SK278660B6 - Synthetic zeolite and preparation method thereof - Google Patents

Abstract

This patent is dealing with synthetic zeolite, a character of which is seen based on the X-ray diagram, represented by the values described in the table I and this zeolite is prepared based on the reaction mixture containing YO2/X2O3 = 10 up to 80, H20/YO2 = 5 up to 100, OH/YO2 = 0,01 up to 1,0 M/YO2 = 0,01 up to 2,0, R/YO2=0,05 up to 1,0, while these measures are expressed in molar ratio, and where R means hexamethylenimine and M alkaline metal or metal closed to alkaline earth, where the resource of Y oxide contains minimum 30 weight percent of the solid YO2 and this reaction mixture is being kept at the temperature of 80 up to 300 Celsius degrees, for 24 hours up to 60 days, until the crystals closed to the above mentioned material are not created.

Description

Technical field

The present invention relates to synthetic zeolite and to a process for its preparation. These materials are used in the catalytic conversion of organic compounds.

BACKGROUND OF THE INVENTION

Zeolite materials, both natural and synthetic, have, as has been shown in the past, catalytic properties for various types of hydrocarbon conversions. Certain zeolite materials are ordered, porous crystalline aluminosilicates having a certain crystalline structure, as determined by X-ray diffraction in which there are a large number of smaller cavities that can be interconnected by a plurality of smaller channels or pores. These cavities and pores have a uniform size in specific zeolite materials. Since the dimensions of these pores are suitable for adsorption of molecules of certain sizes and not accepting larger size materials, these materials are known as molecular sieves and are used in a number of ways where these properties are desirable.

These molecular sieves, both natural and synthetic, contain a considerable width of crystalline silicates containing a positive ion. These silicates can be described as solid three-dimensional structures of SiO ₄ and an oxide of a Group IIIA element of the Periodic Table of Elements, e.g. A10 ₄ in which the tetrahedra are cross-linked by shared oxygen atoms whereby the ratio of the total Group IIIA element, e.g. aluminum and silicon atoms to 1: 2 oxygen atoms. The electrovalence of a tetrahedra containing a Group III A element, e.g. aluminum, is balanced by the inclusion of a cation in the crystal, e.g. an alkali metal or alkaline earth metal cation. This can be expressed by the ratio of the Group III A element, e.g. aluminum, to a number of different cations, such as Ca / 2, Sr / 2, NA, K or Li, equal to a unit. One type of cation may be exchanged for another either wholly or partially by different ion exchange cation exchange techniques. By such cation exchanges it is possible to alter the properties of the silicates by the appropriate choice of cations.

These techniques have led to the formation of large amounts of synthetic zeolites. Many of these zeolites have been marked with a letter or other conventional symbols, such as zeolite A (US Patent No. 2882243), zeolite X (US Patent No. 2882444), zeolite Y (US Patent No. 31130007), zeolite ZK-5 (US patent) zeolite ZK-4 (US patent no.3314752), zeolite ZSM-5 (US patent no.3702886), zeolite ZSM-11 (US patent no.3709979), zeolite ZSM-12 (US patent no. 3832449), zeolite ZSM-20 (US Patent No. 3972983), ZSM-35 (US Patent No. 4016245) and zeolite ZSM-23 (US Patent No. 4076842).

The SiO ₂ / Al ₂ 0 ₃ ratio in these zeolites often changes. For example, zeolite X can be synthesized with SiO ₂ / Al ₂ O ₃ ratios of 2 to 3; zeolite Y from 3 to 6. In some zeolites, the upper limit of the SiO ₂ / Al ₂ 0 ₃ ratio is not limited. ZSM-5 is one such example where the SiO ₂ / Al ₂ O ₃ ratio is at least 5 up to the limits of current analytical measurement techniques. U.S. Pat. No. 3,918,171 (Re.29948) discloses a porous crystalline silicate made from a reaction mixture that contains non-specific aluminum added in the recipe and which exhibits an X-ray diffraction pattern characteristic of ZSM-5. U.S. Patent Nos. 4,061,724, 4,738,665, and 410,442 disclose crystalline silicates with varying aluminum and boron contents.

SUMMARY OF THE INVENTION

In a first aspect, the present invention relates to a synthetic porous crystalline material characterized by an X-ray diffraction pattern comprising the values shown in Table I of the description and having an equilibrium adsorption capacity of greater than 10% by weight. % to water vapor, greater than 4.5 wt. on cyclohexane vapor and greater than. weight. on n-hexane vapor.

