DE3215069A1 - Synthetic, crystalline metal silicate and metal borosilicate compositions, and preparation thereof - Google Patents

Description

Synthetic, crystalline metal silicate and borosilicate

Compositions and their manufacture

The present invention relates to novel crystalline metal silicate and Metal boro (or boron) silicate compositions. The invention particularly relates to a method for the preparation of these compositions and certain catalytic conversion processes in which these compositions are used.

It is known that both natural and synthetic zeolitic material are catalytically useful for has different types of reactions, particularly hydrocarbon conversions. The well-known crystalline Aluminosilicate zeolites are usually referred to as "molecular sieves" and are characterized by their highly ordered, crystalline structure and smoothly dimensioned Pores are identified and are from each other based on the composition, the crystal structure, the Adsorption properties and the like. Distinguishable. The term "molecular sieves" is derived from the possibility

ability of the zeolite material, selectively molecules Adsorb based on their size and shape.

The processes for making these crystalline synthetic zeolites are well known in the art. One A family of crystalline aluminosilicate zeolites designated ZSM-5 is described in U.S. Patent 3,702,886; the disclosure of this patent specification is hereby also disclosed in the present specification. The family of ZSM-5 compositions have a characteristic X-ray diffraction pattern and can also, in molar ratios expressed in terms of oxides, can be identified as follows:

0.9 + 0.2M _2/0: W ₂ O: 5-100YO _2: zH ₂ 0

where M is a cation, η the valence of this cation, W aluminum and / or gallium, Y silicon and / or germanium and ζ represent 0 to 40. In a preferably synthesized form, the zeolite has the following formula, expressed in molar ratios of the oxides:

0.9 + 0.2M _O / 0: Al ₀ O: 5-100SiO _9: zH ₉ 0

""" C-ITi. T-J c. C.

where M is a mixture of alkali metal cations, especially sodium, and tetraalkylammonium cations, the alkyl

groups preferably contain 2 to 5 carbon atoms. 25th

The US-PS 3 9 ^ 1 871 relates to new crystalline organometallic silicates, which are essentially free of Group IIIA metals, i.e. aluminum and / or gallium. the Disclosure of this patent specification is hereby made for disclosure of the present description. It it is stated therein that the amount of alumina present in the known zeolites in direct It appears to be related to the acidic properties of the product obtained and that a low alumina content was recognized as beneficial to achieve a low acidity level, which in many cat-

lytic reactions to low coke-producing properties and low aging rates. A typical process for producing the organosilicates is in that a mixture containing a tetraalkylammonium compound, Sodium hydroxide, an oxide of a metal other than a Group IIIA metal, an oxide of silicon and water, converts, Ms crystals of organometallic silicates have formed. It will in the patent also stated that the family of crystalline organometallic silicates have a specific X-ray diffraction pattern which is similar to that of the ZSM-5 zeolites. Lesser amounts of aluminum oxide are used in the patent are considered and are mainly the presence of aluminum impurities in the Reactants used and / or equipment used.

Crystalline silica compositions are disclosed in U.S. Patent 3,844,835 described. The crystalline silica material can also contain a metal promoter, which may be an element of Group IIIA, Group VB, or Group VIB.

U.S. Patent 4,088,605 is directed to the synthetic production of a zeolite such as ZSM-5 which has an aluminum-free outer shell. The patent states in column 10, line 20ff, that it is crucial for the production of the aluminum-free outer shell that the reactive aluminum is removed from the reaction mixture. ^{ου It is} therefore necessary, as stated in this patent, that the zeolite is processed and the crystallization medium is replaced by an aluminum-free mixture in order to obtain the crystallization of SiOp on the surface of the zeolite. This can be achieved by completely replacing the reaction mixture with

be performed or by having any remaining aluminum ion in the original reaction mixture Reagents such as gluconic acid or ethylenediamine tetraacetic acid (EDTA), complex binds. 5

Crystalline borosilicate or borosilicate compositions are disclosed in DE-OS 27 46 790. This registration specifically relates to borosilicates obtained by conventional processes for the production of aluminosilicate zeolites can be obtained. It is stated therein that where care is taken, aluminum comes out remove the borosilicate crystal structure because of its negative influence on special conversion processes, the molar ratio of SiOo / AlpO ^ is slightly above 2000 to 3000 can be and that this ratio is generally only due to the availability of aluminum-free Raw materials is restricted.

DE-OS 28 48 849 relates to crystalline aluminosilicates of the ZSM-5 zeolite series. These particular zeolites have a SiO _{2 ZAl 2} O ^ molar ratio greater than 20 and are made from a reaction mixture which is a source of SiO ₂ , Al ₂ O ,, a quaternary alkyl ammonium compound and a metal compound including such Group VIII metals as ruthenium, Palladium and platinum.

