DE1442851C - Process for the production of synthetic crystalline zeolites - Google Patents

Description

1 2

Crystalline aluminosilicate zeolites consist of struc- separating mixtures of straight-chain and mixed

turell essentially consists of an open three-dimensional-branched-chain molecule with 4 or more carbon

Sional network of SiO ₄ - and AlO ^ tetrahedra. Atoms of matter or a separation of straight-chain

These tetrahedra are by proportionate to molecules with 4 or more carbon atoms of

cross-linked by oxygen atoms, so that the ratio 5 to effect cyclic compounds, it was previously

from oxygen atoms to the sum of aluminum necessary, first an exchange of the initially

and silicon atoms is two. The negative obtained sodium zeolites A with another ion,

Electrovalence of the aluminum-containing tetrahedra, e.g. calcium or magnesium, to perform and

The inclusion of cations in the crystal results in an exchange of the sodium by a

balanced, e.g. B. of alkali or alkaline earth ions. io such replacing ion to the extent of

Many zeolites have a crystal structure that induce _{at least about 40 ° / 0.} That he has channels with molecular dimensions. The giving product in which calcium is the introduced ion. internal spaces are generally originally formed, technically and commercially, as molecular sieve Hch, they are occupied by water of hydration. Known after at least 5 A. This zeolite has larger pores . The interval between 5.5 angstrom units is
dimensions of the openings in the crystal lattice It is a process for the production of synthetic limits the size and shape of the molecules that can be pre-adsorbed from nitrogen-containing crystalline zeolites. A separation has therefore been proposed in which an aqueous mixture of a mixture of different molecules on the basis of soluble alkyl-substituted or partially substituted on the basis of molecular dimensions is possible, derivatives of ammonium hydroxide, "silicate ions, in which certain molecules are adsorbed by the zeolite aluminums, alkali ions and Produces water, while others are barred from admitting its composition within the following. This property of many crystalline domains lies:
Zeolites have led to them being used as “molecular sieves” to R ₂ O / A1 ₂ O ₃ = a
describe. SiCVAl ₂ O ₃ = b

There are already a number of synthetic crystalline H ₂ O / Al ₂ O ₃ == c

Zeolites have been produced. These are basically 30

location of the composition, the crystal structure and where R ammonium or some or all of the adsorption properties can be distinguished from one another and from alkyl-substituted derivatives of ammonium and a, b naturally occurring zeolites. The presence of a number of zeolites, which mean parameters, this mixture to a temperature similar but different properties, 35 temperature in the range of 25 to 300 ° C below the self allows in an advantageous manner the selection of a pressure heated until the desired zeolite crystals have formed a special limb with optimal properties for, which is then filtered off and a special use. be washed until the draining wash water

It is known to add a synthetic zeolite to a pH value in equilibrium with the crystals

known as "Zeolite X". Such a 40 from 9 to 11 has. In this process, for

Material and its manufacture are in the USA.- Manufacture of Tetramethylammonium Zeolite N-A U.S. Patent 2,882,244. A

another synthetic zeolite known as "zeolite A" R = tetramethylammonium

is known is in U.S. Patent 2,882,243 a = 1.5 to 3.5

described. This latter zeolite becomes an- 45 b = over 4 to 10

initially preserved in its sodium form, that is, as a c = 170 to 460

Sodium aluminosilicate. Such a material is in his.

capable of treating water and straight-chain compounds. According to the proposed method, a three or fewer carbon atoms, e.g. B. methane, zeolite NA obtained, which has a pore size of about ethane, n-propane, methanol, ethanol, n-propanol 50 3 Å and separations of mixtures of u. Sodium zeolite A is molecules with dimensions of about 3.9 Å, such as, however, incapable of any appreciable methane, from a mixture of methane and MoIe-scope straight-chain compounds with more than kulen with dimensions below about 3 Å, such as CO ₂ and adsorb 3 atoms in the chain. Only after water, allowed. The proposed zeolites are intended to replace, through ion exchange, an essential part, in particular as an adsorbent.
Proportion of sodium ions of the originally obtained object of the invention is the production of sodium zeolites A by divalent ions, for. B. synthetic crystalline zeolites, which lead to a calcium or magnesium, are its pores own selective adsorption of straight-chain molecules shafts such that a separation of straight-chain of more than 3 carbon atoms from a mixture of hydrocarbons with more than 3 carbon atoms 60 such molecules with non-straight-chain Coals made from a mixture with branched chain or cyclic hydrogens are capable when the zeolite is caused to see compounds. Sodium zeolite A, is in its sodium form, that is, without the need for what is known commercially as molecular sieve 4 A, first the sodium form of the zeolite is accordingly unable to convert from its crystalline form to any other form.
To admit structure molecules the largest dimension of which is greater than about 4.9 Angstrom units. To produce a setting of an aqueous ammonium derivative, silicate, zeolite A, dsr is able to produce a reaction containing aluminate and alkali ions

mixture until the desired zeolite crystals are formed and obtaining these crystals is characterized in that a reaction mixture of the the following composition, expressed in molar ratios of oxides

about 2.5 to 15, SiO ₂ Al ₂ O ₃ from Na ₂ O about 25th until 50, H ₂ O Na ₂ O + C ₈ H ₁₈ N from + C ₈ H ₁₈ N

SiO ₂

from about 1 to 2, where C ₈ H ₁₈ N ₂ O is derived from the N, N'-dimethyltriethylenediammonium ion, at a temperature of about 20 to 120 ^° C. until the crystals form and the crystals obtained are kept at a temperature in the range of about 200 to 60O ⁰ C heated.