The synthetic zeolite of the present invention is similar to the compositions designated PSI1-3 described in U.S. Patent No. 4,430,409. However, the crystalline material does not contain all the components present in the PSH-3 compositions. In particular, the material of the invention is not contaminated with crystal structures other than ZSM-12 or ZSM-5, exhibits unusual sorption capacities and excellent catalytic efficiency when compared to PSH-3 compositions synthesized according to US Patent No. 4,439,409.

The crystalline material of the present invention can be synthesized by crystallizing a reaction mixture containing sources of the desired oxides together with a hexamethylene diluent. However, it has been found to be advantageous when the crystalline material of the invention is a silicate, therefore it is important to use a silicon source having a relatively high solids content.

Accordingly, in a second aspect, the present invention relates to a process for preparing a synthetic crystalline material according to said first aspect, comprising reacting a mixture capable of forming said material by crystallization. Said mixture contains in molar ratios YO ₂ / X ₂ O ₃ = 10 to 80, H ₂ O / YO ₂ = 5 to 100, OH / YO ₂ = 0, 01 to 1,0, M / YO ₂ = 0, 01 to 2, and R 0 / Y0 = ₂ = 0.05 to 1, 0, wherein R represents hexamethyleneimine and M is an alkali metal or alkaline earth metal, wherein the source of Y oxide containing 30 wt% solid YO _2, and the mixture was maintained at 80 to 300 ° C for 24 hours to 60 days, until crystals of said material are formed.

The synthetic zeolite of the present invention has a composition characterized by a molar ratio of X ₂ 0 ₃ : / n / YO ₂ where n is at least 10, X is a trivalent element selected from the group consisting of aluminum, boron, iron and gallium and Y is a tetravalent element selected from the group comprising silicon and germanium. Preferably, X is aluminum, Y is silicon and n is preferably 10 to 150, more preferably 10 to 60 and most preferably 20 to 40. In as-synthesized form, the material in anhydrous form and in moles of oxides per mole of YO ₂ has the following formula: (0.005-0) , 1) Na ₂ 0: (1 -4) R: X ₂ O ₃ : nYO ₂ where R is an organic group. Na and R components are associated with the material due to their presence during crystallization and are readily removable by post-crystalline methods, which are described in more detail below.

The crystalline material of the present invention is thermally stable and has a high specific surface area (greater than 400 m ² / g) and an unusually large sorption capacity compared to similar crystalline structures. As is evident from the above formula, the crystalline material of the present invention is synthesized almost free of Na cations. It can therefore be used as a catalyst with acid efficiency without an exchange step. If desired, the original sodium cations in the as-synthesized material can be replaced, at least in part, by techniques known in the art, by exchanging ions for other cations. Preferred exchanged cations include metal ions, hydrogen ions, hydrogen precursors, e.g. ammonium ions and mixtures thereof. Preferred cations are those which deliberately affect the catalytic activity of certain hydrocarbon conversion reactions. These include hydrogen, rare earth metals and metals of Groups IIA, ΠΙΑ, IVA, 1B, IIB, IIIB, IVB and VII of the Periodic Table of the Elements.

In its calcined form, the crystalline material of the invention can be obtained as uniform crystal phases with small amounts or undetectable crystal phase impurities and has an X-ray diffraction pattern that differs from the diagrams of known crystalline materials by the lines shown in Table I below:

Table I

Interplanar d-distance (A) relative intensity,

I / _{D D} x 100

30.0 ± 2.2 W-M

22, 1 ± 1, 3 W more specific lines shown in Table II below: Table II

Interplanar d-distance (A) relative intensity, 30.0 ± 2.2 I / L _by x100

22.1 ± 1.3W-M

3.91 ± 0.07W

M-VS and the more specific lines shown in Table III: Table III

Interplanar d-distance (A) relative intensity.

30.0 ± 2.2 I / 100 100 22.1 ± 1.3 W-M 6.00 ± 0.10 W 4.64 ± 0.08 W-M 4.06 ± 0.07 W 3.91 ± 0.07 W-S Most specific calcined M-VS crystalline material according to the invention has an X-ray diffraction pattern which includes the lines below in Table IV: Table IV Interplanar d-distance (A) relative intensity, 30.0 ± 2.2 I / O _by x 100 22.1 ± 1.3 W-M 12.36 ± 0.2 W 11.03 ± 0.2 M-VS 8.83 ± 0.14 M-S 6.86 ± 0.14 M-VS 6.18 ± 0.12 W-M 6.00 ± 0.10 M-VS 5.54 ± 0.10 W-M 4.92 ± 0.09 W-M 4.64 ± 0.08 W 4.41 ± 0.08 W 4.25 ± 0.08 W-M 4.10 ± 0.07 W 4.06 ± 0.07 W-S 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

