DK175290B1 - Novel synthetic porous crystalline material - used as adsorbent and catalyst for organic conversion reactions - Google Patents

Abstract

Synthetic porous crystalline material has equilibrium adsorption capacities of greater than 10 wt.% for water vapour, greater than 4.5 wt.% for cyclohexane vapour, and greater than 10 wt.% for n-hexane vapour, and is characterised by an X-ray diffraction pattern having at least the first two lines in the Table (I) pref. all the lines, and more pref. a number of further specified lines. (W = 0-20; M = 20-40; S = 40-60; VS = 60-100).

Description

DK 175290 B1 i

The present invention relates to a synthetic porous crystalline material, a process for its preparation, and its use in catalytic conversion of organic compounds.

5

It is known that naturally occurring and synthetic zeolites possess catalytic properties in connection with various hydrocarbon conversion reactions.

Certain zeolitic materials are ordered porous crystalline aluminosilicates with a well-defined crystal structure which can be determined by X-ray diffraction and which contain a large number of smaller voids which may be interconnected with a number of even smaller channels or pores. These cavities or pores are of uniform size for a particular zeolitic material. Since the dimensions of these pores are such that they allow access to adsorption molecules of certain dimensions, while not allowing access to larger-sized molecules, these materials have been referred to as "molecular sieves" and used in a variety of ways, where one takes advantage of these characteristics.

Such molecular sieves, both natural and synthetic, include a wide variety of crystalline silicates containing 25 positive ions. These silicates can be described as a rigid three-dimensional network of SiO 2 and oxides from - Group IIIA in the periodic system of the elements, e.g.

AlO 2, wherein the tetrahedrons are cross-linked by dividing J oxygen atoms, the ratio of the total amount of Group IIIA element, e.g. aluminum, and silicon and oxygen atoms are 1: 2. The electrovalence of the Group IIIA tetrahedron element, e.g. aluminum, is balanced by the presence of a cation in the crystal, e.g. an alkali metal or an alkaline earth metal cation. This can be expressed by the fact that for the group of element of Group IIIA, e.g. aluminum, and the number of different cations such as

I DK 175290 B1 I

I 2 I

In Ca / 2, Sr / 2, Na, K or Li, equals 1. A type of cation can be I

You are either completely or partially exchanged with another I

In type of cation using conventional ion exchange technique. IN

With such a cation exchange it is possible that I

5, the properties of a given silicate vary by appropriate I

In the choice of cation. IN

I The prior art includes manufacturing a wide variety of I

In synthetic zeolites. Many of these zeolites are denoted by I

In 10 letters or other appropriate symbols, e.g. IN

zeolite A, described in U.S. Patent No. 2,882,243, I

In zeolite X, described in U.S. Patent No. 2,882,244, I

In zeolite Y, disclosed in U.S. Patent No. 3,130,007, I

In zeolite ZK-5, described in U.S. Patent No. 3,247,195, I

In zeolite ZK-4, described in U.S. Patent No. 3,314,752, I

In zeolite ZSM-5, described in U.S. Patent No. 3,702,886, I

In zeolite ZSM-11, described in U.S. Patent No. 3,709,979, I

In zeolite ZSM-12, described in U.S. Patent No. 3,832,449, I

In zeolite ZSM-20, described in U.S. Patent No. 3,972,983, I

In zeolite ZSM-35, described in U.S. Patent No. 4,016,245, I

You and I

In zeolite ZSM-23, described in U.S. Patent No. 4,076,842

The SiO2 / Al ratio in a zeolite is often variable. IN

For example, in For example, zeolite X can be prepared with a SiO2 / Al2Og ratio I

I in the range 2-3; zeolite Y in the range of 3-6. In certain I

In zeolites, there is no upper limit for SiC 2 / A 2 O 2 ratio - I

one. For example, ZSM-5 is mentioned, where SiO2 / Al2O2 forms

the team is at least 5 and where the upper limit is only set

In 30 of the limitations of the known analytical techniques. In the US “I

U.S. Patent No. 3,941,871 (Re. 29,948) discloses an I

porous crystalline silicate prepared from a reaction

tions mixture, which does not include intentionally added I

In alumina and with the ZSM-5 zeolite characteristic I

In 35 x-ray diffraction pattern. In U.S. Patent No. 4,061 I

Crystalline I is described in 724, 4,073,865 and 4,104,294

In silicates with different alumina and metal contents. IN

3 DK 175290 B1

The invention relates to a synthetic porous crystalline material characterized by an X-ray diffraction pattern with values substantially as shown in Table I 5 of the present application and with equilibrium adsorption capacities greater than 10% by weight for water vapor, greater than 4.5% by weight for cyclohexane vapor and greater than 10% by weight for n-hexane vapor.

The porous crystalline material in question is apparently related to the "PSH-3" materials described in U.S. Patent No. 4,439,409. However, the crystalline material in question does not contain all the constituents contained in the PSH materials. In particular, it should be noted that the material of the invention does not contain impurities in the form of other crystal structures, such as ZSM-12 or ZSM-5, that it exhibits exceptional sorption capabilities and has exceptional utility as a catalyst in comparison with those of U.S. Pat. 439,409 made PSH-3 materials.

