silicate 4 produced in this manner had the following chemical composition.

Silicate 5 This silicate was prepared in substantially the same way as Silicate 1, except that the starting material was an aqueous mixture containing A1(NO3)3 instead of Fe(NO3)3 and having the molar composition: were different.

The silicate thus produced had the following chemical composition.

Silicate 6 This silicate was prepared in substantially the same manner as Silicate 1, except that the starting mixture was Fe. The difference was that it was an aqueous mixture containing (NO3)3 and having the following molar composition:

Silicates 1-6 produced as above were all B
It had an X-ray powder diffraction pattern that substantially matched the table.

Thermal stability of silicate 1-6 and 7g Yoi AnnO
Table C shows the amount of water for r + 7K Tsuruchi★Chashusho L1 shu AHφ★. Silicates 7-12 Sequentially, silicates 1-6 were baked at 500° C. for 4 hours, boiled with 1.0 molar NH4NO3 solution,
by washing with water, boiling again with 1.0 molar NH4NO3 solution, washing with water, drying at 120°C for 2 hours and baking at 500°C for 4 hours.
Starting silicates 1-6 were used to prepare silicates 7-12, respectively.

"Silicate 13-15 Sequentially, silicates 1, 3 and 6 were baked at 500°C for 4 hours, and 0.5 mol of K2
Boil with CO3 solution for 6 hours, wash with water, and boil at 120℃
The starting silicate 1,3
Silicates 3-15 were produced using silicates 3-15 and 6, respectively.

The silicate thus produced had the following overall composition, expressed in moles of oxide: Silicate 13 Silicate 14 30Si02. Silicate 15 Among the silicates 1-15 described above, silicate 1
-4, 7-10, 13 and 14 are the silicates of the present invention.

Iron-free silicates 5, 6, 11, 12 and 15
are outside the scope of the present invention and are included in this patent application for comparison. A comparison of the overall composition of silicates 13 and 14 with that of silicates 1 and 3, respectively, shows that iron is present in an irreplaceable state in the silicates of the present invention.

Furthermore, in the silicates of the invention, the negative electrical valence of the iron and/or aluminum is present in such a way that in this case essentially one monovalent cation is present in place of each iron and/or aluminum atom. It can be seen that this is supplemented by exchangeable cations. The overall composition of zeolite 15 shows that the problem of exchangeable cations does not exist in the absence of iron and aluminum atoms in the silicate. Production of p-xylene from isobutylene Silicates 7-9, 11 and 12 were tested as catalysts in the production of p-xylene from isobutylene.

For this purpose, over a fixed bed of these silicates isobutylene was added at atmospheric pressure, at a temperature of 400°C and at 4 kg·Kg.
It passed at a space velocity of −1·h−1. The results of these experiments are shown in Table D. The results shown in Table D are from isobutylene to p-xy. Iron-containing silicate of the present invention when applied as a catalyst for selectively producing urethane (Experiment 1-3)
is better than the related iron-free silicate (Experiment 4).
and 5).

Production of Aromatics from Methanol (Experiment 6) Silicate 8 was tested as a catalyst in the production of aromatics from methanol.

For this purpose, methanol was passed through the fixed bed of silicate at a pressure of 5 bar, a temperature of 350 DEG C. and a space velocity of 1 kpkg-1.h-1. In this way, 28.7 pbW of a liquid oxygen-free mixture of organic compounds was obtained from 100 pbW of methanol as a starting material. The average carbon number of the compounds in this mixture was 9.5. The mixture contained 59.6% by weight C6+ aromatics, distributed as follows across the various compounds. 0. of benzene. Heel amount %, toluene 2. Heel weight %, p-xylene 2
．． 4% by weight, m-xylene 2.4%, 0-xylene 4.5% by weight, C9 monoaromatics 15.0% and C1
♂Aromatic 32. Capacity%.

Production of aromatic gasoline from n-hexadecane (Experiment 7)
Silicate 9 was tested as a catalyst in the production of aromatic gasoline from n-hexadecane.

For this purpose, n-hexadecane was passed through the fixed bed of silicate at a pressure of 5 bar, a temperature of 375 DEG C. and a space velocity of 11.l@-1.h@-1. The charge was completely converted to a product having the following composition. Composition: The liquid product contained 45% aromatics by weight.

Example 1 A grade of silicate (16-25) was produced as follows.

Silicates 16-18 Silicates 16 were prepared in substantially the same manner as Silicates 1, with the difference that in this case the starting mixture was an aqueous mixture having the following molar ratios.