Table IV - continued

Interplanar d-distance (A) relative intensity,

I / O 'x 100

3.20 ± 0.05W-M

3.14 ± 0.05W-M

3.07 ± 0.05W

2.99 ± 0.05W

2.82 ± 0.05W

2.78 ± 0.05W

2.68 ± 0.05W

2.59 ± 0.05W

These values were determined by standard techniques. The radiation was a K-alpha doublet of copper and a dicractometer equipped with a scintillation counter with a connected computer was used. The heights of maximum I and the position as a function of 2 theta, where theta is the Bragg angle, were determined using computer algorithms coupled to a diffractometer. From this, relative intensities, 100 I / I _o , were determined, where I _o is the intensity of the strongest line or maximum and (pos.) The interplanar distance in Angstrom units (A), corresponding to the recorded lines. In Tables I to IV, the relative intensities indicated by the symbols W = = weak, M = medium, S = strong and VS = very strong, as intensities may be indicated as follows: W = 0-20 M = 20-40 S = 40-60 VS = 60-100

X-ray diffraction patterns are characteristic of all kinds of crystalline compositions. The sodium form as well as the other cationic forms show essentially the same diagrams with some small changes in interplanar distances and changes in relative intensity. Other small variations may arise depending on the Y to X molar ratio, e.g. silicon to aluminum, in the individual formulas, as well as at the degree of their heat treatment.

The crystalline material of the invention may be prepared from a reaction mixture comprising alkali metal and alkaline earth metal (M) sources, e.g. sodium or potassium in the form of a cation, the oxide of the trivalent element X, e.g. aluminum, a tetravalent element oxide Y, e.g. silicon, an organic control agent (R) as described below, and water. Said reaction mixture has a composition expressed in molar ratios of oxides, within the following ranges:

reactants suitable great Y0 ₂ / X ₂ 03 10-80 10-60 H ₂ 0 / Y 0 ₂ 5-100 10-50 oh ₂ / 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 material according to the invention is advantageous if the source of Y ₂ comprises at least 30% by weight of solid Y ₂ , especially if Y ₂ is silica. Preferred commercially available silica sources include Ultrasil (precipitated, spray-dried silica containing about 90% by weight silica) and HiSil (precipitated hydrated SiO 2 containing about 87% by weight silica, about 6% by weight free, such as the YO ₂ source contains at least 30 wt% solid YO ₂ is silica Preferred commercially available silica sources include Ultrasil (precipitated, spray dried silica containing about 90 wt% silica) and HiSil (precipitated hydrated SiO ₂ containing about 87 wt.% silica, about 6 wt.% free water, and about 4.5 wt.% hydrated bound water having a particle size of about 3 wt.

276 bone (about 0.02 μιη). If another silica source is used, e.g. Q-Brand (sodium silicate containing about 28.8% by weight SiO ₂ , 8.9% by weight Na ₂ O and 62.3% by weight H ₂ O) was found not to yield the material of the invention by crystallization or only in small amounts and instead of 5 impurities of other crystalline structures, e.g. ZSM-12th Therefore, preferably the YO ₂ source contains at least 30 wt. % solid YO ₂ , preferably silica and even more preferably at least 40 wt. solid Y0 ₂ .

The organic control reagent (R) used in the synthesis of the present crystalline material from said reaction mixture is hexamethyleneimine having the following structural formula:

Crystallization of the present crystalline material 20 can be carried out or under static conditions or with stirring in a suitable reaction vessel, such as a polypropylene vessel or teflon-lined autoclaves or stainless steel autoclaves. Crystallization is generally carried out at a temperature of 80 ° C to 25 ° C for 24 hours to 60 days. The crystals are then separated from the liquid and isolated.

Crystallization is carried out in the presence of at least 0.01 percent, preferably 0.10 percent and even more preferably 1 seed crystals (based on total weight) of the desired crystalline product.

Before being used, the catalyst or adsorbent material of the invention should be calcined to remove some or all of the organic components. 35

The crystalline material of the invention may be used in combination with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or noble metals such as platinum or palladium, where the hydrogenation-dehydrogenation function is guaranteed. Such a component may be present in the composition via co-crystallization, ion exchange in the composition, its impregnation or intensive physical mixing. This component may be impregnated into or onto the material of the invention, such as in the case of platinum, by treating the silicate with a solution containing a platinum ion. Platinum compounds suitable for this purpose include chloroplatinic acid, platinum (II) chloride and various compounds containing a platinum-amine complex.

