Synthetic porous crystalline material and method thereof

 

(57) Abstract:

Synthetic porous crystalline material characterized by an x-ray diffraction pattern having the values given in the table. 1 description receive from the reaction mixture, containing sodium cations, a source of silicon, containing at least 30 wt.% solid silicon oxide, aluminum oxide, water, hexamethylenimine. 2 S. p. f-crystals, 13 tables.

The invention relates to a synthetic porous crystalline material, the method of its production and its use in catalytic conversion of organic compounds.

It is known that zeolite materials, both natural and artificial, have catalytic properties for various types of hydrocarbon conversion. Some zeolite materials are ordered, as, for example, porous crystalline aluminosilicates having a definite crystalline structure determined by x-ray diffraction, having a large number of smaller cavities which may be interconnected near still smaller channels or pores. These cavities and pores are uniform in size within a particular zeolite material. Since the dimensions of these pores are such that on ialy became known as "molecular sieves" and have different application taking advantage of these properties.

Such molecular sieves, both natural and synthetic, include a wide variety containing positive ions of the crystalline silicates. These silicates can be described as rigid three-dimensional structure of SiO4and the oxide of the element Periodic table group IIIA, such as AlO4in which the tetrahedra are cross linked by oxygen atoms, while the ratio of the element of group IIIA, for example, aluminum, and silicon atoms to oxygen atoms is 1: 2. Electrovalent tetrahedra containing an element of group IIIA, such as aluminum, is balanced by the inclusion in the crystal of cations, for example alkali metal or alkaline-earth metal. This can be expressed by the fact that the element of group IIIA, such as aluminum, to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of cation can be replaced totally or partially by another type of cation using conventional ion exchange techniques. By means of such cation exchange, it was possible to change the properties of the silicate by the proper choice of cation.

The techniques of the prior art led to the formation of a large number of synthetic zeolites. the Olite And (U.S. patent N 2882243), zeolite X (U.S. patent N 2882244), zeolite Y (U.S. patent N 3130007), zeolite ZK-4 (U.S. patent N 3314752), zeolite ZSM-5 (U.S. patent N 3702886), zeolite ZSM-11 (U.S. patent N 3709979), zeolite ZSM-12 (U.S. patent N 3832449), zeolite ZSM-20 (U.S. patent N 3972983), zeolite ZSM-35 (U.S. patent N 4016245) and ZSM-23 (U.S. patent N 4076842).

The ratio of SiO2/Al2O3the specific zeolite changes frequently. For example, zeolite X can be synthesized with a ratio of SiO2/Al2O3from 2 to 3; zeolite Y, from 3 to 6. In some zeolites, the upper limit of the ratio of SiO2/Al2O3unlimited. ZSM-5 is one such example where the ratio of SiO2/Al2O3is at least 5 and up to the limits of existing analytical methods of measurement. In U.S. patent N 3941871 (Re 29948) discloses a porous crystalline silicate made from a reaction mixture that does not contain carefully added aluminum oxide, and showing x-ray diffraction pattern characteristic of ZSM-5. In U.S. patent N 4061724, 4073865 and 4104294 described crystalline silicate with varying content of aluminum oxide and metal.

The first aspect of the invention is a synthetic porous crystalline material, harakterizuyu what I have equilibrium adsorption capacity of more than 10 wt. for water vapor, more than 4.5 wt. for cyclohexane vapor and more than 10 wt. for vapours of n-hexane.

Porous crystalline material according to the invention looks similar to a song called "SH-3 and described in U.S. patent N 4439409. However, the present crystalline material does not contain all components that are present in the compositions PSH-3. In particular, the composition of the present invention is not contaminated with other crystalline structures, such as ZSM-12 or ZSM-5, shows unusual adsorption ability and unique catalytic usefulness when compared with compositions PSH-3, synthesized in accordance with U.S. patent N 4439409.

The crystalline material according to the invention can be synthesized by crystallization of the reaction mixture containing sources of essential oxides together with directing agent, hexamethylenimine. However, it was found important that especially where the crystalline material according to the invention is a silicate, it is preferable to use a source of silicon dioxide with a relatively high solids content.

