KR970007310B1 - Synthetic porous crystalline material, its synthesis - Google Patents

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Synthetic porous crystalline material and preparation method thereof

The present invention relates to synthetic porous crystalline materials, methods for their preparation and their use in the catalytic conversion of organic compounds.

All zeolitic materials, including natural and synthetic materials, have been demonstrated to have contact properties for several types of hydrocarbon conversion reactions. Certain zeolitic materials are ordered porous crystalline aluminosilicates with a clear crystal structure as measured by X-ray diffraction, inside which there are a number of tiny cavities that can be interconnected with several small channels or pores. have. These cavities and pores are uniform in size in certain zeolitic materials. These pores are known as molecular sieves because they are capable of adsorbing certain types of molecules while rejecting larger ones, and are being applied in many ways to exploit these properties.

These molecular sieves of natural or synthetic origin include a wide range of cation-containing crystalline silicates. These silicates are composed of SiO ₄ crosslinked with tetrahedera by the sharing of oxygen atoms and the element oxides of group IIIA of the periodic table so that the ratio of all elements of group IIIA to oxygen atoms, such as aluminum and silicon atoms, is 1: 2. For example, it has a rigid 3D skeleton structure of AlO ₄ . The electric atoms of the IIIA group element-containing tetrahedera, such as aluminum, can be balanced by the inclusion of cations in the crystals.

This can be expressed as the ratio of the group IIIA element such as aluminum to various various cations such as Ca / 2, Si / 2, Na, K or Li. One type of cation can be partially or wholly ion exchanged with various other types of cations using conventional methods of ion exchange. This cation exchange was able to change the properties of aluminosilicate given by the proper choice of cations.

Prior art regarding the formation of various various synthetic zeolites is known. Most of these zeolites are designated by letters or other convenient symbols as illustrated below: Zeolite A (US Pat. No. 2,882,243), Zeolite X (US Pat. No. 2,882,244), Zeolite Y (US Pat. No. 3,130,007), Zeolite ZK. -5 (US Pat. No. 3,247,195), Zeolite ZK-4 (US Pat. No. 3,314,752), Zeolite ZSM-5 (US Pat. No. 3,702,866), Zeolite ZSM-11 (US Pat. No. 3,709,979), Zeolite ZSM-12 (US Pat. No. 3,832,449 Zeolite ZSM-20 (US Pat. No. 3,972,983), zeolite ZSM-35 (US Pat. No. 4,016,245), zeolite ZSM-38 (US Pat. No. 4,046,859) and zeolite ZSM-23 (US Pat. No. 4,076,842).

The ratio of SiO ₂ / Al ₂ O ₃ in a given zeolite may vary. For example, zeolite X can synthesize a ratio of SiO ₂ / Al ₂ O ₃ to 2/3 and zeolite Y to 3/6. In some zeolites there is no upper limit to this SiO ₂ / Al ₂ O ₃ ratio, and ZSM-5 is an example of this and the SiO ₂ / Al ₂ O ₃ ratio reaches at least 5 up to the limit of this analytical method. U.S. Patent 3,941,871 (Reissue Patent 29,948) describes a method for synthesizing porous crystalline silicates in a reaction mixture free of alumina and whose X-ray diffraction pattern is such as ZSM-5. US Pat. Nos. 4,061,924, 4,073,865 and 4,104,294 describe crystalline silicates of varying alumina and metal content.

The first aspect of the present invention is represented by the X-ray diffraction pattern having the values in Table 1 of this specification, the equilibrium adsorption capacity is 10% by weight or more for water vapor, 4.5% by weight or more for cyclohexane vapor and n- It relates to a synthetic porous room crystalline material, characterized by at least 10% by weight relative to hexane vapor.

The porous crystalline material according to the invention relates to a composition named PSH-3 as described in US Pat. No. 4,439,409. However, the crystalline material does not contain all the components contained in the PSH-3 composition. In particular, the compositions of the present invention are completely different from other crystalline structures such as ZSM-12 or ZSM-5 and exhibit specific absorption capacity and unique contact properties when compared to PSH-3 compositions synthesized according to US Pat. No. 4,439,409. .