The crystalline material of the present invention 50 may be formed into different particles of different sizes. In general, the particles can be shaped as a powder, a granulate or a molten product such as an extrudate. In the latter case, the crystalline material may be extruded before drying or may be partially dried and then extruded.

The crystalline material of the present invention, when used or as an adsorbent or as a catalyst in methods for converting organic compounds, should be at least partially dehydrated. This can be achieved by heating to a temperature in the range of 200 ° C to 595 ° C in an atmosphere such as air, nitrogen, and the like. and at atmospheric pressure or a pressure lower or higher than atmospheric pressure for between 30 minutes and 48 hours. Dehydration can also be carried out at room temperature only by placing the silicate under vacuum, but a longer period of time is required to achieve a sufficient degree of dehydration.

The crystalline material of the present invention can be used to catalyze various organic conversions, including, for example, hydration of C ₂ -C 7 such as propylene, to alcohols and ethers under reaction conditions that include a temperature of from 50 to 300 ° C, preferably from 90 to 250 ° C, a pressure of at least 5 kg / cm ² , preferably at least 20 kg / cm ^2, and a water / olefin mole ratio of from 0.1 to 30, preferably 0.2 to 15.

As with other catalysts, it is possible to incorporate the crystalline material of the invention with another material resistant to temperature and other conditions used in organic conversion processes. Such materials include active or inactive materials and zeolites of synthetic or natural origin, as well as inorganic materials such as clays, silica and / or metal oxides such as alumina. This may be either of natural origin or in the form of gel-like precipitates or gels comprising mixtures of silica and metal oxides. The use of the material in conjunction with the new crystal, i. coupling with it during synthesis of a new crystal that is active leads to a change in catalyst conversion and / or selectivity in certain organic conversion processes, preferably the active materials serve as diluents to control the degree of conversion in the process so that products can be obtained economically and without other response rate control devices. These materials can be incorporated into clays of natural origin, e.g. bentonite and kaolin to improve the crush strength of the catalyst under normal conditions. Said materials, i. clays, oxides, etc., act as binders on the catalyst. It is desirable to provide a catalyst having good resistance to crushing, since in commercial use it is desirable to protect the catalyst from disintegration into a pulverulent material. These clay binders are commonly used only to improve the crush resistance of the catalyst.

Natural clays that can be used as composites with the new crystalline material include montmorillonite and kaolin types of clays, these include subbentonify and kaolins commercially known as Dixie, McNamee, Georgia and Florida, or others in which the main mineral component is halloysite, kaolinite , dickite, nacrit, or anauxite. These clays may be used in the raw state as extracted or processed by calcination, acid treatment or chemically modified. Binders suitable for use with the crystals of the invention also include inorganic oxides, especially alumina.

As an additive to said materials, the novel crystalline material may comprise a porous matrix material such as silica-alumina, silica-magnesium, silica-zirconia, silica-toric oxide, silica-beryllium oxide, silica-titanium dioxide. as well as topical compositions such as silica-alumina-thorium oxide, silica-alumina-zirconia, silica-alumina-magnesium oxide, and silica-magnesium-zirconia.

The ratio of the finely divided components of the crystalline material to the inorganic oxide matrix varies widely, with crystals comprised between 1 and 90 percent by weight, and more preferably, when the composite is prepared in the form of beads, between 2 and 80 percent by weight of the composite.

The present invention is explained in more detail by the following examples and the accompanying drawings, in which: FIG. 1 to 5 are X-ray diffraction diagrams of the calcined products of Examples 1, 3, 4, 5 and 9. Whenever the sorption data for comparing the sorption capacities of water, cyclohexane and / or nhexane is given in the examples, the equilibrium adsorption values were determined as follows:

The weighed sample of calcined adsorbent was contacted with the desired clean adsorbate vapor in an adsorption chamber evacuated to less than 1 mm Hg and contacted with 1.6 kPa of water vapor and 5.3 kPa of n-hexane or cyclohexane vapor, pressures less than equilibrium pressure para-liquid of the respective adsorbate at 90 ° C. The pressure was kept constant (with about ± 0.5 mm Hg) by the addition of adsorbate vapor under a controlled manostat during the adsorption period, which did not exceed 8 hours. Once the adsorbate is adsorbed by the new crystalline material, a valve is opened by depressurizing the pressure with a pressure switch to allow larger amounts of vapor adsorbate to enter the chamber to maintain said pressures. The sorption is complete when the pressure change is not sufficient to activate the manostat. The weight gain is calculated as the adsorption capacity of the sample in g / 100 g of calcined adsorbent. The synthetic material of the present invention always exhibits equilibrium adsorption values greater than 10% by weight. % to water vapor, greater than 4.5 wt.%, usually greater than 7 wt. % on cyclohexane vapor and greater than 10 wt. on n-hexane vapor.