U.S. Patent 4,113,658 relates to the precipitation of metal compounds on carrier material and describes the decomposition of urea to form ammonia, which in turn causes the formation of precipitates of the metal hydroxides, which are deposited on a solid support material. The application of this technique to the production of crystalline zeolites is not suggested. 35

The prior art has shown zeolitic catalysts having a wide variety of catalytic and chemical properties adsorptive properties provided; however, there is still a need for crystalline material with different and / or enhanced catalytic properties. For example, are an important use crystalline material the conversion process of oxygenated compounds, like the conversion of Dimethyl ether and methanol into aliphatic compounds and the conversion of synthesis gas or hydrocarbons, like ethylene, in a considerable degree of conversion and considerable selectivity.

The present invention relates to the preparation of crystalline metal silicate compositions by a Procedure "in which one

(a) a first mixture which is a tetraalkylammonium salt, contains an alkali metal hydroxide, silicon dioxide and water,

(b) an ar ei te mixture, the water, a soluble one Source of a metal whose hydroxide precipitates at a pH above 7 and an amount of urea or a Compound which, after hydrolysis, releases ammonia, the amount contributing to the precipitation of the hydroxide of the metal is effective, produces,

(c) mixing together an amount of the first mixture and an amount of the second mixture effective to form a reaction mixture result in an aluminum content of less than about 100 parts by weight / million (based on silicon dioxide) and has a composition in terms of molar ratios of the oxides set in the following Areas falls;

OH "/ SiO ₂ 0.05-3

Q ⁺ / (Q ⁺ + A ⁺ ) 0.01-1

H ₂ O / OH "10-800

SiO ₂ / M ₂ / _m 0 10-10,000

where Q is a tetraalkylammonium ion, A is an alkali metal ion, M is the metal and m is the valence of the metal, the hydroxide of the metal forming a precipitate forms,

(d) holding the reaction mixture at a temperature of about 50 to about 25O ⁰ C, are formed until crystals of the metal silicate, and

(e) Separate the crystals and recover.

Corresponding borosilicates are produced by adding a soluble boron compound to the reaction mixture.

The crystalline metal silicates and metal borosilicates produced by "the above method have a X-ray diffraction diagram, which is essentially that j of ZSM-5 zeolite, and have a composition given in molar ratios of the oxides, as in the ί

expressed in the following formula A:

(0.2-8O) R ₀ O: (0.1-2O) M ₉ O: (0-40) B _o 0, i100Si0 ₉ : (0-20O) H ₉ O - tz. ε- j £ ■ * -

η m
where R is a tetraalkylaramonium cation, ammonium cation,

Hydrogen cation, alkali metal cation, metal cation or their mixture, η the valency of R, M a metal, the hydroxide of which precipitates at a pH above 7, and m ² ^ the valency of this metal, the composition having an aluminum content of less than 100 parts by weight / Million owns.

The catalytic properties of these metal silicates become evident in a conversion process in which an oxygenated (oxygen-containing) compound, such as methanol, dimethyl ether and / or mixtures thereof, with the crystalline metal silicate prepared by the above process. These metal silicates are also useful in a process for the polymerization of ethylene in which ethylene is under

Bringing uretransformation conditions with the crystalline silicate prepared by the above method.

Another conversion process in which the inventive Metal silicates are used, includes a process for converting synthesis gas, the hydrogen and contains carbon monoxide, into hydrocarbons and / or oxygenated compounds, whereby one in this process the synthesis gas is produced under conversion conditions with the crystalline silicate composition according to the method described above.

A new class of crystalline metal silicate and metal borosilicate compositions has now been found. These crystalline compositions are prepared by a process which requires careful control of the amount of aluminum in the reaction mixture and further that the reaction mixture contains: (a) a metal whose hydroxide precipitates at a pH above 7 and (b) Urea or a compound which liberates ammonia upon hydrolysis and that the liberation of ammonia causes the formation of the metal hydroxide in the reaction mixture. The formation of the metal hydroxide precipitate is described herein as "urea precipitation". In a further embodiment, a boron source is added to the reaction mixture so that the crystalline compositions can additionally contain B ₂ O.

The silicates according to the invention are produced by that a reaction mixture containing a tetraalkylammonium ion, e.g. B. tetrapropylammonium bromide or hydroxide, an alkali metal, i.e. sodium hydroxide, a soluble salt of a metal whose hydroxide is in a pH above 7 is insoluble, a silicon oxide, water as well as a lot of ar. Urea or a compound that

A 41

releases ammonia after hydrolysis, the amount which causes the precipitation of the metal hydroxide, is sufficient, and wherein the composition has molar ratios in the following ranges:

Broadly preferred

OH "/ SiO ₂ 0.05-3 0.20-0.90

Q ⁺ / (Q ⁺ + A ⁺ ) 0.01 - 1 0.03 - 0.9

H ₂ O / OH "10-800 20-500

SiO ₂ / M ₂ / _m O 10-10,000 30-4000

where Q is a tetraalkylammonium ion, A is an alkali metal ion, M is the metal and m is the valence of this metal, heated and the mixture is kept at an elevated temperature for a long enough time to form crystals of the product. Typical reaction conditions consist in heating the reaction mixture to an elevated temperature, for example 50 to about 250 ^° C. and higher, for a period of about 6 hours to 60 days. The preferred temperature is between about 100 and 190 ^° C .; the preferred time is between about 1 and about 16 days. The reaction mixture can be heated at elevated pressure, for example in an autoclave, or at normal pressure, for example by refluxing. The preferred method of heating the reaction mixture is carried out at reflux temperature.

