HU213311B - Synthetic porous crystalline composition and process for producing it - Google Patents

Abstract

The material, for use in catalytic conversion of organic cpds., has an X-ray diffraction spectrum with given peaks, and is made by reacting a mixt. contg. sodium cations, a source of silica contg. at least 30 wt.% SiO2, aluminium oxide, water and hexamethylene imine, which is allowed to crystallise under suitable conditions

Description

The present invention relates to a synthetic, porous crystalline material composition having the composition

X ₂ O ₃ : (n) Expresses the molar ratio YO ₂ where n is at least 10,

X represents a trivalent element and Y represents a trivalent element.

The invention also relates to a process for preparing the composition. The composition of the invention can be used for the catalytic conversion of organic compounds.

Natural and synthetic zeolites are capable of catalyzing different types of hydrocarbon conversions. Some zeolite materials are ordered, porous crystalline aluminosilicates having a crystalline structure defined by X-ray diffraction; a large number of smaller cavities are located within this structure, which are interconnected by a number of even smaller passages or pores. These cavities and pores in a given zeolite material are the same size. Because of the size of these pores, they accept and adsorb molecules of a certain size while exclude the larger ones, these materials have become known as "molecular sieves" and have exploited their properties in many ways.

These natural and synthetic molecular sieves include a wide variety of crystalline silicates containing positive ions. These silicates [SiO4®] and the group IIIA elements of the Periodic Table may be described as a rigid three-dimensional lattice in which the tetrahedrons may be transversely joined so that one or more of their O ² and thus the ratio of the group IIIA element, such as aluminum, to silicon atoms relative to O ² atoms is 1: 2. The electron valence of a tetrahedron containing a group IIIA element is compensated by the inclusion of a cation, such as an alkali metal or alkaline earth metal cation, in the expression of a group IIIA element such as aluminum and various cations such as Ca ² ©, Sr ² ©, NA®, K® or Li® ion ratio 1. One type of cation can be partially or wholly replaced by other types of ion exchange methods. Such ion exchange, by the proper choice of cation, allows the properties of a given silicate to be changed.

A variety of synthetic zeolites have been produced using prior techniques. Many of these zeolites are designated by a letter or other suitable symbol, exemplified by zeolite A (U.S. Pat. No. 2,882,243), zeolite X (U.S. Pat. No. 2,882,244), zeolite Y (3,130,007). Zeolite ZK-5 (U.S. Patent 3,247,195), Zeolite ZK-4 (U.S. Patent 3,314,752), Zeolite ZSM-5 (U.S. Patent 3,702,886). zeolite ZSM-11 (U.S. Pat. No. 3,709,979), zeolite ZSM-12 (U.S. Pat. No. 3,832,449), zeolite ZSM-20 (U.S. Pat. No. 3,972,983). description),

ZSM-35 (US 4,016,245) and zeolite ZSM-23 (US 4,076,842).

The SiO ₂ / Al ₂ O ₃ ratio of a given zeolite is often variable. For example, zeolite X has a SiO ₂ / Al ₂ O ₃ ratio of 2 to 3 and zeolite Y has a 3 to 6 ratio. In some zeolites, there is no upper limit for the SiO ₂ / Al ₂ O ₃ ratio. An example of this is ZSM-5, where the SiO ₂ / Al ₂ O ₃ ratio is at least 5 and reaches the limit of current analytical techniques. U.S. Patent 3,941,871 discloses a porous crystalline silicate with an unspecified amount It is prepared from a mixture containing Al ₂ O ₃ and has an X-ray diffraction pattern typical of ZSM-5 zeolite. A 4,061,724; U.S. Patent Nos. 4,073,865 and 4,104,294 disclose crystalline silicates containing various amounts of Al ₂ O ₃ and metal.

In a first aspect, the present invention relates to a synthetic porous crystalline composition having an X-ray diffraction pattern substantially containing the values shown in Table I of this specification and having an equilibrium adsorption capacity of greater than 10% by weight for water vapor, greater than 4.5% by weight for cyclohexane vapor. more than 10% by weight relative to hexane vapor.

The porous crystalline composition of the present invention appears to be related to the compositions described in U.S. Patent No. 4,439,409, entitled "PSH-3". However, the crystalline composition of the present invention is not expected to contain all of the components present in the PSH-3 formulations. The composition of the present invention is not substantially contaminated by other crystalline structures, such as ZSM-12 or ZSM-5, having unusual sorption capacity and unique catalytic efficiency as compared to PSH-3 formulations synthesized according to U.S. Patent 4,439,409.

