CN1314589C - Porous material and its synthesis method - Google Patents
Porous material and its synthesis method Download PDFInfo
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- CN1314589C CN1314589C CNB2004100666362A CN200410066636A CN1314589C CN 1314589 C CN1314589 C CN 1314589C CN B2004100666362 A CNB2004100666362 A CN B2004100666362A CN 200410066636 A CN200410066636 A CN 200410066636A CN 1314589 C CN1314589 C CN 1314589C
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Abstract
The present invention relates to a porous material and a synthesis method thereof, particularly to a porous material with the characteristics of composite pore canals and a synthesis method thereof. In the method, at least one of amorphous silicon dioxides, silica sol, solid silicon oxides, silica gel, diatomite or water glasses is used as a silicon source, at least one of sodium aluminate, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxides, aluminum oxides, kaoline or montmorillonite is used as an aluminum source, and at least one of lithium hydroxides, sodium hydroxides, potassium hydroxides, rubidium hydroxides or cesium hydroxides is used as a raw material; the reaction mixture comprises the components of the following molar ratios: the molar ratio of SiO2 to Al2O3 of 5 to 1000, the molar ratio of OH<-> to SiO2 of 0.01 to 5.0, the molar ratio of H2O to SiO2 of 5 to 30 and the molar ratio of R to SiO2 of 0.05 to 2.0, wherein the R is a template agent; the technical scheme comprises the steps that the porous material is synthesized by aging the reaction mixture at a temperature of 0 to 100 DEG C for 1 to 120 hours and crystallizing the aged reaction mixture at a temperature of 90 to 200 DEG C for 1 to 200 hours; the porous material with micrometer level macropores and nanometer level micropores is synthesized. The porous material can be used in the industrial production.
Description
Technical field
The present invention relates to a kind of porous material and synthetic method thereof.
Background technology
Industrial, porous material is widely used as catalyzer and support of the catalyst.Porous material can be divided into three major types: micropore (Microporous,＜2nm), mesopore (Mesoporous, 2～50nm) and macropore (Macroporous,＞50nm).Porous material has higher relatively specific surface and unimpeded pore passage structure, is good catalytic material or support of the catalyst therefore.
Poromerics such as zeolite etc. because the aperture is little, can only be used as small molecules sorbent material or catalyzer.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.Therefore can change the skeleton character of 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 has good catalytic activity, good shape selectivity and can realize good selectivity by modification various organic reactions.U.S. Pat 6162426 (1999) has been reported the β zeolite before roasting, is 0～2 acid treatment with pH, can be used for the transalkylation reaction of aromatic hydrocarbons.Chinese patent ZL99113568.7 has reported that the transformation efficiency of hydrogen peroxide and third rare selectivity all were significantly improved when titanium-silicon molecular sieve catalyst was used for third rare epoxidation reaction after acetate is handled.U.S. Pat 3962364 introduced a kind of with phosphoric to the catalyzer that the ZSM-5 zeolite carries out modification, when being used for the reaction of benzene and ethylbenzene manufactured from ethylene, the selectivity of ethylbenzene and the stability of catalyzer all are improved.
Mesopore material such as MCM-22 (US4954325), MCM-48, HMS etc. are the another class novel molecular sieve catalytic materials of succeeding in developing recently.It not only has big aperture, also has very high specific surface (～1000m simultaneously
2/ g).The oversized hole material then has bigger duct.Yet the surface acidity of mesopore and oversized hole material is very weak, is not suitable as an acidic catalyst.Therefore must improve over-all propertieies such as its acidity and hydrothermal stability by suitable synthetic and modification.
All do not relate in the document in the past and have micron order macropore and nanometer level microporous porous material simultaneously.The micron order macropore can be used as reaction channel, so the existence of micron order macropore has improved internal diffusion effectively.Nano grade pore is an acid sites, i.e. active centre, and the place of catalyzed reaction, both synergies can improve catalytic performance.Therefore this novel porous material will be the catalytic material that a class has prospect very much.
Summary of the invention
One of technical problem to be solved by this invention provides the novel porous material of not mentioning in a kind of document in the past, and it has compound pore passage structure, has micropore and oversized hole simultaneously.
Two of technical problem to be solved by this invention provides the synthetic method of this novel porous material of not mentioning in a kind of document in the past.
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 porous material comprises the composition of following molar relationship: Al
2O
3: (n) SiO
2, n=5 in the formula～1000, described material has compound pore passage structure, has micron order macropore and nanometer level microporous simultaneously, and wherein in volume percent, 0.1～10 micron macropore is that the micropore of 55～85%, 0.4～2 nanometer is 15～43%.