As is customary in the preparation of silicate compositions, when the reaction mixture is refluxed, large amounts of sodium chloride, along with some sulfuric acid, are added to the reaction mixture to ensure crystallization of the product. Therefore, when preparing by refluxing, the OH ~ / SiO ₂ ratios and similar ratios tend to give different values than the values obtained when working in an autoclave.

* 43

Of course, when preparing the reaction mixture for the heating step the reaction mixture is kept essentially free of aluminum, i.e. it contains less than 100 parts by weight / million.

Optionally, a soluble boron source can be added to the reaction mixture to facilitate the preparation of the To enable borosilicate types of metal silicates according to the invention. When such an addition is carried out the composition of the reaction mixture, expressed in molar ratios, contains the following molar ratio, which, in addition to the quantities listed above, includes:

Broadly preferred

SiO ₂ / B ₂ O ₃ 2-1000 12-500

The digestion of the gel particles is carried out until crystals form. The solid product is released from the reaction medium separated, e.g. by cooling the whole to room temperature, filtering off and washing with water. That above product is for example at 110 ° C during dried about 8 to 25 hours or more. Of course, milder conditions can be used if desired e.g. room temperature under vacuum.

The crystalline silicate compositions prepared according to the above process are essentially free of aluminum, i.e., they contain less than about 100 parts by weight per million and can be expressed as molar ratios of the oxides as indicated in formula A above. In one possible embodiment contains the composition BpO ^. In preferred Embodiments is the metal whose hydroxide forms the precipitate, iron, cobalt, bismuth, chromium, Molybdenum, nickel, tin, platinum or mixtures thereof.

Members of this family of crystalline metal silicate and metal borosilicate compositions have a definite character te crystal structure exhibited by the X-ray diffraction pattern of ZSM-5 zeolite. Although the X-ray diffraction diagram these silicates do not differ from that of a zeolite of the ZSM-5 type, there are considerable ones Differences. The compositions differ in that the present compositions im In contrast to the ZSM-5 zeolites, no aluminosilicates and actually contain less than 100 ppm aluminum. Also the catalytic properties of zeolites of the ZSM-5 type and the compounds according to the invention are different. When converting dimethyl ether Both compounds show extremely high yields (over 80%) while the present compositions Forms considerably more aliphatic hydrocarbons and fewer aromatics than a ZSM-5 type zeolite.

An important feature of the invention is a method of activating the new crystalline composition according to the invention for improved use in various conversion processes. Generally this includes Activation procedure:

(a) a heat treatment of the dried silicate composition at, for example, about 200 to about 900 ⁰ C, preferably about 400 to about 600 ° C, for about 1 to about 60 hours, preferably from atmospheric to about 20 hours, containing in a molecular oxygen can be about 10 degrees.

In a preferred embodiment, the activation process comprises :

(1) Heat treatment of the dried silicate composition at, for example, about 200 to about 900 ° C, preferably about 400 to about 600 ⁰ C, for about 1 to about 60 hours, preferably about 10 to about 20 h;

(2) Ion exchange of the heat-treated silicate composition with a material that decomposes on further heat treatment and forms a compound, which has a hydrogen cation;

(3) Washing and drying of the replaced silicone compositions etching;

(4) Heat treating the dried silicate using the method of step (1).

Those skilled in the art will recognize that steps (1) through (4) of the preferred embodiment and step (a) above work well are known and are commonly used methods of activating zeolite-type catalysts. The composition according to the invention can be used in "suitable Manner can be used in the form in which it is obtained after step (4) or after step (a). the Heat treatment can be carried out in any atmosphere as known to those skilled in the art and is preferred wisely carried out in air.

If desired, the activation process can also be used the redox treatment included in the BE-PS 886 090 is described. This treatment includes a heat treatment with a reducing agent is carried out; it is carried out following step (a) or step (4) of the above activation process practically carried out as follows:

(b) or (5) treatment of the heated silicate composition with a reducing agent for about 1 to about 80 hours, preferably about 2 to about 40 hours, at about 200 to about 900 ^° C., preferably about 400 to about 600 ^° C.; and

(c) or (6) heat treating the reduced silicate using the method of step (a) or (1).

Any reducing agent or compound which, under the treatment conditions, is a reducing agent forms such as dimethyl ether can be used. Dimethyl ether and hydrogen are preferred because of their proven effectiveness.

The activation procedure described here does not including redox treatment results in a catalytically active composition that has useful conversion rates and useful selectivities in the reactions catalyzed by the compositions of the invention and is the preferred method of activation. Although it is to achieve a usable Catalyst is not necessary to follow the redox treatment, the treatment according to the invention can Compositions with redox treatment following oxidative activation, some modification in of selectivity, which is usually of a lesser nature. Therefore, it can be used in cases where it is economical is justified or where a small change in selectivity is required Redox treatment can be applied.