Another aspect of the invention consists in a method of producing synthetic Chris is Rial during crystallization, moreover, the reaction mixture contains a sufficient number of cations of alkaline or alkaline-earth metal, a source of tetravalent oxide YO2containing at least about 30 wt. solid YO2the source of trivalent oxide X2ABOUT3water, hexamethylenimine, and maintenance of the mentioned reaction mixture under sufficient crystallization conditions until crystals form the above-mentioned material.

The crystalline material of the present invention has a composition involving the molar ratio

X2O3: (n)YO2where X is a trivalent element, such as aluminum, boron, iron and/or gallium, preferably aluminum; Y is a tetravalent element such as silicon and/or germanium, preferably silicon; and n is at least 10, usually from 10 to 150, preferably from 10 to 60, and most preferably from 20 to 40. In the synthesized thus form the material has a formula, on an anhydrous basis and in expressions of gram molecules of oxides on n-gram-molecules YO2that resembles the following:

(0,005-0,1)Na2O: (1-4)R:X2O3:nYO2where R is an organic part. Na and the components of R are associated with the traditional methods and are described in more detail below.

The crystalline material according to the invention is thermally stable and has a large surface area (>400 m2/g) and usually larger adsorption capacity in comparison with similar crystalline structures. As is evident from the above formulas, the crystalline material of the present invention is synthesized almost free from cations Na. It can therefore be used as a catalyst with acid activity without stage exchange. To the desired extent, however, the original sodium cations are synthesized so material can be replaced by using the well-known in the art techniques, at least in part, by ion exchange with other cations. Preferred replacing cations include metal ions, hydrogen ions, ions of the precursor of hydrogen, for example ammonium, and mixtures thereof. Practically preferred cations are those that fit catalytic activity to certain reactions of hydrocarbon conversion. These include hydrogen, rare earth metals and metals of groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic table of elements.

In its calcined form, the crystalline Madeleine the inclusion of crystalline phases and has a picture of the x-ray diffraction, great paintings from other known crystalline materials by the lines listed in table. 1, more precisely the lines that are listed in the table. 2, and more precisely the lines that are listed in the table. 3.

Most accurately, calcined crystalline material according to the invention has the diffraction pattern of x-rays, which includes the line, are given in table. 4.

These values were determined using standard techniques. The radiation was the K-alpha dipole copper and diffractometer equipped with a scintillation counter associated with the computer. Peak-peak, 1, and position as a function of 2 theta, where theta is the Bragg angle, were determined using algorithms on the computer associated with diffractogram. Here were determined relative intensities, 100 I/Iowhere Iorepresents the intensity of the strongest line or peak, and d (abs.) represents the interplanar distance in angstroms (a), corresponding to the recorded lines. In table. 1-4 comparative intensity is given in symbols, W-weak, M-medium, S-strong, and VS-very strong. These intensities can be described as follows:

W=0-20

M=20-40

S=40-60

VS=60-100

It should be understood,aricescu composition. The sodium form as well as other cationic forms, detects essentially the same picture with minor shifts in interplanar distance and variation in relative intensity. Other minor deviations may occur depending on the relationship of Y to X, for example of silicon to aluminum, the particular sample, as well as on the degree of thermal treatment.

The crystalline material according to the invention can be obtained from a reaction mixture containing sources of cations of alkaline or alkaline-earth metal (M), e.g. sodium or potassium, an oxide of trivalent element X, e.g. aluminum, an oxide of tetravalent element Y, e.g. silicon, an organic directing agent (R), described in more detail below, and water, and specified the reaction mixture has a composition in expressions of molar ratios of oxides, within the following ranges:

