PL165909B1 - Synthetic porous crystalline material and method of obtaining same - Google Patents

Abstract

Synthetic, porous crystalline material with the composition determined by the molar relationship Χ2Ο3: (n) YO2, in which n is at least 10, X is a trivalent root and Y is a root tetravalent, characterized by that has the X-ray diffraction distribution for the distance interplanar d corresponding to the relative I / Io intensity shown in the following table: PL 165909 Β1 Interplanar distance d (1 10 "1 nm) Relative intensity I / Io x 100 30.0 ± 2.2 W-M 22.1 + 1.3 watts where I is the intensity of the altitude peaks, and Io is the strength of the strongest line or peak intensity, the relative intensity W is weak, and M is the mean intensity.

Description

The invention relates to a synthetic, porous, crystalline material useful in the catalytic conversion of organic compounds.

Zeolite materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion. Certain zeolite materials, such as porous crystalline aluminosilicates, have a specific crystal structure as determined by X-ray diffraction, where there are a large number of small cavities that can be connected through a number of even smaller channels or pores. These cavities and pores are of equal size in a given zeolite material. Since the dimensions of these pores are such that they allow the adsorption of molecules of a certain size but would not be able to adsorb them for larger sized molecules, these materials have become known as molecular sieves and are used in many ways to take advantage of these properties.

Such molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline silicates. These silicates can be described as a rigid, three-dimensional skeleton structure with SiOa and an oxide of an element belonging to group IIIA of the periodic table, e.g. AlOa, where tetrahedra are interconnected by common oxygen atoms, with the ratio of an element belonging to group IIIA, e.g. aluminum , together with silicon atoms to oxygen atoms is 1: 2. The electrochemical valence of tetrahedra containing an element belonging to group IIIA, e.g. aluminum, is compensated by inclusion in the crystal of a cation, e.g. an alkali metal or an alkaline earth metal cation. This can be expressed as the ratio of an element belonging to group IIIA, e.g. aluminum, to the number of different cations such as Ca / 2, Sr / 2, Na, K or Li is equal to one. One type of cation may be replaced either wholly or partially by another type of cation using an ion-exchange technique in a conventional manner. By such a cation exchange, it has been possible to change the properties of the respective silicate by selecting the appropriate cation.

Hitherto known methods have resulted in a wide variety of synthetic zeolites. Many of these zeolites are designated with a letter or other convenient symbol, e.g., zeolite A (US Patent No. 2,882,243), zeolite X (US Patent No. 2,882,244), zeolite Y (US Patent No. No. 3,130,007), ZK-5 zeolite (U.S. Patent No. 3,247,195), ZK-4 zeolite (U.S. Patent No. 3,314,752), ZSM-5 zeolite (U.S. Patent No. 3 702 886), ZSM-11 zeolite (U.S. Patent No. 3,832,449), ZSM-20 zeolite (U.S. Patent No. 3,972,983), ZSM-35 zeolite (U.S. Patent No. 4,016,245 ) and ZSM-23 zeolite (U.S. Patent No. 4,076,842).

The SiO2 / AhO3 ratio in a given zeolite is often variable. For example, zeolite X can be synthesized with a SiO2 / AhO3 ratio of 2 to 3; zeolite Y - from 3 to 6. In some zeolites

The upper limit of the S1O2 / Al2O3 ratio is unlimited. The ZSM-5 is one such example where the ratio is at least 5 and above the limits of current analytical measurement methods. U.S. Patent No. 3,941,871 (Re. 29,948) describes a porous, crystalline silicate made from a reaction mixture containing no intentionally added alumina and exhibiting the X-ray diffraction pattern characteristic of ZSM-5. U.S. Patent Nos. 4,061,724,4,073,865 and 4,104,294 describe crystalline silicate with varying alumina and metal contents.

The invention relates to a synthetic, porous crystalline material having a composition determined by the molar relationship X2O3: (n) YO2, in which n is at least 10, X is a trivalent element, and Y is a tetravalent element. According to the invention, this material is characterized by an X-ray diffraction distribution containing the values given in Table 2 of the description and has an equilibrium adsorption capacity of more than 10% by weight for water vapor, more than 4.5% by weight for cyclohexane vapor and more than 10% by weight for n-hexane vapor. .

The porous crystalline material of the present invention is related to the compositions named PSH-3 described in US Pat. No. 4,439,409. However, the crystalline material of the present invention does not appear to contain all the components clearly present in the PSH-3 compositions. In particular, the composition of the invention is not contaminated with other crystalline structures such as ZSM-12 or ZSM-5, has remarkable absorption capacity and unique catalytic performance compared to PSH-3 compositions synthesized according to US Pat. United States of America 4,439,409.

X-ray diffraction distribution characterizing the PSH-3 zeolite known from the aforementioned US patent U.S. 4,439,409 is listed in Table 1.