The crystalline material of this invention can be prepared by crystallizing a reaction mixture containing source materials for the necessary oxides as well as a hexethyleneimine control agent. However, it has been found, especially if the crystalline material of the invention is a silicate, that it is important to use a relatively high solid silica source material. 1 2 3 4 5 6

The invention thus also relates to a process for preparing the present synthetic crystalline 3 material, in which a reaction mixture 4 can be prepared which can produce the material by crystallisation, the reaction mixture containing sufficient 6 amounts of alkali or alkaline earth metal cations, a source material for tetravalent. YO2 oxide containing at least approx. 30% by weight solid YO2 source material for trivalent

I DK 175290 B1 I

I 4 I

In Χ20 ^ ox ^ 'water and hexamethylenimine, holding reaction I

In the mixture under sufficient crystallization conditions- I

In claims until crystals of the material are formed. IN

The crystalline material of this invention has a composite I

In theorem with the molar ratio: I

I x203: (n) Y02 I

In which X is a trivalent element such as aluminum, boron, I

In iron and / or gallium, preferably aluminum, Y is an I

In tetravalent element such as silicon and / or germanium, I

Preferably in silicon and n is at least 10, usually 10- I

150, preferably 10-60, especially 20-40. In its fresh preparation- I

In 15-membered form, the material has the following formula, on anhydrous I

In base and expressed by oxide moles per n mole of Y02: I

(0.005-0.1) Na 2 O: (1-4) R: X 2 O 3: nYO 2 I

In 20 where R is an organic component. The Na and R components I

associated with the material as a result of their presence

room during crystallization and easily removed by post-I

crystallization methods described in detail herein

In the following. IN

I 25 I

In the subject crystalline material, thermal I

In stable and large surface area (greater than 400 m2 / g)

I and unusually large sorption capacity compared to I

similar crystal structures. As can be seen from the above- I

In the final formula, the subject material I is prepared

In almost no content of Na cations. Therefore, you can

is used as a catalyst with acid activity without need I

In for a replacement step. However, the original I

In sodium cations in the freshly prepared material, in the I

To the extent desired and using known I

In techniques, at least partially replaced by I

In other cations by ion exchange. Speaking as preferred I

5 DK 175290 B1 replacement cations come metal ions, hydrogen ions, precursors for hydrogen ions, e.g. ammonium, as well as mixtures thereof. Particularly preferred are cations which adapt the catalytic activity in connection with certain hydrocarbon conversion reactions. Examples of this include hydrogen, rare earth and group IIA, IIIA, IVA, IB, IIB, HIB, IVB or VIII elements in the periodic system of the elements.

In its calcined form, the crystalline material of the present invention appears to consist of a single crystal phase with only few or no trace crystal phases based on impurities. The material further has an X-ray diffraction pattern that differs from the patterns of other known crystalline materials along the lines listed in Table I below:

TABLE I

Interplanar d distance Relative intensity (A) I / I x 100 o 30.0 ± 2.2 weak means 22.1 ± 1.3 weak 1, preferably along the lines given in Table II below:

I DK 175290 B1 I

i 6 I

I TABLE II

In Interplanar d distance Relative intensity I

I 5 (A) l / lQ x 100 I

In 30.0 ± 2.2 weak agent I

In 22.1 ± 1.3 weak I

In 3.91 ± 0.07 medium-very strong. IN

I 10 I

In particular, by the lines listed in Table III below:

I TABLE III

15 Interplanar d distance Relative intensity I

I (Å) I / Io x 100 I

30.0 ± 2.2 weak agent! IN

In 22.1 ± 1.3 weak I

6.00 ± 0.10 weak agent I

In 4.06 ± 0.07 weak-strong I

3.91 ± 0.07 medium-very strong I

I The calcined crystalline material of the prior art

In the present invention, in particular, an X-ray diffraction I

In pattern with the lines given in Table IV below:

I 30 I

I 35 I

7 DK 175290 B1

TABLE IV

Interplanar D Distance Relative Intensity (Å) I / I x 100 5 _ _ 30.0 ± 2.2 Weak 22.1 ± 1.3 Weak 12.36 ± 0.2 Medium-Very Strong 10 11.03 ± 0.2 medium-strong 8.83 ± 0.14 medium-very strong 6.86 ± 0.14 weak-medium 6.18 ± 0.12 medium-very strong 6.00 ± 0.10 weak-medium 5.54+ 0.10 Weak 4.92 ± 0.09 Weak 4.64 ± 0.08 Weak 4.41 ± 0.08 Weak 4.25 ± 0.08 Weak 4.10 ± 0.07 Weak strong 4.06 ± 0.07 weak-strong 3.91 ± 0.07 medium-very strong 3.75 ± 0.06 weak-medium 3.56 ± 0.06 weak-medium 3.42 ± 0.06 very strong 3.30 ± 0.05 weak agent. 3.20 ± 0.05 weak 3.14 ± 0.05 weak 3.07 ± 0.05 weak 2.99 ± 0.05 weak 2.82 ± 0.05 weak 2.78 ± 0.05 weak 2.68 ± 0.05 weak 2.59 ± 0.05 weak

These values were determined by standard techniques. The radiation was copper K-α doubled and dif 35 was used