The crystalline material of the present invention can be synthesized by crystallization of the reaction mixture containing the required oxide source together with the hexamethyleneimine directing agent. However, it has been found to be particularly important to use silica sources with relatively high solids content when the crystalline material of the invention is a silicate.

Thus, the second aspect of the present invention contains a sufficient amount of alkali or alkaline earth metal cations, tetravalent oxide YO ₂ member with at least about 30% by weight solid YO ₂ , trivalent oxide X ₂ O ₃ member, water and hexamethyleneimine Preparing a reaction mixture capable of forming a synthetic crystalline material according to the first aspect of the present invention upon crystallization as a reaction mixture, which is then brought under sufficient crystallization conditions until crystals of the materials are formed. It relates to a method for producing a synthetic crystalline material, characterized in that advection in stages.

The crystalline material according to the present invention has a composition including the following molar relationship.

X ₂ O ₃ : (n) YO ₂

In the above, X is a trivalent element such as aluminum, boron, iron and / or gallium, preferably aluminum and Y is a tetravalent element such as silicon and / or germanium, preferably silicon, n Is at least 10, usually 10 to 150, preferably 10 to 60 and most preferably 20 to 40.

In the above synthetic form, the crystalline material has the following formula in terms of anhydrides and also in terms of moles of oxide per mole of YO ₂ n:

(0.005-0.1) Na ₂ O (1-4) R: X ₂ O ₃ : n YO ₂

In the above, R is an organic moiety.

The Na and R components are combined with the crystalline material due to their presence in crystallization, and can also be easily separated by post-crystallization, which will be described later in detail.

The crystalline material of the present invention is thermally stable and its absorption capacity is exceptional when compared with very large and similar crystal structures with a surface area of 400 m / gm or more. As can be seen from the general formula above, the crystalline material of the present invention is synthesized with little Na cation. Therefore, it can be used as a catalyst having an acid action without undergoing an exchange step. However, the original sodium cation in the synthesized material can be changed at least in part by ion exchange with other cations according to well known methods. Preferred here as cations are metal ions, hydrogen ions, hydrogen precursors such as ammonium and mixtures thereof. Particularly preferred cations are those which impart a coupling action for certain hydrocarbon conversion reactions.

Examples are hydrogen, rare earth metals and metals of IIA, IIIA, IVA, IB, IIB, IIIB, IVB and Group VIII in the periodic table.

In the case of certain forms, the crystalline material of the present invention consists of a single crystalline phase with little or no detectable impurity crystalline phase, and is distinguished by X-ray patterns of well-known crystalline materials by the lines in Table 1 below. It has a line diffraction pattern.

TABLE 1

Specifically, they are distinguished by the lines in Table 2 below.

TABLE 2

More specifically, they are distinguished by the lines in Table 3 below.

TABLE 3

Most preferably the calcined crystalline material of the present invention has an X-ray diffraction pattern comprising the lines in Table 4 below.

TABLE 4

The above values are measured by standard methods.

The radiation was measured using a diffractometer with a K-alpha doublet of copper and a scintillation counter and a coupling computer. The peak highlight, i.e., position as a function of I and 2θ, where θ is the Bragg angle, is computed and measured on a computer equipped with a diffractometer. From this, the relative strengths corresponding to the recording wires are also measured, i.e. 100 I / Io (where Io is the strength of the strongest line or peak) and d (obs.) (Inter-plane distance in Angstrom units (A)). . In Table 1-4, the relative strengths are indicated by the symbols W (weak), M (medium), S (strong), and VS (very strong), and the strength can be expressed as

W = 0-20

M = 20-40

S = 40-60

VS = 60 -100

The X-ray diffraction pattern above is a characteristic of the present crystalline composition. The sodium and other cationic forms in the composition show a pattern that is substantially the same as the change in minor shift and relative strength at interplanar distances. On the other hand, other minor changes may also occur depending on Y / X, for example silicon / aluminum, the proportion of the particular sample and the degree of heat treatment.