Table 1

Interplanar distance d (1 10 ^U nm) Relative intensity I / Io x 100 1 2 12.63 100 10.92 thirty 8.84 60 6.86 5 6.15 40 5.50 15 4.61 1 4.60 1 4.39 15 4.09 twenty 3.91 thirty 3.75 5 3.56 3

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1 2 3.41 100 3.30 2 3.19 3 3.11 2 2.836 2 2.694 3

In Table 1, d and I / Io have the meanings set out below.

The crystalline material of the invention is synthesized by crystallizing a reaction mixture containing sources of the desired oxides together with hexamethyleneimine targeting agent. However, it has been found, especially when the crystalline material of the invention is silicate, that it is important to use a silica source with a relatively high solids content.

The preparation of a synthetic, porous crystalline material with the above-defined composition consists in the preparation of a reaction mixture capable of forming the produced material after crystallization, containing sufficient amounts of alkali metal or alkaline earth metal cations, an oxide source of the tetravalent element YO2 containing at least 30% by weight of solid YO2, an oxide source of the trivalent element XiO3, water and hexamethyleneimine, and maintaining this reaction mixture under sufficient conditions for crystallization until crystals of the material produced are formed.

The crystalline material according to the invention has the following molar composition: X2O3: (n) YO2, in which formulas X is a trivalent element such as aluminum, boron, iron and / or gallium, preferably aluminum, Y is a tetravalent element, such as silicon and / or germanium, preferably silicon, n is at least 10, usually from 10 to 150, preferably from 10 to 60 and most preferably from 20 to 40. In the form immediately after synthesis, this material has the formula, on an anhydrous basis and with the indication the number of moles of oxides per n moles of YO2 as follows: (0.005-0.1) Na2O: (1-4) R: X2O3: (n) YO2, wherein R is an organic group. The Na and R components are bound to the material by their presence during crystallization and are easily removed by post-crystallization methods which will be discussed in detail later.

The crystalline material according to the invention is thermally stable and has a large surface area (greater than 400 m2 / g) and an extremely high absorption capacity compared to similar crystal structures. It can be seen from the above formula that the crystalline material of the invention is synthesized almost entirely without Na cations. It can therefore be used as an acid-acting catalyst without an exchange step. However, to the necessary extent, the primary sodium cations in the material immediately after synthesis can be replaced by known methods, at least in part, by ion exchange with other cations. Preferred exchangeable cations are metal ions, hydrogen ion, hydrogen precursor ions, e.g. ammonium, and mixtures thereof. Particularly preferred cations are those that adjust the catalytic performance for certain hydrocarbon transformation reactions. They include hydrogen, rare earth metals, and metals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, and VIII of the periodic table of the elements.

In its calcined form, the crystalline material of the invention appears to be formed from a single crystalline phase with little or no detectable crystal phases of impurities, and has an X-ray diffraction pattern that differs from that of other known crystalline materials by the lines given in Table 2.

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Table 2

Interplanar distance d (1 10 ' ¹ nm) Relative intensity I / Io x 100 30.0 ± 2.2 W-M 22.1 ± 1.3 IN

more precisely with the lines given in table 3

Table 3

Interplanar distance d (1 10 ' ¹ nm) Relative intensity I / Io x 100 30.0 ± 2.2 W-M 22.1 ± 1.3 IN 3.91 ± 0.07 M- VS

and even more precisely with the lines given in table 4

Table 4

Interplanar distance d (1 10-1 nm) Relative intensity I / Io x 100 30.0 ± 2.2 W-M 22.1 ± 1.3 IN 6.00 ± 0.10 W-M 4.64 ± 0.08 IN 4.06 ± 0.07 W-S 3.91 ± 0.07 M-VS

More specifically, the calcined crystalline material of the present invention has an X-ray diffraction pattern that includes the lines shown in Table 5.

Table 5

Interplanar distance d (1 10 ' ¹ nm) Relative intensity I / I0 x 100 1 2 30.0 ± 2.2 W-M 22.1 ± 1.3 IN 12.36 ± 0.2 M-VS

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1 2 11.03 ± 0.2 M-S 8.83 ± 0.14 M-VS 6.86 ± 0.14 W-M 6.18 ± 0.12 M-VS 6.00 + 0.10 W-M 5.54 ± 0.10 W-M 4.92 ± 0.09 IN 4.64 ± 0.08 IN 4.41 ± 0.08 W-M 4.25 ± 0.08 IN 4.10 ± 0.07 W-S 4.06 ± 0.07 W-S 3.91 ± 0.07 M-VS 3.75 ± 0.06 W-M 3.56 ± 0.06 W-M 3.42 ± 0.06 VS 3.30 ± 0.05 W-M 3.20 + 0.05 W-M 3.14 ± 0.05 W-M 3.07 + 0.05 IN 2.99 ± 0.05 IN 2.82 ± 0.05 IN 2.78 ± 0.05 IN 2.68 ± 0.05 IN 2.59 ± 0.05 in