The crystalline composition of the present invention is crystallized with a mixture of sources of the desired oxides with a hexamethyleneimine directing agent. However, it has been found that the crystalline composition according to the invention is a silicate having a relatively high solids content.

Therefore, the present invention also relates to a process for preparing the synthetic crystalline composition of the invention. Accordingly, a mixture is prepared from which the material according to the invention can be formed during crystallization; the mixture contains sufficient amounts of an alkali or alkaline earth metal cation, a tetravalent YO ₂ oxide source containing at least 30 wt% solid YO ₂ , a trivalent X ₂ O ₃ oxide source, water and hexamethyleneimine, and the mixture is required to form crystals of the period under crystallization conditions.

The composition of the crystalline composition according to the invention is thus

X ₂ O ₃ : is given by (n) Y0 ₂ molar ratio, where

X is a trivalent element such as aluminum, boron, iron and / or gallium, preferably aluminum,

HU213 311 Β

Υ is a tetravalent element such as silicon and / or germanium, preferably silicon, and n is at least 10, usually 10-150, preferably

10-60, most preferably 20-40.

Assuming the anhydrous state and expressed as the oxide-mole per n-mol YO ₂ ratio, the material synthesized as described above has the formula:

(0.005-0.1) Na ₂ O: (1-4) R: X ₂ O ₃ : nYO ₂ , wherein R is an organic group. The Na and R components are bound to the material by virtue of their presence during crystallization and can be easily removed by the subsequent crystallization methods described in more detail below.

The crystalline composition of the present invention is thermally stable, has a high specific surface area [greater than 400 m ² / g] and has an unusually high sorption capacity compared to similar crystalline structures. As can be seen from the above formula, the crystalline composition of the present invention is crystallized in a form substantially free of sodium cations. Therefore, it can be used as a catalyst with acid activity without ion exchange. However, the original sodium cations of the synthesized composition may be replaced to the desired extent with other cations by well known ion exchange techniques. Preferred replacement cations include metal ions, hydrogen ions, hydrogen precursors such as ammonium ions and mixtures thereof. Particularly preferred are the cations which control the catalytic activity at certain hydrocarbon conversions. These include metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Table of the Hydrogen, Rare Earths, and Elements.

The compositions of the invention, in their calcined form, appear to be composed of a single crystalline phase which is substantially free of crystalline impurities and an X-ray diffraction pattern distinguished from other known crystalline materials by the lines listed in Table I below:

Table I

Relative intensity between grid planes, distance d 10 “ ¹⁰ m I / I _o ^x 100

30.0 ± 2.2 W-M

22.1 ± 1.3 W more specifically in II. Lines listed in table 1:

II. spreadsheet

Relative intensity between grid planes, distance d 10 ^-10 m I / I _O x 100

30.0 ± 2.2 W-M

22.1 ± 1.3 W

3.91 ± 0.07 M-VS and more specifically in the following III. Lines listed in table 1:

III. spreadsheet

Distance d between grid planes (A) Relative intensity, I / IoxlOO 30.0 ± 2.2 W-M 22.1 ± 1.3 W 6.00 ± 0.10 W-M 4.64 ± 0.08 W 4.06 ± 0.07 W-S 3.91 ± 0.07 M-VS Most specifically, the calcined crystalline composition of the present invention has an X-ray diffraction pattern as shown in FIG. contains the lines listed in Table 1: ARC. spreadsheet Between grid planes Relative intensity, distance d (A) I / I _o xl00 30.0 ± 2.2 W-M 22.1 ± 1.3 W 12.36 ± 0.2 M-VS II, 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 W 4.64 ± 0.08 W 4.41 ± 0.08 W-M 4.25 ± 0.08 W 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 W 2.99 ± 0.05 W 2.82 ± 0.05 W 2.78 ± 0.05 W 2.68 ± 0.05 W 2.59 ± 0.05 w

These values were determined by standard methods. A K-alpha doublet of copper was used as the radiation source and a diffractometer equipped with a scintillation counter and a computer connected thereto were used for measurement. Peak heights and positions as a function of 2 theta - where theta was determined by the Bragg angle algorithm with a computer connected to the diffractometer. From these we determined the relative intensities of 100 * x I / I _o , where I _o is the intensity of the strongest line of the peak at 10 ^_1 ° m, and the distance between planes d. I-IV. The relative intensities in the tables are given by the following symbols: W = weak, M = medium, S = strong and VS = very

HU213 311 Β strong. Based on the intensities, these values are usually as follows:

W = 0-20

M = 20-40

S = 40-60

VS = 60-100

The X-ray diffraction pattern is characteristic of all types of crystalline compositions of the invention. Sodium form and other cationic forms give essentially the same picture with smaller shifts between planes and changes in relative intensity. Other minor changes may occur depending on the Y: X ratio of the sample, such as the Si: Al ratio and the degree of heat treatment.