The crystalline material according to the invention can be an alkali or alkaline earth metal (M), for example a cationic source of Na or Ka, a trivalent element such as an oxide of Al, a tetravalent element such as an oxide of silicon, organic (R ) From a reaction mixture containing a direct agent (described in greater detail below) and water. The above reaction mixture has the following composition with respect to the molar ratio of oxides:

Crystallization of the material according to the invention is facilitated when the YO ₂ member contains at least 30% by weight of solid YO ₂ , in particular when YO ₂ is silica.

Suitable commercially available sources of silica include Ultrasil (precipitation containing about 90% silica by weight, spray dried silica) and HiSil (about 87% silica, about 6% free water and about 4.5% by weight). Precipitated SiO ₂ ) having a particle size of about 0.02 microns. However, when using other silica sources, for example Q-brands (sodium silicate consisting of about 28.8% by weight SiO ₂ , 8.9% by weight Na ₂ O and 62.3% by weight H ₂ O) the crystals according to the invention It has been found that crystallization of the sex material rarely occurs, and instead other crystal structures of impurity phases such as ZSM-12 are formed.

Accordingly, the YO ₂ member preferably contains at least 30% by weight of solid YO ₂ , preferably silica, more preferably at least 40% by weight of solid YO ₂ .

The organic direct agent (R) used to synthesize the crystalline material of the present invention from the above reaction mixture is hexamethyleneimine having the structure

Crystallization of the crystalline material according to the invention can be carried out by stirring in a suitable reaction vessel such as a polypropylene jar or Teflon-coated or stainless steel autoclave or left alone. Crystallization is generally carried out at temperatures between 80 ° C. and 225 ° C. for 24 hours-60 days. The resulting crystals are then separated and recovered from the liquid.

Crystallization is promoted in the presence of seed crystals of the desired crystalline product of at least 0.01%, preferably at least 0.10%, more preferably at least 1% by total weight.

The crystalline material synthesized above must be calcined to remove all or part of the organic components before use as catalyst or absorbent.

The crystalline material according to the present invention is a hydrogenated component capable of performing a hydrogenation-dehydrogenation function such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium or manganese or a precious metal such as platinum or palladium and It can be used directly as a catalyst in combination. The above components may be present in the composition in base exchange, dipping or direct physical mixing. In addition, the above components can be immersed by treating the silicate with a solution containing platinum metal-containing ions in the case of platinum. Accordingly, platinum compounds suitable for this purpose include various kinds of compounds containing chloroplatinic acid, platinum chloride and platinum amine complexes.

The crystalline material according to the invention can be shaped into particles of various sizes. Generally speaking, the particles can be made into shaped bodies such as powders, granules or extrudates. In the latter case, the crystalline material may be extruded before drying or partially dried and then extruded.

The crystalline material of the present invention should be dehydrated at least partially when used as a catalyst or an adsorbent in organic compound conversion reactions. It can be carried out by heating in the range from 30 minutes to 48 hours. In addition, the dehydration reaction can be carried out at room temperature by replacing silica only in vacuum, but more time is required to obtain sufficient dehydration degree.

The crystalline material of the invention has a temperature of 50-300 ° C., preferably a temperature of 90-250 ° C., a pressure of at least 5 kg / cm 2, preferably at least 20 kg / cm 2, and 0.1-20, preferably 0.2-15 It can be used to promote various organic conversion reactions such as hydration of C ₂ -C ₇ olefins such as propylene with alcohols and ethers under the reaction condition of the water / olefin molar ratio.

As with most catalysts, the crystalline materials of the present invention can be combined with other materials that can withstand the temperatures and other conditions used in organic conversion reactions.

Such materials include active and inert materials and synthetic or natural zeolites, as well as minerals such as clays, metal oxides such as silica and / or alumina, the latter being gel or gel phases containing natural or mixtures of silica and metal oxides. It may be in the form of a precipitate. When a material is used in combination with a new catalyst, it tends to alter the conversion and / or selectivity of the catalyst in any organic conversion reaction. Since the inert material acts as a diluent to control the amount of conversion in any given reaction, the product can be obtained economically and uniformly without using other means of controlling the reaction rate. These materials can be bonded to natural clays such as bentonite and kaolin to improve the catalyst grinding strength in actual operation. The above materials, such as clays and oxides, function as binders for catalysts. In actual use, it is preferable to prepare a catalyst having excellent grinding strength because it is good to prevent the catalyst from being pulverized into powder form. The above clay binders are usually used only for the purpose of improving the grinding strength of the catalyst.

