Micro-pore zeolite, preparation method and application thereof

Abstract

The present invention provides an organosilicone porous zeolite, synthetic method and its application, mainly resolves the problem of organosilicone-free in the porous zeolite structure by the present technology, provides a porous zeolite containing organosilicone in structure. It includes constitute of following mol relation: (1 / n)Al2O3:SiO2:(m / n)R, n=10-350, m=0.02-50, R is at least one of alkyl, alkanes and alkenes or phenyl; wherein Si29NMR between -80-+50ppm containing at least a Si29 NMR peak, X-ray diffraction pattern computer has d-distance max in 13.2+ / -0.2, 12.3+ / -0.1, 10.9+ / -0.3, 9.1+ / -0.3, 6.8+ / -0.2, 6.1+ / -0.2, 5.6+ / -0.2, 4.4+ / -0.3, 4.0+ / -0.3, 3.6+ / -0.2, 3.4+ / -0.1 and 3.3+ / -0.2. The porous zeolite may catalyst component or absorption agent for organic compound conversion.

Description

technical field

[0001] The invention relates to a microporous zeolite, a preparation method and application thereof. Background technique

[0002] In industry, porous inorganic materials are widely used as catalysts and catalyst supports. Porous materials have relatively high specific surface area and smooth pore structure, so they are good catalytic materials or catalyst supports. Porous materials generally include: amorphous porous materials, crystalline molecular sieves, and modified layered substances.

[0003] The basic framework structure of crystalline microporous zeolites is based on the rigid three-dimensional TO 4 (SiO 4 , AlO 4 etc.) unit structure; in this structure TO 4 Oxygen atoms are shared in a tetrahedral manner, and the skeleton tetrahedron such as AlO 4 The charge balance of is through surface cations such as Na + , H + existence is maintained. It can be seen that the framework properties of zeolite can be changed by cation exchange. At the same...

Examples

Embodiment 1

[0023] Sodium aluminate (containing 42.0% by weight Al 2 o 3 ) 6.1 grams and 2.0 grams of sodium hydroxide are dissolved in 270 grams of water, then add 34.7 grams of hexamethyleneimine under the situation of stirring, then add 150 grams of silica sol (containing 40% by weight SiO 2 ), dimethyldichlorosilane 6.5 grams, the material proportion (mol ratio) of reactant is:

[0024] SiO 2 / Al 2 o 3 =40

[0025] NaOH / SiO 2 =0.05

[0026] Dimethyldichlorosilane / SiO 2 =0.05

[0027] Hexamethyleneimine / SiO 2 =0.35

[0028] h 2 O / SiO 2 =20

[0029] After the reaction mixture was stirred evenly, it was put into a stainless steel reaction kettle, and crystallized at 150° C. for 55 hours while stirring. After taking out, it is filtered, washed and dried. SiO was obtained by chemical analysis 2 / Al 2 o 3 The molar ratio was 42.3.

[0030]After drying the sample was determined, its Si 29 The NMR solid-state nuclear magnetic spectrum peak appears at -18.4ppm. Its X-ray d...

Embodiment 2

[0034] Sodium aluminate (containing 42.0% by weight Al 2 o 3 ) 6.1 grams and 2.0 grams of sodium hydroxide are dissolved in 180 grams of water, then add 6.6 grams of trimethylchlorosilane under the situation of stirring, hexahydropyridine 43.0 grams, then add 150 grams of silica sol (containing 40% by weight SiO 2 ), the material ratio (molar ratio) of reactant is:

[0035] SiO 2 / Al 2 o 3 =40

[0036] NaOH / SiO 2 =0.05

[0037] Chlorotrimethylsilane / SiO 2 =0.06

[0038] Hexahydropyridine / SiO 2 =0.50

[0039] h 2 O / SiO 2 =15

[0040] After the reaction mixture was stirred evenly, it was put into a stainless steel reaction kettle, and crystallized at 152° C. for 50 hours while stirring. After taking out, it is filtered, washed and dried. SiO was obtained by chemical analysis 2 / Al 2 o 3 The molar ratio was 42.1.

[0041] After drying the sample was determined, its Si 29 The NMR solid-state nuclear magnetic spectrum peak appears at 15.2ppm. Its X-ray diffract...

Embodiment 3

[0045] Dissolve 5.1 grams of aluminum oxide and 2.0 grams of sodium hydroxide in 540 grams of water, then add 42.5 grams of hexamethyleneimine while stirring, then add 60 grams of solid silicon oxide and 3.2 grams of hexamethyldisilazane , the material ratio (molar ratio) of reactant is:

[0046] SiO 2 / Al 2 o 3 =20

[0047] NaOH / SiO 2 =0.05

[0048] Hexamethyldisilazane / SiO 2 =0.04

[0049] Hexamethyleneimine / SiO 2 =0.5

[0050] h 2 O / SiO 2 =30

[0051] After the reaction mixture was stirred evenly, it was put into a stainless steel reaction kettle, and crystallized at 163° C. for 50 hours while stirring. After taking out, it is filtered, washed and dried. SiO was obtained by chemical analysis 2 / Al 2 o 3 The molar ratio was 17.7.

