CN100567149C - Organic silicon micro-pore zeolite and synthetic method thereof - Google Patents
Organic silicon micro-pore zeolite and synthetic method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of organic silicon micro-pore zeolite and synthetic method thereof, mainly solve in the prior art and do not contain organosilyl problem in the synthetic micro-pore zeolite skeleton structure, provide to contain organosilyl micro-pore zeolite in a kind of skeleton structure.It comprises the composition of following molar relationship: (1/n) Al
2O
3: SiO
2: (m/n) R, n=5 in the formula～1000, m=0.01～300, R is at least a in the alkyl or phenyl; Its Si
29NMR solid state nmr collection of illustrative plates-80～+ include a Si at least between the 50ppm
29The nuclear magnetic resonance spectrum peak; Its X-ray diffracting spectrum is 11.14 ± 0.05, and 9.99 ± 0.05,9.74 ± 0.05,6.36 ± 0.05,5.99 ± 0.05,5.70 ± 0.05,5.57 ± 0.05,4.98 ± 0.05,4.26 ± 0.05,3.83 ± 0.05,3.75 ± 0.05,3.72 ± 0.05,3.65 ± 0.05,3.44 there is d-spacing maximum value at ± 0.05,3.32 ± 0.05 and 3.05 ± 0.05 dust places.This micro-pore zeolite can be used as sorbent material or the catalyst component that organic compound transforms usefulness.
Description
Technical field
The present invention relates to a kind of organic silicon micro-pore zeolite and synthetic method thereof.
Background technology
Industrial, porous inorganic material is widely used as catalyzer and support of the catalyst.Porous material has higher relatively specific surface and unimpeded pore passage structure, is good catalytic material or support of the catalyst therefore.Porous material roughly can comprise: unformed porous material, crystalline molecular sieve and modified layered material etc.
The basic skeleton structure of crystalline microporous zeolite is based on the three-dimensional TO of inflexible
4(SiO
4, AlO
4Deng) modular construction; TO in this structure
4Be to share Sauerstoffatom, skeleton tetrahedron such as AlO in the tetrahedron mode
4Charge balance be by surperficial positively charged ion such as Na
+, H
+Existence keep.This shows the skeleton character that can change zeolite by the cationic exchange mode.Simultaneously, in the structure of zeolite, exist pore canal system abundant, that the aperture is certain, the interlaced formation tridimensional network in these ducts.Just be based on said structure, zeolite not only to various organic reactions have good catalytic activity, good shape selectivity and by modification can realize good selectivity (US6162416, US4954325, US5362697).
The artificial crystalline micro-pore zeolite usually is to adopt hydrothermal method synthetic, and often adopts specific template or directed agents to synthesize specific zeolite molecular sieve.These template or directed agents usually are organic compounds containing nitrogen.Yet there is corresponding relation between template or directed agents and the specific zeolite molecular sieve.As: for having micropore MFI structure ZSM-5, US3702886 finds to adopt tetrapropyl ammonium (TPA) to synthesize as directed agents, and US4151189 finds to adopt C
2～C
9Primary amine be that directed agents also can be synthesized.Other disclose the method for Tetrabutylammonium bromide as the synthetic ZSM-11 of directed agents that adopt as US3709979, US3832449 discloses and adopted tetraethyl ammonium is the method for the synthetic ZSM-12 of directed agents, US4016245 discloses and adopted quadrol is the method for the synthetic ZSM-35 of directed agents, Zeolite (1991, Vol11, P202) having introduced the employing tetraethyl ammonium hydroxide is the method for the synthetic Beta zeolite of directed agents, US4439409 discloses the method that adopts the synthetic PSH-3 zeolite of hexamethylene imine, US4954325 discloses the method that adopts the synthetic MCM-22 of hexamethylene imine, it is directed agents that US5362697 and ZL94192390.8 disclose with the hexamethylene imine, has the method for stable stratiform MWW structure MCM-56 by the control crystallization time is synthetic, it is the method for the synthetic non-stratiform MCM-49 of directed agents with the hexamethylene imine that US5236575 has introduced, Nature (1998, Vol396, P353) to disclose with the hexamethylene imine be directed agents to magazine, adopt the demixing technology preparation to have the method for the ITQ-2 of MWW structure.The skeleton structure of above-mentioned crystalline zeolite all is to be fundamental element with inorganic silicon oxide and inorganic oxide aluminium, contains organosilyl zeolite and synthetic method in the skeleton structure and does not appear in the newspapers.