Porous material in the technique scheme has following XRD diffraction data:
| 2θ | I/I 0 |
| 7.2±0.1 | 77.9 |
| 8.0±0.1 | 55.6 |
| 9.6±0.2 | 50.0 |
| 12.9±0.2 | 33.0 |
| 14.5±0.2 | 55.7 |
| 20.3±0.2 | 48.7 |
| 22.7±0.5 | 78.7 |
| 25.2±0.1 | 67.0 |
| 26.1±0.1 | 100 |
| 27.0±0.1 | 66.5 |
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 porous material, carry out according to the following steps:
(1) silicon source, aluminium source, alkali, organic formwork agent and water are mixed, reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=5～1000, OH
-/ SiO
2=0.01～5.0, H
2O/SiO
2=5～30, R/SiO
2=0.05～2.0, R is the organic amine template of carbon more than five;
(2) with above-mentioned reaction mixture 0～100 ℃ of ageing 1～120 hour;
(3) will be under the crystallization temperature be 90～200 ℃ and agitation condition through the reaction mixture of above-mentioned processing, crystallization took out after 1～200 hour, through wash, drying makes porous material.
In the technique scheme, the silicon source is selected from least a in soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; The 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; Alkali is that mineral alkali is selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide.Reaction mixture with the molar ratio computing preferable range is: SiO
2/ Al
2O
3=5～200, OH
-/ SiO
2=0.05～1.0, H
2O/SiO
2=10～22, R/SiO
2=0.1～0.6.The preferred version of organic amine is for being a kind of or its mixture that is selected from normal hexyl Amine, heptyl amice, octylame, amino dodecane, cetylamine, hexahydroaniline, hexamethylene imine, cetyl trimethylammonium bromide, tetraethyl ammonium hydroxide or the TPAOH.Crystallization temperature preferable range is 100～180 ℃, and crystallization time preferable range is 2～80 hours.Ageing temperature preferable range is 10～80 ℃, and the digestion time preferable range is 2～100 hours.Among the present invention, also can add porous material SHY-1 that the present invention makes as crystal seed in reaction mixture, the crystal seed add-on is 0.5～10% of a mixture total weight amount.
The present invention is by to the modulation of each component relative content in the reaction mixture with to the control of crystallization process, low water silicon than and short crystallization time condition under synthesized porous material with specific pore passage structure.
The present invention is further elaborated below by embodiment.
Description of drawings
Accompanying drawing 1 is the X-ray diffraction spectrogram of synthetic porous material.
Embodiment
[embodiment 1]
With sodium aluminate (Al
2O
342.0 weight %) 16.0 grams are dissolved in the 180 gram water, add sodium hydroxide 8.0 grams and make it dissolving, add positive cetylamine R then under stirring condition
1120.5 gram, TPAOH R
240 gram and cetyl trimethylammonium bromide R
37.3 gram adds silicon sol (SiO again
240 weight %) 300 grams are after waiting to stir, 40 ℃ of following ageings 72 hours.Reaction-ure mixture with molar ratio computing is: SiO
2/ Al
2O
3=30, OH
-/ SiO
2=0.1, R
1/ SiO
2=0.25, R
2/ SiO
2=0.10, R
3/ SiO
2=0.01, H
2O/SiO
2=10.Pack into then in the stainless steel cauldron, under agitation condition in 175 ℃ of crystallization 5 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 28.6.Specific surface area is 550 meters
2/ gram.In volume percent, 0.1～10 micron macropore is that the micropore of 57.4%, 0.4～2 nanometers is 42.6%, 0.52 centimetre of total pore volume
3/ gram.XRD analysis exists specific zeolite structured.
[embodiment 2]
With sodium metaaluminate (Al
2O
340 weight %) 6.07 grams are dissolved in the 468 gram water, add sodium hydroxide 48 grams and make it dissolving, add hexamethylene imine R then under stirring condition
479.2 gram and cetyl trimethylammonium bromide R
37.3 gram adds silicon sol (SiO again
240 weight %) 300 grams are after waiting to stir, 80 ℃ of following ageings 120 hours.Reaction-ure mixture with molar ratio computing is: SiO
2/ Al
2O
3=80, OH
-/ SiO
2=0.6, R
4/ SiO
2=0.4, R
3/ SiO
2=0.01, H
2O/SiO
2=18.Pack into then in the stainless steel cauldron, under agitation condition in 150 ℃ of crystallization 50 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 76.6.Specific surface area is 420 meters
2/ gram.In volume percent, 0.1～10 micron macropore is that the micropore of 84.4%, 0.4～2 nanometers is 15.6%, 0.47 centimetre of total pore volume
3/ gram.XRD analysis exists specific zeolite structured.