0.8 [(C3H7)4N]200.3Na20Fe2
03200S102●55F (20. Silicate 1-6
Silicates 17 were prepared from silicate port 6 in the same manner as silicates 7-12 were prepared from silicate ports 6, respectively.

Sequentially, silicate 16 was calcined at 500°C for 4 hours, boiled with a 1.0 molar NaNO3 solution, washed with water, boiled again with a 1.0 molar NaNO3 solution, washed with water, and boiled with a 1.0 molar NaNO3 solution, washed with water, Silicate 8 was prepared from silicate 16 by drying for 1 hour and baking at 500° C. for 4 hours.

Silicate 18 produced in this manner had the following chemical composition. Silicate 19 This silicate was prepared in substantially the same way as Silicate 1, but in this case the starting mixture was an aqueous mixture containing Ga(NO3)3 in addition to Fe(NO3)3, and had the following molar composition: The points were different.

Silicate 19 produced in this manner had the following chemical composition.

Silicates 20 and 21 Silicate 20 was prepared in substantially the same manner as Silicate 1, with the difference that in this case the starting mixture was an aqueous mixture without NaNO3 and had the following molar composition:

Silicate 21 was prepared from Silicate 20 by baking at 500° C. for 4 hours.

Silicates 22 and 23n-butylamine 6.18y
1 water glass (28% SlO2; 8% Na2O) 46.2
y and water 56.2y was mixed with Fe2(
SO4) 3・9H201.3y1112S043.75
y and a second mixture consisting of 77y of water.

After stirring the mixture thus obtained at room temperature for 2 hours,
The mixture was heated under autogenous pressure with stirring in an autoclave at 50°C for an hour. After the reaction mixture was cooled, the silicate formed was separated, washed with water until the pH of the wash water was about 8, and dried at 120° C. for 2 hours. Silicate 23 was prepared from silicate 22 thus obtained in the same way as silicate 7-12 was prepared from silicate 1-6, respectively. Silicate 23 thus obtained had the following chemical composition. Silicate 24 Silicate 24 was prepared in substantially the same manner as Silicate 23, but in this case the first mixture contained an n of 6.18 fI.
-The difference was that it contained 8.4y piperidine instead of butylamine.

Silicate 24 produced in this manner had the following chemical composition. Silicate 25 This silicate was prepared in substantially the same manner as Silicate 24, except that in this case the second mixture did not contain Fe2(SO4)3.

Silicate 25 thus produced was an amorphous product that did not adsorb water. This example shows that the presence of iron plays an important role in the formation of crystalline products.
Silicates 16, 19, 20 produced as above
and 23 had an X-ray powder diffraction pattern substantially consistent with Table B.

The thermal stability of silicates 16, 19, 20, 23 and 24 and the amount of water that they adsorb at 25° C. and saturated steam pressure after dehydration at 400° C. in vacuo are shown in Table E. Silicate 24 had an X-ray powder diffraction pattern (irradiation: CU-Kα, wavelength: 0.15418 nm) as shown in Table F.

*IO=Intensity of the strongest isolated reflection appearing in the diagram
The letters used in Table F to describe the degree reflexes have the following meanings: SP = sharp; NL = 7 level;
BD = wide; θ = angle according to Bratz's law.

Among silicates 16-25, silicate 25, which is an amorphous product, falls outside the scope of the present invention but is included in this patent application for comparison.

One-step production of aromatic hydrocarbon mixture from 0H2/Cq mixture (Experiment 8) A catalyst was prepared by mixing ZnO-Cr2O3 composition with silicate 17 in a weight ratio of 5:1.

Both materials were present in the catalyst in the form of particles of 0.15-0.3 diameter. This catalyst was tested for the one-step production of aromatic hydrocarbon mixtures starting from H2/CO mixtures. The tests were carried out in a 50 ml reactor in which there was a fixed catalyst bed with a capacity of 7.5 ml.

A H2/CO mixture with a molar ratio of 2:1 was heated to 375 °C
temperature, 30 bar pressure and 1000N1 gas/1
The catalyst was contacted at a space velocity of catalyst/hour.

The results of this experiment were as follows. Production of aromatic gasoline from n-hexadecane (Experiment 9) Silicate 17 was tested as a catalyst in the production of aromatic gasoline from n-hexadecane.

For this purpose, n-hexadecane was passed through a fixed bed of this silicate at a pressure of 5 bar, a temperature of 375 DEG C. and a space velocity of 114 e1-1 h-1. The entire charge was converted to a product having the following composition: The liquid product contained 4% aromatics by weight.