The new zeolite obtained by the process is hereinafter referred to as "Zeolite ZK-5". the Production of this zeolite has the advantage that the previous practice of base exchange, which is after State of. Technology was seen as important,

ίο is avoided and still a zeolite with the desired pore properties is obtained.

The new zeolite ZK-5 also has the advantage that it is a very useful catalyst and that the hydrogen form of zeolite ZK-5 is of particular value as a hydrocarbon conversion catalyst has. .

The zeolite ZK-5 obtained according to the present invention is a crystalline synthetic material having the composition

0.3 to 0.7 R ₂ 0: 0.3 to 0.7 M ₂ 0: 1 Al ₂ O ₃ : 4.0 to 6.0 SiO ₂ · YH ₂ O

herein R denotes a nitrogen-containing cation derived from Ν, Ν'-dimethyltriethylenediammonium, and m is the valence of R; M is a metal and η is its valence; F is a number between about 6 and about 10. Smaller deviations in the molar ratios of these oxides within the ranges given by the above formula do not result in any appreciable change in the crystal structure or the physical properties of the zeolite.

According to one embodiment of the invention, can the crystalline zeolites ZK-5 obtained for the production of a hydrogen-aluminosilicate catalyst with a gaseous or liquid medium containing hydrogen ions or convertible into hydrogen ions Contains ions, are treated until the zeolite has a metal content of less than about 4 percent by weight having.

According to a particular embodiment of the invention, the zeolite ZK-5 is prepared from reaction mixtures containing Ν, Ν'-dimethyltriethylenediamonium ions, and in particular by heating a mixture of the oxides of materials in an aqueous solution, the chemical compositions of which are completely as mixtures of the oxides Na ₂ O, Al ₂ O ₃ , [(CH ₃ ) ₂ (CH ₂ CH ₂ ) ₃ N ₂ ] O, SiO ₂ and H ₂ O can be represented, expediently at a temperature of about 100 ° C. over a period in the range from 2 hours to 250 hours or longer. The composition of the reaction mixture, expressed as molar ratios of the oxides, preferably falls within the following ranges:

about 2.5 to 15, SiO ₂ Al ₂ O ₃ from Na ₂ O about 25th until 50, H ₂ O Na ₂ O + C ₈ H ₁₈ N ₂ O from + C ₈ H ₁₈ N ₂ O

SiO,

from about 1 to 2.

The product which crystallizes from the hot reaction mixture is separated off, expediently by centrifugation or filtration, and washed with water. until the effluent wash water has a pH of about 8 to about 12 in equilibrium with the zeolite. The material thus obtained is then preferably air or an oxygen-containing gas at a temperature in the range of about 200 to 600 ⁰ C, activated by heating in an inert atmosphere.

The usual method of making ZK-5 zeolite involves reacting sodium aluminate with 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanesilicate in aqueous solution. The response is in carried out a suitable vessel, which is made for example of metal or glass and closed can be used to avoid loss of water. The reaction mixture is initial stirred continuously or periodically to ensure homogeneity. After this mixing it can Stirring should be stopped as it is unnecessary to remove the reaction mass during formation and crystallization of the zeolite in motion, although mixing during these latter stages will not prove to be has proven harmful.

The crystallization processes can be carried out satisfactorily at temperatures in the range from about 90 to about 120 ^° C., the pressure being equal to atmospheric pressure or at least that pressure which corresponds to the vapor pressure of water in equilibrium with the mixture of reactants. Although temperatures as low as about 20 ^° C. can be used, such lower temperatures require a long reaction time. A temperature of about 95 to 100 ^° C. is preferably used. Heating is continued until the desired crystalline zeolite product is formed. The zeolite crystals are then separated from the mother liquor and washed, preferably with distilled water, until the effluent wash water has a pH between about 8 and about 12 in equilibrium with the product.

For a satisfactory use as an adsorbent, the zeolite ZK-5 should be replaced by min-

at least partial dehydration can be activated. Such activation can be brought about, for example, by heating the zeolite to temperatures in the range from about 200 to 600 ^° C. in an inert atmosphere, preferably air, under atmospheric or reduced pressure, or by keeping the zeolite at room temperature under vacuum.

During the synthesis of zeolite ZK-5 it was found that the composition of the reaction mixture is critical. In particular, the presence of Ν, Ν'-Dimethyltriethylendiammoniumionen in this Mixture important for the production of zeolite ZK-5. In the absence of such ions there was no Obtained zeolite ZK-5. The crystallization temperature and the length of time that the crystallization temperature are maintained are important variables in the yield of crystalline material. Under certain conditions, e.g. B. too low a temperature for too short a time no crystalline product obtained. Extreme conditions can also lead to the formation of materials which are different from zeolite ZK-5. It has been found that the addition of vaccine in the form of Crystals of ZK-5 zeolite formed earlier in the reaction mixture increased the rate of crystallization elevated.

In the resulting crystalline synthetic aluminosilicate, the negative electrovalence is des Aluminosilicate balanced by a cation consisting essentially of a metal such as sodium and by a nitrogen-containing cation which comes from the Ν, Ν'-dimethyltriethylenediammonium ion; the Zeolite is further characterized by a uniform effective pore diameter of about 5.5 angstrom units marked.