I DK 175290 B1 I

I I

In a fractometer with scintillation counter and a connected I

In computer. The peak heights, I, and the positions of the peaks out- I

In printed in degrees 2 theta, where theta is the Bragg angle, you became

I determined using algorithms on the one with dif- I

In the 5 fractometer connected computer. From this they were determined

In relative intensities, 100 I / IQ, where you denote I

In the intensity of the strongest line or peak, and the I

At interplanar distance, d, in Angstom units (Å), corresponding I

In to the measured lines. The relative intensities are in Table I

I 10 I-IV expressed by the symbols very weak, medium, strong and I

In very strong, and generally in the intervals:

In weak 0-20 I

Mean = 20-40 I

In 15 strong = 40-60 I

In very strong = 60-100 I

It should be noted that this X-ray diffraction pattern is I

Characteristic of all species of the present invention

In 20 crystalline material. The sodium form and certain other I

In cationic forms, practically the same pattern I exhibits

With certain minor shifts in interplanar spacing and variation

In relative intensity tions. Others may occur

In variations depending on the particular sample's X / Y-, e.g. IN

In 25 silicon / aluminum ratios and the material's thermal I

In treatment. IN

The crystalline material of this invention can be prepared

I from a reaction mixture containing source materials I

I for alkali or alkaline earth metal cations (M), e.g. IN

In sodium or potassium cations, an oxide of a trivalent I

In element X, e.g. aluminum, an oxide of a tetravalent I

In element Y, e.g. silicon, an organic control agent I

I (R), which is described in the following, as well as water,

In the reaction mixture having a composition which I

In terms of oxide molar ratio, falls within the following I

At intervals: I

9 DK 175290 B1

Reactants Applicable Preferred Y02 / X203 10-80 10-60 5 H2O / Y02 5-100 10-50 oh "/ yo2 0.01-1.0 0.1-0.5 m / yo2 0.01-2.0 0.1-1.0 R / Y0 0.05-1.0 0.1-0.5 10

It has been found that crystallization of the subject material is favored if the source material for Y02 contains at least 30% by weight of solid Y02, especially if Y02 is silica. Speaking as suitable commercially available 15 source materials for silica, Ultrasil (a precipitated, spray-dried silica containing about 90% by weight of silica) and HiSil (a precipitated hydrated SiO2 material containing about 87% by weight of silica, about 6% by weight) are available. % free H2 O and approx.

4.5 wt% bonded hydration H 2 O and having a particle size of approx. 0.02 in). If another source material is used for silica, e.g. Q-Brand (a sodium silicate consisting of about 28.8 wt% SiO 2, 8.9 wt% Na 2 O and 62.3 wt% H 2 O) provides only little or none of the present material by crystallization. Instead, impurity phases are formed by other crystal structures, e.g. Therefore, the ZSM-12.YO2 source material preferably contains at least 30% by weight solid YO2, preferably silica, especially at least 40% by weight solid YO2.

The organic control agent (R) used for synthesizing the crystalline material used in the above reaction mixture is hexamethylenimine having the following structural formula:

I DK 175290 B1 I

I 10 I

island

I H I

In the crystallization of the crystalline I in question

I material can be carried out under static conditions I

In or while stirring in a suitable reaction vessel such as I

eg. polypropylene containers, or in teflon lined auto- I

In piano or stainless steel autoclaves. Crystallization I

You are generally carried out at a temperature in the range of 80-1

At 225 DEG C. for a period of time between ca. 24 h and 60 d. Then I

In, the crystals are separated from the liquid and recovered. IN

Crystallization is promoted by the presence of at least I

In 0.01%, preferably 0.10%, especially 1% seed crystals I

20 (based on the total weight) of the desired crystalline I

In product. IN

Before being used as a catalyst or adsorbent I

In the medium, the freshly prepared crystalline I

In material is calcined to remove part of or I

In all the organic constituents. IN

In the crystalline material of the invention, you can

I is used as a catalyst in intimate combination with an I

In hydrogenation component such as tungsten, vanadium, I

In molybdenum, rhenium, nickel, cobalt, chromium, manganese or an I

In precious metal, e.g. platinum or palladium, where to

In, a hydrogenation dehydrogenation function is performed. So- I

Such components can be introduced into the material at the same time

In crystallization, base exchange into the material, impregnated

Thus, into or into intimate physical mixing thus. And I

Such component may be impregnated into or onto the material

11 DK 175290 B1 in the case of platinum, e.g. by treating the silicate with a solution containing a platinum-metal-containing ion. Thus, speaking as suitable platinum compounds comes chloroplatinic acid, platinum chloride as well as various compounds containing platinum-amine complexes.

The crystalline material in question can be made with widely different particle sizes. In general, the particles may be present as a powder, a granule or a shaped product, e.g. an extrudate. In the latter case, the crystalline material can be extruded before drying or partially dried and then extruded.

Whether the present material is used as an adsorbent or as a catalyst in a process for the conversion of organic compounds, it should be dehydrated at least partially. Dehydration can be carried out by heating to a temperature in the range 200-595 ° 0 in an atmosphere such as air, nitrogen, etc., and at atmospheric, subatmospheric or superatmospheric pressure for between 30 minutes and 48 hours. The dehydration can also be carried out at room temperature simply placing the silicate in a vacuum, but in that case longer time is required to provide a suitable degree of dehydration.