These values were determined by standard methods. The radiation contained the copper K-alpha doublet, a diffractometer equipped with a scintillation counter and connected to a computer was used. The intensity of the peaks I, and the positions as a function of 2 theta, where theta is the Bragg angle, were determined using algorithms on a computer linked to the diffractometer. On this basis, the relative intensities were determined, 100 I / Io, where Io is the intensity of the strongest line or peak, and d is the interplanar spacing in Angstrom units (1-10 ' ¹ nm), corresponding to the recorded lines. In Tables 2-6, the relative intensities are given by

165 909 symbols W = weak, M = medium, S = strong and VS = very strong. Such intensity markings can be broadly defined as follows:

W = 0-20 M = 20-40 W = 40-60 VS = 60-100

To better visualize the main differences between the PSH-3 zeolite known from Patent Specification No. 4,439,409 and the inventive zeolite MCM-22, they are summarized in Table 6.

Table 6

Interplanar distance d (1 · 10-1 nm) Relative intensity I / Io x 100 30.0 ± 2.2 W-M 22.1 ± 1.3 in 6.00 ± 0.10 W-M 4.25 ± 0.08 in 4.10 ± 0.07 W-S 4.06 ± 0.07 doublet (singlet in PSH-3) 3.07 ± 0.05 in 2.99 ± 0.05 in 2.78 ± 0.05 in

It should be understood that this X-ray diffraction pattern is characteristic of all samples of the crystalline composition. The sodium form as well as the other cationic forms show essentially the same distribution with some slight shifts in the interplanar spacing and little change in relative intensity. There may also be other slight variations depending on the Y: X ratio, e.g., silicon: aluminum, in a given sample as well as depending on its degree of heat treatment.

The crystalline material according to the invention can be prepared from a reaction mixture containing sources of an alkali metal or alkaline earth metal (M), e.g. sodium or potassium (cation), an oxide of a trivalent element X, e.g. aluminum, an oxide of the tetravalent element Y, e.g. silicon, an organic factor driving (R), to be described in detail below, and water, this reaction mixture having a composition, in molar ratios of oxides, in the following ranges:

Reagents Useful Beneficial YO2 / X2O3 10 - 80 10 - 60 H2O / YO2 5 - 100 10 - 50 OH / YO 2 0.001 1.0 0.1 - 0.5 M / YO2 0.01 - 2.0 0.1 - 10 R / YO2 0.05 - 1.0 0.1 - 0.5

It has been found that the material according to the invention crystallizes advantageously when the source of YO2 contains at least 30% by weight of YO2 in the solid state, in particular when YO2 is silicon dioxide. Suitable commercially available silica sources are Utrasil (precipitated spray-dried silica containing about 90% by weight of silicon dioxide) and HiSil (precipitated, hydrated SiO2 containing about 87% by weight of silicon dioxide)

165,909 silicon, about 6 wt.% Free H 2 O and about 4.5 wt.% Bound H 2 O for hydration, with a particle size of approx. 0.02 µm). If another source of silica is used, e.g. Q-Brand (sodium silicate containing approx. 28.8% by weight of SiO2, 8.9% by weight of Na2O and 62.3% by weight of H2O), little or no crystallization of the crystalline material according to of the invention, and instead impurity phases of other crystal structures, e.g. ZSM-12, are formed. Preferably, therefore, the source of YO2 comprises at least 30% by weight of YO2 in solid form, preferably silicon dioxide, and even more preferably at least 40% by weight of YO2 in solid form.

The organic targeting agent (R) used in synthesizing the crystalline material from the above reaction mixture is hexamethyleneimine, which has the structural formula shown in the figure.

Crystallization of the crystalline material can be carried out either in a static state or with stirring in a suitable reaction vessel, e.g. polypropylene vessels or in Teflon lined or stainless steel autoclaves. The crystallization is usually carried out at a temperature of 80-225 ° C for 24 hours to 60 days. The crystals are then separated from the liquid.

Crystallization is facilitated by the presence of at least 0.01%, preferably 0.10%, and even more preferably 1% seed crystals (based on total weight) of the desired crystalline product.

Before being used as a catalyst or adsorbent, the crystalline material in its synthesized state should be calcined to remove some or all of any optional organic constituents.

The crystalline material according to the invention can be used as a catalyst in close association with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a noble metal such as platinum or palladium, where the hydrogenation-dehydrogenation function is to take place. Such a component can be introduced into the composition by co-crystallization by cation exchange in the composition, by saturating it, or by thoroughly mixing it physically therewith. Supersaturation or impregnation of the composition with such a component can take place, for example in the case of platinum, by treating the silicate with a solution containing a platinum metal ion. Suitable platinum compounds for this purpose include chloroplatinic acid, platinum chloride, and various platinum-amine complex compounds.