The sodium oxide present in the reaction mixture comes from sodium aluminate. The used Solution of 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanesilicate (Ν, Ν'-dimethyltriethylenediammonium silicate) is expedient by dissolving silicon dioxide gel in a solution of 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanedihydroxyd produced. On Instead of silica gel, other sources of silica can be used, e.g. B. hydrosols of silica, silicate esters, silica gel gels, and freshly made low molecular weight silicas. The above-mentioned dihydroxide can be prepared in any suitable manner. In general, it is obtained by complete methylation of 1,4-diazoniabicyclo- (2,2,2) -octane, the also known as triethylenediamine, prepared with methyl iodide to l ^ dimethyl-l ^ diazoniabicyclo- (2,2,2) -octanediodide which is converted into dihydroxide by subsequent reaction with silver hydroxide. Other ways of working can also be used be used to form the N, N'-dimethyltriethylenediamonium hydroxide, e.g. More colorful Use of dimethyl sulfate for methylation and subsequent conversion into the hydroxide with Barium hydroxide. The Ν, Ν'-dimethyltriethylenediammonium hydroxide can also be used as such in place of the silicate and added to the reaction mixture which contains the source of silica.

There are critical differences with regard to the composition and the sorption properties of zeolite ZK-5 and zeolite A. Zeolite ZK-5 contains more silicon and less sodium and Aluminum as zeolite A. There was a clear difference in terms of sorption properties of these two zeolites. The table below shows the differences in terms of the chemical and physical properties observed for the two zeolites are summarized:

Ma ₂ O

Mole percent
Al ₂ O ₃

SiO ₂ lattice parameters, a.

Sorption per 100 g of zeolite

H ₂ O

Cyclohexane

3-methylpentane

Zeolite 4 A.
Zeolite ZK-5

25 "
6 to 12

25th
15 to 18

50
65 to 80 12.32 ± 0.2 Ä
18.68 ± 0.2 Å

24
19 to 24

11 to 14

<2

From the above information it can be seen that although both the zeolite 4 A and the zeolite ZK-5 possessed good sorption properties for water and the property cyclohexane and 3-methylpentane to rule out, however, a pronounced difference in the sorption properties of the two zeolites with regard to the sorption of η-hexane. While the zeolite 4 A was unable to convert η-hexane in To sorb any appreciable extent, the zeolite ZK-5 exhibited good sorption properties for this straight-chain hydrocarbon, while it is a branched-chain hydrocarbon (3-methylpentane) and excluded a cyclic hydrocarbon (cyclohexane). Such a selective sorption characteristic is extremely valuable in effecting separation of straight chain hydrocarbons from a mixture "of the same with branched-chain or cyclic hydrocarbons, as it occurs in petroleum, and avoids the previous need for the sodium ions originally contained replace the zeolite A with at least about 40% calcium ions to form an adsorbent with the above-mentioned sorption properties. '

In addition to the adsorption properties, the rejection properties of zeolite ZK-5 are important. the The interspace channels of this zeolite are such that in their narrowest points molecules with critical dimensions greater than about 5.5 angstrom units cannot enter the channels. Be accordingly Molecules with critical dimensions greater than about 5.5 angstrom units rejected by the zeolite, while those with smaller critical dimensions are adsorbed.

The zeolite ZK-5 can be used in any suitable form as an adsorbent for purposes such as those above

are specified. For example, a column of powdered crystalline Material give excellent results, the same is true for a pelletized form that is produced by pressing a Mixture of zeolite ZK-5 and a 'suitable binder, e.g. B. clay, is obtained into pellets. the Zeolite ZK-5 can also be contained in a matrix of inorganic oxide gel, which is for example from an intimate mixing of the zeolite in finely divided form with a hydrogel of an inorganic one Oxide or by dispersion in a hydrosol of an inorganic oxide with subsequent gelation of the resulting hydrosol results. The composition prepared in this way can according to known Methods of forming particles of the desired size and shape, e.g. B. to spherical Gel particles which contain the finely divided zeolite completely distributed therein. In the case of the inorganic oxide gel it can be silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide, titanium oxide and the like. Or Combinations of two or more such oxides act.

The adsorbents which can be considered according to the invention do not only comprise the sodium form of the ZK-5 zeolite with sodium as the exchangeable cation as described in the above Way is made, but also the crystalline materials that result from such Zeolites by partially or completely replacing the sodium ions with other cations can be obtained. The sodium cations can, at least partially, be replaced by other ions, including monovalent or divalent cations, e.g. B. lithium and magnesium, group I metal ions of the periodic table, e.g. Potassium and silver, Group II metal ions, e.g. B. Calcium and Strontium, Metal ions of the transition metals, e.g. B. nickel, the rare earth metals, z. B. cerium, lanthanum, praseodymium, Neodymium, samarium and their mixtures with one another and / or the other rare earths, and other ions, e.g. B. hydrogen and ammonium, which behave as metals in zeolite ZK-5 by Can replace metal ions without any appreciable change in the basic structure of the zeolite crystal to cause. When the sodium cations or other metallic cations by hydrogen ions or ions convertible to hydrogen ions are replaced, the material is very useful as a a hydrocarbon catalyst such as the one below will be described in more detail. The transition metals are those whose atomic numbers are 21 to 28, 39 to 46 and 72 to 78 inclusive, namely scandium, Titanium, vanadium, chromium, manganese, iron, cobalt, nickel, yttrium, zirconium, niobium, molybdenum, Ruthenium, rhodium, palladium, hafnium, tantalum, tungsten, rhenium, osmium, iridium and platinum.

The ion exchange of the sodium form of the ZK-5 zeolite can be carried out by conventional methods. A preferred continuous method is to place zeolite ZK-5 in a series of vertical columns to fill an aqueous solution of a soluble salt of the cation to be introduced into the zeolite, one after the other to pass through the beds and switch the flow from the first bed to the second bed, . when the zeolite in the first bed is ion exchanged to the extent desired. The spatial Arrangement of the aluminum, silicon and oxygen atoms that make up the underlying crystal lattice of the Forming zeolites remains with a partial or complete replacement of the sodium by others Cations essentially unchanged. For the identification of zeolites, the

X-ray powder diffraction pattern found useful. X-ray powder diffraction diagrams of Zeolite ZK-5 were obtained using normal methods. The radiation was that K ”£‹ a doublet of copper, and a violinist

o counter spectrometer with a strip chart recorder used.