As noted above, and as is known to those skilled in the art, the process of making zeolites, e.g., aluminosilicates, is well known. However, it is a critical feature of the present invention that the crystalline silicate composition be prepared using a reaction mixture which, based on weight percent silica, is less than about 100 parts by weight / million aluminum ions, preferably less than about 50 parts by weight / million. Million, and contains a hydrolyzable source of ammonia such as urea. Apart from other differences from known, crystalline silicate compositions, the silicate and borosilicate compositions formed here are essentially free of aluminum

minium, with the molar ratio of SiC ^ / AlpCU being about 8000 \ ond is even 30,000.

It is not known why the crystalline compositions according to the invention provide such unexpected properties, e.g. improved selectivity with DME and low hydrocarbon yield and high DME yield with methanol for the silicates and high C, - ₊ yield with ethylene and synthesis gas for the Borosilicates. It is possible that the urea precipitation provides the metal hydroxide in a finely divided form that is not achieved in other metal-containing reaction mixtures, and that the metal is arranged in the crystal structure in a manner which is the case with silicates according to the prior art, which is described after other processes are produced, is not achieved, so that the catalytic properties of the compositions according to the invention differ from those of other metal silicates and borosilicates.

The crystalline metal silicates and borosilicates according to the invention are produced by urea precipitation, which causes a metal hydroxide to precipitate in finely divided form. When urea decomposes, it gives Free ammonia, which forms ammonium hydroxide in water. This causes the uniform change in pH the aqueous mixture. With a strong base such as B. caustic soda, you get a strongly localized and rapid increase in pH, which gradually increased to a moderate pH increase with diffusion, convection and / or mixing reduced. Urea doesn't work that way; with urea the increase in pH is gradual and uniform throughout the mixture.

It is crucial for the process according to the invention that the metal hydroxide precipitate is finely divided Form by the method described here as urea

Ii W · ·> w «

Precipitation occurs. As mentioned above, result in strong. Bases not this desired precipitation. Urea and others Compounds that release ammonia upon hydrolysis are the materials that make up the metal hydroxides in the im Failure within the scope of this invention. Therefore, urea precipitants are among the useful ones such compounds as urea, acetamide, their hydrolyzable derivatives and the like.

The metals of the compositions according to the invention are any metals which precipitate with urea leave, i.e. any metals whose salt is soluble and whose hydroxide precipitates at a pH above 7. Most metals fall under this provision; however, there are some, such as sodium and potassium, that are clearly not included. Usable metals include bismuth, cobalt, chromium, iron, molybdenum, nickel, Ruthenium, tin, tungsten, palladium and platinum. Those skilled in the art can use routine procedures and without excessive Lot of attempts to single out a number of possible candidates by dissolving soluble metal salts in water and adding a source of hydroxide ions until the pH is above 7.

In making the crystalline compositions of the present invention, it is important that essentially Aluminum-free raw material is used. The essentially aluminum-free raw material for silicon dioxide may be any of those commonly used for the synthetic preparation of zeolites, e.g.

powdered, solid SiO ₂ , silica, colloidal SiO ₂ or dissolved SiO ₂ . A preferred source of SiO ₂ is Cab-O-Sil, sold by Cabot Co ..

The essentially aluminum-free alkali metal hydroxide is sodium hydroxide, potassium hydroxide and / or mixtures

out of this. Sodium hydroxide is preferred. The essentially Aluminum-free tetraalkylammonium compound can be tetrapropylammonium hydroxide, chloride, bromide and be the like.

In a similar manner, suitable metal salts which are essentially free of aluminum can be used and are soluble in the reaction mixture. Among the various metal salts that are used preferably include the following: Group IVA tin; Group VA - bismuth; Group VIB - chromium, molybdenum, Tungsten; Group VIII - iron, cobalt, nickel, ruthenium, palladium, platinum. The chloride is often very useful.

In the possible embodiments, the aluminum-free source of boron can be boron oxide, boric acid, sodium borate and be the like.

If a chelating agent is part of the reaction mixture, ethylenediamine-tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), δ-hydroxyquinoline-S-sulfonic acid (8HQS) and the like can be used.

The particular crystalline compositions described are inactive when tested for their catalytic properties without being calcined; this is possibly due to the fact that the intracrystalline, free space is occupied by the organic cations from the formation solution. However, they can be activated by heat treatment using known techniques, such as heating in an inert atmosphere or air at 200 to 900 ^° C. for 1 to 60 hours. This can be followed by ion exchange with ammonium salts and further heat treatment at 200 to 900 ^° C., if desired.