Summary of the invention
One of technical problem to be solved by this invention is not contain organosilyl problem in the synthetic micro-pore zeolite skeleton structure in the prior art, and the novel organosilicon of not mentioning in a kind of prior art micro-pore zeolite is provided, and contains organosilicon in its skeleton structure.
Two of technical problem to be solved by this invention provides the synthetic method of this novel organosilicon micro-pore zeolite of not mentioning in a kind of prior art.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of organic silicon micro-pore zeolite comprises the composition of following molar relationship: (1/n) Al
2O
3: SiO
2: (m/n) R, n=5 in the formula～1000, m=0.01～300, R is at least a in the alkyl or phenyl;
The Si of described zeolite
29NMR solid state nmr collection of illustrative plates-80～+ include a Si at least between the 50ppm
29The nuclear magnetic resonance spectrum peak;
The X-ray diffracting spectrum of described zeolite is 11.14 ± 0.05, and 9.99 ± 0.05,9.74 ± 0.05,6.36 ± 0.05,5.99 ± 0.05,5.70 ± 0.05,5.57 ± 0.05,4.98 ± 0.05,4.26 ± 0.05,3.83 ± 0.05,3.75 ± 0.05,3.72 ± 0.05,3.65 ± 0.05,3.44 there is d-spacing maximum value at ± 0.05,3.32 ± 0.05 and 3.05 ± 0.05 dust places.
In the technique scheme, the preferable range of n is 10～500, and the preferable range of m is 0.05～200.Described alkyl preferred version is that carbonatoms is 1～8 alkyl, and more preferably scheme is for being selected from methyl or ethyl.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of synthetic method of organic silicon micro-pore zeolite comprises:
A) organosilicon source, inorganic silicon source, aluminium source, alkali, organic formwork agent and water are mixed, with the SiO in the inorganic silicon source
2Be benchmark, reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=5～1000, organosilicon source/SiO
2=0.001～1, OH
-/ SiO
2=0.01～5.0, H
2O/SiO
2=5～100, organic formwork agent/SiO
2=0.01～2.0;
B) be under 90～200 ℃ of conditions with above-mentioned reaction mixture in the crystallization temperature, react after 1～200 hour and take out, make organic silicon micro-pore zeolite through washing, drying.
In the technique scheme, inorganic silicon source preferred version is to be selected from least a in silicon sol, solid oxidation silicon, silica gel, silicon ester, diatomite or the water glass.Organosilicon source preferred version is to be selected from least a in halosilanes, silazane or the organoalkoxysilane; Wherein the halosilanes preferred version is to be selected from least a in trimethylchlorosilane, dimethyldichlorosilane(DMCS), chlorotriethyl silane, diethyl dichlorosilane, dimethyl chloride bromo-silicane, dimethyl ethyl chlorosilane, dimethylbutyl chlorosilane, 3,5-dimethylphenyl chlorosilane, dimethyl isopropyl chloride silane, dimethyl tertiary butyl chloride silane, dimethyl stearyl chlorosilane, methyl phenyl vinyl chlorosilane, vinyl trichloro silane or the diphenyl dichlorosilane; The silazane preferred version is to be selected from least a in hexamethyldisilazane, heptamethyldisilazane, tetramethyl-disilazane, divinyl tetramethyl-disilazane or the phenylbenzene tetramethyl-disilazane; Organoalkoxysilane is selected from least a in trimethylethoxysilane, dimethyldiethoxysilane, trimethylammonium methoxy silane, dimethyldimethoxysil,ne, trimethoxy-benzene base silane or the phenylbenzene diethoxy silane.Aluminium source preferred version is to be selected from least a in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, aluminum oxide, kaolin or the polynite.Alkali is mineral alkali, and preferred version is to be selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide.The organic formwork agent preferred version is to be selected from least a in ethamine, quadrol, hexanediamine, diethylamine, triethylamine, propylamine, butylamine, hexylamine, tetraethylammonium bromide, 4-propyl bromide, Tetrabutyl amonium bromide, tetraethyl ammonium hydroxide, TPAOH or the TBAH.