The crystalline composition of the present invention can be prepared from a reaction mixture containing an alkali or alkaline earth metal such as sodium or potassium cation (M), a trivalent element (X) such as aluminum oxide and an organic (R) control agent (described in more detail below);

the composition of the mixture, expressed as the molar ratio of oxides, covers the following ranges:

reagents Useful advantageous YO2 / X2O3 10-80 10-60 H2O / YO2 5-100 10-50 OH® / YO ₂ 0.01-1.0 0.1-0.5 m / yo ₂ 0.01-2.0 0.1-1.0 r / yo ₂ 0.05-1.0 0.1-0.5.

It has been found that the crystallization of the composition according to the invention is favorably influenced if the YCl 2 source contains at least 30% by weight of solid YO ₂ , especially when YO ₂ corresponds to SiO ₂ . Commercially available sources of silicic acid include Ultrasil (precipitated spray-dried silica containing about 90% by weight of silica) and HiSil (about 87% by weight of silica, about 6% by weight of free H ₂ O and about 4.5% by weight of bound H _2). Precipitated hydrated SiO ₂ containing ot (hydrate) having a particle size of about 0.02 µm).

When using another source of silica, such as Q-Brand (sodium silicate containing about 28.8% SiO ₂ , 8.9% Na ₂ O and 62.3% H ₂ O), only crystallization few or no crystalline compositions of the invention are formed and instead become impure phases of crystalline structures such as ZSM-12. Therefore, preferably, the YO ₂ source comprises at least 30% by weight of solid YO ₂ , preferably silica, more preferably at least 40% by weight of solid YO ₂ .

In the mixture used to prepare the crystalline composition of the present invention, the organic control agent R is hexamethyleneimine (1).

Crystallization of the crystalline composition according to the invention can be carried out with or without stirring in a suitable container such as propylene vessels, or in Teflon-lined or stainless steel autoclaves. The crystallization is generally carried out at 80 to 225 ° C for 24 hours to 60 days, after which the crystals are separated from the liquid and isolated.

Crystallization may be facilitated by inoculating the mixture with 0.01% (preferably 0.11%, more preferably 11%) of the desired crystalline product (based on the total amount).

Before being used as a catalyst or adsorbent, the crystalline composition must be calcined to remove all or part of the organic constituents.

The crystalline composition of the present invention can be used as a catalyst in combination with hydrogenation components such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium to perform hydrogenation / dehydrogenation. Such a component may be incorporated into the composition by blend crystallization, base exchange, impregnation or physical mixing. For impregnation, for example in the case of platinum, the silicate is treated with a solution of a platinum metal ion. Suitable platinum compounds for this purpose include various compounds containing chloroplatinic acid, platinum (II) chloride and platinumamine complexes.

The crystalline composition of the present invention can be converted to very different particle sizes. The particles may be in the form of powders, granules or a molded product such as an extrudate. In the latter case, the crystalline product may be extruded before drying, or partially dried and then extruded.

When the crystalline composition according to the invention is used as an adsorbent or catalyst in the conversion process of organic compounds, it must be at least partially dehydrated. This can be carried out by heating at 200-595 ° C, for example in air, nitrogen, atmospheric pressure or lower or higher, for a period of 30 minutes to 48 hours. Dehydration can also be performed at room temperature by placing the silica in vacuo, but proper dehydration requires a longer time.

The crystalline material according to the invention can be used to catalyze a number of organic conversion processes, for example the conversion of C 2 -C 7 olefins such as propylene to alcohols and ethers at temperatures of 50 to 300 ° C, preferably 90 to 250 ° C, at least 5.5 x 10 4 Pa. at a pressure of at least 2.2 x 105 Pa, using a water to olefin molar ratio of 0.1 to 30, preferably 0.2 to 15.