The crystalline material of this invention can be used as a catalyst in a wide variety of organic conversion processes, e.g. hydration of hydrogen nerf such as propylene for alcohols and ethers under reaction conditions comprising a temperature in the range 50-300 ° C, preferably 90-250 ° C, pressure of at least 5 kg / cm 2, preferably at least 20 kg / cm 2, and a water / olefin mole ratio in the range of 0.1-30, preferably 0.2-15.

As with many catalysts, it may be desirable to incorporate the present crystal.

I DK 175290 B1 I

I 12 I

In linseed material with another material which is resistant I

For temperature and other operating conditions used

You know about various organic transformation processes. Such you

In materials include active and inactive materials and I

In 5 synthetic or naturally occurring zeolites and I

In inorganic materials such as clays, silica and / or I

In metal oxides, e.g. alumina. The latter can either be I

In naturally occurring or in the form of gelatin I

spoon precipitates or gels containing mixtures of I

In 10 silica and metal oxides. Use of an active material

together with the new crystalline material, i.e. IN

In combination with this or present during manufacture I

I of this may change the conversion and / or selectivity

In the density of the catalyst by certain organic conversion I

In 15 processes. Inactive materials suitably serve as I

In diluents for controlling the rate of conversion at I

In a given process so that the products can be manufactured

You financially without the use of any other means

In regulating the rate of reaction. The materials you can

I 20 is incorporated into naturally occurring clays, e.g. IN

In bentonite and kaolin, to increase the catalyst I

crushing strength under commercial operating conditions. IN

In these materials, i.e. clays, oxides, etc., I

You act as binders to the catalyst. It is your wish

To prepare a catalyst with good crushing I

In strength, because it is desirable for commercial use

In preventing the catalyst from breaking down into an I

In powder-like material. You have these clay binders

I have usually only been used to increase crushing I

In the strength of the catalyst. IN

As an example of naturally occurring clay types that you can

In combination with the new crystal, you can mention montmorillo- I

In the nit and kaolin families. These families include sub- I

In 35 bentonites and kaolins known under the designations I

In Dixie, McNamee, Georgia and Florida clays, as well as I

In others wherein the major mineral constituent is halloysite, I

DK 175290 B1 13 kaolinite, dickite, nacrit or anauxite. Such clay types can be used in raw, untreated condition or after calcination, acid treatment or chemical modification. In addition, to speak as binders which can be conveniently combined with the crystal in question, inorganic oxides, especially alumina, come.

In addition to the aforementioned materials, the present crystal can be composed with a porous matrix material such as silica alumina, silica magnesium oxide, silica zirconia, silica thorium oxide, silica beryllium oxide, silica titanium oxide, and ternary compounds such as silica alumina oxide. silica-alumina-zirconia, silica-alumina-magnesium oxide, and silica-magnesium-zirconia.

The relative ratios of finely divided crystalline material to inorganic oxide gel matrix may vary within wide limits, with the crystal content ranging from 1 to 90% by weight. The ratio is usually in the range of 2 to 80% by weight, especially in the manufacture of balls.

In the following, the invention is further illustrated by a number of examples with reference to the drawing, in which Figures 1-5 show X-ray diffraction patterns of the calcined product mentioned in Examples 1, 3, 4, 5 and 9 respectively. The sorption data set forth in these examples, which are included for comparison of the sorption capacities of water, cyclohexane and / or n-hexane, are equilibrium adsorption values determined as follows:

A weighed sample of the calcined adsorbent was contacted with pure vapors of the desired adsorbate in an adsorption chamber evacuated to less than 1 mm, the adsorbent being contacted with 12 Torr water vapor and 40 Torr n-hexane or cyclohexane vapor, at pressures that were

I DK 175290 B1 I

I 14 I

At less than the liquid / vapor weight pressure of the particular I adsorbate at 90 ° C. The pressure was kept constant (within I about ± 0.5 mm) by the addition of adsorbate vapor regulated II with a manostat during the adsorption period not exceeding 8 h. When the new crystal adsorbed the adsorbate II, the pressure drop caused that the monostat opened a valve, II which added more adsorbate vapor to the chamber, so that II the above-mentioned control pressure was restored. The sorption I I was completed when the pressure change was not sufficient for I I 10 to activate the monostat. The weight gain was calculated and I I used as a measure of the adsorption capacity of I samples expressed in g / 100 g of calcined adsorbent. The present II synthetic material always has equilibrium adsorption values greater than 10% by weight for water vapor, greater than II 4.5% by weight, usually greater than 7% by weight for cyclo-II hexane vapor, and greater than 10% by weight for n-hexane vapor. IN

EXAMPLE 1 12.86 g of sodium aluminate (43.5% Al₂O₂, 32.2% Na₂O, -25.6% H₂O) were dissolved in a solution containing 12.8 g of 50% NaOH solution and 1320 g H2 O. To this was added 57.6 g of hexamethylenimine. The resulting solution was added to 109.4 g of Ultrasil, a precipitated spray-dried silica material (about 90% SiO 2).

The reaction mixture had the following composition, expressed in molar ratio:

SiO2 / Al2O3 = 30.0 OH / SiO2 = 0.18 H2O / SiO2 = 44.9

Na / SiO 2 = 0.18 R / SiO 2 = 0.35 where R is hexamethylenimine.

The mixture was crystallized in a stainless steel reactor with stirring at 150 ° C for 7 d. The crystalline product was filtered, washed with water and dried at 120 ° C.