The peak heights, / and the positions as a function of 2 Θ, where Θ is the Bragg angle, "were taken from the spectrometer sheet. The relative intensities were obtained from this

100 /

where I _{0 is} the intensity of the strongest line or peak, and d (obs.), the interplanar distance in Å, calculated according to the recorded lines. X-ray powder diffraction values for ZK-5 zeolite are given in Table A below:

Table A.

h k I 110 /// "· 100 d-k 200 18th 13.3 220 100. 9.41 310 6th 6.62 222 41 5.93 321 48 5.41 400 2 5.03 330 6th 4.69 420 50 4.41 332 34 4.19 422 22nd 3.98 510 18th 3.81 521 6th 3.66 530.433 13th 3.41 611 35 3.21 620 28 3.02 541 • 21 2.94 622 2 2.88 631 26th 2.81 543,710,550 9 2.75 640 11th 2.64 721,653,552 2 2.59 730 9 2.54 732.651 3 2.45 811,741,554 1 2.37. 822.660 2 2.30 831,750,743 3 2.20 662 2 2.17 910.833 1 2.14 842 3 2.06 921,761,655 2 2.04 830,851,754 3 2.02 932.763 1/2 1.97 941,853,770 2 1.93 10, 00,860 2 1.89 10,2,0,862 5 1.87 10,3,1,952,765 5 1.83 5 1.79

209 618/29

It has further been found that zeolite ZK-5 is useful not only as such, but also as highly active hydrocarbon conversion catalysts can be obtained by treating the crystalline aluminosilicates designated as ZK-5 with a gaseous or liquid medium that contains hydrogen ions or which can be converted into hydrogen ions Contains ions in an amount sufficient to impart catalytic properties to the material. The catalysts obtainable according to this embodiment of the invention have a wide range of sizes in catalytic activity, they can be used in extremely small concentrations, and they allow certain hydrocarbon conversion processes to be carried out with favorable and controllable speeds or rates at temperatures that are much lower than those previously used. In the catalytic cracking of hydrocarbon oils to hydrocarbon products of lower molecular weight The reaction speeds or rates per unit volume of catalyst range achievable with the catalysts of the invention, up to thousands of times the speeds or rates achieved with the best silicon-containing catalysts proposed to date will. These catalysts can also be used directly as the only catalytic component or as Intermediate products in the manufacture of further modified contact masses with catalytic properties to be used. Such modified contact masses can do this with a gaseous or liquid treated aluminosilicate as such or a dispersed mixture of the with a gaseous medium or liquid medium treated aluminosilicates with a predetermined amount of one inert and / or catalytically active material that is used as a base, support, carrier, binder, Matrix or promoter for the catalyst component is used.

The medium-treated zeolite ZK-5 can be prepared by treating zeolite ZK-5 with a Brings gaseous or liquid medium into contact, the hydrogen ions or convertible to it Contains ions, washes the treated material free of soluble anions and then the product dries and by heating at temperatures ranging from about 204 to 815 ° C for a period of time thermally activated between 1 and 48 hours. The resulting product is an activated aluminosilicate of a strongly acidic character containing less than about 4.0 weight percent metal and im essentially corresponds to the hydrogen form of the ΖΚ-5 precursor. If this product is below alone or combined in a state of particle size less than 40 microns, dispersed or in intimately mixed with an inorganic oxide gel in any other way, it is extremely active as Catalyst for hydrocarbon conversion.

The gaseous or liquid medium that is used to form The catalyst composition used may be non-aqueous or hydrous Be medium and include gases, polar solvents or aqueous solutions. Typical sources of hydrogen ions are z. B. organic and inorganic acids, while ammonium ions are typical ions that are capable of conversion to hydrogen ions. For reasons of economy and ease of manufacture in large-scale operations, continuously or batchwise Treatment makes water the preferred medium. For this reason they are correspondingly organic Solvents less preferred, but they can be used provided the solvent ionization of the acid or ammonium compound is permitted. Typical solvents are z. B. cyclic and acyclic ethers, e.g. B. dioxane, tetrahydrofuran, ethyl ether, diethyl ether, diisopropyl ether and the like; Ketones e.g. B. acetone and methyl ethyl ketone; Esters, e.g., ethyl acetate and propyl acetate; Alcohols e.g. B. ethanol, propanol, butanol, etc., as well as various other solvents, e.g. B. dimethylformamide.

The hydrogen ions or the ammonium ions can be present in the medium in an amount which depends on the pH of the liquid or gaseous Medium varies within wide limits. For example, the pH value for media is the hydrogen ions contained, in the range of about 1.0 to 7.0 and preferably within a pH range of 3.8 to 4.5. When ammonium ions are used, either alone or in combination with hydrogen ions, lies the pH in the range 4.5 to 12.0 'and preferably within the limit of about 4.5 to 8.5.