As with many other catalysts, the crystalline composition of the present invention can be incorporated into other materials that are heat resistant and resistant to other conditions used in organic conversion processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites, as well as inorganic materials such as clays, silica and / or metal oxides such as alumina. The latter may be naturally occurring or may be in the form of gelatinous precipitates or gels containing a mixture of silica and metal oxides. If it is new during the crystallization of the crystalline composition according to the invention

When an active substance is used in combination with HU213311 Β crystal, i.e. in combination with it, the latter tends to alter the conversion and / or the selectivity of the catalyst in some organic conversion processes. Inactive materials can be used as diluents to control the amount of conversion in a given process so that the products can be produced economically and in a controlled manner without using other means to control the rate of crystallization. These materials can be incorporated into naturally occurring clays such as bentonite and kaolin to improve the breaking strength of the catalyst under industrial operating conditions. These materials, i.e. clays, oxides and others, serve as binders for the catalyst. It is desirable to provide a catalyst with a high refractive resistance, since in industrial applications it is desirable to prevent the catalyst from splitting into powdery materials. These clay binders are customarily used only to improve the breaking strength of the catalyst.

Naturally occurring clays that can be mixed with the new crystal include the montmorillonite and kaolin family, which includes the subbentonites and kaolins commonly known as Dixie, McNamee, Georgia, and Florida, or others in which the main mineral constitutent is halloysite, kaolinite, , naked or anauxite. Such clays may be used in their raw state in their original form, or in their pre-calcined, acid-treated or chemically modified forms. Suitable binders for mixing with the crystals of the invention are also inorganic oxides, namely aluminum oxide.

In addition to the above materials, the new crystal can also be mixed with porous matrix material such as silica alumina, silica magnesium, silica zirconia, silica beryllium oxide, silica titanium dioxide, and temeric compositions such as silica mixtures of alumina-thorium-oxide, silica-thymphold-zirconia, silica-alumina-magnesium and silica-magnesium-zirconia.

The relative proportions of the finely divided crystalline composition and the inorganic oxide matrix may vary considerably, such that the crystalline content is from 1 to 90% by weight and more generally from 2 to 80% by weight of the composition, particularly in the form of beads.

The invention will now be described in more detail with reference to the examples and accompanying drawings; 1-5. Fig. 4A is an X-ray diffraction pattern of the calcined products of Examples 1, 3, 4, 5 and 9. In the examples, where sorption data are reported for comparison with the sorption capacity for water, cyclohexane and / or n-hexane, equilibrium adsorption values were determined as follows:

The weighed sample of the calcined adsorbent is contacted with the desired pure adsorbate vapor in an evacuated adsorption chamber to a pressure of less than 133 Pa and contacted with water vapor at 1600 Pa and n-hexane or cyclohexane vapor at 5332 Pa; these pressures are less than the equilibrium pressure of the adsorbate in question at 90 ° C. The pressure is kept constant (± 66.6 Pa) by adding the adsorbate vapor with manostat control over the adsorption period, which does not exceed 8 hours. As the new crystal adsorbate adsorbs, as a result of the pressure drop, the manostat opens a valve that allows more adsorbate vapor into the chamber and thus restores the above regulatory pressures. Sorption is complete when the change in pressure is no longer sufficient to operate the manostat. The weight gain, the adsorption capacity of the sample, is expressed as g / 100 g of calcined adsorbent. The equilibrium adsorption values of the synthetic composition of the invention are always greater than 10% by weight for water vapor, greater than 4.5% by weight, generally 7% by weight for cyclohexane vapor and greater than 10% for n-hexane vapor.

Examination of alpha values shows that the alpha value is an approximate indicator of the catalytic cracking activity of the catalyst (compared to a standard catalyst) and gives a relative reaction rate constant (conversion rate of n-hexane per catalyst volume per unit time) relative to highly active silica alumina cracking catalyst with an alpha value of 1 (rate constant = 0.016 sec ^-1 ). The alpha test is described in U.S. Patent 3,354,078 and in Journal of Catalysis 4, 522-529 (1965). Note that in many acid catalyzed reactions, such as toluene disproportionation, xylene isomerization, alkene conversion, and methanol conversion, the "true" rate constants are proportional to the alpha value of the crystalline silicate in question (see Natur. 309: 589-591 (1984)).

Example 1

12.86 g of sodium aluminate (43.5% Al ₂ O ₃ , 32.2% Na ₂ O, 25.6% H ₂ O) are dissolved in 1320 g of water containing 12.8 g of 50% NaOH solution . To this solution was added 67.6 g of hexamethyleneimine. To the resulting solution

109.4 g of Ultrasil (precipitated by spray-dried silica; about 901% SiO ₂ ) are added.

The composition of the mixture is as follows (expressed in molar ratios):

SiO ₂ / Al ₂ O ₃ = 30.0

OH7SiO ₂ = 0.18

H2O / S1O2 = 44.9

Na / SiO ₂ = 0.18

R / SiO ₂ = 0.35 where R = hexamethyleneimine.