Natural clays that can be combined with the novel catalysts synthesized in the present invention include the following examples. Montmorillonite and kaolins, including subbentonite, and kaolin or major minerals, commonly known as Dixie, McNamee, Georgia, and Florida clays, include halloysite, kaolinite, dickite, and nacrite. Or other substance that is anoxite. Such clays may be used in the mined raw material state, or may be used by calcining, acid treatment or chemical modification. Binders useful in combination with the crystals of the present invention are inorganic oxides, in particular alumina.

In addition to the materials described above, the novel crystals of the present invention can be used with porous matrix materials. Examples of such porous matrices are: silica-alumina, silica-magnesia, silica-zirconia, silica-toria, silica-berilia, silica-titania, And ternary compositions such as silica-alumina-toria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.

The relative proportions of finely separated crystalline materials and inorganic oxide matrices vary widely, where the crystal content ranges from 1-90% by weight of the composite, usually 2-80 of the composite when the composite is made in the form of beads Weight percent range.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings. 1-5 show the X-ray diffraction patterns of the fired products of Examples 1, 3, 4, 5 and 9, respectively. In these examples, the absorption data is presented as a comparison of absorption capacity for water, cyclonehexane and / or n-hexane, which is the equilibrium adsorption value measured as follows:

The calcined adsorbent sample was weighed and contacted with the desired pure adsorbate vapor in the adsorption chamber, evacuated to 1 mm or less, at 12Orr steam and 40 Torr n-hexane or at a pressure lower than the vapor-liquid equilibrium pressure of each adsorbent at 90 ° C. Contact with cyclohexane vapor. The pressure above is maintained within ± 0.5 mm by the addition of adsorbate vapor controlled by manostatt during the adsorption period not exceeding 8 hours. Once the adsorbate is adsorbed by the new catalyst, the pressure drops so that the Manostat opens the valve, thus allowing more adsorbate vapor to enter the adsorption chamber to restore the above control pressure.

Adsorption ends when the pressure change is not sufficient to activate the manostat. The weight increase is then calculated in grams for the adsorption capacity of the sample per 100 grams of calcined adsorbent. Synthetic materials of the present invention always exhibit equilibrium adsorption values of at least 10% by weight relative to water vapor, usually at least 7% by weight relative to cyclohexane vapor and at least 10% by weight relative to n-hexane vapor. Investigation of the alpha value shows that the alpha value represents the catalytic cracking action of the catalyst as compared to the standard catalyst, and the relative velocity is higher than that of the high active silica-alumina decomposition catalyst which takes the alpha value as 1 (rate constant = 0.016sec ⁻¹ ). Constants (normal hexane conversion rate per unit time and catalyst volume). Alpha tests are described in US Pat. No. 3,354,078 and in Journal of Catalysis, Vol. IV, PP. 522-529 (August 1965). In many acid catalyst reactions, the high velocity constant is proportional to the alpha value for any particular crystalline silicate catalyst, i.e., toluene disproportionation, xylene isomerization, alkene conversion and methanol conversion rate (see The Active Site of Acidic Aluminosilicate Catalysts, Nature, Vol. 309, No. 5969, pp. 589-591, 14 June 14, 1984).

Dissolve 12.86 g of sodium aluminate (43.5% Al ₂ O ₃ , 32.2% Na ₂ O, 25.6% H ₂ O) in a solution of 12.8 g of 50% NaOH solution and 1320 g of H ₂ O, and 57.6 g of hexamethyleneimine Add. The resulting solution is added to 109.4 g of Ultrasil, ie precipitated, atomized silica (about 90% SiO ₂ ).

The reaction mixture has the following composition in molar ratio.

SiO ₂ / Al ₂ O ₃ = 30.0

OH ^- / SiO ₂ = 0.18

H ₂ O / SiO ₂ = 44.9

Na / SiO ₂ = 0.18

R / SiO ₂ = 0.35

Wherein R is hexamethyleneimine.