The reagents are Preferably Useful

YO2/X2O310-80 10-60

H2O/YO25-100 10-50

HE-/YO20,01-1,0 0,1-0,5

M/YO20,01-2,0 0,1-1,0

R/YO20,05-1,0 0,1-0,5

It is found that the crystallization of the material according to the invention is improved if the source YO2contains at least 30 wt. solid Y the sources of silica include ultrasil (a precipitated, dried by spraying the silica containing about 90 wt. silicon dioxide) and Hisil (a precipitated, hydrated SiO2containing about 87 wt. silica, about 6 wt. free H2O and about 4.5 wt. related H2O of hydration and having a particle size of about 0.02 microns. If you use a different source of silicon dioxide, for example, Q-Brand (a sodium silicate comprised of about 28.8 wt. SiO2, 8,9 wt. Na2O and 62.3 wt. H2About), it is found that the crystallization results in fewer or no crystalline material according to the invention, but instead are formed polluting phases of other crystal structures, such as ZSM-12. Preferably so that the source YO2contains at least 30 wt. solid YO2preferably silicon dioxide, and more preferably at least 40 wt. solid YO2.

Organic directing agent (R), used in the synthesis of the crystalline material from the above reaction mixture, is hexamethylenimine, which has the following structural formula:

< / BR>
Crystallization of this crystalline material may be carried out in a stat is x vessels or coated with Teflon or stainless steel autoclaves. Crystallization is usually conducted at a temperature of from 80 to 225aboutC for from 24 hours to 60 days. Thereafter, the crystals are separated from the liquid and removed.

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

Before use as a catalyst or adsorbent synthesized crystalline material must be calcined to remove part or completely of any organic constituent.

The crystalline material according to the invention can be used as a catalyst in close combination with a hydrogenation component, such as tungsten, vanadium, molybdenum, rhenium, Nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where it should be made a function of the hydrogenation of dehydrogenization. Such components can be introduced into the composition by cocrystallization, casinoonline included in or directly physically mixed into it. Such components can be inserted into the impregnation or outside, such as, for example, in the case of platinum, by processing the goals include chloroplatinic acid, platinum chloride and various compounds containing the amine complex of platinum.

The crystalline material according to the present invention can have a wide variety of particle sizes. Generally speaking, the particles can be in the form of powder, pellets or molten product, such as extrudate. In the latter case, the crystalline material can be extruded before drying or partially dried and then extruded.

The crystalline material according to the present invention when used as adsorbent or catalyst in the process of conversion of organic compounds must be dehydration at least partially. This can be done by heating to a temperature in the range from 200 to 595aboutIn the atmosphere, such as air, nitrogen, etc. and at atmospheric, subatmospheric or superatmospheric pressures in the period from 30 minutes to 48 hours Dehydration can also be performed at room temperature merely by placing the glass in a vacuum, but within a longer period of time to obtain a substantial degree of dehydration.

The crystalline material according to the invention can be used as a catalyst in the Finow, such as propylene, broken and ethers with reaction conditions including a temperature of from 50 to 300aboutC, preferably from 90 to 250aboutC, a pressure of at least 5 kg/cm2preferably at least 20 kg/cm2and the water/olefin molar ratio of from 0.1 to 30, preferably 0.2 to 15.

As in the case of many catalysts, crystalline material according to the invention can be combined with another material resistant to the temperatures and other conditions used in the process of organic conversion. 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 aluminum. The latter may be either natural or in the form of gelatinous precipitation or gels including mixtures of silicon dioxide or oxides of metals. The use of the material in conjunction with a new crystal, for example, United with them or present during synthesis of the new crystal, which is active, causing the desire to change the conversion and/or selectively of the catalyst in certain organic processes of conversion. Inactive mA is s can be obtained economically and consistently without the use of other means to control the speed of the reaction. These materials can be incorporated into naturally occurring clays, e.g. bentonite and kaolin, to improve the crushing strength of the catalyst under the conditions of the industrial process. Such materials, such as clays, oxides, etc., act as binders for the catalyst. It is desirable to have a catalyst with good crushing strength as an industrial application, it is desirable to prevent from destruction in powder covered synthesised material material. These clay binders are usually used only to improve strength on the destruction of the catalyst.