The mixture was crystallized in a stainless steel stirrer at 150 ° C for 7 days. The crystalline product is filtered off, washed with water and dried at 120 ° C. After 20 hours of calcination at 538 ° C, the X-ray diffraction diagram contains the major lines shown in Table V. Figure 1 shows an X-ray diffraction diagram of the calcined product. Measuring the sorption capacity of the calcined material gives the following results:

H ₂ 0 (1600Pa) 15.2% by weight

HU213 311 Β

Cyclohexane (5320 Pa) 14.6% by weight n-Hexane (5320 Pa) 16.7% by weight

The surface area of the calcined crystalline composition is 494 m ² / g.

Chemical composition of the calcined product:

Components Weight%

SiO ₂ 66.9 Al2O3 5.40 So 0.03 N 2.27 Ash 76.3 S1O2 / Al2O3 molar ratio = 21.1 Table V. 2 theta angles Inter-plane d-spacing (l (Γ ¹ ° m) I / I _o 2.80 31.55 25 4.02 21.98 10 7.10 12.45 96 7.95 11.12 47 10.00 8.85 51 12.90 6.86 11 14.34 6.18 42 14.72 6.02 15 15.90 5.57 20 17.81 4.98 5 19.08 4.65 2 20.20 4.40 20 20.91 4.25 5 21.59 4.12 20 21.92 4.06 13 22.67 3.92 30 23.70 3.75 13 25.01 3.56 20 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 2

A portion of the calcined crystalline composition of Example 1 was tested by the alpha test. The resulting alpha value is 224.

3-5. example

Mixtures of three different compounds having the composition shown in VI. shown in the table. Mixtures are prepared with sodium aluminate, sodium hydroxide, Ultrasil, hexamethyleneimine (R) and water.

The mixtures were maintained at 150 ° C, 143 ° C and 150 ° C for 7.8 and 6 days, respectively, with stirring (350 rpm) in an autogenous stainless steel autoclave. The solid product was separated from the unreacted components by filtration, washed with water and dried at 120 ° C. The product crystals are analyzed by X-ray diffraction, sorption capacity, surface area measurement and chemical analysis. The products have been found to correspond to the novel crystalline composition according to the invention. The results of the sorption test, surface area measurement and chemical analysis are also shown in Table VI. Table. The x-ray diffraction diagrams of the calcined (538 ° C, 3h) products of Examples 3, 4 and 5 are illustrated in Figures 2, 3 and 4, respectively. Sorption measurement and surface area measurement were performed on the calcined product.

VI. spreadsheet

Example number 3 Synthesis mixture, molar ratios 4 5 S1O2 / Al2O3 30.0 30.0 30.0 OH- ^{/ Sio} 2 0.18 0.18 0.18 H2O / S1O2 19.4 19.4 44.9 Na / SiO ₂ 0.18 0.18 0.18 R / S1O2 0.35 0.35 0.35

Product composition,% by weight

SiO ₂ 64.3 68.5 74.5 Al2O3 4.85 5.58 4.87 So 0.08 0.05 0.01 N 2.40 2.33 2.12 Ash 77.1 77.3 78.2 S1O2 / AI2O3 molar ratio 22.5 20.9 26.0 Adsorption,% by weight H ₂ O 14.9 13.6 14.6 cyclohexane 12.5 12.2 13.6 n-Hexane 14.6 16.2 19.0 Surface area, m ² / g 481 492 487

Example 6

Samples of calcined (538 ° C, 3h) crystalline silicate compositions of Examples 3, 4 and 5 were tested by the alpha test; Alpha values of 227, 180 and 187 were obtained.

Example 7

The calcined sample of the crystalline silicate of Example _{4 was} impregnated with Pt / NH _3/4 Cl _{2 until up to} about 1% by weight of Pt. The composition is then air dried at 349 ° C for 3 hours.

Example 8

One gram of the composition obtained in Example 7 is transferred into a small reactor with a preheater and an embedded thermocell as a catalyst. The catalyst is heated at 482 ° C in a stream of H _{2 to} reduce the Pt component. N-decane and H ₂ gas are introduced above the catalyst; the WHSV value decane 0.4H ^_1 and a hydrogen / hydrocarbon mole ratio

100/1. The reaction is carried out at a temperature in the range 130 to 250 ° C at atmospheric pressure.