The above reaction mixture is placed in a stainless steel reactor and crystallized for 7 days while stirring at a temperature of 150 ° C. The quenched product is then filtered, washed with water and dried at 120 ° C. Next, after firing at 538 ° C. for 20 hours and X-ray diffraction, the main lines listed in Table V were included. 1 shows the X-ray diffraction pattern of the fired product. On the other hand, the absorption capacity of the fired material was as follows:

H ₂ O (12 Torr) 15.2 wt%

Cyclohexane (40 Torr) 14.6 wt%

n-hexane (40 Torr) 16.7 wt%

The calcined crystalline material had a surface area of 494㎡ / g and the chemical composition was as follows:

TABLE 5

Example 2

An alpha test with a portion of the calcined crystalline material of Example 1 showed an alpha value of 224.

Example 3-5

Three synthetic reaction mixtures are prepared separately using the compositions in Table 6 and prepared with sodium aluminate, sodium hydroxide, ultrasil, hexamethyleneimine (R) and water. The reaction mixture is then placed in a stainless steel autoclave and stirred for 7 days at 150 ° C., 8 days at 143 ° C. and 6 days at 150 ° C. under autogenous pressure while stirring (350 rpm). Solids are filtered off from the unreacted components, washed with water and dried at 120 ° C. X-ray diffraction, absorption, surface area and chemical analysis of the crystalline product resulted in a new crystalline material. The above results are shown in Table 6 and X-ray diffraction patterns are shown in FIGS. Following are the absorption and surface area measurements of the calcined product.

TABLE 6

Example 6

Alpha testing of the crystalline silicates obtained by firing (538 ° C., 3 hours) in Examples 3, 4 and 5 showed alpha values of 227, 180 and 187, respectively.

Example 7

The crystalline silicate obtained by firing in Example 4 was impregnated in a Pt (NH ₃ ) ₄ Cl ₂ solution and then heated in air at a temperature of 349 ° C. for 3 hours.

Example 8

As a catalyst, 1 g of the product of Example 7 is placed in a small reactor equipped with a preheater and a heating pair, and heated to a temperature of 482 ° C. under hydrogen flow to reduce the Pt component. Then, normal decane and hydrogen were added to the catalyst at 0.4hr ⁻¹ WHSV and hydrogen / hydrocarbon molar ratio of 100/1 in decane, and the reaction was carried out at a temperature of 130-250 ° C. and atmospheric pressure.

The results of the above experiments are shown in Table 7, and the crystalline materials changed to ZSM-5 (US Pat. No. 3,702,886), ZSM-11 (US Pat. No. 3,709,979) and Zeolite Beta (US Pat. No. 3,308,069) as comparative examples. Experimental results are shown. From these results it is observed that the crystalline silicate of the present invention is a very active catalyst for n-decane hydrocarbon conversion and has good isomerization action. In Table 7, 5MN / 2MN represents the molar ratio of 5-methylnonane / 2-methylnonane. Because of the position of the methyl group, 5-methylnonane causes some steric hindrance inside the zeolite pores.

The 5Mn / 2Mn ratio provides information on the porosity of the zeolite to be tested.

TABLE 7

Example 9

To prepare a large amount of the crystalline material according to the invention, 1200 g of hexamethyleneimine is added to a solution consisting of 268 g of sodium aluminate, 267 g of a 50% NaOH solution and 11,800 g of H ₂ O. 2280 g of Ultrasil Silica are added to the combined solution. The resulting mixtures of 5 are placed in a reactor and stirred at 145 ° C. (about 200 rpm) to crystallize. Crystallization time was 59 hours. The product is washed with water and dried at 120 ° C.

The X-ray diffraction pattern of the calcined (538 ° C.) catalyst product is shown in FIG. 5 and proves that the product is the crystalline material of the present invention. The chemical composition, surface area and adsorption analysis of the product are shown in Table 8 below.

TABLE 8

Example 10

25 g of the solid crystal product of Example 9 was calcined at a temperature of 538 ° C. under a nitrogen flow for 5 hours, followed by 16 hours at 538 ° C. under 5% oxygen gas (N ₂ ).