The crystalline materials according to the invention can be shaped into particles of various sizes. Generally speaking, the particles may be in the form of a powder, granules or a shaped product, e.g. extruded. In the latter case, the crystalline material may be extruded prior to drying, or partially dried and then extruded.

The crystalline material according to the invention, when used as an adsorbent or as a catalyst in the conversion of organic compounds, should be dehydrated, at least partially. This can be done by heating to a temperature ranging from 200 ° C to 595 ° C in an atmosphere such as air, nitrogen, etc. and at or above or below atmospheric pressure for a period of 30 minutes to 48 hours. Dehydration can also be carried out at room temperature by just placing the silicate in a vacuum, but a longer time is then needed to obtain a sufficient degree of dehydration.

The crystalline material of the invention can be used to catalyze a wide variety of organic conversion processes including, by way of example, the hydration of C2-C7 olefins such as polypropylene to alcohols and ethers under reaction conditions ranging from 50 to 300 ° C, preferably from 90 to 250 ° C. ° C, a pressure of at least 4.9102 kPa, preferably at least 19.6102 kPa, and a water / olefin molar ratio of 0.1-30, preferably 0.2-15.

As with many catalysts, such a catalyst may contain the crystalline material of the invention along with other material that is resistant to the temperatures and other conditions employed in organic transformation processes. Such materials include active and inactive materials and synthetic or natural zeolites as well as inorganic materials such as clays, silica and / or metal oxides such as alumina. The latter can

165,909 be either of natural origin or in the form of gelatinous deposits or gels containing mixtures of silica and metal oxides. The use of any material in conjunction with a new crystal, e.g., a new crystal that is active, combined with it or present during synthesis, tends to alter the conversion and / or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the rate of conversion in a given process so that products can be obtained economically and correctly without the use of other means for controlling the rate of reaction. These materials may be included in naturally occurring clays such as e.g. bentonite and kaolin to improve the fracture toughness of the catalyst under technical operating conditions. These materials, i.e., clays, oxides, etc., serve as binders for the catalyst. It is desirable to make a catalyst having a good fracture toughness as it is desirable in industrial applications to prevent the catalyst from disintegrating into powder. Such aluminum binders have normally only been used to improve the fracture toughness of the catalyst.

Naturally occurring clays that can be used in conjunction with the new crystal include the montmorillonite and koalin families, which families include the kaolin subbentonites known as Dixie, McNamee, Georgia, and Florida and others where the main mineral is halloyite, kaolinite, dickite , nacrit or anauxit. Such clays can be used raw as they were originally mined, or after calcination, acid treatment or chemical modification. Binders suitable for use with this crystal also include inorganic oxides, primarily alumina.

In addition to the above materials, the new crystal can be used in conjunction with a porous matrix material such as compositions; silica - alumina, silica, magnesium oxide, silica - zirconia, silica - thorium oxide, silica - beryllium oxide, silica - titanium oxide, and three-component compositions such as silica - alumina - thorium oxide, silica - alumina - zirconia, silica - alumina - magnesium oxide, silica - magnesium oxide - zirconium oxide.

The relative proportions of the fine crystalline material and the niorganic oxide matrix may vary widely with a crystal content of 1 to 90% by weight and more, especially when the composite is made in the form of granules, within the range

- 80% by weight of the composite.

The invention will now be described in more detail in the examples with reference to the accompanying drawings, in which Figs. 1-5 show the X-ray diffraction distributions of the calcined product of Examples I, III, IV, V, IX, respectively. In these examples, whenever absorption data is reported to compare absorption properties for water, cyclohexane and / or n-hexane, these are the equilibrium adsorption values defined as follows:

The weighed sample of the calcined adsorbent was contacted with the vapor of the pure adsorbate in the adsorption chamber pumped down to a pressure below 1, (33:10 ² Pa and contacted with water vapor under 1C2 Pa pressure and n-hexane or cyclohexane vapor under the pressure of 53.32 pressures were lower than the vapor-liquid equilibrium pressure for a given adsorbate at a temperature of 90 ° C. The pressure was kept constant (with an accuracy of +/- 0.5. 102 Pa) by adding adsorbate steam controlled by the pressure stabilizer during adsorption, which was not stable longer than 8 hours. When the adsorbate was adsorbed by the new crystal, the pressure drop caused the pressure stabilizer to open a valve that let more adsorbate vapor into the chamber to restore the above pressures. Sorption was complete when the pressure change was no longer sufficient to activate the stabilizer The increase in weight was calculated as the sample adsorption capacity in g / 100 g of calcined adsorbant. y according to the invention always shows equilibrium adsorption values greater than 10 wt% for steam, greater than 4.5 wt%, usually greater than 7 wt% for cyclohexane vapor and greater than 10 wt% for n-hexane vapor.