Natural clay that can be used with the new crystal include the montmorillonite and kaolin families which include abbandonati and the kaolins commonly known as Dixie, McNamee, Georgia and Florida or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anoxic. Such clays can be used in its raw state as they are mined or initially calcined, treated with acid or chemically modified. The binder used for the connection with a real crystal, also include inorganic oxides, usually aluminium dioxide.

Ohm, such as, silica-alumina, silica-magnesia, cream Navy dioxide-zirconium dioxide, silicon dioxide-thorium dioxide, silicic anhydride-beryllium oxide, silicon dioxide-titanium dioxide, as well as ternary compositions, such as silicon dioxide-aluminum oxide-thorium dioxide, silicon dioxide-aluminum oxide, zirconium dioxide, silicon dioxide-aluminum oxide, magnesium oxide and silicon dioxide, magnesium dioxide-zirconium dioxide.

Comparative proportions of finally divided crystalline material and inorganic matrix oxides varies very widely with the contents of the crystal from 1 to 90% by weight and more usually, when the composite is prepared in the form of beads, in the range from 2 to 80 wt. the composite.

Hereinafter the invention is described in more detail by examples, which are given adsorption data for comparison of adsorption capacities for water, cyclohexane and/or n-hexane, they represent the equilibrium adsorption values determined as follows.

A weighed sample of the calcined adsorbent was put into contact with desire is fired steam pressure of 12 Torr with steam n-hexane or cyclohexane with the addition of 40 Torr, pressure less than the equilibrium pressure of the vapor-liquid corresponding adsorbent at 90aboutC. the Pressure was maintained constant (within 0.5 mm) by adding a pair of adsorbate controlled Monostatos during adsorption, which did not exceed 8 hours as the adsorption is carried adsorbate new crystal reduced pressure forced manostat to open the valve, which let in additional pairs of adsorbate in the camera to restore the pressure. The acquisition was completed, when the pressure change was not material to actuate manostat. Weight gain was calculated as the adsorption capacity of the sample in g/100 g of calcined adsorbent. Synthetic material of the present invention always shown the values of the equilibrium adsorption of more than 10 wt. for water vapor, more than 4.5 wt. usually more than 7 wt. for cyclohexane vapor and more than 10 wt. for a pair of n-hexane.

When checking the alpha value, it was found that the alpha value is an approximate indicator of the catalytic cracking activity of the catalyst compared to a standard catalyst and it gives the constant comparative speed (rate of normal hexane conversion to oz silicon dioxide-aluminum anhydride, taken as an alpha of 1 (rate constant 0,016 sec-1). The alpha test is described in U.S. patent N 3354078 and in the Journal of catalysis Journal of Catalysis) volume IV, C. 522-529 (August 1965). It is observed that typical constant speed for many acid-natalizumab reactions is proportional to the alpha value for a particular crystalline silicate catalyst, i.e., the speed for the disproportionation of toluene, xylene isomerization, the conversion of alkene and reforming of methanol (see Active position acidic aluminosilicate catalysts, Nature, I. 309, N 5969, S. 589-591, 14.06.84).

P R I m e R 1. Sodium aluminate (43.5% of Al2O3, 32.2% of Na2O, 25.6% OF H2O), 12,86 g was dissolved in a solution containing 12.8 g of 50% NaOH solution and 1320 g H2O. To this was added and 57.6 g of hexamethyleneimine. The resulting solution was added to 109,4 g Ultrasil precipitated, spray dried silica (about 90% of SiO2).

The reaction mixture had the following composition in molar ratios:

SiO2/Al2O330,0

HE-/SiO20,18

H2O/SiO244,9

Na/SiO20,18

R/SiO20,35 where R is hexamethylenimine.

The mixture was crystallized in a reactor of stainless steel with paramashivaaboutC. After 20 h of calcination at 538aboutWith the picture of the x-ray diffraction was the main lines that are listed in the table. 5. The measured adsorption capacity of calcined material was a

H2O (12 Torr) of 15.2 wt.