After calcination for 20 hours at 538 ° C, the X-ray diffraction pattern had the main lines shown in Table V. Figure 1 25 shows the X-ray diffraction pattern of the calcined product. The sorption capacities of the calcined material were also measured, yielding the following results: H 2 O (12 Torr) 15.2 wt% Cyclohexane (40 Torr) 14.6 wt% n-hexane (40 Torr) 16.7 wt%

The surface area of the calcined crystalline material was measured at 494 m 2 / g.

The chemical composition of the calcined material was found to be as follows:

I DK 175290 B1 I

I 16 I

I Component Weight% I

In SiO 2 66.9 I

I A12 ° 3 5/40 I

In Na 0.03

N, 2.27

I Ash 76.3 I

In SiO ^ A ^ O ^, molar ratio = 21.1 I

I TABLE V I

I I

In Grades 2 Theta Interplanar D-Distance (Å) I / II

I 2.80 31.55 25 I

I 4.02 21.98 10 I

I 15 7.10 12.45 96 I

I 7.95 11.12 47 I

I 10.00 8.85 51

I 12.90 6.86 11 I

I 14.34 6.18 42 I

I 20 1 4.72 6.02 1 5 I

I 15.90 5.57 20 I

I 17.81 4.98 5 I

I 19.08 4.65 2 I

I 20.20 4.40 20 I

I 25 20, 9 1 4.25 5 I

I 21.59 4.12 20 I

I 21.92 4.06 13 I

I 22.67 3.92 30 I

I 23.70 3.75 13 I

I 30 2 5.01 3.5 6 20 I

I 26.00 3.43 100 I

26.96 3.31 14 I

27.75 3.21 I

I 28.52 3.13 10 I

35 29.01 3.08 5 I

29.71 3.01 5 I

31.61 2.830 5 I

17 DK 175290 B1 32.21 2.779 5 33.35 2.687 5 34.61 2.592 ..5 EXAMPLE 2

An amount of the crystalline product calcined in Example 1 was tested with the alpha test and the alpha value determined at 224.

EXAMPLES 3-5

Three separate synthesis reaction mixtures were prepared with the compositions listed in Table VI. The mixtures were prepared with sodium aluminate, sodium hydroxide, ultrasil, hexamethylenimine (R) and water. The mixtures were kept at 150 ° C, 143 ° C and 150 ° C, for 7, 8 and 6 d, respectively, in a stainless steel autoclave which was stirred (350 rpm) under autogenous pressure.

The solids were separated from the unreacted ingredients by filtration and then washed with water followed by drying at 120 ° C. The product crystals were analyzed by X-ray diffraction, sorption, surface area and chemical analysis. The products were found to be the new crystalline material in question. The results of sorption, surface area and chemical analysis are also shown in Table VI. The x-ray diffraction patterns of the products calcined in Examples 3, 4 and 5 (538 ° C for 3 hours) are shown in Figures 2, 3 and 4. The sorption and surface measurements, respectively, were made on the calcined product.

35

I DK 175290 B1 I

I 18 I

I TABLE VI

In Example # 3 4..5 I

I 5 Synthesis mixture, molar ratio I

In SiO2 / Al2 O3 30.0 30.0 30.0 I

I OH / S102 0.18 0.18 0.18 I

I H2O / S102 19.4 19.4 44.9 I

I Na / S102 0.18 0.18 0.18 I

I 10 R / S102 0.35 0.35 0.35 I

In Product Composition, weight% I

I S102 64.3 68.5 74.5 I

I A12 ° 3 4.85 5.58 4'87 I

I Na 0.08 0.05 0.01 I

I N 2.40 2.33 2.12 I

I Ash 77.1 77.3 78.2 I

In SiO 2 / Al 2 O 3, molar ratio 22.5 20.9 26.0 I

In Adsorption, wt% I

In H2 O 14.9 13.6 14.6 I

In Cyclohexane 12.5 12.2 13.6 I

I n-hexane 14.6 16.2 19.0 I

I Surface area, m2 / g 481 492 487 I

In Example 6 I

Amounts of the calcined in Examples 3, 4 and 5 (538 ° C in 3 L

For 30 h) crystalline silicate products were tested with alpha-I

In the test and had alpha values of 227, 180 and I respectively

In 187. I

EXAMPLE 7 I

I 35 I

A calcined sample of the crystalline silicate of I

In Example 4, impregnated with Pt (NH 2) 4Cl 2 solution to I

19 DK 175290 B1 approx. 1 wt% Pt. This material was then heated in air at 349 ° C for 3 hours.

EXAMPLE 8 5 g of the final product of Example 7 was introduced as a catalyst in a small preheater reactor and thermocouple. The catalyst was then heated at 482 ° C in flowing hydrogen to reduce the Pt component. Normal decane and hydrogen were introduced over the catalyst to obtain a weight-based space velocity of 0.4 h -1 in decane and a hydrogen / hydrocarbon mole ratio of 100/1. The reaction was carried out in the temperature range 130-250 ° C under atmospheric pressure.