In one embodiment of the treatment with the gaseous or liquid medium, a procedure is used in which zeolite ZK-5 or a derivative of the same, in which the ions marked with R are partially or completely replaced by metal cations, with the desired gaseous or liquid medium are brought into contact until metallic cations effective / decreased by an amount of at least 5O ° / o ^un d is preferably 60 to 75 ° ₀ or more, to provide a crystalline Wasserstoffaluminosilicat, which has a metal content of less than about 4, 0 percent by weight and preferably less than 2 or 3 percent by weight. The effective treatment with the gaseous or liquid medium to produce the corresponding hydrogen aluminosilicate varies with the duration of the treatment and the temperature at which it is carried out. Elevated temperatures tend to increase the rate of treatment while the duration changes inversely with the hydrogen ion or ammonium concentration of the gaseous or liquid medium. In general it can be said that the temperatures used range from temperatures below room temperature of 24 ° C. up to temperatures below the decomposition temperature of the aluminosilicate. Following the medium treatment, the treated aluminosilicate is washed with water, preferably with distilled water, until the washing water flowing off has a washing water pH, ie between about 5 and 8. The aluminosilicate is then dried and activated by heating in an inert atmosphere at temperatures in the range of about 204 to 815 ° C, with ammonium ions, if present, undergoing conversion to hydrogen ions.

The aluminosilicate material can be analyzed for its metal ion content by known methods will. The analysis includes the examination of the draining laundry medium for anions, which are obtained as a result of the treatment in the washing medium, as well as a determination of and a Correction for anions from soluble substances

11 12

or decomposition products of insoluble Substan- isator product is then preferably in an inert

zen, which are otherwise in the aluminosilicate as pollutants, atmosphere close to the temperature necessary for the environment

cleanings are present, in the outflowing wash 'change comes into consideration, precalcined, he can

go medium. but also initially during use in the

Which are calcined to carry out the medium treatment of the 5 conversion process. Im all-aluminosilicate in practice, the composition is generally about 65 to can be dried batchwise or continuously at atmospheric 315 ° C and then in air or a A chemical, subatmospheric or superatmospheric atmosphere consisting of nitrogen, hydrogen, herischen Printing. It can be a lium, exhaust gas, or some other inert gas during dehumidification the hydrogen ions, and / or the ammonium temperatures in the range of about 204 to 805 ° C above ions in the form of a molten material, for periods ranging from 1 to 48 hours or more Steam, an aqueous or a non-aqueous calcined.

Dissolve slowly through a fixed bed of the Alumino- A preferred embodiment of this aspect silicats are conducted. If desired, one of the invention is the use of {monobloc Hydrothermal treatment or an equivalent of 15 hydrogen aluminosilicate catalyst particles in one non-aqueous treatment with polar solvents silicon-containing gel matrix in which the catalyst in by introducing the aluminosilicate and the liquid is present in such proportions that the or gaseous medium in a closed giving product about 2 to 95 percent by weight, reservoir, which is kept under its autogenous pressure, preferably about 5 to 50 percent by weight, of the alumina, be effected. Similarly, containing 20 silicats in the final composition, The compositions of hydrogen aluminos- or vapor phase contact, provided that the silicate and silicon-containing gel can be different the melting point or the evaporation temperatures are established methods in which the the acid or ammonium compound aluminosilicate is combined with silicon dioxide, below the decomposition temperature of the alumino-25 while the latter is in a water-containing additive lie. stand, z. B. in the form of a hydrosol, one

Those with a gaseous or liquid medium hydrogel, a wet gelatinous precipitate

treated compositions as claimed in or a mixture thereof. So. can z. B. silicon

This embodiment of the invention produced dioxydgel, which by hydrolysis of a basic

have broad applicability as an alkali silicate solution with an acid, e.g. B. hydrochloric acid,

Catalysts in a variety of hydrochloric acid, etc., formed directly with

Material conversion processes including isomerization finely divided aluminosilicate are mixed, which

tion, dealkylation, alkylation, disproportionation - a particle size smaller than 40 microns and preferably

tion, hydration of olefins, amination of oils has in the range of 2 to 7 microns. The Ver-

finen, hydrocarbon oxidation, dehydrogenation, demixing of the two constituents can in any one

hydration of alcohols, desulphurization, hydration, take place in the desired manner, e.g. B. in a spherical

tion, hydroforming, reforming, Hydrokrak- mill or in other types of kneading mills. In

Curing, oxidation, polymerization and the like. The catalysis-like manner can be the aluminosilicate in one

Sators are exceptionally stable and can be dispersed in the hydrosol by reaction

especially in the case of those mentioned above and an alkali metal silicate with an acid or an al-

It is possible to use methods obtained at cold coagulant temperatures. The

in the range from room temperature (21 ° C) up to hydrosol is then in bulk to a hydrogel

about 538 ° C, including allowing to set, which is then dried and placed in

rather processes in which the catalyst is broken by chopping off the desired shape,

burn combustible deposits periodically re- 45 or it is passed through a nozzle into a bath of oil or

is generated. Due to their high catalytic another water-immiscible suspension medium

Activities are distributed to spherically shaped »pearl particles of the catalysts especially useful

bar to obtain various hydrocarbon catalyst effects. The one obtained in this way

conversion process, such as alkylation, aluminosilicate-silicon containing gel is free of soluble

washed at relatively low temperatures with low 5 ° borrowed salts and then in the desired

Amounts of catalyst, resulting in a minimal amount of th way dried and / or calcined.

unwanted side reactions and operating costs The silicon-containing gel matrix can also consist of a

is achieved. Multiple gels consist of a predominant amount

The hydrogen aluminosilicate compositions contain one or more metals or silica Can be used as a catalyst itself or as an intermediate 55 their oxides from groups II, III, IV, V, VI, VII product in the manufacture of further modified and includes VIII of the periodic table. Especially be-contact masses from inert and / or catalytically preferred multiple gels of silicon dioxide with active materials that are otherwise used as a basis, carrier, metal oxides of groups Ha, IHb and IVa des Binder, matrix or promoter for the aluminum periodic table, the metal oxide being magnesium silicate serve to be used. The catalyst 60 oxide, aluminum oxide, zirconium oxide, beryllium oxide can be in powdered, granular or shaped additive or thorium oxide. The production of multiple booths Formed in beads or gels is known and generally includes working pellets of fine-grained particles with a particle size either with separate precipitation or with size of about 0.03 to 9 mm clear mesh size. common precipitation in which a suitable salt In cases where the catalyst is being molded, e.g. B. 65 of the metal oxide added to an alkali silicate by extrusion, the aluminosilicate can before being and an acid or base as that is required Drying extruded or first dried or partially added to the corresponding oxides are dried out and then be extruded. The catalyze falling. The silicon under consideration here