Cyclohexane

(40 Torr) of 14.6 wt.

n-Hexane (40 Torr) of 16.7 wt.

The surface area of the calcined crystalline material was measured and was 494 m2/,

The chemical composition of the calcined material was determined as follows, wt.

SiO266,9

Al2O35,40

Na 0,03

N 2,27

Ash 76,3

SiO2/Al2O3molar

ratio

21,1

P R I m m e R 2. A portion of the calcined product of example 1 was tested in the alpha test and found that the alpha value is 224.

P R I m e R s 3-5. Three separate synthetic reaction mixtures were prepared with compositions shown in table. 6. Mixtures were prepared with sodium aluminate, sodium hydroxide, Ultrasil, hexamethylenimine (R) and water. The mixture was kept at 150, 143 and 150aboutWith, respectively, for 7, 8 and 6 days, respectively, in an autoclave of stainless steel, with perhaps by filtration and then washed with water, dried at 120aboutC. the Crystals of the product were analyzed by x-ray diffraction, sorption, surface area and chemical analyses. Products represented a new crystalline material according to the present invention. The results of sorption, surface area and chemical analyses are also presented in table. 6. Picture of x-ray diffraction calcinatory (538aboutC for 3 h) of the products of examples 3, 4 and 5, respectively, and had the main lines that are listed in the table. 7. Measurement of sorption and surface area were carried out on caliciviruses product.

P R I m e R 6. Quantity of calcined (538aboutC for 3 h) crystalline silicate products of examples 3, 4 and 5 were tested in the alpha test and alpha value amounted to 227, 180 and 187, respectively.

P R I m e R 7. Calcinated sample of crystalline silicate according to example 4 was connected with a solution of Pt(NH3)4Cl2up to about 1 wt. Pt. This material was then heated in air at 349aboutC for 3 h

P R I m e R 8. 1 g of the resulting product from example 7 was charged as a catalyst in a small reactor with pre-heater and built CLASS="ptx2">

Normal Dean and hydrogen were charged over the catalyst with a bulk velocity of 0.4 h-1the Dean and the molar ratio of hydrogen to hydrocarbon 100/1. The reaction was carried out at a temperature in the range of 130-250aboutAnd atmospheric pressure.

The results of this experiment are summarized in table. 8, together with the results of the same experiment, but with a crystalline material, replaced by ZSM-5 (U.S. patent N 3702886), ZSM-11 (U.S. patent N 3709979) and Zeolite Beta (U.S. patent N 3308069) presented for comparison. It is seen that the crystalline silicate of the present invention is a highly active catalyst for hydroconversion n-decane and has a good activity for isomerization. In table. 8 "5N/2MN" represents a molecular ratio of 5-methylnonane/2 methylnonane. Due to the position of its methyl group to the 5-methylnonane has more spatial resistance penetration into the pores of the zeolite. The ratio 5N/2MN provides information about the porosity of the tested zeolite.

P R I m e R 9. To demonstrate a greater preparation of the crystalline material of the present invention 1200 g of hexamethyleneimine was added to the solution containing 268 g of sodium aluminate, nes crystallized under stirring about (200 rpm) at 145aboutWith a 5-gallon reactor. The time of crystallization 59 PM Product was washed with water and dried at 120aboutC.

Picture of x-ray diffraction of crystals of calcined (538aboutC) the product has a main line that are listed in the table. 9 and shows the product, other issues of a crystalline material according to the present invention. The chemical composition of the product, the surface area and the adsorption results of the analysis were as follows:

Product composition, wt.

FROM 12.1

N 1,98

Na 640 hours per thousand

Al2O35,0

SiO274,9

SiO2/Al2O3, molar

the ratio of 25.4

Adsorption, wt.

Cyclohexane 9,1

n-Hexane 14,9

H2ABOUT 16,8

The area of over-

in particular, m2/g 479

P R I m e R 10. 25 g of crystalline product of example 9 was calcined in flowing nitrogen atmosphere at 538aboutC for 5 h, followed by blowing 5% oxygen (balance N2) for 16 hours at 538aboutC.