If the alpha-value is tested, it should be noted that the alpha-value is an approximate indication of the catalytic cracking activity of the catalyst compared to the standard catalyst and gives the relative rate constant (normal hexane conversion rate per catalyst volume per unit time) compared to the activity of the highly active catalyst. silica-alumina evaluated as alpha 1 (rate constant = 0.016 s ^-1 ). The alpha test is described in U.S. Pat. 3354078 and Journal of Catalysis, Vol. IV, p. 522-529 (August 1965). It is necessary to state that the true rate constants of many acid catalyzed reactions are proportional to the alpha value per single crystalline silicate catalyst, i. 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

12.68 g of sodium aluminate (43.5% Al 2 O 3, 32.2% Na ₂ O, 25.6% H 2 O) are dissolved in a solution containing 12.8 g of a 50% NaOH solution and 1320 g of water. To this solution was added 57.6 g of hexamethyleneimine. To the resulting solution was added 109.4 g of Ultrasil, precipitated by spray-dried silica (about 90% SiO ₂ ).

The reaction mixture has the following composition in molar ratios:

SiO ₂ / Al ₂ 0 ₃ = 30.0

OH7Si0 ₂ = 0.18

H ₂ O / SiO ₂ = 44.9

Na / SiO ₂ = 0.18

R f SiO 3 = 0.35 where R is hexamethylenimine. The mixture was crystallized in a stainless steel reactor with stirring 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 pattern contains the main lines shown in Table V. FIG. 1 is a diffraction pattern of the X-rays of the calcined product. The following sorption capacities of the calcined material were measured:

% H ₂ O (1.6 kPa) 15.2 wt.

% cyclohexane (5.3 kPa) 14.6 wt. n-hexane (5.3 kPa) 16.7 wt.

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

The chemical composition of the calcined material was

determined as follows: component weight. % Si0 ₂ 66.9 Article ₂ 0i 5.40 On the 0.03 N 2.27 ash 76.3 SiO ₂ / Al ₂ 0 ₃ , molar ratio = 21.1 Table V degrees interplanar 2 theta distance (A) 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 product of Example 1 was tested in an alpha assay and was found to have an alpha value of 224.

Examples 3 to 5

Three synthesis reaction mixtures were prepared in the composition shown in Table VI. The mixtures were prepared from sodium aluminate, sodium hydroxide, Ultrasil, hexamethylenimine (R) and water. The mixtures were maintained at 150 ° C, 143 ° C and 150 ° C for 7, 8 and 6 days, in a stainless steel autoclave, stirred (350 rpm) at autogenous pressure. The solid was separated from the unreacted components by filtration, and then washed with water followed by drying at 120 ° C. The product crystals were analyzed by X-ray diffraction, specific surface area by sorption and chemical analyzes. The product has been found to be the novel crystalline material of the present invention. The results of the sorption, specific surface and chemical analysis are also shown in Table VI. The X-ray diffraction patterns of the calcined (538 ° C for 3 hours) products of Examples 3, 4 and 5 are shown in FIG. 2, 3 and 4. Sorption and specific surface determination were performed on the calcined product. 10 entry into zeolite pores. The 5MN / 2MN ratio provides information about the porosity of the zeolite tested.

Zeolite SiO .- / A1.O.

catalyst mol. heart rate-TCipre% isotr .. 5MN / 2MN

In zeo.ite SOi conversion at 50% 5% 20% Example 7

Be: and 30

7.O, 9 174

5G 107

O, 15 0.24

0.11 0.15

189 o, ee o, 59

Table VI

Example # 3 4 5 synthesis mixture, mol. ratio

SiO ₂ / Al ₂ 0 ₃ 30.0 30.0 30.0 15 OH7Si0 ₂ 0, 18 0.18 0.18 H ₂ 0 / SiO ₂ 19.4 19.4 44.9 Na / SiO ₂ 0.18 0.18 0.18

product composition, wt.