When the alpha value is tested, it is noted that the alpha value is a rough indication of the catalytic cracking activity of the catalyst compared to a standard catalytic converter12

165 909 rem and gives the relative velocity (normal rate of hexane conversion to catalyst volume per unit time) constant compared to the analogous factor for the highly active silica-alumina cracking catalyst taken as alpha = 1 (speed constant = 0.016 s- ¹ ). The alpha test is described in US Pat. No. 3,354,078 and in the Journal of Catalysis, Vol. IV, pages 522-529 (August 1965). It is noted that the specific rate constants for many acid catalyzed reactions are proportional to the alpha value for a given crystalline silicate catalyst, i.e., rates for toluene disproportionation, xylene isomerization, alkene conversion, and methanol conversion (see The Active Site of Acidic Aluminosilicate Catalysts Nature, Vol. 309, No. 5969, pp. 589-591, June 14, 1984).

Example 1 Sodium aluminate (43.5% AhO3, 32.2% Na2O, 25.6% H2O), 12.86 g, was dissolved in a solution containing 12.8 g of 50% NaOH solution and 1320 g of H2O. Thereto was added 57.6 g of hexamethyleneimine. The resulting solution was added to 109.4 g of Ultrasil material (precipitated spray-dried silica (about 90% SiO2).

The reaction mixture had the following composition, in molar ratios:

SiO2 / Al2O3 = 30.0

OH7SiO2 = 0.18

H2O / SiO2 = 4, 9

Na / SiO2 = 018

R / SiO2 = 0.35 wherein R is hexamethyleneimine.

Crystallization of the mixture was carried out in a stainless steel reactor with stirring at 150 ° C for 7 days. The crystalline product was filtered off, washed with water and dried at 120 ° C. After 20 hours calcination at 538 ° C, the X-ray diffraction pattern consisted mainly of the lines given in Table 7. Figure 1 shows the X-ray diffraction pattern of the calcined product. The absorption properties of the calcined material after the measurement turned out to be as follows:

H2O (15,996 · 10 ² Pa) 15.2% by weight

Cyclohexane (53.32102 Pa) 14.6% by weight n-hexane (53.32102 Pa) 11 ,,%

The surface area of the calcined crystalline material was as measured by 494 m2 / g.

The chemical composition of the calcined material was determined as follows:

Component% by weight

SiOi 66.9

Al2O3 5.40

At 0.03

N 2.27

Ash 76.3

SiO ^ AhO3, molar ratio = 21.1

Table 7

Degrees of 2 theta Interplanar distance d (1 10'1 nm) I / Io 1 2 3 2.80 31.55 25 4.02 21.98 10 7.10 12.45 96 7.95 11.12 47

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1 2 3 10.00 8.85 51 12.90 6.86 11 14.34 6.18 42 14.72 6.02 15 15.90 5.57 twenty 17.81 4.98 5 19.08 4.65 2 20.20 4.40 twenty 20.91 4.25 5 21.59 4.12 twenty 21.92 4.06 13 22.67 3.92 thirty 23.70 3.75 13 25.01 3.56 twenty 26.00 3.43 100 26.96 3.31 14 27.75 3.21 15 28.52 3.13 10 29.01 3.08 5 29.71 3.01 5 31.61 2.830 5 32.21 2,779 5 33.35 2.687 5 34.61 2.592 5

Example II. A portion of the calcined crystalline product of Example 1 was tested alpha and found to have an alpha value of 224.

Example III-V. Three separate synthetic reaction mixtures were prepared with the compositions shown in Table 8. These mixtures were prepared from sodium aluminate, sodium hydroxide, a material called Ultrasil, hexamethyleneimine (R) and water. The mixtures were held at temperatures of 150 ° C, 143 ° C and 150 ° C, respectively, for 7.8 and 6 days, respectively, in a stainless steel autoclave under spontaneous pressure with agitation (350 rpm). The solids were separated from the unreacted components by filtration, then rinsed with water and then dried at 120 ° C. Product crystals were examined by diffraction

165,909 X-rays, absorption, surface area check and chemical analysis. The product has been found to be the new crystalline material according to the invention. The results of the absorption test, surface area and chemical analysis are given in Table 6. The X-ray diffraction distributions of the calcined (538 ° C for 3 h) products of Examples III, IV and V are shown in Figures 2, 3 and 4, respectively. Absorption and area measurements surface were related to the calcined product.

Table 8

Example number III IV V Synthesis mixture SiO2 / Al2O3 molar ratios 30.0 30.0 30.0 OH7SiO2 0.18 0.18 0.18 H2O / S1O 19.4 19.4 44.9 Na / SiO2 0.18 0.18 0.18 R7SiO2 0.35 0.35 0.35 Product composition, wt% S1O2 64.3 68.5 74.5 Al2O 3 4.85 5.58 4.87 On 0.08 0.05 0.01 N 2.40 2.33 2.12 Ash 77.1 77.3 78.2 SiO2 / Al2O3, molar ratio 22.5 20.9 26.0 Adsorption,% by weight H2O 14.9 13.6 14.6 Cyclohexane 12.5 12.2 13.6 n-hexane 14.6 16.2 19.0 Surface area, m / kg 481 492 487

Example VI. Certain amounts of the calcined (538 ° C for 3 hours) crystalline silica products of Examples 3, 4, and V were tested in the alpha test and found to have alpha values of 227, 180, and 187, respectively.