Reaction mixture is with the SiO in the inorganic silicon source
2Be benchmark, with the molar ratio computing preferable range be: SiO
2/ Al
2O
3=10～500, organosilicon/SiO
2=0.005～0.5, OH
-/ SiO
2=0.05～1.0, H
2O/SiO
2=10～80, organic formwork agent/SiO
2=0.05～1.0.Crystallization temperature preferable range is 100～200 ℃, and crystallization time preferable range is 5～240 hours.
Organic silicon micro-pore zeolite called after SHY-2 of the present invention.
Organic silicon micro-pore zeolite SHY-2 of the present invention can be used as sorbent material or the catalyst component that organic compound transforms usefulness.
Organic silicon micro-pore zeolite SHY-2 of the present invention can be used as sorbent material, for example is used in gas phase or liquid phase separating out at least one component from the mixture of multiple component.So at least a component can partially or substantially be separated from the mixture of various components fully, mode is to allow mixture contact with this organic silicon micro-pore zeolite, selectively this a kind of component of sorption.
Organic silicon micro-pore zeolite SHY-2 of the present invention can be used as the catalyzer that organic compound transforms usefulness.Vapor phase alkylation of benzene and ethene etc. for example.
The present invention is by to the modulation of each component relative content in the reaction mixture with by the control to crystallization process, synthesized have specific pore passage structure, skeleton contains organosilyl micro-pore zeolite, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Aluminum nitrate 4.3 grams are dissolved in the 540 gram water, add sodium hydroxide 24.0 grams and make it dissolving, under condition of stirring, add 4-propyl bromide 66.5 grams then, add solid oxidation silicon 60.0 grams again, dimethyldichlorosilane(DMCS) 2.6 grams, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝100
NaOH/SiO
2＝0.6
Dimethyldichlorosilane(DMCS)/SiO
2=0.02,
4-propyl bromide/SiO
2=0.25
H
2O/SiO
2＝30
After the question response mixture stirs, in the stainless steel cauldron of packing into, under stirring state in 185 ℃ of crystallization 60 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 95.5.
Dried sample after measured, its Si
29NMR solid core magnetic spectrum the nuclear magnetic resonance spectrum peak occurs at-18.5ppm.Its X-ray diffraction data see Table 1.
Table 1
[embodiment 2]
With sodium aluminate (Al
2O
342.0 weight %) 6.1 grams are dissolved in the 720 gram water, add sodium hydroxide 1.6 grams and make it dissolving, add hexanediamine 46.4 grams then under condition of stirring, add silicon oxide 60 grams again, hexanediamine 3.9 grams, trimethylchlorosilane 2.2 grams, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝40
NaOH/SiO
2＝0.4
Trimethylchlorosilane/SiO
2=0.02,
Hexanediamine/SiO
2=0.40
H
2O/SiO
2＝40
After the question response mixture stirs, in the stainless steel cauldron of packing into, under stirring state in 150 ℃ of crystallization 55 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 41.
Dried sample after measured, its Si
29NMR solid core magnetic spectrum the nuclear magnetic resonance spectrum peak occurs at 15.9ppm.Its X-ray diffraction data see Table 2.