[0052] After drying the sample was determined, its Si 29 The NMR solid-state nuclear magnetic spectrum peak appears at 15.8ppm. Its X-ray diffraction data are shown in Table 3.

[0053] table 3

[0054]

technical field

[0001] The invention relates to a microporous zeolite, a preparation method and application thereof. Background technique

[0002] In industry, porous inorganic materials are widely used as catalysts and catalyst supports. Porous materials have relatively high specific surface area and smooth pore structure, so they are good catalytic materials or catalyst supports. Porous materials generally include: amorphous porous materials, crystalline molecular sieves, and modified layered substances.

[0003] The basic framework structure of crystalline microporous zeolites is based on the rigid three-dimensional TO 4 (SiO 4 , AlO 4 etc.) unit structure; in this structure TO 4 Oxygen atoms are shared in a tetrahedral manner, and the skeleton tetrahedron such as AlO 4 The charge balance of is through surface cations such as Na + , H + existence is maintained. It can be seen that the framework properties of zeolite can be changed by cation exchange. At the same...

Examples

Embodiment 1

[0023] Sodium aluminate (containing 42.0% by weight Al 2 o 3 ) 6.1 grams and 2.0 grams of sodium hydroxide are dissolved in 270 grams of water, then add 34.7 grams of hexamethyleneimine under the situation of stirring, then add 150 grams of silica sol (containing 40% by weight SiO 2 ), dimethyldichlorosilane 6.5 grams, the material proportion (mol ratio) of reactant is:

[0024] SiO 2 / Al 2 o 3 =40

[0025] NaOH / SiO 2 =0.05

[0026] Dimethyldichlorosilane / SiO 2 =0.05

[0027] Hexamethyleneimine / SiO 2 =0.35

[0028] h 2 O / SiO 2 =20

[0029] After the reaction mixture was stirred evenly, it was put into a stainless steel reaction kettle, and crystallized at 150° C. for 55 hours while stirring. After taking out, it is filtered, washed and dried. SiO was obtained by chemical analysis 2 / Al 2 o 3 The molar ratio was 42.3.

[0030]After drying the sample was determined, its Si 29 The NMR solid-state nuclear magnetic spectrum peak appears at -18.4ppm. Its X-ray d...

Embodiment 2

[0034] Sodium aluminate (containing 42.0% by weight Al 2 o 3 ) 6.1 grams and 2.0 grams of sodium hydroxide are dissolved in 180 grams of water, then add 6.6 grams of trimethylchlorosilane under the situation of stirring, hexahydropyridine 43.0 grams, then add 150 grams of silica sol (containing 40% by weight SiO 2 ), the material ratio (molar ratio) of reactant is:

[0035] SiO 2 / Al 2 o 3 =40

[0036] NaOH / SiO 2 =0.05

[0037] Chlorotrimethylsilane / SiO 2 =0.06

[0038] Hexahydropyridine / SiO 2 =0.50

[0039] h 2 O / SiO 2 =15

[0040] After the reaction mixture was stirred evenly, it was put into a stainless steel reaction kettle, and crystallized at 152° C. for 50 hours while stirring. After taking out, it is filtered, washed and dried. SiO was obtained by chemical analysis 2 / Al 2 o 3 The molar ratio was 42.1.

[0041] After drying the sample was determined, its Si 29 The NMR solid-state nuclear magnetic spectrum peak appears at 15.2ppm. Its X-ray diffract...

Embodiment 3

[0045] Dissolve 5.1 grams of aluminum oxide and 2.0 grams of sodium hydroxide in 540 grams of water, then add 42.5 grams of hexamethyleneimine while stirring, then add 60 grams of solid silicon oxide and 3.2 grams of hexamethyldisilazane , the material ratio (molar ratio) of reactant is:

[0046] SiO 2 / Al 2 o 3 =20

[0047] NaOH / SiO 2 =0.05

[0048] Hexamethyldisilazane / SiO 2 =0.04

[0049] Hexamethyleneimine / SiO 2 =0.5

[0050] h 2 O / SiO 2 =30

[0051] After the reaction mixture was stirred evenly, it was put into a stainless steel reaction kettle, and crystallized at 163° C. for 50 hours while stirring. After taking out, it is filtered, washed and dried. SiO was obtained by chemical analysis 2 / Al 2 o 3 The molar ratio was 17.7.

[0052] After drying the sample was determined, its Si 29 The NMR solid-state nuclear magnetic spectrum peak appears at 15.8ppm. Its X-ray diffraction data are shown in Table 3.

[0053] table 3

[0054]

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