Each ₃ g of the above fired material sample is separately ion exchanged with 100 ml of 0.1 N TEABr, TPABr and LaCl ₃ solution. Each ion exchange is performed 24 hours at ambient temperature and repeated three times. The ion exchanged sample is then collected by filtration and washed to remove halides and to dry. The composition of the ion exchanged sample is shown below, demonstrating that the crystalline silicates of the present invention are superior in other ion exchange capacities.

11 to implementation

The La-ion exchange sample above is sized 14-25 mesh and calcined at 538 ° C. in air for 3 hours.

The alpha value of the calcined material was 173.

Example 12

The La-ion exchange calcined material sample prepared in Example 11 is steamed vigorously for 2 hours at 649 ° C. in 100% steam. The alpha value of the steamed sample was 22, and its crystalline silicate was found to have excellent stability under vigorous hydrothermal treatment.

Example 13

To the solution of 6.75 g of 45% KOH solution and 290 g of H ₂ O, 17.5 g of boric acid was added to prepare a crystal of the present invention having X consisting of boron. To this was added 57.8 g of uracil silica and the resulting mixture was completely homogenized, followed by 26.2 g of hexamethyleneimine.

The reaction mixture has the following composition in molar ratio:

SiO ₂ / B ₂ O ₃ = 6.1

OH ^- / SiO ₂ = 0.06

H ₂ O / SiO ₂ = 19.0

K / SiO ₂ = 0.06

R / SiO ₂ = 0.30

Wherein R is hexamethyleneimine.

The reaction mixture was placed in a stainless steel reactor and stirred for 8 days at 150 ° C. to crystallize, and the crystalline product was filtered, washed with water and dried at 120 ° C. A portion of the product was calcined at 540 ° C. for 6 hours and found to have the following absorption capacity:

H ₂ O (12 Torr) 11.7 wt%

7.5% by weight of cyclohexane (40 Torr)

n-hexane (40 Torr) 11.4 wt%

In addition, the surface area of the calcined crystalline material was 405 m 2 / g. The chemical composition of the fired material is as follows:

Example 14

A portion of the crystalline calcined material prepared in Example 13 is treated with NH ₄ Cl and calcined again. The alpha value of the final crystalline product was 1 in the alpha test.

Example 15

To a solution of 15.7 g of a 50% NaOH solution and 1160 g of HO, 35.0 g of a dispersion was added to prepare a crystalline material of the present invention having X consisting of boron, to which 240 g of HiSi1 silica was added, followed by addition of 105 g of hexamethyleneimine. do.

The reaction mixture has the following composition in molar ratio:

SiO ₂ / B ₂ O ₃ = 12.3

OH ^- / SiO ₂ = 0.056

H ₂ O / SiO ₂ = 18.6

Na / SiO ₂ = 0.056

R / SiO ₂ = 0.30

In the above, R is hexamethyleneimine.

The reaction mixture was placed in a stainless steel reactor and stirred for crystallization at 300 ° C. for 9 days, and the crystalline product was filtered, washed with water and dried at 120 ° C. The absorption capacity of the calcined (6 hours, 540 ° C) material is as follows:

H ₂ O (12 Torr) 14.4 wt%

4.6% by weight of cyclohexane (40 Torr)

n-hexane (40 Torr) 14.0 wt%

The surface area of the crystalline plastic material was 438㎡ / g, and the chemical composition of the plastic material was as follows:

Example 16

A portion of the calcined crystalline material of Example 15 was tested by alpha test and found to have an alpha value of 5.

Example 17

In order to demonstrate the importance of using a silica source containing at least 30% solid silica in the process of the present invention, Example 3 uses Q-brand sodium silicate (containing only about 29% by weight solid silica) as the silica source. Repeat. In this example, 67.6 g of aluminum sulfate was dissolved in a solution of 38.1 g of A ₂ SO ₄ (96.1%) and 400 g of water, and the resulting solution was mixed with 120 g of hexamethyleneimine, which was then Q-brand sodium silicate (28.8% SiO). ₂ and 9% Na ₂ O) to a mixture of 712.5 g of water and 351 g of water. The resulting mixture has the following composition in molar ratio.