Table 2
[embodiment 3]
Tai-Ace S 150 1.2 grams are dissolved in the 450 gram water, add sodium hydroxide 12.0 grams and make it dissolving, under condition of stirring, add 4-propyl bromide 79.8 grams then, add silicon sol 150 grams (silica content 40 weight %) again, dimethyldiethoxysilane 5.9 grams, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝300
NaOH/SiO
2＝0.3
Dimethyldiethoxysilane/SiO
2=0.04,
4-propyl bromide/SiO
2=0.30
H
2O/SiO
2＝30
After the question response mixture stirs, in the stainless steel cauldron of packing into, under stirring state in 145 ℃ of crystallization 70 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 281.3.
Dried sample after measured, its Si
29NMR solid core magnetic spectrum the nuclear magnetic resonance spectrum peak occurs at-19.7ppm.Its X-ray diffraction data see Table 3.
Table 3
[embodiment 4]
Aluminum nitrate 2.8 grams are dissolved in the 540 gram water, add sodium hydroxide 20 grams and make it dissolving, under condition of stirring, add 4-propyl bromide 79.8 grams then, add solid oxidation silicon 60 grams again, hexamethyldisilazane 4.8 grams, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝150
NaOH/SiO
2＝0.5
Hexamethyldisilazane/SiO
2=0.03,
4-propyl bromide/SiO
2=0.3
H
2O/SiO
2＝30
After the question response mixture stirs, in the stainless steel cauldron of packing into, under stirring state in 145 ℃ of crystallization 38 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 156.
Dried sample after measured, its Si
29NMR solid core magnetic spectrum the nuclear magnetic resonance spectrum peak occurs at 14.9ppm.Its X-ray diffraction data see Table in 4.
Table 4
[embodiment 5]
Aluminum nitrate 21.3 grams are dissolved in the 720 gram water, add sodium hydroxide 20 grams and make it dissolving, under condition of stirring, add 4-propyl bromide 80 grams then, add solid oxidation silicon 60 grams again, dimethyldiethoxysilane 5.1 grams, the material proportion of reactant (mol ratio) is:
SiO
2/Al
2O
3＝20
NaOH/SiO
2＝0.5
Dimethyldiethoxysilane/SiO
2=0.04,
4-propyl bromide/SiO
2=0.3
H
2O/SiO
2＝40
After the question response mixture stirs, in the stainless steel cauldron of packing into, under stirring state in 135 ℃ of crystallization 35 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 20.5.
Dried sample after measured, its Si
29NMR solid core magnetic spectrum the nuclear magnetic resonance spectrum peak occurs at-21.1ppm, and its X-ray diffraction data see Table in 5.
Table 5
[embodiment 6]
Get 50 gram [embodiment 2] synthetic powdered samples, 550 ℃ of roastings 5 hours then with the nitric acid exchange of 1M 3 times, are filtered, drying.Afterwards,, add that 5 (weight) % nitric acid is mediated, extruded moulding is the bar of 1.6 * 2 millimeters of φ with 20 gram aluminum oxide thorough mixing, 120 ℃ of oven dry, 550 ℃ of roastings 5 hours are prepared into the catalyzer that needs.
Ethene and benzene vapor phase alkylation.
The catalyst loading of getting the above-mentioned preparation of 2.0 grams feeds the mixture of ethene and benzene then in fixed-bed reactor.Reaction conditions is: weight ethylene air speed=5.0 hour
-1, benzene and ethylene molar ratio are 10,480 ℃ of temperature of reaction, reaction pressure 0.1MPa.Continuous operation 24 hours, reaction result is: conversion of ethylene is about 99%, ethylbenzene selectivity 95%, diethylbenzene selectivity 4.8%.
Claims (8)
1, a kind of organic silicon micro-pore zeolite comprises the composition of following molar relationship: (1/n) Al
2O
3: SiO
2: (m/n) R, n=5 in the formula～1000, m=0.01～300, R is at least a in the alkyl or phenyl;
The Si of described zeolite
29NMR solid state nmr collection of illustrative plates-80～+ include a Si at least between the 50ppm
29The nuclear magnetic resonance spectrum peak;
The X-ray diffracting spectrum of described zeolite is 11.14 ± 0.05, and 9.99 ± 0.05,9.74 ± 0.05,6.36 ± 0.05,5.99 ± 0.05,5.70 ± 0.05,5.57 ± 0.05,4.98 ± 0.05,4.26 ± 0.05,3.83 ± 0.05,3.75 ± 0.05,3.72 ± 0.05,3.65 ± 0.05,3.44 there is d-spacing maximum value at ± 0.05,3.32 ± 0.05 and 3.05 ± 0.05 dust places.