15

The results of this experiment are summarized in Table VII together with the results of the same experiment, with the exception that the crystalline materials were ZSM-5 (U.S. Patent No. 3,702,886), ZSM-11 (U.S. Patent No. 20,709 979) and Zeolit Beta (U.S. Patent No. 3,308,069), which are included for purposes of comparison. It is seen that the crystalline silicate of this invention is a very active catalyst in the hydron formation of n-decane and exhibits good isomerization activity. In Table VII, the 25 "5MN / 2MN" indicates the 5-methylnonane / 2-methylnonane molar ratio. Due to the position of the methyl group, 5-methylnonane provides slightly greater steric resistance upon introduction into the pores of zeolites. The 5NM / 2MN ratio provides information on the porosity of the zeolite tested.

30 35

I DK 175290 B1 I

I 20 I

In Table VII

In SiO 2 / Al 2 O 3% isom. 5MN / 2MN I

In Catalytic Ratio Temp. (° C) v. 50% 5% 20% I

In 5 sator-zeolite at 50% conversion. Isom. IN

In zeolite conversion I

In Ex. 7 20.9 174 70 0.15 0.24 I

I ZSM-5 50 187 65 0.11 0.15 I

I 10 ZSM-11 40 187 94 0.36 0.41 I

I ZSM-23 85 211 90 0.27 0.28 I

I Beta 30 189 76 0.68 0.59 I

EXAMPLE 9 I

I To illustrate a greater preparation of this I

In crystalline material traded 1200 g of hexa- I

In methylenimine added to a solution containing 268 g of I

In 20 sodium aluminate, 267 g of 50% NaOH solution and 11 800 g of I

In H2 ° 280 280 Ultrasil silica was added to the combi

In the dissolved solution. The mixture was crystallized under 1

In stirring (about 200 rpm) at 145 ° C in a 5 gallon I

In reactor. The crystallization time was 59 hours. The product was I

In 25 washed with water and dried at 120 ° C. IN

In the X-ray diffraction of the calcined (538 ° C) product crystals

Figure 5 shows a pattern showing that the product is I

In the crystalline material in question. Analysis of I

In the chemical composition of the product, surface area and I

In adsorption gave the following result:

I 35 I

21 DK 175290 B1

TABLE VIII

Product Composition C 12.1 wt% 5 N 1.98 wt%

Na 640 ppm Al2 O3 5.0 wt%

SiO2 74.9% by weight

SiO2 / Al2O3, molar ratio 25.4 10

Adsorption,% by weight

Cyclohexane 9.1 n-hexane 14.9 H2 O 16.8

Surface area, m * / g 479 EXAMPLE 10 20 An amount of 25 g of the solid crystal product of Example 9 was calcined in a flowing nitrogen atmosphere at 538 ° C for 5 hours, followed by purification with 5% oxygen gas (in N2) for an additional 16 h at 538 ° C.

25 Samples of each 3 g of the calcined material were each ion exchanged with 100 ml of 0.1N TEABr, TPABr and LaClg solution. Each exchange was carried out at ambient temperature for 24 hours and repeated 3 times. The exchanged samples were collected by filtration, washed with water until they contained no halide and then dried. The compositions of the yielded samples are shown in the table below, which shows the yielding capacity of the crystalline silicate in connection with various ions.

Yarns TEA TPA LA

35

I DK 175290 B1 I

I 22 I

In Ion Compositions,% by weight%

I Na 0.095 0.089 0.063 I

I N 0.30 0.38 0.03 I

C 2.89 3.63

I 5 La 1.04 I

In Example 11 I

In the above La yielded sample, size was adjusted I

In 10 to 14-25 mesh and then calcined in air at 538 ° C for 3 L

The h. The calcined material had an alpha value of 173. I

In Example 12 I

The sample calcined in Example 11 of the La yield I

In material was subjected to vigorous steam treatment at I

649 ° C in 100% steam for 2 hours. The steam treated sample had I

H has an alpha value of 22, which shows that its crystalline I

silicate showed very good stability under high hydro

In 20 thermal treatment. IN

EXAMPLE 13

I For the preparation of the crystal with X contained i

25 containing boron, an amount of 17.5 g of boric acid was added to 1

a solution containing 6.75 g of 45% KOH solution and 290 l

g H2 O. To this was added 57.8 g of Ultrasil silica, and I

The mixture was thoroughly homogenized. An amount of 26.2 l

g of hexamethylenimine was added to the mixture.

I 30

The reaction mixture had the following composition expressed in molar ratios: B1

SiO2 / B203 = 6.1 OH / SiO2 = 0.06 H2O / SiO2 = 19.0 K / SiO2 = 0.06 R / SiO2 = 0.30 where R is hexamethylenimine.

The mixture was crystallized in a stainless steel reactor 10 with stirring at 150 ° C for 8 d. The crystalline product was filtered, washed with water and dried at 120 ° C. An amount of the product was calcined for 6 hours at 540 ° C and the sorption capacities were determined as follows: 15 H2 O (12 Torr) 11.7 wt%

Cyclohexane (40 Torr) 7.5% by weight n-hexane (40 Torr) 11.4% by weight

The surface area 20 of the calcined crystalline material was measured at 405 m 2 / g.

The chemical composition of the calcined material was determined and found to be:.