Example VII. A calcined sample of the crystalline silicate from Example 4 was saturated with a Pt / NH3 / 4Cl2 solution to about 1 wt% Pt. This material was then heated in air at 349 ° C for 3 h.

Example VIII. One gram of the resulting product from Example 7 was charged as catalyst to a small preheater reactor with incorporated thermocouple. The catalyst was then heated at a temperature of 482 ° C in the presence of a flow of hydrogen to reduce its Pt content. Normal decane and hydrogen were fed to the catalyst to obtain an hourly weight hour flow rate of 0.4 h ^-1 in decane and a hydrogen / hydrocarbon molar ratio of 100: 1. The reaction was carried out in the temperature range of 130-250 ° C at atmospheric pressure.

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The results of this experiment are summarized in Table 9 together with the results of the same experiment in which the crystalline material was replaced by ZSM-5 (US Patent No. 3,702,886), ZSM-11 (US Patent No. 3,709,979 ) and Zeolitte Beta (U.S. Patent No. 3,308,069) for comparative purposes. It has been observed that the crystalline silicate according to the invention is a very active catalyst for n-decane hydroconversion and is isomerizable. In Table 7, 5 MN / 2 MN is the molecular ratio of 5-methylnonane / 2-methylnonane. Due to the position of its methyl group, 5-methylnonane has a slightly greater hindrance in entering the zeolite pores. The 5 MN / 2 MN ratio provides information about the porosity of the tested zeolite.

Table 9

Catalyst SiO2 / Al2O3 zeolite molar ratio Temperature for transformation 50% (° C) % isome. at the transformation 5 MN / 2 MN 5% isom. 20% isom. Example VII 20.9 174 70 0.15 0.24 ZSM-5 50 187 65 0.11 0.15 ZSM-11 40 187 94 0.36 0.41 ZSM-23 85 211 90 0.27 0.28 Beta 30 189 76 0.68 0.59

Example IX. To demonstrate the preparation of the crystalline material according to the invention, 1200 g of hexamethyleneimine was added to a solution containing 268 g of sodium aluminate, 267 g of 50% NaOH solution and 11.800 g of H2O. 2280 g of Ultrasil silica was added to the combined solution. This mixture was crystallized with stirring (ca 200 rpm) at 145 ° C in a 19 L reactor. The crystallization time was 69 h. The product was rinsed with water and dried at 120 ° C.

The X-ray diffraction distribution of the calcined (538 ° C) crystalline product is shown in Figure 5. This distribution demonstrates that the product is the crystalline material of the invention. The product chemical composition, surface area and adsorption analysis results were as follows:

Table 10

Composition of the product C. 12.1% by weight N 1.98% by weight On 640 ppm Al2O3 5.0% by weight SiO2 74.9% by weight SiO2 / Al2O3, molar ratio 25.4 Adsorption,% by weight Cyclohexane 9.1

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n-hexane 14.9 H2O 16.0 2 Surface area m / g 479

Example 10 25 g of the crystalline solid product of Example 9 was calcined under nitrogen flow at 538 ° C for 5 h, followed by a gas purging with 5% oxygen (residual N2) for a further 16 h at 538 ° C.

A single 3 g sample of the calcined material was ion exchanged separately with 100 ml of a 0.1N TEABr, TPABr and LaCb solution. Each such exchange was carried out at ambient temperature for 24 hours and repeated 3 times. The replacement samples were collected by filtration, rinsed with water to remove halides, and dried. The composition of the samples after exchange is given in the table below which shows the ability to exchange the crystalline silicate for various ions.

Exchange ions TEA TPA La Ionic composition,% by weight On 0.095 0.089 0.063 N 0.30 0.38 0.03 C. 2.89 3.63 - La - - 1.04

Example XI. The above La-exchange sample was sieved through a No. 14-25 sieve and then calcined in air at 538 ° C for 3 hours. The calcined material had an alpha 173 value.

Example XII. The calcined La-exchange material sample of Example 11 was steeply steamed at 649 ° C with 100% steam for 2 h. The steamed sample had a value of alpha = 22, demonstrating that its crystalline silicate has very good stability under severe hydrothermal treatment.

Example XIII. To prepare the macrocrystalline where X is boron, 17.5 boric acid was added to a solution containing 6.75 g of a 45% KOH solution and 290 g of H2O. Thereto was added 57.8 g of Ultrasil silica and the mixture was thoroughly homogenized. 26.2 g of hexamethyleneimine was added to this mixture.

The reaction mixture had the following composition in molar ratios:

SiO2 = 6.1

OH7SiO2 = 0.06

H2O / SiO = 19.0

K / SiO2 = 0.06

R / SiO2 = 0.30 wherein R is hexamethyleneimine.