Production of p-xylene by methylation of toluene (Experiment 1)
0) Silicate 17 was tested as a catalyst in the production of p-xylene by methylation of toluene.

For this purpose, an equimolar mixture of toluene and methanol was passed through the fixed bed of silicate at a pressure of 5 bar, a temperature of 375 DEG C. and a space velocity of 11.1-1.h-1. The results of the experiment were as follows. Toluene conversion rate: 44% by weight Methanol conversion rate: 10% by weight, C.

Selectivity to monoaromatics: 65% C, p- in monoaromatic fraction
Amount of xylene: 80% Separation of p-xylene from a mixture of p-xylene and m-xylene (Experiment 11) Silicate 18 was tested to separate p-xylene from a mixture of p-xylene and m-xylene. .

For this purpose, a xylene partial pressure of 0.3/gal and 80
A mixture of equimolar amounts of p-xylene and m-xylene at a temperature of .degree. C. was passed through the silicate in the gas phase and diluted with nitrogen. After 4 hours, the silicate was desorbed with toluene at 80°C. Gas-liquid chromatography of toluene solution shows that p-xylene and m-xylene are 42:1 in it.
It was shown that they were present in a molar ratio of Separation of p-xylene from a mixture of p-xylene and o-xylene (Experiment 12) Separation of p-xylene from a mixture of p-xylene and m-xylene By the same method as described above, p-xylene and o-xylene were separated. - Silicate 18 was tested in separating p-xylene from a mixture with xylene.

Claims (1)