The dioxide content of the silicon-containing gel matrix is generally in the range from 55 to 100 percent by weight, the metal oxide content being in the range from 0 to 45 μ / ₀ . Minor amounts of promoters or other materials that may be present in the composition include cerium, chromium, cobalt, tungsten, uranium, platinum, lead, zinc, calcium, magnesium, lithium, silver, nickel and their compounds.

The hydrogen aluminosilicate catalyst can also be incorporated into an alumina gel matrix, conventionally by adding ammonium hydroxide, ammonium carbonate, etc. to one Aluminum salt, e.g. B. aluminum chloride, aluminum sulfate, aluminum nitrate, etc., in an amount for formation made of aluminum hydroxide, which is converted into aluminum oxide after drying has been. The hydrogen aluminosilicate catalyst can be mixed with the dried alumina, or it can be introduced while The aluminum oxide is in the form of a hydrosol, a hydrogel, or a wet gelatinous precipitate is located.

The following examples serve to further illustrate the invention.

marked:

B ei s ρ i e 1 1

410 g (2.88 moles) of methyl iodide was placed in a 1-1 three-necked round bottom flask equipped with a stirrer, reflux condenser, and addition funnel. The flask was immersed in ice water and a solution of 148.4 g (1.32 mol) of triethylenediamine dissolved in 400 ml of absolute alcohol was added through the dropping funnel over the course of 1 hour. A solid product separated out from the reaction mixture during the reaction. The mixture was then stirred at room temperature of about 27 ° C. for 0.5 hours. A further 10 g of methyl iodide were then introduced into the mixture and the latter was stirred on a steam bath for 0.5 hours at reflux temperature of about 78 ° C. Excess methyl iodide and alcohol were then evaporated from the flask. The remaining solid product was collected on a Buchner funnel and washed with absolute ethanol. After recrystallization from a water-ethanol mixture and drying in air, a sample of the crystalline product was analyzed and identified as 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanediodide; this is by the following formula H ₂ C-

CH ₃

CH ₂
CH ₂

N-

CH ₃

CH ₂

CH,

The above listed compound was then converted to the dihydroxide as indicated in the example below.
20th

Example 2

By reacting a solution of 200 g of silver nitrate, dissolved in 500 ml of water, with an i-solution of 50 g of sodium hydroxide dissolved in 300 ml of water was used to produce silver hydroxide! A precipitate formed of silver hydroxide, and this was collected on a funnel and washed with water, to remove excess sodium hydroxide.

The moist silver hydroxide, 200 ml of water and 191 g of l, 4-Diazoniabicyclo- (2,2,2) -octanijodid, which as in Example 1 was placed in a 1-1 ball mill and rotated for 3 hours held. »

The resulting reaction mixture was filtered through a filter funnel with a sintered disk, and the Residue in the funnel was washed with about 200 ml of water. The colorless filtrate was how through Titration was found to be an approximately 2N basic solution. The solution was evaporated in vacuo, to increase concentration. After the volume was reduced enough, by about To give 3N solution, the mixture was filtered through a sintered filter funnel. That I The resulting clear colorless filtrate was a solution of 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanedihydroxide.

A solution containing the silicate * and 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanions was obtained by dissolving silica gel in the above Dihydroxide solution prepared according to the following equation:

CH ₃

H ₂ C ^ ^ QH ₂
CH ₂

CH ₂

CH ₃

CH ₂

(OH) ₂ + SiO ₂ - ~>.

CH ₃

H ₂ C ^ ^ CH ₂
CH ₂

H, C.

CH ₂

CH ₃

CH ₂

SiO ₃ + H ₂ O

this was done according to the example below.

Example 3

9.2 g of silica gel were gently heated in 102 ml of a 2.99 η solution of 1,4-dimethyll, 4-diazoniabicyclo- (2,2,2) -octanedihydroxyd, which had been prepared according to Example 2, dissolved. The resulting solution was nitrided. The filtrate was a solution of l ^ -dimethyl-l ^ -diazoniabicyclo- (2,2,2) -octanesilicate.

The latter solution was used in the manufacture of the novel synthetic described above Zeolites used according to the example below.

Example 4

A solution of 3.45 g of sodium aluminate in 10 ml of water was placed in a mixing vessel. According to Example 3 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanedisilicate solution prepared was diluted to 122 ml total volume and quickly added to the aluminate solution.

The composition of the resulting reaction mixture, in terms of the oxides, was as follows:

5.9 mole percent Na ₂ O

45.0 mole percent 1,4 - dimethyl - 1,4 - diazonia-

bicyclo (2,2,2) octane oxide
4.0 mole percent Al ₂ O ₃

45.1 mole percent SiO ₂

A light gel formed immediately. The mixture was heated for 8 days at 95 to 10O ⁰ C, and Prpben were tested the mixture daily, to determine the degree of crystallization occurred. After 5 days, the degree of crystallinity did not appear to change any more.