Separate 3 g samples calcined material was subjected to ion exchange with 10 ml of 0.1 N TEABr and Trug and LaCl3in solution, separately. Each exchange was asusual filter, washing water for cleaning Gulidov and dried. Compounds substituted samples are shown below and demonstrate the exchange capacity of this crystalline silicate for different ions.

Ions exchange Thea TRA La

Ion composition, wt.

Na 0,095 0,089 0,063

N 0,3 0,38 0,03

WITH 2.89 3,63

La 1,04

P R I m e R 11. The above sample with replacement La was sorted according to size 14 and 25 smaller and then calcined in air at 535aboutC for 3 hours, Calcined material had an alpha value 173.

P R I m e R 12. Calcinated sample La-exchange material of example 11 was subjected to steam at 649aboutWith 100% pair within 2 hours steamed sample had a value of alpha 22, showing that the crystalline silicate has a very good stability under severe hydrothermal treatment.

P R I m e p 13. For preparation of this crystal with X, including boron, 17,5 g of boric acid was added to the solution containing 6.75 g of 45% KOH and 290 g of N2O. To this was added of 57.8 g of silica Ultrasil and the mixture was thoroughly homogenized. To the mixture was added to 26.2 g of hexamethyleneimine.

The reaction mixture had the following to the219,0

K/SiO20,06

R/SiO20,30 where R represents hexamethylenimine.

The mixture was crystallized in a reactor of stainless steel with stirring at 150aboutC for 8 days. The crystalline product was filtered, washed with water and dried at 120aboutC. a Portion of the product was calcined for 6 h at 540aboutWith and had the following adsorption abilities:

H2O (12 Torr) to 11.7 wt.

Cyclohexane (40 Torr) to 7.5 wt.

n-Hexane (40 Torr) to 11.4 wt.

The surface area of the calcined crystalline material was measured and amounted to 405 m2/,

The chemical composition of the calcined material, wt.

N 1,94

Na 175 hours per thousand

TO 0,60

Bor 1,04

Al2O3920 hours per thousand

SiO275,9

Ash 74,11

SiO2/Al2O3, molar

the ratio 1406

SiO2(Al+B)2O3molar

the ratio of 25.8

Whether the material has a picture of the x-ray diffraction, which includes lines that are listed in the table. 10.

P R I m e R 14. A portion of the calcined crystalline product of example 13 was treated with NH4Cl, the 1.

P R I m e R 15. For the preparation of the present crystalline material with an X, including boron, 35,0 g of boric acid was added to a solution of 15.7 g of 50% NaOH and 1160 g H2O. To this solution was added 240 g of silica Hisil and then 105 g of hexamethyleneimine. The reaction mixture had the following composition in molar ratios:

SiO2/B2O312,3

HE-/SiO20,056

H2O/SiO218,6

Na/SiO20,056

R/SiO20,30 where R represents hexamethylenimine.

The mixture was crystallized in a reactor of stainless steel with stirring at 300aboutC for 9 days. The crystalline product was filtered, washed with water and dried at 120aboutC. the Measured adsorption capacity of calcined material (6 h at 540aboutC) were:

H2(12 Torr) to 14.4 wt.

Cyclohexane

(40 Torr) to 4.6 wt.

n-Hexane (40 Torr) of 14.0 wt.

The surface area of the calcined crystalline material was measured and amounted to 436 m2/,

The chemical composition of the calcined material was determined as follows, wt.

N 2,48

Na 0,06

Bor 0,83

Al2O30,50

SiO, molar

ratio

28,2.

Whether the material has a picture of the x-ray diffraction, which contains lines that are listed in the table. 11.

P R I m e R 16. A portion of the calcined crystalline product of example 15 was tested in the alpha test and found that it has a value of alpha 5.

P R I m e R 17. In a solution containing 1.0 hours 45% solution of potassium hydroxide KOH and 42,9 including water, were injected 1,3 including boric acid, H3IN3. To this solution was added 8,56 including precipitated silica Ultrasil, and then 3,88 hours of hexamethylenimine.