The results of this experiment are shown in Table VII. Table. For comparison, the results of a similar experiment where ZSM-5 (U.S. Patent No. 3,702,886) and Zeolite beta (U.S. Patent No. 3,308,069) were used instead of the crystalline composition. It can be observed that the crystalline silicate of the present invention is a very active catalyst for the hydroconversion of n-decane and has good isomerization activity. VII. In the Table, "5MN / 2MN" refers to the 5-methyl-nonane / 2-methyl-nonane molar ratio. Due to the position of its methyl group, 5-methyl-nonane can penetrate into the pores of the zeolite to a lesser extent for spatial reasons. The 5MN / 2MN ratio provides information on the porosity of the zeolite to be tested.

VII. spreadsheet

Zeolite catalyst SiO2 / / AI2O3 molar ratio of zeo- litban Month- MERS. (° C) 50% con- version to isomerization -polymerization % 50% con- version- at 5mn / 2MN 5 t% muscle. 20% muscle Example 7 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 9

This example illustrates the preparation of a larger amount of the crystalline composition of the invention. 1200 g of hexamethyleneimine were added to a solution of 268 g of sodium aluminate, 267 g of 501% NaOH solution and 11,800 g of water, and 2280 g of Ultrasil silica were added. The mixture was crystallized with stirring (about 200 rpm) at 145 ° C in a 22.5 liter reactor. The crystallization time was 59 hours. The product was washed with water and dried at 120 ° C.

The X-ray diffraction diagram of the calcined (538 ° C) crystalline product is shown in Figure 5 and shows that the product is identical to the crystalline composition of the present invention. The results of the chemical composition, surface area and adsorption of the product are as follows.

VIII. spreadsheet

Product composition

C, 12.1%

N, 1.98% by weight

Na 640 ppm

Al2O3 5.0% by weight

74.9% by weight of S1O2

SiO2 / Al2O3, molar ratio 25.4

Adsorption,% by weight

Cyclohexane 9.1 n-Hexane 14.9

H ₂ O 16.8

Surface area, m ² / g 479

Example 10

25 g of the solid crystalline composition of Example 9 were calcined in a stream of N ₂ gas at 538 ° C for 5 hours and then purged with 5 wt% O ₂ for 16 hours at 538 ° C (N ₂ balance).

One 3 g sample of the calcined composition was subjected to ion exchange using 100 ml of 0. 1 TEABr (tetraethylammonium bromide), TPABr and LaCl 3 solution. The ion exchange was carried out at ambient temperature for 24 hours and repeated three times. The ion-exchanged samples were collected by filtration, washed with water to halogen-free and dried. The composition of the ion-exchanged samples is given below, together with the exchange capacity of the crystalline silicate of the invention for the various ions.

Replaceable ions TEA TPA La Ion composition,% by weight So 0,095 0.089 0,063 N 0.30 0.38 0.03 C 2.89 3.63 - La - - 1.04

Example 11

The above La-exchanged sample was converted to a particle size of 14-25 1.19-0.7 mm and calcined in air at 538 ° C for 3 hours. The calcined material has an alpha value of 173.

Example 12

All. The calcined sample of the La-exchanged material of Example 1b is heavily vaporized for 2 hours at 649 ° C in 100% relative humidity. The alpha value of the steamed sample is 22, indicating that the crystalline silicate is very stable under conditions of vigorous hydrothermal treatment.

Example 13

To obtain a crystalline material wherein X is boron, 17.75 g of boric acid are added to a solution of 6.75 g of 45% w / w KOH and 290 g of H ₂ O. thereafter

Ultrasil silica (57.8 g) was added to the solution and the mixture was thoroughly homogenized. To the mixture was added 26.2 g of hexamethyleneimine.

Composition of the mixture in molar ratios:

SiO ₂ / B ₂ O ₃ = 6.1

OH7SiO ₂ = 0.06

H ₂ O / SiO ₂ = 19.0

K / SiO ₂ = 0.06

R / SiO ₂ = 0.30

HU213311B wherein R is hexamethyleneimine.

The mixture was crystallized with stirring in a stainless steel reactor at 150 ° C for 8 days. The crystalline product is filtered off, washed with water and dried at 120 ° C. Part of the product was calcined for 6 hours at 540 ° C. Sorption capacity of the calcined product:

11.7% by weight

7.5% by weight

11.4% by weight surface area

H ₂ 0 (1600 Pa)

Cyclohexane (5320 Pa) n-Hexane (5320 Pa)

The calcined crystalline is 405 m ² / g.