R / SiO ₂ 0.35 0.35 0.35 20 SiO ₂ 64.3 68.5 74.5 ai ₂ 0 ₃ 4.85 5.58 4.87 On the 0.08 0.05 0.01 ash 77.1 77.3 78.2 N 2.40 2.33 2.12 25 SiO ₂ / Al ₂ 0 ₃ , mol. ratio 22.5 20.9 26.0

Adsorption, wt%

H ₂ 0 14.9 13.6 14.6 cyclohexane 12.5 12.2 13.6 30 n-hexane 14.6 16.2 19.0 specific surface, m ² / g481 492 487

Example 6

The calcined (538 ° C for 3 hours) samples of the crystalline silicate product of Examples 3, 4 and 5 were tested in the alpha assay and were found to have alpha values of 227, 180 and 187.

Example 7 40

A calcined sample of the crystalline silicate of Example 4 was impregnated with a Pt (NH ₃ ) ₄ Cl _{2 solution} to about 1 wt. Pt. This material was then heated in air at 349 ° C for 3 hours.

Example 8

One gram of the product of Example 7 was placed as a catalyst in a small reactor with a preheater and a built-in thermocouple. The catalyst was then heated to 482 ° C in a stream of hydrogen to reduce the Pt 50 component. Normal decane and hydrogen were introduced over the catalyst at a rate of 0.4 h ^-1 WHSV decane at a 100/1 hydrogen / hydrocarbon molar ratio. The reaction was carried out at a temperature of 130 to 250 ° C at atmospheric pressure. 55

The results of this experiment are shown in Table VII, together with the results of the same experiment, but with the replacement of crystalline material ZSM-5 (US Patent No. 3702886), ZSM-1 (US Patent No. 3709979) and zeolite beta (US Patent No. 3308069). ) for comparison. It has been found that the crystalline silicate of the present invention is a very active catalyst for the conversion of n-decane and has good isomerization activity. In Table VII, 5MN / 2MN is the 5-methylnonane / 2-methylnonane molecular ratio.

Due to the location of its methyl group, 5-methyl-65-tylnonane provides a slightly higher steric hindrance to

Example 9

To demonstrate the large-scale preparation of crystalline material, 1200 g of hexamethylenimine is added to a solution containing 268 g of sodium aluminate, 267 g of 50% sodium hydroxide solution and 11,800 g of water. To this solution was added 2.280 g of Ultrasil silica. The mixture was crystallized at 145 ° C in a 5-gallon reactor with stirring (about 200 rpm). The crystallization time was 59 hours. The product was washed with water and dried at 120 ° C.

The X-ray diffraction pattern is shown in FIG. 5 and demonstrates that the product is a crystalline material according to the present invention. The chemical composition of the product, the specific surface area and the results of the adsorption analyzes are given below:

Table VIII

Product composition

C

N

On the

Al ₂ 0;

Si0 ₂

SiO ₂ / Al ₂ 0 ₃ , mol. ratio

Adsorption, wt% cyclohexane n-hexane

H ₂ O specific surface area, m2 / g

12.1 wt.

1.98 wt.

640 ppm

5.0 wt.

74.9 wt.

25.4

9.1

14.9

16.8

479

Example 10

A 25 gram sample of the crystalline solid product of Example 9 was calcined in a stream of nitrogen at 538 ° C for 5 hours, then 5% oxygen-containing gas (N 2 equilibrium) was fed for a further 16 hours at 538 ° C.

Individual 3g samples of calcined material are treated ionically with 100 ml of 0.1N TEABr, TPABr and LaCl ₃ solution. Each ion exchange is carried out at ambient temperature for 24 hours and repeated three times. The exchanged samples are filtered, washed with water to remove halides and dried. The composition of the ion exchange processed samples is in the following table to demonstrate the exchange capacity of the crystalline silicate of the present invention to different ions.

Exchanged ions TEA TPA la ionic composition,% by weight On the 0,095 0,089 0,063 N 0.30 0.38 0.03 C 2.89 3.63 la - - 1.04

Example 11

Said La-swap sample was processed to a size of 14 to 25 mesh, and then calcined in air at 538 ° C for 3 hours. The calcined material has an alpha value of 173.

Example 12

The calcined sample of La-exchanged material of Example 11 was steamed under rough conditions at 649 ° C with 100 steam for 2 hours. The steamed sample has an alpha value of 22, indicating that the crystalline silicate has very good stability under rough hydrothermal processing conditions.