[embodiment 3]
Aluminum nitrate 21.3 grams are dissolved in the 612 gram water, add sodium hydroxide 48 grams and make it dissolving, under stirring condition, add hexamethylene imine R then
479.2 gram and cetyl trimethylammonium bromide R
314.6 gram adds silicon sol (SiO again
240 weight %) 300 grams, 30 gram crystal seeds are after waiting to stir, 50 ℃ of following ageings 2 hours.Reaction-ure mixture with molar ratio computing is: SiO
2/ Al
2O
3=40, OH
-/ SiO
2=0.6, R
4/ SiO
2=0.4, R
3/ SiO
2=0.02, H
2O/SiO
2=22.Pack into then in the stainless steel cauldron, under agitation condition in 160 ℃ of crystallization 15 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 42.5.Specific surface area is 435 meters
2/ gram.In volume percent, 0.1～10 micron macropore is that the micropore of 76.0%, 0.4～2 nanometers is 29.0%.XRD analysis exists specific zeolite structured.
[embodiment 4]
Aluminum nitrate 42.6 grams are dissolved in the 180 gram water, add sodium hydroxide 48 grams and make it dissolving, under stirring condition, add organic amine template hexamethylene imine R then
449.5 gram and cetyl trimethylammonium bromide R
336.4 gram adds silicon sol (SiO again
240 weight %) 300 grams, 54 gram crystal seeds are after waiting to stir, 50 ℃ of following ageings 5 hours.Reaction-ure mixture with molar ratio computing is: SiO
2/ Al
2O
3=20, OH
-/ SiO
2=0.6, R
4/ SiO
2=0.25, R
3/ SiO
2=0.05, H
2O/SiO
2=10.Pack into then in the stainless steel cauldron, under agitation condition in 130 ℃ of crystallization 72 hours.After the taking-up after filtration, washing, drying.Get SiO through chemical analysis
2/ Al
2O
3Mol ratio is 20.5.Specific surface area is 397 meters
2/ gram.In volume percent, 0.1～10 micron macropore is that the micropore of 84.1%, 0.4～2 nanometers is 15.9%.XRD analysis exists specific zeolite structured.
Claims (9)
1, a kind of porous material comprises the composition of following molar relationship: Al
2O
3: (n) SiO
2, n=5 in the formula～1000 is characterized in that described material has compound pore passage structure, have micron order macropore and nanometer level microporous simultaneously, wherein in volume percent, 0.1～10 micron macropore is that the micropore of 55～85%, 0.4～2 nanometer is 15～43%.
2, porous material according to claim 1 is characterized in that having following XRD diffraction data:
2θ I/I
0
7.2±0.1 77.9
8.0±0.1 55.6
9.6±0.2 50.0
12.9±0.2 33.0
14.5±0.2 55.7
20.3±0.2 48.7
22.7±0.5 78.7
25.2±0.1 67.0
26.1±0.1 100
27.0±0.1 66.5
。
3, the synthetic method of porous material according to claim 1, carry out according to the following steps:
(1) silicon source, aluminium source, alkali, organic formwork agent and water are mixed, reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=5～1000, OH
-/ SiO
2=0.01～5.0, H
2O/SiO
2=5～30, R/SiO
2=0.05～2.0, R is the organic amine template of carbon more than five;
(2) with above-mentioned reaction mixture 0～100 ℃ of ageing 1～120 hour;
(3) will be under the crystallization temperature be 90～200 ℃ and agitation condition through the reaction mixture of above-mentioned processing, crystallization took out after 1～200 hour, through wash, drying makes porous material.
4, the synthetic method of porous material according to claim 3 is characterized in that described silicon source is selected from least a in soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; 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 that mineral alkali is selected from least a in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or the cesium hydroxide.
5, the synthetic method of porous material according to claim 3 is characterized in that reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=5～200, OH
-/ SiO
2=0.05～1.0, H
2O/SiO
2=10～22, R/SiO
2=0.1～0.6, wherein R is an organic formwork agent.
6, the synthetic method of porous material according to claim 3 is characterized in that described organic amine is selected from a kind of or its mixture in normal hexyl Amine, heptyl amice, octylame, amino dodecane, cetylamine, hexahydroaniline, hexamethylene imine, cetyl trimethylammonium bromide, tetraethyl ammonium hydroxide or the TPAOH.
7, the synthetic method of porous material according to claim 3 is characterized in that the ageing temperature is 10～80 ℃, and digestion time is 2～100 hours.
8, the synthetic method of porous material according to claim 3 is characterized in that the crystallization temperature is 100～180 ℃, and the crystallization time is 2～80 hours.
9, the synthetic method of porous material according to claim 3 is characterized in that in reaction mixture adding the porous material that makes by claim 3 as crystal seed, and the crystal seed add-on is 0.5～10% of a mixture total weight amount.
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| CN1751994A (en) | 2006-03-29 |
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