When determining the chemical composition of the calcined material, the following data were obtained:

N, 1.94%

Na 1.75 ppm

K 0.60% by weight

Boron l, 04% by weight

A1 ₂ C> 3 920 ppm

SiO ₂ 75.9% by weight

Ash 74.11% by weight

SiO ₂ / Al ₂ O 3, molar ratio = 1406 SiO ₂ = / (Al + B) ₂ O ₃ , molar ratio = 25.8

Example 14

A portion of the calcined crystalline product of Example 13 was treated with NH 4 Cl and calcined again. The final crystalline product has an alpha value of 1 (based on alpha test).

Example 15

To obtain a crystalline product wherein X is boron, 35.0 g of boric acid are added to a solution of 16.7 g of 50% NaOH and 1160 g of water. To the resulting solution was added 240 g of HiSil silica followed by 105 g of hexamethyleneimine. Composition of the mixture in molar ratios:

SiO ₂ / B ₂ O ₃ ⁼ 12.3

OH7SiO ₂ = 0.056

H ₂ O / SiO ₂ = 18.6

Na7SiO ₂ = 0.056

R / SiO ₂ = 0.30 where R is hexamethyleneimine.

The mixture was crystallized with stirring at 300 ° C for 9 days in a stainless steel reactor. The crystalline composition is filtered off, washed with water and dried at 120 ° C. Sorption capacity of the calcined material (6 hours at 540 ° C):

H ₂ O (1600 Pa) 14.4% by weight Cyclohexane (5320 Pa) 4.6% by weight n-Hexane (5320 Pa) 14.0% by weight The calcined crystalline material surface t < 438 m ² / g. The chemical composition of the calcined material is as follows component Crowd% N 2.48 So 0.06 B 0.83 A1 ₂ O ₃ 0.50 SiO ₂ 73.4 SiO ₂ / Al ₂ O 3, molar ratio = 249 SiO ₂ / (Al + B) ₂ O ₃ , molar ratio = 28.2

The area

Example 16

Examining a portion of the calcined crystalline product of Example 15 in an alpha test, the product was found to have an alpha value of 5.

Example 17

It is important to use a source of silica containing at least 30% by weight of solid silica in the process of the invention. To confirm this, the procedure of Example 3 is repeated, but the silica source is "Q-Brandt" sodium silicate, which contains only about 29% by weight of solid silica.

67.6 g of aluminum sulfate are dissolved in a solution of 38.1 g of H2SO4 (96.1% by weight) and 400 g of water. The resulting solution was mixed with 120 g of hexamethyleneimine and added

712.5 g of Q-Brandt sodium silicate (28.8 wt% SiO ₂ and 8.9 wt% Na ₂ O) and 3 51 g water. Composition of the mixture obtained, expressed in molar ratios:

SiO ₂ / Al ₂ O ₃ = 30.0

OH7SiO ₂ = 0.18 _H2 O / _SiO2 = 19.4 Na / _SiO2 = 0.60 R / _SiO2 = 0.35

This mixture was thoroughly mixed and crystallized in a stainless steel reactor at 246 ° C for 8 days. The solid product was isolated by filtration from the unreacted components, washed with water and dried at 120 ° C. The product was analyzed by X-ray diffraction and found to be an amorphous mixture of magadite and mordenite. The crystals of the invention cannot be detected therein.

Example 18

This example compares the effect of the crystalline product of the present invention on the hydration properties of propylene with the similar activity of ZSM-12 and PSH-3 prepared according to Example 4 of U.S. Patent 4,439,409.

To obtain the crystalline product of the present invention, 1.59 g of a mixture of hexamethyleneimine, 3.5 parts of 50% NaOH, 3.5 parts of sodium aluminate, 30.1 parts of Ultrasil VN3 silica and 156 parts of deionized water are added. The mixture was then heated to 143 ° C and crystallized at this temperature with stirring. After complete crystallization, the crystals are separated from the liquid by filtration, washed with water and dried. Aluminum oxide was added to some of the crystals to give a mixture of 65% zeolite and 35 parts alumina. To this is added water so that the resulting catalyst can be extruded. This catalyst is activated by calcination in a stream of nitrogen at 540 ° C, then ion-exchanged with an aqueous solution of ammonium nitrate and the product calcined in air at 540-650 ° C.