This mixture was crystallized in a stainless steel reactor with stirring at 150 ° C for 8 days. The crystalline product was filtered off, washed with water and dried at 120 ° C. Part of the product was calcined for 6 h at 540 ° C and found to have the following absorption properties:

H2O (15.996 · 102 Pa) 117% by weight

Cyclohexane (53.3210 ² Pa) 7.5% by weight n-hexa (53.32 · 1θ2 Pa) 11.4% by weight

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The surface area of the calcined crystalline material as measured was 405 m2 / g. The chemical composition of the calcined material was determined as follows:

N

On

K.

Boron

Al2O3

SiO2

Ash

SiO2 / AkO3, SiO2 molar ratio (Al + B) 2O3, molar ratio

1.94% by weight 175 ppm

0.60 wt.% 1.04 wt.% 920 ppm

73.9 wt.% 74.11 wt.% = 1406 = 25.8

Example XIV. Part of the calcined crystalline product of Example 13 was treated with NHCl and calcined again. The final crystalline product was tested alpha and found to have the value alpha = 1.

Example XV. To prepare the crystalline material in which X is boron, 35.0 g of boric acid was added to a solution containing 15.7 g of 50% NaOH solution and 1160 h of H2O. To this solution was added 240 g of silica, HiSil, followed by 105 g of hexamethyleneimine. This reaction mixture had the following composition in molar ratios:

SiO2 / Br2O3 = 12.3

OH7SiO2 = 0.056

H2O / SiO2 = 18.6

Na / SiO2 = 0.056

R / SiO2 = 0.30 wherein R is hexamethyleneimine.

This mixture was crystallized in a stainless steel reactor with stirring at 300 ° C for 9 days. The crystalline product was filtered off, washed with water and dried at 120 ° C. The absorption properties of the calcined material (6 h at 540 ° C) were measured as follows:

H 2 O (15.996 10 × Pa) 14.4 wt.% Wt. G

Cyclohexane (53.32 · ^ Pa) 4.6% by weight n-hexane (53.32 · 102 Pa) 14.0% by weight

The measured surface area of the calcined crystalline material was 438 m2 / g.

The chemical composition of the calcined material was as follows:

Component N Na Bor Al2O3 SiO2

SiO2 / Al2Ol, molar ratio SiO2 (Al + B) 2O3, molar ratio wt% 2.48 0.06 0.33 0.00 73.4 = 249 = 28.2

Example XVI. A portion of the calcined crystalline product of Example 15 was tested alpha and found to be alpha = 3.

Example XVII. To demonstrate the importance of using a silica source containing at least 30% silica and as a solid in the material of the present invention, Example 3 was repeated but sodium silicate Q-Brand (containing only about 29% by weight of solid silica) was used as the silica source. In this example, 67.6 g of aluminum sulfate was dissolved in a solution containing 38.1 g of H 2 SO 4 (96.1%) and 400 g of water. The resulting solution was mixed with 120 g of hexamethyleneimine and added to a mixture containing 712.5 g of Q-Brand sodium silicate (28.8% SiO2 and 1.9% ο Na2O) and 351 g of water. The resulting mixture has the following composition, expressed in mole ratios:

SiO2Al2O3 = 30.0

OH7SiO2 a 0.18

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H2O / S.iO2 = 1919

Na / SiO2 = 0, <6)

R / SiO2 = 0.5 was thoroughly mixed and crystallized while stirring in a stainless steel reactor at 246 ° C for 8 days. The solid components of the product were separated from the unreacted components by filtration and then rinsed with water and then dried at 120 ° C. The product was tested for X-ray diffraction and found to be a mixture of amorphous material, magadiite and mordenite. No crystals according to the invention were found.

Example XVIII. In this example, the properties of the catalytic material of the invention for propylene hydration were compared to those of the ZSM-12 and PSH-3 materials made according to Example 4 of US Pat. United States of America 4,439,409.

The crystalline material according to the invention was prepared by adding 15.9 parts by weight of hexamethyleneimine to a mixture containing 3.5 parts of 50% NaOH, 3.5 parts of sodium aluminate, 30.1 parts of Ultrasil VN3 silica and 156 parts of deionized H 2 O.

The reaction mixture was heated directly to 143 ° C and stirred in an autoclave at this temperature to effect crystallization. After full crystallization was achieved, the resulting crystals were separated from the remaining liquid by filtration, washed with water, and dried. Some of these crystals were combined with alumina to form a mixture containing 65 parts by weight of zeolite and 35 parts of alumina. Sufficient water was added to this mixture so that the resulting catalyst could be shaped by extrusion. This catalyst was activated by calcination in nitrogen at 540 ° C, followed by exchange with an aqueous 1.0N ammonium nitrate solution and calcination in air at 540 - 650 ° C.