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

SiO2/H2O312,2

OH/SiO20,06

R/SiO20,30

H2O/SiO218,8

K/Si 0,06

The mixture was subjected to crystallization in the reactor with stirrer at 150aboutC for 8 days.

X-ray diffraction analysis showed the presence of material MCM-22.

The composition of the product,

N 1,49

TO 0,51

0.74

Al2O31020 ppm

SiO281,3

Ash 84,6

SiO2/Al2O31355

SiO2/B2O339,6

P R I m e R 18. In a solution containing 8,44 including boric acid and 3.3 hours 50% rastvoreniya Ultrasil, and then of 25.9 hours of hexamethylenimine.

The reaction mixture had the following composition

SiO2/Al2O3202

SiO2/B2O312,3

OH/Si 0,06

R/Si 0,30

H2O/Si 18,6

Na/Si 0,06.

This mixture was subjected to crystallization in the reactor with stirrer at 150aboutC for 168 h

X-ray diffraction analysis showed the presence of MCM-22.

Product composition, wt.

N 1,90

Na 655 ppm

B 0,75

Al2O30,74

SiO277,0

Ash 81,2

SiO2/Al2O3178

SiO2/B2O336,8

P R I m e R 19. In a solution containing 1,6 including a 50% aqueous solution of sodium hydroxide (NaOH) and 115 including water, were introduced to 2.75 hours of boric acid. There was added 1,1 including gallium oxide (III), (Ga2O3), 10,5 hours of hexamethylenimine and 23.2 hours of silica Ultrasil, and then 1.0 hours of the seed crystals of MCM-22.

The reaction mixture had the following composition:

SiO2/B2O3the 15.6

SiO2/Ga2O359,3

OH/Si 0,30

R/Si 0,30

H2O/SiO218,4

This mixture was subjected to crystallization at 150aboutC for 10 days.

X-ray diffraction analysis showed the presence of MCM-22.

Product composition, wt.

SiO2/B2O357,9

SiO2/Ga2O365,8

SiO2/Al2O31094

P R I m e R 20. To demonstrate the importance of using source of silicon dioxide containing at least 30% solid silica, in the method according to the present invention was repeated example 3, but with sodium silicate Q-Brand (containing only about 29 wt. solid oxide silicon) is used as the source of silicon dioxide. In this example of 67.6 g of aluminum sulfate was dissolved in a solution of 38.1 g H2SO4(96,1%) and 400 g of water. The resulting solution was mixed with 120 g of hexamethyleneimine and added to the mixture 712,5 g of Q-Brand sodium silicate (28.8% of SiO2and 8.9% Na2O) and 351 g of water.

The resultant mixture having the following composition, expressed in molar ratios:

SiO2/Al2O330,0

OH-/SiO20,18

H2O/SiO219,4

Na/SiO20,60

R/SiO20,35 was thoroughly mixed and crystallized with stirring in a reactor of stainless steel with 246aboutC for 8 days. The particulate product was separated from unreacted components by filtration and then water washed, followed by drying at 120aboutC. P Is, is ahadeeth (magadiite), and mordenite (mordenite). No crystals of the present invention were found.

P R I m e R 21. In this example, the properties of the hydration of propylene crystalline material of the invention were compared with the properties of ZSM-12 and PSH-3, obtained according to example 4 of U.S. patent N 4439409.