The resulting solid crystalline product was collected on a filter, washed with water and purged with air at 350 ° C. A gray solid with the following sorption capacity was obtained:

water
Cyclohexane.
η-hexane ...

g sorted per 100 g sample

19.34

1.82

11.84

Analysis of the zeolite product showed the following composition:

Na ₂ O
Al ₂ O ₃
SiO ₂

Weight percent

7.0
24.2
67.3

Mole percent

7.7
16.1
76.2

normal 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanedihydrocyd solution was prepared. The mixture was 9 days uhd heated at 95 to 100 ⁰ C then dried as in Example 4. FIG.

Shares of the resulting product were flushed with air at 350 to 550 ⁰ C. The former treatment resulted in a gray material while the latter treatment resulted in a white product. The sorption capacity of this latter material was as follows:

g sorbed per 100 g sample

water
Cyclohexane.
η-hexane ...

20.6 0.9

12.7

The analysis of the zeolite product was as follows:

Weight percent mole percent Na ₂ O 7.7 8.3

Al ₂ O ₃ .
SiO ₂ .

24.5 67.5

16.1 75.6

X-ray diffraction analysis indicated that this material was zeolite ZK-5. '

Example

A solution of 3.45 g of sodium aluminate and 0.8 g of sodium hydroxide in 15 ml of water was in a Mixing vessel introduced.

9.2 g of silica gel were dissolved in 127 ml of a 3.59 μm solution of 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanedihydroxide dissolved. The solution thus obtained was with water to a total volume of 167 ml and added to the mixing vessel with stirring. A few milligrams of the example 5 produced zeolite product were added to the reaction mixture to allow crystallization to facilitate.

The composition of the resulting reac-. tion mixture, expressed in the form of the oxides, was as follows:

7.1 mole percent Na ₂ O
53.6 mole percent C ₈ H _la N ₂ O

3.2 mole percent Al ₂ O ₃
36.0 mole percent SiO ₂

The X-ray diffraction analysis showed the product to be highly crystalline and the X-ray powder diffraction pattern given in Table A above.

The novel zeolite having the above composition and X-ray diffraction pattern was named Zeolite ZK-5.

Example 5

It was carried out as a reaction in the same manner and with the same reactants in Example 4, except that the Disilicatlösung using 111 ml of a 2.74 The thus-prepared mixture was heated for 41 hours at 95 to 100 ⁰ C. The at the end of that time resulting solid product was collected on a Buchner funnel, washed with water and purged with air at 500 ⁰ C.

The sorbent capacity of the resulting white solid zeolite product was as follows:

g sorbed each

100 g sample

water

Cyclohexane.
η-hexane ...

22.95

1.41

12.92

Analysis of the zeolite product was as follows: weight percent mole percent

Na ₂ O 9.16 10.2

Al ₂ O ₃ 25.8 17.4

SiO ₂ 63.0 72.4

X-ray diffraction analysis indicated that this material was zeolite ZK-5.

209 618/29

The much shorter time required for crystallization compared to Examples 4 and 5, is believed to be attributable to the presence of added zeolite product at the start of the reaction.

Example 7

A reaction was carried out in the same manner and with the same reactants as in Example 5, except that it was operated on a 2.7 times scale as in the previous example. The reaction mixture obtained in this way was kept at 95 to 100 ^° C. for 8 days before the crystallization was complete.

The product was purged with air at 350 ° C. It possessed the following sorption abilities:

water

Cyclohexane
n-hexane ...

g sorbed each
100 g sample

20.66

1.44

13.80

The composition of this material identified by X-ray diffraction as zeolite ZK-5 was as follows:

Weight percent mole percent

SiO ₂ ... ·. · 70.3 77.8

'Examples

A solution of 4.4 g of sodium aluminate in 6 ml of water was placed in a mixing vessel. To this, 61 ml of a 2.35 normal 1,4-dimethyl-1,4-diazoniabicyclo- (2,2,2) -octanedihydroxide solution, in which 4.13 g of silicon dioxide gel had been dissolved, were added with stirring. The resulting mixture was heated at 95 to 100 ° C for 72 hours. The forming product was collected, washed and purged with air at 350 ⁰ C.

The zeolite product had the following sorption properties:

g sorbed each
100 g sample

23 96

1043

1230

The zeolite product had the following analysis:

Weight percent mole percent

■ yy _asser

Cvclohexane
n-hexane

⁴⁵

5 °

Al ₂ O ₃
SiO ₂

27.5
56.8

15.1
18.8
66.0

The sodium ions in zeolite ZK-5 can be replaced with ammonium ions and the latter thermally decomposed to give ammonia and a hydrogen or acid zeolite, as shown in the example below.
ν & β

Example 9

A sample of zeolite prepared according to Example 5

ίο ZK-5 was treated with concentrated ammonium hydroxide and then with 250 ml of a saturated ammonium chloride solution. The zeolite was then washed with water until it was free of chloride ions. The resulting material, after rinsing at 350 ^° C., contained 0.64 percent by weight Na ₂ O, compared with 7.7 percent by weight Na ₂ O in the original zeolite. The ¹ product had the following sorption properties:

²⁰ water

Cvclohexane

η-hexane

g sorbed each
100g sample

21.00

1 31

* 1200

^a 5 Part of this acid zeolite was moistened with water and rinsed at 350.degree. He owned the following

³ ° cyclohexane
n-hexane

1.61
13.62

The above sorption values show that zeolite ZK-5 is stable in the acid form in water.