The crystalline compositions can either be in the alkali metal form, e.g. the sodium form, the ammonium form, the hydrogen form or other monovalent or multivalent cationic forms can be used. Either the ammonium or the hydrogen form is preferred used. They can also be used in intimate combination with hydrogenating components, such as tungsten, vanadium, copper, molybdenum, rhenium, iron, nickel, cobalt, chromium, manganese, or a precious metal, like platinum or palladium if a hydrogenation-dehydrogenation function can be done. Such a component can be added to the composition by replacement or Impregnation get into it or be intimately mixed with it physically. Such a component can be found in or get on the catalyst by impregnation, as in the case of platinum, by treating the crystalline Composition with a platinum-containing ion. Suitable platinum compounds are chloroplatinic acid, Platinum (II) chloride and various platinum-amine complexes containing compounds.

When the catalyst is used either as an adsorbent or as a catalyst in one of the aforementioned processes it can be heat treated as described above.

For members of the present family of crystalline compositions the originally associated cations can be replaced by a wide variety of other cations can be replaced according to methods well known in the art. Typical replacement cations include hydrogen, Ammonium and metal cations including their mixtures. From the replacing metal cations become such metal cations as rare earth metals, manganese and calcium as well as metals of the group II of the periodic table, e.g. zinc, and group VIII

of the periodic table, e.g. nickel, is preferred. These replacing cations are included in the definition of R in the formula used herein included to the invention Describe compositions. 5

Typical ion exchange techniques involve contacting members of the borosilicate family with a saline solution of the desired replacement cation or cations. A wide variety of salts can be used; chlorides, nitrates and sulfates are particularly preferred. Examples of techniques of ion exchange are described in a wide variety of patents, such as U.S. Patents 3,140,249, 3,140,251 and 3,140,253.

Subsequent to contact with the salt solution of the desired replacement cation, the crystalline compositions are preferably washed with water and ^{dried at a temperature in the range from 65 to about 315 °} C. and then heat-treated as described above.

Regardless of the cations that the sodium is synthesized in Replacing the shape of the catalyst, the spatial arrangement of the atoms that make up the basic crystal lattice remains form in any given composition according to the invention, essentially by that described benen replacement of sodium or other alkali metal unchanged, as can be seen by powder X-ray diffraction diagram of the ion-exchanged material. For example, the X-ray diagram gives various, ion-exchanged Compositions is a graph essentially the same as that of ZSM-5 zeolite.

When these compositions are activated, they have catalytic properties comparable to those of others Silicate and borosilicate compositions resulting from this

■ *

B »

m w

Reaction mixtures not containing metal ions were produced, but which were ion-exchanged, to incorporate these same metal ions into the composition are different. For reasons still unknown the compositions of the invention behave the same metal ions, e.g. a metal ion of the group VIII, contain, different, depending on whether the metal ion of Group VIII as part of the crystal structure when it is formed, i.e. by urea precipitation from the Reaction mixture, has been formed or whether there is subsequent ah the formation of the structure by such means as Ion exchange, was introduced into the structure.

The compositions made by the present invention are made in a wide variety of special sizes. Generally speaking, they can Particles in the form of a powder, granules or as a shaped product, e.g. as an extrudate with a particle size, which is sufficient to pass through a sieve with a mesh size of 46 mm (2 mesh Tyler) and to be retained on a 0.147 mm (100 mesh Tyler) mesh screen. In cases where the catalyst has been shaped, such as by extrusion molding, the composition may be extruded before drying or dried or partially dried and then extruded.

In the case of many catalysts, it is desirable to use a different material in the composition according to the invention

incorporate that versus temperatures and other conditions used in organic conversion processes is constant. Such materials include active and inactive material and synthetic or natural occurring crystalline compositions as well as inorganic material, e.g. clays, silicon dioxide and / or metal oxides. The latter can either be natural

borrowed or in the form of gel-like precipitates or gels including mixtures of SiO ₂ and metal oxides. The use of a material together with the present catalyst leads to an improvement in the conversion and / or selectivity of the catalyst in certain organic conversion processes. Inactive material is conveniently used to control the amount of conversion in a given process so that the products can be obtained economically and in an orderly manner without the use of other means of controlling the rate of the reaction. Typically, zeolites have been incorporated into naturally occurring clays such as bentonite and kaolin in order to improve the crush strength of the catalyst under commercial process conditions. This material, ie clays, oxides, etc., serves as a binder for the catalyst. It is desirable to provide a catalyst having good crush strength because, in a chemical process, the catalyst is often treated or used in such a way that the catalyst tends to break into a powdery material which presents difficulties in processing. These clay binders were used to improve the breaking strength of the catalyst.

In addition to the substances mentioned above, the catalyst can be composed of a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, Silica-Thorium Oxide, Silica-Beryllium Oxide, Silica-Titanium Oxide, as well as with ternary Compositions such as silica-alumina-thoria , Silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel.

The following examples of the invention are given as specific embodiments of, and show some of the unique characteristics of the claimed _s crystalline compositions. However, they are in no way intended to limit the present invention "

example 1

This example illustrates the preparation of various members of the new crystalline silicates according to FIG Invention including the following:

Iron silicate catalyst I

Iron borosilicate catalyst II & III

Cobalt Silicate Catalyst IV

Cobalt borosilicate catalyst V.