For the preparation of ZSM-12, 1 part by weight of ZSM-12 seed crystal was 41.5 parts by weight of "Hi-Sil 233" silica, 67.7 parts by weight of 50% tetraethylammonium bromide, 7.0 parts by weight of 50% NaOH solution and 165.4 to a mixture of deionized water. The mixture was immediately heated to 138 ° C and crystallized in an autoclave with stirring at this temperature. Full crystalline8

After reaching a spin, the crystals were separated from the remaining liquid by filtration, washed with water and dried. Combining some of the crystals with Al ₂ O ₃ gives a mixture of 65 parts zeolite and 35 parts Al ₂ O ₂ . Water is added to the mixture so that the resulting catalyst can be converted into an extrudate. This catalyst is activated by calcination in N ₂ gas at 540 ° C, ion exchange with aqueous NH ₄ NO ₃ solution and calcined at 650 ° C.

The hydration of the propylene is carried out at 166 ° C and 7000 kPa; the propylene HSV is 0.6. The results obtained after 2 days of steaming are shown in Table IX. table compares:

IX. spreadsheet

PSH-3 Invention of com- zíció ZSM-12 Propylene Conversion (%) 1.9 27.8 10.8 Water Conversion (%) 5.7 33.7 8.1 IPA selectivity 88.7 76.7 74.6 DIPE selectivity 2.9 22.3 23.1 Oligomer selectivity 8.4 1.2 2.3

IPA = isopropyl alcohol DIPE = diisopropyl ether The above results clearly show the advantageous properties of the composition of the invention compared to zeolite PSH-3 and ZSM-12. The composition of the present invention achieves a higher conversion rate, coupled with good selectivity for diisopropylbenzene and low levels of propylene oligomer formation.

Claims (7)

CLAIMS distance d (10 ', ¹⁰ m) Claims 1. A synthetic porous crystalline composition having the composition of FIG X ₂ O ₃ : (n) Expresses the molar ratio YO ₂ where n is at least 10, X denotes a trivalent element and Y denotes a tetravalent element, characterized in that its X-ray diffraction pattern is determined by the following data: between grid planes distance (d) relative intensity (10 ^_1 ° m) Ι / Ι _ο χ100 (%) 30.0 + 2.2 0-40 22.1 ± 1.3 0-20 where I is the intensity I _o of the peak intensity of the strongest line in the 55 ° to 10 ^_1 in m, and the equilibrium adsorption capacity for water vapor viewed in the composition greater than 4.5 wt%, 4.5 wt% of cyclohexane larger and n more than 10% by weight with respect to hexane vapor. gn Synthetic porous crystalline composition according to claim 1, characterized in that the X-ray diffraction pattern is determined by the following data: distance between grid planes d relative intensity (10 ^_1 ° m) I / I _o x100 (%) 30 + 2.2 0-40 22, Hl, 3 0-20 3.91 + 0.07 20-100; wherein I, I _p are as defined above. Synthetic porous crystalline composition according to claim 1, characterized in that its X-ray diffraction pattern is determined essentially by the following data: distance between grid planes d (10 ^_1 ° m) relative intensity I / I _o * 100 (%) 30.0 + 2.2 0-40 22.1 + 1.3 0-20 6.00 + 0.10 0 ^ 10 4.64 + 0.08 0-20 4.06 + 0.07 0-60 3.91 + 0.07 20-100 wherein I, I _p, are as defined above. Synthetic porous crystalline composition according to claim 1, characterized in that its X-ray diffraction pattern is determined by the following data: relative intensity between lattice planes I / IoXlOO (%) 30.0 + 2.2 22.1 ± 1.3 12.36 ± 0.2 11.03 ± 0.2 8.83 + 0.14 6.86 + 0.14 6.18 + 0.12 6.00 & 0.10 5.54 & 0.10 0-40 0-20 20-100 20-80 20-100 0-60 20-100 0 → 40 0-40 where I, I _{o has} the meaning given above. The crystalline composition of claim 1, wherein X is aluminum and Y is silicon, and n is as defined in claim 1. The crystalline material according to claim 5, wherein n is from 20 to 40 and X and Y are as defined in claim 5. 7. A process for the preparation of a synthetic crystalline composition according to claim 1, wherein the composition is in the following mole ratios: YO ₂ / X ₂ O ₃ = 10-80 H ₂ O / YO ₂ = 5-100 ΟΗ ^θ / ΥΟ ₂ = 0.01–1.0 Μ / ΥΟ ₂ = 0.01-2.0 R / YO ₂ = 0.05 to 1.0 where R is hexamethyleneimine and M is an alkaline or alkaline earth metal; the mixture comprises an alkali or alkaline earth metal cation containing 5 tetravalent Y-oxide sources containing at least 30% by weight of solid YO ₂ , a trivalent X-oxide source, water and hexamethyleneimine, and the mixture at a temperature of 80-225 ° C, It is crystallized for 24 hours to 60 days.