Example 13

For the preparation of crystalline material wherein X is boron with 17.5 g of boric acid is added to a solution containing 6.75 g of 45% potassium hydroxide solution and 290 g of water. To this solution was added 57.8 g of Ultrasil silica and the mixture was carefully homogenized. 26.2 g of hexamethylenimine are added.

The reaction mixture has the following composition in molar

ratios: Si0 ₂ / B ₂ 0 ₃ 6.1 OH '/ SiO ₂ 0.06 H ₂ O / SiO ₂ 19.0 K7SiO ₂ 0.06 R / Si0 ₂ 0.30 wherein R is hexamethylenimine.

The mixture was crystallized in a stainless steel reactor with stirring at 150 ° C for 8 days. The crystalline product is filtered off, washed with water and dried at 120 ° C. A portion of the product was calcined for 6 hours at 540 ° C, and was found to have the following sorption capacities: H ₂ O (1.6 kPa) 11.7 wt.

% cyclohexane (5.3 kPa) 7.5 wt. n-hexane (5.3 kPa) 11.4 wt.

The specific surface area of the calcined material was 405 m ² / g.

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

N 1.94 wt.

At 175 ppm

% To 0.60 wt.

boron 1.04 wt

Al ₂ 0 ₃ 920 ppm

S10 ₂ 75, 9% by weight.

ash 74.11 wt.

SiO ₂ / Al ₂ O ₃ , mol. ratio. = 1406 SiO ₂ / (Al + B) 203, molar ratio = 25.8

Example 14

A portion of the calcined crystalline product of Example 15 was treated with NH ₄ Cl and further calcined. The final crystalline product was tested in the alpha assay and was found to have an alpha value of 1.

Example 15

To prepare a crystalline material of the invention wherein X is boron, 35.0 g of boric acid is added to a solution of 15.7 g of 50% sodium hydroxide solution and 1160 g of water. To this solution was added 240 g of HiSil silica, followed by 105 g of hexamethyleneimine. The reaction mixture has the following composition in molar ratios.

Si0 ₂ / B ₂ 0 ₃ 12, 3 OH / SiO 0, 056 H ₂ O / SiO ₂ 18.6 Na / SiO ₂ = 0.056 R / SiO ₂ 0.30 wherein R is hexamethylenimine.

The mixture was crystallized in a stainless steel reactor with stirring at 300 ° C for 9 days. The crystalline product is filtered off, washed with water and dried at 120 ° C. The following sorption capacities of the calcined material (6 hours at 540 ° C) were measured: H 2 O (1.6 kPa) 14.4 wt.

% cyclohexane (5.3 kPa) 4.6 wt.

% n-hexane (5.3 kPa) 14.0 wt.

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

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

N2,48

Na0.06 boron0.83

Al ₂ 0 ₃ 0.50

SiO, 73.4

SiO ₂ / A1 ₂ 0 ₃ , mol. ratio = 249

SiO ₂ / (Al + B) 203, mol. ratio = 28, 2

Example 16

A portion of the calcined crystalline product of Example 15 was tested in an alpha assay and was found to have an alpha value of 5.

Example 17

To illustrate the importance of using a silica source containing at least 30% solid silica, Example 3 was repeated except that Q-Brand sodium silicate (containing only about 29% solid silica) was used as the silica source. In this example, 67.6 g of aluminum sulfate was dissolved in a solution of 38.3 g of sulfuric acid (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% SiO ₂ and 8.9% Na ₂ O and 351 g water). :

Si0 ₂ / Äl ₂ 0 ₃ 30.0 OH7SiO ₂ = 0.18 H, 0 / Si0 ₂ = 19.4 Na / SiO ₂ = 0, 60 RlsII. = 0.35

The mixture is carefully mixed and crystallized by stirring in a stainless steel reactor at 246 ° C for 8 days. The solid products are separated from the unreacted components by filtration, and then washed with water and dried at 120 ° C. The product was analyzed by X-ray diffraction and was found to be a mixture of amorphous material, magadite and mordenite. No crystals of the present invention have been discovered.