N 1.94 wt% Na 175 ppm K 0.60 wt%

Drill 1.04 wt% A1203 920 ppm

SiO2 75.9 wt% Ash Ash 74.11 wt%

SiO2 / Al2O3, molar ratio = 1406

SiO2 / (A1 + B) 203, molar ratio = 25.8 35

I DK 175290 B1 I

I 24 I

EXAMPLE 14 I

An amount of the crystalline I calcined in Example 13

In product was treated with NH 4 Cl and recalculated again

In 5 crystalline final product was tested with the alpha test and I

In its alpha value was determined to 1. I

In Example 15 I

I 10 For the preparation of the subject crystalline

In material where X contains boron, an amount of 35.0 I was obtained

In g of boric acid added to a solution of 15.7 g of 50% NaOH-I

In solution and 1160 g of H2 O. To this solution was added I

In 240 g HiSil silica followed by 105 g hexamethylenimine. IN

In the reaction mixture, the following composition had expressed I

I in mole ratio: I

In SiO 2 / B2 ° 3 = 12.3 I

I OH / SiO 2 = 0.056 I

I H 2 O / SiO 2 = 18.6 I

I Na / SiO 2 = 0.056 I

I R / SiO 2 = 0.30 I

In which R is hexamethylenimine. IN

I 25 I

The mixture was crystallized in a stainless steel reactor I

With stirring at 300 ° C for 9 days. The crystalline product I

I was filtered, washed with water and dried at 120 ° C. The ten

In the sorption capacity of calcined materials (6 hours at 540 ° C)

In 30 testers were measured for:

In H 2 O (12 Torr) 14.4% by weight I

In Cyclohexane (40 Torr) 4.6% by weight I

In n-hexane (40 Torr) 14.0% by weight I

I 35 I

DK 175290 B1 25

The surface area of the calcined crystalline material was measured at 438 m 2 / g.

The chemical composition of the calcined material was determined to:

Component Weight% N 2.48

Na 0.06 Boron 0.83 Al2 O3 0.50

SiO2 73.4

SiC> 2 / Al2 O3, molar ratio = 249 SiO2 / (Al + B) 203, molar ratio = 28.2 EXAMPLE 16 20 An amount of the crystalline product calcined in Example 15 was tested with the alpha test and its alpha value was determined at 5.

EXAMPLE 17

To demonstrate the importance of using a silica source material containing at least 30% solid silica in the present process, Example 3 was repeated but using Q-Brand sodium silicate 30 (containing only about 29% by weight solid silica) as source material for silica. In this example, 67.6 g of aluminum sulfate was dissolved in a solution of 38.1 g of H2 SO4 (96.1%) and 400 g of water. The resulting solution was mixed with 120 g of hexamethylenimine and added to a mixture of 712.5 g of Q-Brand sodium silicate (28.8% SiO2 and 8.9% Na2O) as well as 351 g of water. The resulting mixture having the following composition, expressed in molar ratio:

I DK 175290 B1 I

I 26 I

I SiO2 / Al2 O3 = 30.0 I

I 0.H "/ SiO2 = 0.18 I

I H 2 O / Si O 2 = 19.4 I

I Na / SiO 2 = 0.60 I

I R / SiO 2 = 0.35 I

You were thoroughly mixed and crystallized with stirring in I

In a stainless steel reactor at 246 ° C for 8 d

The 10 ferns were separated from unreacted components at 1

filtration, then washed with water followed by I

In drying at 120 ° C. The product was analyzed by X-ray

In diffraction and was determined as a mixture of amorphous I

In material, magadiite and mordenite. No one was there

15 crystals of the subject material I

In Example 18 I

In this example, the subject crystalline I

In 20 materials propylene hydration properties compared I

I with the same properties of that of Example 4 of US I

In U.S. Patent No. 4,439,409, ZSM-12 and PSH-3- I prepared

In material. IN

The crystalline material of the present invention

invention was prepared by the addition of 15.9% by weight

In parts hexamethylenimine to a mixture containing 3.5 L

In parts 50% NaOH, 3.5 parts sodium aluminate, 30.1 parts I

In Ultrasil VN3 silica and 156 parts deionized H2 O. React I

The reaction mixture was immediately warmed to 143 ° C and stirred 1

I in an autoclave at this temperature to induce I

In crystallization. After obtaining complete crystallinity I

the resulting crystals were separated from the residue

The liquid was filtered and then washed with I

In 35 water and dried. A quantity of the crystals was combined

I with alumina to form a mixture of 65 parts by weight I

In zeolite and 35 parts by weight of alumina. Water was added to 1

B1 this mixture in an amount sufficient; that the resulting catalyst material could be formed into extrudates. The catalyst was activated by calcination in nitrogen at 540 ° C, followed by exchange with aqueous 5 1.0N ammonium nitrate and calcination in air at 540-650 ° C.

Zeolite ZSM-12 was prepared by adding 1 part by weight of ZSM-12 graft material to a mixture containing 41.5 parts of Hi-Sil 233 silica, 67.7 parts of 50% tetraethyl-10 ammonium bromide, 7.0 parts of 50% NaOH and 165, 4 parts deionized H ^ O. The reaction mixture was immediately warmed to 138 ° C and stirred in an autoclave at this temperature to obtain crystal formation. After obtaining complete crystal formation, the resulting crystals were separated from remaining liquid by filtration, then washed with water and dried. An amount of the crystals was combined with alumina to form a mixture of 65 parts by weight of zeolite and 35 parts by weight of alumina. Water was added to this mixture 20 in an amount sufficient to allow the resulting catalyst material to be formed into extrudates. The catalyst was activated by calcination in nitrogen at 540 ° C. followed by exchange with aqueous 1.0N ammonium nitrate and calcination at 650 ° C.