Iron silicate Catalyst I.

A sodium silicate solution (A) which contained less than 100 ppm aluminum (based on SiO ₂ ) was prepared by dissolving 80 g of high-purity silicon dioxide (Cab-0-Sil) in a boiling solution of 700 ml of water and 55 g. a 50 to 52% aqueous NaOH solution prepared. A second solution (B), the 85 g NaCl, 33 g tetrapropylammonium bromide (TPA-Br), 23 g conc. Sulfuric acid and 300 ml of water was prepared. While both solutions were at room temperature, solution B was slowly added to the sodium silicate solution with stirring. The pH was then increased to 9 ₉ 04 by the addition of sulfuric acid

lowered to 8.50.
30th

A solution of 6.3 g FeCl, .6H ₂ O, 6.8 g urea and 150 ml water was prepared at room temperature. There were no solids. The solution was heated to the boil and refluxed for 20 h. During the etching, some urea decomposed and developed ammonia, which caused the iron to precipitate. the

321.5 ar "

ferrous slurry was then added to the stirred silicate mixture s ch 2 given.

The entire mixture was added to 2000 ml polypropylene einö ³ "flask, which was partially immersed in a hot oil bath of 120 ° C. A reflux condenser was attached to the flask. After 22 days, the outer flask was removed from the oil bath and cooled. The solid was thoroughly washed with deionized water, collected on a filter and dried at 110 ⁰ C. 92.2 g of the end product were obtained. The dried material was analyzed by X-ray and had the same graph as that published for ZSM-5 type aluminosilicate (zeolite).

A portion (37.9 g) of the dried sample was calcined at 538 ° C. for 16 hours, losing $ 12.9 of its initial weight. The calcined sample was mixed with a solution of 60 g of NH ^ Cl in 300 ml of water and refluxed for 4 h. After washing, the exchange was repeated for 16 hours. The material was filtered, washed and dried. Before the test, the ammonium ion form had been converted into the H ion form by heating in air at 538 ^° C.

analysis

before ion exchange Fe = 1.29 ^ Al = 74 ppm after ion exchange Fe = 1.52 $ Al = 77 ppm

Iron borosilicate

Catalysts II and III

Two crystalline iron borosilicate catalysts were prepared using the same general procedure as the catalyst I prepared, but 8.9 g of boric acid were dissolved in solution B. Both catalysts showed the X-ray ZSM-5 type powder diagram. More information for each catalyst is given below.

* W W W VV catalyst II 3215i Growing time (days) 12th analysis III before ion exchange 12th Fe 1.2% B. 0.38% Al 31 ppm 1.31% after ion exchange 0.54% Fe 1.4% 26 ppm B. 0.28% Al 32 ppm 1.30% Cobalt silicate and cobalt borosilicate 0.28% Catalysts IV and V 52 ppm

Two catalysts were prepared in the same way as catalysts I, II and III, except _{that 8.5 g of Co (NO ^) 2 .6H 2} O, 12.5 g of urea and 175 ml of water were used instead of the iron-urea solution were used. Further information for each catalyst is given in the table below.

Catalyst IV V

added boric acid no Yes Growing time (days) 13th 13th analysis before ion exchange Co 1.63% 1.65% Al 19 ppm 25 ppm B. - 0.44% after ion exchange Co 1.28% 0.83% Al 30 ppm 35 ppm B. - 0.33% Example 2

The iron silicate and iron borosilicate of Example 1 (catalysts I, II and III) were tested for their catalytic

see properties checked and compared with catalysts, which are labeled A, B and C and which were produced by other methods.

Catalyst A was an iron silicate made without a chelating agent. The catalyst is similar that disclosed in Example 6 of GB-PS 155 928 (DE-OS 27 55 770).

Catalyst B was an iron silicate made with a chelating agent.

Catalyst C was an iron borosilicate made with a chelating agent, which is the subject matter of US Pat American patent application according to the attorney's file en-Fr. * 3463 is.

Catalyst C was prepared as follows. 80.0 g of silica (Cab-O-Sil) produced in the vapor phase were dissolved in 55.0 g of 50% NaOH and 800 ml of water. The solution was placed in a 2000 ml flask made of polypropylene, which was ^{immersed in an oil bath at 120 °} C. for 24 h. A reflux condenser was attached to the flask.

A second solution was prepared containing 85.0 g NaCl, 33 »0 g tetrapropylammonium bromide, 8.9 g boric acid, 19.0 g concentrated sulfuric acid and 350 ml of water.

While both solutions were at room temperature, the second solution slowly became the sodium silicate solution with stirring given.