Example 18

In this example, the propylene hydration properties of the crystalline material of the present invention were compared with the ZSM-12 and PSH-3 materials prepared according to Example 4 of US Patent No. 5,768,549. 4,439,409th

The crystalline material of the invention was prepared by adding 15.9 parts by weight of hexamethyleneimine to a mixture containing 3.5 parts of 50% sodium hydroxide, 3.5 parts of sodium aluminate, 30.1 parts of Ultrasil VN3 silica and 156 parts of deionized water. The reaction mixture was directly heated to 143 ° C (290 ° F) and stirred in an autoclave at the crystallization temperature. After complete crystallization, the crystals formed are separated from the remaining liquid

Filter, wash with water and dry. A portion of the crystals are combined with alumina to form a mixture of 65 parts by weight of zeolite and 35 parts of alumina. Water is added to this mixture so that the resulting catalyst can be extruded. The catalyst was activated by calcination in nitrogen at 540 ° C followed by treatment with aqueous 1.0 N ammonium nitrate and calcined in air at 540-650 ° C.

ZMS-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 silica, 67.7 parts of 50% tetraethylammonium bromide, 7.0 parts of 50% sodium hydroxide, and 165.4 parts of deionized water. The reaction mixture is directly heated to 138 ° C and stirred in an autoclave at crystallization temperature. Upon complete crystallization, the resulting crystals were separated from the remaining liquid by filtration, washed with water and dried. A portion of the crystals were combined with alumina to form a mixture of 65 parts by weight of zeolite and 35 parts of alumina. Water is added in an amount sufficient to form the catalyst formed as an extrudate. 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.

The propylene hydration is carried out at a temperature of 166 ° C, a pressure of 7000 kPa and a WHSV of propylene of 0.6. The results of the two-day experiment are compared in Table IX.

Box IX ®ateriái according to

PSH-3 of the invention ZSM-12

t conversion of propylene 1/9 27.6 10.6 % water conversion 5.7 33.7 8.1 IPA eelectivity 98.7 76.7 74.6 EIPE selectivity 2.9 22.3 23.1 oligoaer selectivity 6.4 1.2 2.3

ipa = isopropyl alcohol lipe - dilsopropyl ether

The above results clearly demonstrate the advantageous properties of the material of the invention when compared to PSH-3 and ZSM-12 in achieving a higher conversion rate associated with good selectivity to diisopropylbenzene and low production of propylene oligomers.

Claims (7)

PATENT CLAIMS Synthetic zeolite, characterized in that it has a composition in terms of the molar ratio X ₂ 0 ₃ : / n / Y 0 _2i wherein n is at least 10, X is a trivalent element selected from the group consisting of aluminum, boron, iron and gallium and Y is tetravalent an element selected from the group consisting of silicon and germanium, and is characterized by an X-ray diffraction pattern containing the following values Interplanar d-distance (A) relative intensity I / O _by x 100 30.0 ± 1.3 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 where W = 0-20, M = 20-40, S = 40-60 and VS = 60-100 a have an equilibrium adsorption capacity of 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 zeolite according to claim 1, characterized by a X-ray diffraction pattern comprising the following values: Interplanar d-distance (A) relative intensity, I / O _o x 100 30.0 ± 22W-M 22.1 ± 1.3W 3.91 ± 0.07M-VS Synthetic zeolite according to claim 1, characterized in that it is characterized by an X-ray diffraction pattern comprising the following values: Interplanar d-distance (A) relative intensity, I / O 'x 100 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 Synthetic zeolite according to claim 1, characterized by: characterized in that it is characterized by diffraction X-ray diagram, values containing the following- Interplanar d-distance (A) relative intensity, I / I _by x 100 30.0 ± 2.2 W-M 22.1 ± 1.3 W 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 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 Synthetic zeolite according to claim 1, characterized in that X is aluminum Y is silicon. Synthetic zeolite according to claim 5, characterized in that n has a value of from 20 to 40. 7. A process for the preparation of a synthetic zeolite according to claim 1, characterized in that a reaction mixture capable of forming said material by crystallization having a molar ratio having the following composition is prepared: Y0 ₂ / X ₂₀ 0 ₃ = 10-80 H ₂ O / Y ₂ = 5-100 OH7YO ₂ = 0.01-1.0 M / Y ₂ = 0.01-2.0 R / Y0 ₂ = 0.05-1.0 wherein R represents hexamethyleneimine and M is an alkali metal or alkaline earth metal, wherein the source of Y oxide containing at least 30% by weight of solid Y0 _2, and the mixture was kept at 80 ° to 300 ° C for 24 hours to 60 days, until crystals of said material are formed. 8. The process of claim 7, wherein the reaction mixture has a composition within the following range: Y0 ₂ / X ₂₀ 0 ₃ = 10-60 H ₂ O / Y ₂ = 10-50 OH7Y0 ₂ = 0.1-1.0 M / Y ₂ = 0.1-1.0 R f / Y ₂ = 0.1-0.5.