2, organic silicon micro-pore zeolite according to claim 1 is characterized in that n=10～500, m=0.05～200; Described alkyl is that carbonatoms is 1～8 alkyl.
3, organic silicon micro-pore zeolite according to claim 2 is characterized in that described alkyl is methyl or ethyl.
4, the synthetic method of the described organic silicon micro-pore zeolite of claim 1 comprises:
A) organosilicon source, inorganic silicon source, aluminium source, alkali, organic formwork agent and water are mixed, with the SiO in the inorganic silicon source
2Be benchmark, reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=5～1000, organosilicon source/SiO
2=0.001～1, OH
-/ SiO
2=0.01～5.0, H
2O/SiO
2=5～100, organic formwork agent/SiO
2=0.01～2.0;
B) be under 90～200 ℃ of conditions with above-mentioned reaction mixture in the crystallization temperature, react after 1～300 hour and take out, make organic silicon micro-pore zeolite through washing, drying.
5, the synthetic method of organic silicon micro-pore zeolite according to claim 4 is characterized in that described inorganic silicon source is selected from least a in silicon sol, solid oxidation silicon, silica gel, silicon ester, diatomite or the water glass; Described organosilicon source is selected from least a in halosilanes, silazane or the organoalkoxysilane; Described aluminium source is selected from least a in sodium aluminate, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride, aluminium hydroxide, aluminum oxide, kaolin or the polynite; Described alkali is mineral alkali, is selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide; Described organic formwork agent is selected from least a in ethamine, quadrol, hexanediamine, diethylamine, triethylamine, propylamine, butylamine, hexylamine, tetraethylammonium bromide, 4-propyl bromide, Tetrabutyl amonium bromide, tetraethyl ammonium hydroxide, TPAOH or the TBAH.
6, the synthetic method of organic silicon micro-pore zeolite according to claim 5 is characterized in that described halosilanes is selected from least a in trimethylchlorosilane, dimethyldichlorosilane(DMCS), chlorotriethyl silane, diethyl dichlorosilane, dimethyl chloride bromo-silicane, dimethyl ethyl chlorosilane, dimethylbutyl chlorosilane, 3,5-dimethylphenyl chlorosilane, dimethyl isopropyl chloride silane, dimethyl tertiary butyl chloride silane, dimethyl stearyl chlorosilane, methyl phenyl vinyl chlorosilane, vinyl trichloro silane or the diphenyl dichlorosilane; Described silazane is selected from least a in hexamethyldisilazane, heptamethyldisilazane, tetramethyl-disilazane, divinyl tetramethyl-disilazane or the phenylbenzene tetramethyl-disilazane; Described organoalkoxysilane is selected from least a in trimethylethoxysilane, dimethyldiethoxysilane, trimethylammonium methoxy silane, dimethyldimethoxysil,ne, trimethoxy-benzene base silane or the phenylbenzene diethoxy silane.
7, the synthetic method of organic silicon micro-pore zeolite according to claim 4 is characterized in that with the SiO in the inorganic silicon source
2Be benchmark, reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=10～500, organosilicon source/SiO
2=0.005～0.5, OH
-/ SiO
2=0.05～1.0, H
2O/SiO
2=10～80, organic formwork agent/SiO
2=0.05～1.0.
8, the synthetic method of organic silicon micro-pore zeolite according to claim 4 is characterized in that the crystallization temperature is 100～200 ℃, and the crystallization time is 5～240 hours.
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| CN109261129B (en) * | 2018-11-21 | 2021-10-29 | 河西学院 | Attapulgite synergistic adsorbent and preparation method and application thereof |
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