25

Propylene hydration was carried out at a temperature of 166 ° C, a pressure of 7000 kPa and a weight-based room rate per hour of 0.6 for propylene. The results after 2 steam treatment are compared in Table 30 IX below.

35

I DK 175290 B1 I

I 28 I

I TABLE IX

I Material according to I

In the PSH-3 invention ZSM-12 I

In 5% propylene conversion 1.9 27.8 10.8 I

In% water conversion 5.7 33.7 8.1 I

In IPA selectivity 88.7 76.7 74.6 I

I DIPE Selectivity 2.9 22.3 23.1 I

In Oligomer selectivity 8.4 1.2 2.3 I

I 10 I

I IPA = isopropyl alcohol DIPE = diisopropyl ether I

The above results clearly show the subject I

In the advantageous properties of materials in comparison with I

In both PSH-3 and ZSM-12 for a higher conversion

In degree of formation while having good selectivity for diiso-I

In propyl benzene and low production of propylene oligomers. IN

I 20 I

I 25 I

I 30 i

I 35 I

Claims (12)

29 DK 175290 B1 1. Synthetic porous crystalline material, characterized in that it has an X-ray diffraction pattern in the main with the following values Interplanar d-distance Relative intensity (A) I / IQ x 100 10 , 3 weak and equilibrium adsorption capacities greater than 10% by weight for water vapor, greater than 4.5% by weight for cyclohexane vapor and greater than 10% by weight for n-hexane vapor. Synthetic porous crystalline material according to claim 1, characterized in that it has an X-ray diffraction pattern substantially with the following values Interplanar d distance Relative intensity (A) I / IQ x 100 30.0 ± 2.2 weak mean 22.1 ± 1.3 weak 3.91 ± 0.07 medium-very strong Synthetic porous crystalline material according to claim 30 1, characterized in that it has an X-ray diffraction pattern in the main with the following values 35 I Interplanar d-distance Relative intensity II (A) 1/1 X 100.. II 5 30.0 ± 2.2 Weak II II 22.1 ± 1.3 Weak II 6.00 ± 0.10 Weak II II 4.06 ± 0.07 Weak-Strong II 3.91 ± 0, 07 medium-very strong II 10 I Synthetic porous crystalline material according to claim II 1, characterized in that it has an X-ray diffraction pattern substantially with the following values II 15 Interplanar d distance Relative intensity II (A) I / Iq x 100 II 30.0 ± 2 , 2 weak-medium II 20 22.1 ± 1.3 weak II 12.36 ± 0.2 medium-very strong II 11.03 ± 0.2 medium-strong II 8.83 ± 0.14 medium-very strong . II 6.86 ± 0.14 weak agent II 6.18 ± 0.12 medium-very strong II 6.00 ± 0.10 weak agent II 5.54 ± 0.10 weak agent II 4.92 ± 0.09 weak II 4.64 ± 0.08 weak II 30 4.41 ± 0.08 weak medium II 4.25 ± 0.08 weak II 4.10 ± 0.07 weak-strong II 4.06 ± 0.07 weak-strong II 3.91 ± 0.07 medium-very strong II 35 3.75 ± 0.06 weak-medium II 3.56 ± 0.06 weak-medium II 3.42 ± 0.06 very strong I DK 175290 B1 31 3.30 ± 0.05 weak average 3.20 ± 0.05 weak average 3.14 ± 0.05 weak average 3.07 ± 0.05 weak 5 2.99 ± 0.05 weak 2.82 ± 0.05 weak 2.78 ± 0.05 weak 2.68 ± 0.05 weak 2.59 ± 0.05 weak 10 Crystalline material according to any one of the preceding claims, characterized in that it has a composition comprising the molar ratio X203: (n) YO2 where n is at least 10, X is a trivalent element and Y is a tetravalent element. Crystalline material according to claim 5, characterized in that X comprises aluminum and Y comprises silicon. Crystalline material according to claim 6, characterized in that n is from 20 to 40. A process for preparing the synthetic crystalline material according to claim 5, characterized in that a reaction mixture is prepared which, by crystallisation, can produce the material, the reaction mixture containing sufficient amounts of alkali or alkaline earth metal cations, a source material for tetravalent Y-oxide containing at least 30% by weight of solid YO2, a source material for trivalent X-oxide, water and hexamethyleneimine, until crystals of the material are formed. DK 175290 B1 I 32 I Process according to claim 8, characterized in that the reaction mixture has a composition which, in terms of mole ratios, falls within the ranges: I Y02 / X203 = 10-80 I H20 / Y02 = 5-100 I oh "/ yo2 = 0.01-1.0 IM / YO2 = 0.01-2.0 IR / YO2 = 0.05-1.0 I where R is hexamethylenimine and M is alkali or soil I alkali metal. Process according to claim 8, characterized in that the reaction mixture has a composition which, in terms of mole ratio, falls within the ranges: I Y02 / X203 , 1-0.5 I m / yo2 = 0.1-1.0 IR / Y02 = 0.1-0.5 I It is hereby declared that this specification and claim I correspond to the original description for PCT / US88 / 04251 . IN