[Claims] 1 a) thermally stable up to temperatures exceeding 600°C;
b) after dehydration at 400° C. in vacuo, more than 3% by weight of water can be adsorbed at 25° C. and saturated water vapor pressure; and; c) in the dehydrated state, the total A crystalline silicate characterized by having a composition represented by the following formula. (1.0±0.3)(R)_2/hO・[aFe_2O
_3・bAl_2O_3・cGa_2O_3〕_y(d
SiO_2・eGeO_2), [wherein R=one or more monovalent or divalent cations; a≧0.1; b≧0;
c≧0; a+b+c=1; y≧10; d≧0.1; e≧
0; d+e=1; and n is the valence of R. 2. The crystalline silicate according to claim 1, characterized in that in the formula representing the overall composition, c and e are equal to 0. 3. Crystalline silicate according to claim 1 or 2, characterized in that in the formula representing the overall composition, a is greater than 0.3 and preferably greater than 0.5. 4. Crystalline silicate according to any one of claims 1 to 3, characterized in that in the formula representing the overall composition, b is equal to 0. 5. Crystalline silicate according to any one of claims 1 to 4, characterized in that in the formula representing the overall composition, y is less than 600 and preferably less than 300. 6. Crystalline silicate according to any one of claims 1 to 5, characterized in that its X-ray powder diffraction pattern contains the reflections shown in particular in Table A. 7 In the silicate according to any one of claims 1 to 6, the silicate is obtained by converting at least a part of the monovalent and/or divalent organic cations introduced during production into hydrogen atoms. A crystalline silicate characterized by: 8. In the silicate according to any one of claims 1 to 7, the exchangeable monovalent and/or
Or a crystalline silicate obtained by replacing at least a part of divalent cations with other cations. 9. Crystalline silicate according to claim 8, characterized in that the alkali metal content is less than 1% by weight. 10. Crystalline silicate according to claim 9, characterized in that the alkali metal content is less than 0.05% by weight. 11. The crystallinity according to any one of claims 8 to 10, characterized in that at least a part of the exchangeable cations are replaced by hydrogen ions, ammonium ions, and/or rare earth metal ions. Silicates. 12 a) thermally stable to temperatures above 600°C; b) capable of adsorbing more than 3% by weight of water at 25°C and saturated water vapor pressure after dehydration at 400°C in vacuo; and c ) In the dehydrated state, expressed in moles of oxide, the overall formula (1.0±0.3
)(R)_2/nO・[aFe_2O_3・bAl_2
O_3・cGa_2O_3〕_y(dSiO_2, eG
eO_2), [wherein R = one or more monovalent or divalent cations; a≧0.1; b≧0; c≧0; a+b+
c=1; y≧10; d≧0.1; e≧0; d+e=1;
And n is the valence of R. ] In the method for producing a crystalline silicate having a composition represented by one or more: one or more Si-compounds, one or more Fe-compounds and optionally one or more compounds of alkali or alkaline earth metals (R_1) and Al-, Ga- and/or or Ge-compounds, and these various compounds, expressed in moles of oxide, have the following molar ratio (R_1)_2
/pO: (R_2)_2/qO≦10 and preferably 0.05-5, (R_2)_2/qO: (SiO_2+
GeO_2) = 0.01-1 and preferably 0.05
-1, 5 and (SiO_2+GeO_2): (Fe_2
O_3+Al_2O_3+Ga_2O_3)≧10 and preferably 10-600 (p and q are each R_
1 and R_2) is maintained at elevated temperature until silicate is formed, and the silicate crystals are subsequently separated from the mother liquor. 13. The mixture is heated to a temperature of 90 to 300°C and preferably 125 to 175°C, preferably with stirring.
maintained at a temperature of for at least 4 hours,
The method according to claim 12. 14. The starting material is an aqueous mixture in which R_1 is present in the form of an alkali metal compound and preferably a sodium compound and R_2 is present in the form of a tetraalkylammonium compound and preferably a tetrapropylammonium compound. 14. The method according to claim 12 or 13, characterized in that: 15. By baking the silicate obtained by the method according to any one of claims 12-14,
A method characterized in that at least part of the monovalent and/or divalent organic cations introduced during production are converted into hydrogen atoms. 16. By contacting the silicate obtained by the method according to any one of claims 12-15 once or several times with a solution containing exchangeable cations, the exchangeable cations introduced during production can be removed. A method characterized in that at least part of the valent and/or divalent cations is replaced by other cations. 17 a) thermally stable to temperatures above 600°C; b) capable of adsorbing more than 3% by weight of water at 25°C and saturated water vapor pressure after dehydration at 400°C in vacuum; and c ) In the dehydrated state, expressed in moles of oxide, the overall formula (1.0±0.3
)(R)_2/n;O[aFe_2O_3・bAl_2
O_3・cGa_2O_3〕_y(dSiO_2・eG
eO_2), [wherein R = one or more monovalent or divalent cations; a≧0.1; b≧0; c≧0; a+b+
c=1; y≧10; d≧0.1; e≧0; d+e=1;
And n is the valence of R. ], or a crystalline silicate having the composition represented by
or crystalline silicates in which at least a small portion of divalent organic cations have been converted into hydrogen atoms, or exchangeable monovalent and/or divalent cations introduced during production in any of the above silicates. Catalyst for the conversion of hydrocarbons and/or oxygen-containing hydrocarbons, comprising a crystalline silicate at least partially substituted with other cations. 18. Catalyst according to claim 17, characterized in that the conversion concerns the dewaxing of gas oil. 19. Catalyst according to claim 17, characterized in that the conversion concerns the production of p-xylene by isomerization of C_3-aromatics. 20 Claim 17, characterized in that the conversion concerns the production of p-xylene by methylation of toluene
Catalysts as described. 21. Catalyst according to claim 17, characterized in that the conversion concerns the production of p-xylene by averaging of toluene. 22. Catalyst according to claim 17, characterized in that the conversion is concerned with improving the quality of gasoline. 23 characterized in that the conversion concerns the production of aromatic hydrocarbons by aromatization of aliphatic hydrocarbons and/or oxygen-containing aliphatic hydrocarbons, preferably obtained in the conversion of a mixture of carbon monoxide and hydrogen. The catalyst according to claim 17. 24. Catalyst according to claim 23, characterized in that the conversion concerns the production of aromatic hydrocarbon mixtures by aromatization of the products obtained in the Fischer-Tropsch hydrocarbon synthesis process. 25. Catalyst according to claim 23, characterized in that the conversion concerns the production of aromatic hydrocarbon mixtures by aromatization of methanol and/or dimethyl ether. 26 As an adsorbent, extractant or desiccant, as an ion exchanger or as a molecular sieve, it is a) thermally stable up to temperatures above 600°C; b) after dehydration at 400°C in vacuo at 25°C and saturated steam and c) in the dehydrated state, expressed in moles of oxide, the total has the following formula (1.0+0.3)(R)_2/nO [aFe_2O
_3・bAl_2O_3・cGa_2O_3]_y(d
SiO_2・eGeO_2), [wherein R=one or more monovalent or divalent cations; a≧0.1:b≧0;
e≧0; a+b+c=1; y≧10; d≧0.1; e≧
0; d+e=1; and n is the valence of R. ], or a crystalline silicate having the composition represented by
or a crystalline silicate in which at least a portion of divalent organic cations have been converted into hydrogen atoms, or at least one of the exchangeable monovalent and/or divalent cations introduced during the production of any of the above silicates. A method using crystalline silicate in which moieties are substituted with other cations. 27. The method of claim 26 for separating p-xylene from a mixture of xylene isomers.