ZSM-12 was prepared by adding 1 part by weight of ZSM-12 seed crystals to a mixture containing 41.5 parts of Hi-Sil 233.67.7 parts of 50% tetraethylammonium bromide, 7.0 parts 50% NaOH, and 165.4 parts deionized H2O . The reaction mixture was heated directly to 138 ° C and stirred in an autoclave at that temperature for crystallization. After full crystallization was achieved, the resulting crystals were separated from the rest of the liquid by filtration, washed with water, and dried. Some of the crystals were combined with alumina to form a mixture of 65 parts by weight of zeolite and 35 parts of alumina. Sufficient water was added to this mixture so that the resulting catalyst could be shaped by extrusion. This catalyst was activated by calcination in nitrogen at 540 ° C, followed by exchange with an aqueous 1.0N ammonium nitrate solution and calcination at 650 ° C.

Propylene was hydration at a temperature of 166 ° C, a pressure of 7000 kPa and a propylene hourly flow rate of 0.6. The results are 2 days in steam and are compared in Table 11.

Table 11

PSH-3 The material according to the invention ZSM-12 % conversion of propylene 1.9 27.8 10.8 % water conversion 5.7 33.7 8.1 Selectivity of the IPA 88.7 76.7 74.6 Selectivity of DIPE 2.9 22.3 23.1 Oligomer selectivity 8.4 1.2 2.3

IPA = isopropyl alcohol. DIPE = diisopropyl ether

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The above results clearly show the advantageous properties of the material of the invention compared to both PSH-3 and ZSM-12 in terms of obtaining a higher conversion rate combined with good selectivity for diisopropyl benzene and poor production of propylene oligomers.

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165 909

165 909 rei

Publishing Department of the UP RP. Circulation of 90 copies. Price PLN 1.00.

Claims (4)

Patent claims 1. Synthetic, porous pore crystalline material with a decimal composition Χ2Ο3: (n) YO2, in which n is at least 10, X is a trivalent element, and Y is a four-valent element, characterized by the fact that it has a diffraction distribution X-rays for the distance between the lines d corresponding to the relative intensity I / Io presented in the following table: Międkeełkskckeknowk distance d (1 · 10 to ¹ nm) Relative intensity I / Io x 100 30.0 ± 2.2 W-M 22.1 ± 1.3 IN where I is the intensity of the jaw height and Io is the intensity of the strongest line or peak, the relative intensity of W is the weak intensity and M is the average intensity. 2. The material according to claim The method of claim 1, characterized in that the m a of the cone ad diffraction and mu for intercellular distances d corresponding to the relative intensity I / Io presented in the following summary: Distance between Oaskszeknowk d (1 10 ' ¹ nm) Relative intensity I / I _by x 10 30.0 ± 2.2 W-M 22.1 ± 1.3 IN 3.91 ± 0.07 M-VS wherein I, Io, W and M are as defined in claim 1 and VS is very strong. 3. Material according to the formula I / I, characterized by the enm that man ^ ka ad ciy / k ^ akc ^ r and kxchange m for the interspendicular distance d corresponding to the relative intensity I / Ioer, presented in the following table: Interval distance d (1 10 ' ¹ nm) Relative intensity I / Io x 100 30.0 ± 2.2 W-M 22.1 ± 1.3 in 6.00 ± 0.10 W-M 4.64 ± 0.08 in 4.06 ± 0.07 in-s 3.91 ± 0.07 M-VS 165 909 wherein I, Io, W and M are as defined in claim 165,909. 1, S is strong and VS is very strong. Material according to claim-1, characterized in that it has the diffraction distribution of the rays mi for the interplanar distances d corresponding to the relative intensity I / Io presented in the following summary: Interplanar distance d (1 10'l nm) Relative intensity I / Io x 100 1 2 30, (0 ± 2.2 W-M 22.1 ± 1.3 IN 12.36 ± 0.2 M-VS 11.03 ± 0.2 M-S 8.83 ± 0.14 M-VS 6.86 ± 0.14 W-M 6.18 ± 0.12 M-VS 6.00 ± 0.10 W-M 5.54 ± 0.10 W-M 4.92 ± 0.09 IN 4.64 ± 0.08 IN 4.41 ± 0.08 W-M 4.25 ± 0.08 IN 4.10 ± 0.07 W-S 4.06 ± 0.07 W-S 3.91 ± 0.07 M-VS 3.75 ± 0.06 W-M 3.56 ± 0.06 W-M 3.42 ± 0.06 VS 3.30 ± 0.05 W-M 3.20 ± 0.05 W-M 3.14 ± 0.05 W-M 3.07 ± 0.05 IN 2.99 ± 0.05 IN 165 909 1 2 2.82 ± 0.05 IN 2.78 ± 0.05 IN 2.68 ± 0.05 IN 2.59 ± 0.05 IN wherein I, Io, W and M are as defined in claim 1, S is strong and VS is very strong.