A third solution, the 8.5 g of 50% NaOH, 13.0 g S-hydroxyquinoline-S-sulfonic acid (8HQS), 300 ml of water and

6.0 g FeCl ^ .6H ₂ O contained, was prepared and added to the above solutions. The pH was 9.1 and was adjusted to 8.5 with ^ S (L. The total weight of the mixture was 1791.3 g.
5

The slurry was placed in a 2000 ml flask made of polypropylene (with a reflux condenser) and partially immersed in an oil bath at 120 ⁰ C for 15 days, after which the flask was removed and cooled. The pH was 10.1 and the weight loss due to evaporation was 25 g. The solid was collected on a filter, washed and dried at 120 ° C. for 24 h. 86.6 g of the Na ⁺ form of the iron borosilicate were obtained. Fe = 1.2%; B = 0.27 / 6.

Catalyst A was prepared as Catalyst C, with however, no boron compound and no 8HQS were used.

Catalyst B was prepared as Catalyst C, with however, no boron compound was used.

The iron silicate catalysts were evaluated as follows.

(1) Test data for dimethyl ether (DME) All catalysts were tested in the H ⁺ form at 1.5 g DME / g cat./h at 0.42 kg / cm ² overpressure (6 psig).

* M * * - τ β » 500 A. 500 32 B. 1506y catalyst I. 82 according to the state
of the technique 99 8HQS Manufacturing
procedure Urea-
precipitation 420 420 Temp., ⁰ C 420 4th 99 5 100 300 % HC yield
(C) 89 4th 8th 100 % HC selective
vitat (C): 14th 3 16 7th ^C 1 5 13th 3 19th 0 7th C ₂ 1 55 17th 14th 8th 6th ^C 3 20th 9 22nd 38 24 5 ^C 4 18th 40 54 26th ^C 5+ 50 15th 7th 28 Ar 5 28

The test values show that the urea precipitation method a catalyst results in the production of aliphatic catalysts prepared by other methods Is superior to hydrocarbon. The differences in coal: the highest.

the hydrocarbon selectivity are at 500 ⁰ C am

(2) Test values for ethylene Not available.

(3) Test values for methanol

The catalysts were tested in the H form at 1.5 g C ₂ H ^ Zg cat./h and a simultaneous _{supply of N 2} (molar ratio CH ₃ OH / N ₂ ~ 1) at 0.42 kg / cm ² Overpressure (6 psig).

26 30

Catalyst I A B

Production - urea - according to the state of the art, precipitation of the technology

Temp., ⁰ C 420 I.
I. 0 500 420 5 % HC yield
te (C) 15th DME 100 2 98 % HC-Selek-
activity (C) ^C 1 0 100 1 ^C 2 0 0 3 10 ^C 3 12th 0 0 ^C 4 45 0 4th ^C 5 ₊
Ar 43
0 0
0 88
3 15th %Oxygen-
Yield (C) 36 51 0 %Oxygen-
selective. (C): co / co ₂ 3 - 97 _

; and with 8HQS 500 420 500 99 92 98 7th 1 9 8th 3 9 5 4th 14th 42 51 17th 16 39 23 22nd 2 29

100 - 10.0 0 0

The test values show that that obtained with Catalyst I. Product selectivities are different from those obtained with catalysts A and B. Compared to A and B, Catalyst I gives high yields of DME and relatively low hydrocarbon yields.

(4) Test data for synthesis gas Not available.

The iron borosilicates were evaluated as follows. Comparative data for iron borosilicates without chelating agents are not included since the compositions are usually amorphous.

3A

(I) Test values for DME

The catalysts were tested in the H -form at 1.5 g DME / g cat./h at a pressure of 0.42 kg / cm ² (6 psig).

Catalyst II III C

Manufacturing
procedure Urea-
precipitation 500 Urea-
precipitation 500 8HQS 420 50 Temp., ⁰ C 420 100 420 100 100 99 ^ HC leachate
te (C) 100 100 S $ HC selective
vity (C): 3 8th VJl 9 ^C 1 3 3 4th VJl 0 6th ^C 2 1 11th 0 16 8th 10 ^C 3 23 40 20th 24 24 25th ^C 4 18th 38 25th 36 54 38 53 5 48 12th 9 12th Ar 2 3

The catalysts II and III show the reproducibility of synthesis and test. The hydrocarbon selectivities these catalysts are very similar to those obtained with C.

(2) Test values for ethylene

The catalysts were tested in the H ⁺ form at 1.5 g ^C 2 ^H Zf / g cat / hour at 420 ° C. and a pressure of 0.42 kg / cm ² (6 psig).
Catalyst II III C_

Manufacturing Urea- Urea- 8HQS procedure precipitation precipitation »-Yield (C) 0 7th 9 $ £ HC selection (C): ^C 1 - 0 0 ^C 2 ^H 6 - 0 14th C ₃ - 2 0 ^C 4 - 34 86 C5 + - 64 0 Ar - 0 0

L ^: "T ^: .Λ ::. 3215G69

A difference in the catalytic properties is observed depending on the manufacturing method. Catalyst III gave mainly Cc ₊ hydrocarbons while C gave mainly Cλ hydrocarbons. 5

(3) Test values for methanol

Both catalysts were used in the H -Fora with 1.5 g CH, OH / g cat./h and an N ₂ feed (molar ratio CH 0H / N ₂ -1) at an overpressure of 0.42 kg / cm (6 psig) tested.