The crystalline material according to the invention was prepared by adding 15,9 including, by weight, of hexamethyleneimine to a mixture containing 3.5 hours 50% NaOH and 3.5 g sodium aluminate, 30,1 h silicic anhydride Ultrasil VN3 and 156 hours of deionized H2O. the Reaction mixture was heated directly to 290aboutF (143aboutC) and stirred in an autoclave at a temperature that ensures crystallization. After achieving complete crystallization, the resulting crystals were separated from the remaining liquid by filtration, washed with water and dried. A portion of the crystals was combined with aluminum oxide for the formation of a mixture of 65 hours, by weight, zeolite and 35 hours aluminum anhydride. To this mixture was added a sufficient amount of water so that the resulting catalyst can be formed into extrudates. This catalyst was activated by calcining in nitrogen at 1000aboutF (540aboutC) next >/P>ZSM-12 was prepared by adding 1 o'clock by weight of seed crystals of ZSM-12 to a mixture containing 41.5 parts of silicic anhydride Hi-sil 233, 67,7 including 50% of bromide of tetraethylammonium, 7,0 including 50% NaOH and 165,4 parts of deionized H2O. the Reaction mixture was heated directly to 280aboutF (138aboutC) and stirred in an autoclave at a temperature of crystallization. After achieving complete crystallization, the resulting crystals were separated from the remaining liquid by filtration, washed and dried. A portion of the crystals was combined with aluminum oxide for the formation of a mixture of 65 hours by weight of zeolite and 35 hours aluminum anhydride. To this mixture was added a sufficient amount of water so that the resulting catalyst can be formed in the form of an extrudate. This catalyst was activated by calcination in nitrogen at 1000aboutF (540aboutC), with subsequent exchange in an aqueous solution of 1.0 N ammonium nitrate and calcining at 1200aboutF (650aboutC).

Hydration of propylene was carried out at a temperature of 330aboutF (166aboutC), a pressure of 1000 psi (7000 kPa) and flow rate of propylene to 0.6. Results 2 days in a pair are compared in table. 12 below.

The above resultaten greater speed of conversion with good selectivity to diisopropylbenzene and a low level of education of oligomers of propylene.

1. Synthetic porous crystalline material, which is the composition of oxides of trivalent metal and silicon, characterized in that as the oxide of trivalent metal material contains aluminum oxide, or boron or gallium, with the following molar ratio: X2O3n SiO2where X is a trivalent metal, n 20 40, this material has the designation of MCM-22 and the following picture of the x-ray diffraction, including the following lines:

Interplanar d-distance, the relative intensity I/I0100

30,0 2,2 W M

22,1 1.3 W

12,36 OF 0.2 M VS

11,03 OF 0.2 M S

8,83 OF 0.14 M VS

6,86 OF 0.14 W M

6,18 TO 0.12 M VS

6,00 0.10 W M

5,54 0.10 W M

4,92 0,09 W

WITH 4.64 0,08 W

TO 4.41 OF 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 OF 0.06 W M

3,56 OF 0.06 W M

3,42 0,06 VS

3,30 OF 0.05 W M

3,20 OF 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

where W is weak (0 to 20) medium (20 to 40), S strong (40 60) and VS very strong (60 100) comparative intensity, and has the ability of equilibrium adsorption of 11.7 to 16.8 wt. for water vapor, 4,6 - of 14.6 wt. for cyclohexane vapor and 11.4 19.0 wt. for vapours of n-hexane.

2. The method of obtaining syntheti preparation of the reaction mixture, containing a sufficient number of cations of alkali metals, a source of silica, a source of an oxide of trivalent metal, water, hexamethylenimine, the crystallization of this mixture, separating the resulting precipitate, drying and calcination, wherein the source of silicon oxide is used oxycodonesee a silicon compound containing at least 30 wt. solid silicon dioxide as the source of oxide of trivalent metal is used oxycodonesee aluminum compounds or boron or gallium, the preparation of the reaction mixture is conducted under conditions providing the following mixture in the molar ratio:

SiO2/X2O36,1 30,0

H2O/SiO218,6 44,9

OH/SiO20,056 0,18

M/SiO20,056 0,18

R/SiO20,30 0,35

where X is aluminum or boron or gallium;

M is alkali metal;

R hexamethylenimine,

and the crystallization is carried out under conditions sufficient for the formation of crystalline material having the following molar ratio of X2O3n SiO2where n 20 40, label MCM-22 and the diffraction pattern of x-rays, including the lines listed in paragraph 1.

 

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