The high catalytic activities achieved with aluminosilicate compositions made in accordance with the present invention are illustrated below in connection with the cracking of a typical hydrocarbon stock feed. In the examples given below, catalyst activity refers to a measure of the cracking activity of the aluminosilicate for n-hexane. In this test, the n-hexane conversion is in rate constant (rate constants) per unit volume of catalyst coll ^Ewan punched and measured against the activity of silica-alumina, which is normalized to a reference activity of 1.0 at 538 ° C. The catalyst activity of the aluminosilicate is then expressed as a multiple of this activity, ie the silica-alumina standard. The silica-alumina reference catalyst contains about 10 percent by weight Al ₂ O ₃ and the remainder

X-ray diffraction analysis showed this product to be a mixture of Zeolite X and Zeolite was ZK-5. The presence of zeolite X is not unexpected as the reaction is the following analysis

13 9 mole percent Na O

38 ^ 4 mole percent C ₈ H ₁₈ N ₂ O
9 4 mole percent Al O
384 mole percent SiO °

had a silica / alumina molar ratio of 4.1, which is consistent with the molar ratio present in reaction mixtures, which is for the manufacture of zeolite X can be used.

B e i s ρ i e 1 10

74.2 g of triethylenediamine [1,4-diazoniabicyclo- (2,2,2) -octane] were dissolved in 200 ml of absolute ethanol, and 205 g of methyl iodide were gradually added over ^{a period of 1½ to 2} hours while the mixture kept at about 0 ° C and stirred. An additional 10 g of methyl iodide was added, the mixture was refluxed for 0.5 to 1 hour and the excess methyl iodide and alcohol were evaporated.

The slurry was then cooled, filtered, with absolute Washed alcohol and filtered again. The solid was then hot in a minimal amount

Dissolve in water and add ethanol until precipitation started. The mix was let stand overnight, filtered and air dried and gently heated; 217 g of N, N'-dimethyltriethylenediammonium iodide were obtained receive.

217 g of N, N '- dimethyltriethylenediammonium iodide, 100 ml of water and silver oxide, which by reaction of 227 g of silver nitrate, dissolved in 21 water, with 56.8 g Sodium hydroxide, dissolved in 1.5 liters of water, was placed in a ball mill ίο and ground overnight.

After washing with water, filtering and evaporating part of the water at 100 mm Hg 270 ml of a 2.74 η solution of N, N'-dimethyltriethylenediammonium hydroxide receive. 15 *

The aforementioned Ν, Ν'-dimethyltriethylenediammonium hydroxide was diluted with water until a 2.35 η solution was obtained, and 443 ml of this solution was mixed with 31 g of silica gel. 355 ml of this mixture was then added to a 'solution of 9.3 g of NaAlO ₂ in 27 ml water, stirred for 2 minutes, then heated to 100 ⁰ C and held for 68 hours at this temperature under stirring. The mixture was then filtered, washed with 200 ml of water and then rinsed ^{with air at 350 and 500 ° C.} The resulting product is an aluminosilicate identified as ZK-5 and has a relative cracking activity for η-hexane of 1.4.

B e i s ρ i e 1 11

3 or 4 g of the crystalline aluminosilicate ZK-5, which had been prepared according to Example 10 and had a particle size of about 5 microns, were _{treated first with an unsaturated solution of NH 4} OH and then with 200 ml of hot, saturated NH ₄ Cl solution . The resulting product was washed with water until the drained liquid did not contain chloride ions, and then calcined. The resulting acid modified aluminosilicate had a relative cracking activity for η-hexane of 440 and gave the following analysis:

Mole percent

Na ₂ O 0.34

Al ₂ O ₃ 16.3

SiO ₂ 83.4

Example 12

2 g of the crystalline aluminosilicate ZK-5, which had been prepared according to Example 10 and one Particle size of about 5 microns was mixed with 200 ml of a 0.1 η HCl solution and then with 200 ml treated with a 1.0 η HCl solution. The product was then washed with water until it drained off Liquid did not contain chloride ions. The resulting acid modified aluminosilicate had. a relative cracking activity for η-hexane of 185 and gave the following analysis:

Mole percent

Na ₂ O ... 0.47

Al ₂ O ₃ 22.5

SiO ₂ 76.8

Claims (6)

Patent claims: 1. Process for the production of synthetic, crystalline zeolites by reacting a aqueous reaction mixture containing ammonium derivative, silicate, aluminate and alkali ions until the desired zeolite crystals are formed and these crystals are obtained, thereby characterized by expressing a reaction mixture of the following composition in molar ratios of oxides SiO ₂
Al ₂ O ₃ from about 2.5 to 15, H ₂ O 'Na ₂ O "+ C ₈ H ₁₈ N ₂ O"
from about 25 to 50, Na ₂ OT ₁ CsH ₁₈ N ₂ O
SiO ₂ " from about 1 to 2, wherein C ₈ H ₁₃ N ₂ O is derived from the N ₁ N'-dimethyltriethylenediammonium ion, at a temperature of about 20 to 120 ⁰ C until the crystals form and the resulting crystals at a temperature in the range heated from about 200 to 60O ⁰ C. 2. The method according to claim 1, characterized in that the reaction mixture is at at a temperature in the range of about 90 to 120 ° C. 3. The method of claim 1 or 2, characterized in that heating the separated crystals at a temperature of about 500 to 550 ⁰ C. 4. The method according to any one of claims 1 to 3, characterized in that the reaction mixture by reacting sodium aluminate and 1,4-dimethyl -1,4-diazoniabicyclo - [2,2,2] - octanesilicate produces in aqueous solution. 5. The method according to any one of claims 1 to 4, characterized in that the crystals with a gas containing hydrogen ions or ions convertible into hydrogen ions shaped or liquid medium until the zeolite has a metal content of below about 4.0 weight percent. 6. The method according to claim 5, characterized in that the out with hydrogen exchanged zeolite washes free of soluble anions and dries at a temperature in the range of voi heated about 204 to 815 ° C for a period of> 1 to 48 hours.