Catalyst __ III

Manufacturing process Urea precipitation 500 420 8HQS 500 Temp., ⁰ C 420 94 94 88 S&IC yield (C) 86 SfiHC selection (C): 3 1 10 ^C 1 1 3 2 11th C ₂ 1 0 6th 22nd 0 O 4th 29 25th ^C 4 15th 89 60 12th 82 2 3 19th Ar 1

The above hydrocarbon selectivities show that catalyst III gave an extraordinarily high C, - ₊ fraction, in particular at 500 ^° C., compared with catalyst C.

(4) Test values for synthesis gas
Not available.

example

The cobalt silicate and the cobalt borosilicate of Example 1 (catalysts IV and V) were tested for their catalytic properties in a series of tests. The results are as follows.
35

(1) Test values for DME Both catalysts were tested in the H -form at 1.5 g DME / g cat./h at an overpressure of 0.42 kg / cm (6 psig).

Catalyst IV V

Composition S: L0 ₂ / Co ₂ 0 ₃ SiO ₂ / B ₂ ( ) ₃ / Co ₂ 0 ₃ Temp., ⁰ C 420 420 500 % HC yield (C) 4th 6th 12th % HC selective. (C): 10 C ₁
C ₂ 52
0 44
4th 30th
5 42 30th 20th ^C 4 3 14th 30th 3 8th 15th 15 _ares 0 0 0

(2) Test values for ethylene Both catalysts IV and V were ^{inactive at 420 °} C. «

(3) Test values for methanol Not available.

(4) Test values for synthesis gas

Not available. 25th

Claims (8)

Applicant: NATIONAL DISTILLERS AND CHEMICAL CORPORATION 99 Park Avenue New York, USA Synthetic, crystalline metal silicate and borosilicate compositions and their manufacture. Claims 1. / Process for the preparation of a crystalline Likat composition, characterized in that one (a) a first mixture which is a tetraalkylammonium salt, contains an alkali metal hydroxide, silicon dioxide and water, (t>) a second mixture, the water, a soluble one Source of a metal whose hydroxide precipitates at a pH above 7 and an amount of urea or a Compound which, after hydrolysis, releases ammonia, the amount contributing to the precipitation of the hydroxide of the metal is effective, produces, 321506 « (c) mixing together an amount of the first mixture and an amount of the second mixture effective to form a reaction mixture result which has an aluminum content of less than about 100 parts by weight per million (based on silicon dioxide) and has a composition in terms of molar ratios of the oxides set in the following Areas falls: OH "/ SiO ₂ 0.05-3 Q ⁺ / (Q ⁺ + A ⁺ ) 0.01 - 1 HO / OH "10-800 SiO ₂ / M _2/0 10-10000 where Q is a tetraalkylammonium ion, A is an alkali metal ion, M is the metal and m is the valence of the metal, the hydroxide of the metal forming a precipitate forms, (d) the reaction mixture is kept at a temperature of about 50 to about 250 ^° C. until crystals of the metal silicate are formed, and (e) Separate the crystals and recover. 2. The method according to claim 1, characterized in that there is a soluble boron compound with the first mixture mixed and that the molar ratios of the oxides in the reaction mixture have an additional molar ratio range from SiO ₂ / B ₂ O, 2-1000 own. 3. The method according to claim 1 and / or 2, characterized in that the metal is iron, cobalt, bismuth, Chromium, molybdenum, nickel, tin, platinum or mixtures thereof are used. · ^: ··· ^: "" ·· ^: $ 321506 4. The method according to any one of claims 1 to 3, characterized in that the crystalline silicate composition is activated by a method which comprises heating the composition in an atmosphere containing molecular oxygen. 5 «The method according to any one of claims 1 to 4, characterized in that a first mixture of Step (a) is used, which additionally contains sulfuric acid and sodium chloride, and that step (d) is below Performs reflux conditions. 6. Crystalline silicate composition produced by the method according to any one of claims 1 to 5 »with of the following composition, expressed as the molar ratios of the oxides: (0.2-8O) R ₂ O: (0.1-2O) M ₂ O: (0-4O) B ₂ O ^ tIOOSiO ₂ : (0-20O) H ₂ O η m where R is a tetraalkylammonium cation, an ammonium cation, hydrogen cation, alkali metal cation, metal cation or a mixture of these, η the valence of R, M a metal, the hydroxide of which precipitates at a pH above 7, and m mean the valence of this metal, and the composition has an aluminum content of less than about 100 parts by weight per million based on silica. 7. Use of the crystalline silicate composition according to claim 6 in the conversion of oxygenated Compound in hydrocarbons. 8. Use of the crystalline silica composition according to claim 6 in the polymerization of ethylene. 35 1 9 · Use of the crystalline silicate composition according to claim 6 in the conversion of hydrogen and hydrogen Synthesis gas containing carbon monoxide into hydrocarbons and / or oxygenated compounds.