SiO ₂ / B ₂ O ₃ = 30.0

OH ^- / SiO ₂ = 0.18

H ₂ O / SiO ₂ = 19.4

Na / SiO ₂ = 0.60

R / SiO ₂ = 0.35

Next, the reaction mixture was placed in a stainless steel reactor and stirred for 8 days at 246 ° C. to crystallize, and the solid product was separated from the unreacted component by filtration, washed with water and dried at 120 ° C. X-ray diffraction testing of the product revealed that it was a mixture of amorphous material, margadiite and mordenite, and no crystals of the present invention appeared.

Example 18

In this example, the propylene hydration characteristics of the crystalline material according to the present invention are compared with those of ZSM-12 and PSH-3 prepared in Example 4 of US Pat. No. 443909.

To a mixture of 3.5 parts of 50% NaOH, 3.5 parts of sodium silicate, 30.1 parts of Ultrasil VN3 silica and 156 parts of deion H ₂ O, 15.9 parts by weight of hexamethyleneimine is added to prepare the crystalline material of the present invention. The reaction mixture is directly heated to 290 ° F. (143 ° C.) and bent completely at room temperature in an autoclave to completely crystallize, then the resulting crystals are separated from the remaining liquid by filtration and washed with water and dried. A portion of the crystal is then combined with alumina to form a mixture of 65 parts by weight of zeolite and 35 parts by weight of alumina, and sufficient water is added to form the resulting crystals into an extrudate. The crystals are then calcined to 1000 ° F. (540 ° C.) in nitrogen to activate, ion exchanged with aqueous 1.0N ammonium nitrate and calcined to 1000 to 12000 ° F. (540 to 650 ° C.) in air.

ZSM-12 was prepared by adding 1% by weight of ZSM-12 seed to a mixture containing 41.5 parts of Hi-Sil 233 silica, 67.7 parts of tetraethyl ammonium bromide, 7.0 parts of 50% NaOH and 165.4 parts of deionized H ₂ O. The reaction mixture is then directly heated to 280 ° F. (138 ° C.) and then agitated in the autoclave to crystallize. Once fully crystallized the resulting crystals are filtered off from the remaining liquid, washed with water and dried. Some of the resulting crystals are combined with alumina to form a mixture of 65 parts by weight of zeolite and 35 parts by weight of alumina, and then sufficient water is added to form the catalyst in the form of extrudates. The catalyst is calcined at 1000 ° F. (540 ° C.) in nitrogen to activate, aqueous 1.0N ammonium nitrate exchange and calcined at 1200 ° F. (650 ° C.).

Propylene hydration and steaming for two days at a temperature of 330 ° F. (166 ° C.), a pressure of 1000 psig (7000 kPa) and a propylene of 0.6 WHSV of 0.6 are shown in Table 9.

IPA = Isopropyl Alcohol

DIPE = diisopropyl ether

The table above shows a high conversion rate with good selectivity for diisopropyl ether and low production rate of propylene oligomers, which shows that the material of the present invention is very good compared to PSH-3 and ZSM-12.

Claims (7)

X-ray diffraction pattern with values in Table 1 of the specification, the equilibrium adsorption capacity for water vapor is at least 10% by weight, the equilibrium adsorption capacity for cyclohexane vapor is at least 4.5% by weight and the equilibrium for n-hexane vapor Synthetic porous crystalline material, characterized in that the adsorption capacity is 10% by weight or more. The synthetic porous crystalline material of claim 1, characterized by an X-ray diffraction pattern having the values in Table 2 of the specification. The synthetic porous crystalline material of claim 1, characterized by an X-ray diffraction pattern having the values in Table 3 of the specification. The synthetic porous crystalline material of claim 1, characterized by an X-ray diffraction pattern having the values in Table 4 of the specification. The crystalline material according to any one of claims 1 to 4, having a molar relationship as follows: X ₂ O ₃ : (n) YO ₂ In the above, n is 10 canceled, X is a trivalent element, and Y is a tetravalent element. 6. The crystalline material of claim 5, wherein X is aluminum and Y is silicon. The crystalline material of claim 6, wherein n is 20-40.