CN101618877B - Micropore-mesopore grading structural material and preparation method thereof - Google Patents
Micropore-mesopore grading structural material and preparation method thereof Download PDFInfo
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- CN101618877B CN101618877B CN2009100555269A CN200910055526A CN101618877B CN 101618877 B CN101618877 B CN 101618877B CN 2009100555269 A CN2009100555269 A CN 2009100555269A CN 200910055526 A CN200910055526 A CN 200910055526A CN 101618877 B CN101618877 B CN 101618877B
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- 238000010438 heat treatment Methods 0.000 claims description 27
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- 229960004418 trolamine Drugs 0.000 claims description 19
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- 239000010703 silicon Substances 0.000 claims description 18
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 17
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 239000002994 raw material Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 8
- 238000010335 hydrothermal treatment Methods 0.000 description 8
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the field of inorganic materials, in particular to a micropore-mesopore grading structural material and a preparation method thereof. A microscopic particle of the micropore-mesopore grading structural material has a three-dimensional penetrated mesopore structure, and the pore wall of the mesopore structure is in a crystallized zeolite structure. The micropore-mesopore grading structural material has favorable hydrothermal stability; because the pore wall of the micropore-mesopore grading structural material is in the crystallized zeolite structure, the micropore-mesopore grading structural material can be applied to the field of catalyst; and the preparation method of the micropore-mesopore grading structural material has the characteristics of simple condition and easy operation and is suitable for industrial production.
Description
Technical field
The invention belongs to field of inorganic materials, be specifically related to a kind of micropore-mesopore grading structure material and preparation method thereof.
Background technology
The micro-pore zeolite molecular screen material has obtained using very widely in industry as traditional solid acid catalyst; The outstanding feature of zeolite molecular sieve is can modulation acid; Can provide simultaneously ducts and the hole of different sizes to play and select the shape effect, thereby the molecular sieve of different pore sizes has the different shape effects of selecting.But since its aperture less (＜1.5nm), reactant and the product diffusion difficulty in the duct has had a strong impact on catalytic efficiency (.Be difficult to diffuse in the duct of molecular sieve like diameter in the reaction raw materials greater than the heavy oil macromole of 1nm; And its narrow and small pore passage structure also influences overflowing fast of reacted product molecule; Cause secondary cracking and green coke amount to increase; Thereby make this part molecular sieve take off activation, greatly reduce catalytic cracking efficient heavy oil.Therefore there is certain limitation in micro-pore zeolite in relating to macromolecular catalytic process.In heavy oil fraction; Molecular diameter occupies suitable ratio greater than the molecule of 1nm; Want pressure fuel just must make that macromole can touch active surface, this is the accessibility in active site, and the narrow and small pore passage structure of zeolite molecular sieve makes it be difficult to satisfy above requirement.So realize macromolecular controlled cracking, the molecular sieve that exploitation has homogeneous, larger aperture seems very necessary.
The mesoporous material that grow up the nineties in last century has overcome the shortcoming of zeolite, has the bigger aperture and the distribution of sizes of homogeneous, and its application in catalytic field shows tempting prospect.Mesoporous material is the type material with huge surface area and rule, orderly pore passage structure of a kind of aperture between micropore and macropore.The research and development of mesoporous material is all significant for theoretical investigation and actual production.It has the excellent specific property that other porous material does not have: the pore passage structure with high-sequential; The single distribution in aperture, and aperture size can change (its aperture can be in 1.5～20nm scope modulation, broken the limitation that conventional molecular sieve bore diameter can not surpass 1.2nm) at relative broad range; Mesoporous shape is various, and hole wall composition and character are adjustable; Through optimizing the mesoporous material that synthesis condition can obtain high thermal stability and hydrothermal stability, in catalysis, absorption, separation and light, electricity, many fields such as magnetic all have a huge potential using value.
But with the zeolite facies ratio, mesopore molecular sieve does not have the repetition single cell structure unit in the micro-pore zeolite, and the inside unit similar does not contain the crystalline structure zone in amorphous oxide, only has the local order structure at mesoporous yardstick.Hole wall owing to mesoporous material is unbodied simultaneously, and hydrothermal stability is relatively poor, and in practical application, most of catalyzed reaction all is under the condition that has water vapour to exist, to carry out, so the application of mesoporous material in catalysis receives very big restriction.How to improve the hydrothermal stability of mesoporous material, the mesoporous material with high hydrothermal stability that the catalyzed reaction requirement is satisfied in preparation has become the synthetic hot research fields of current mesoporous material.
At present reported that several different methods is used to improve the hydrothermal stability of mesoporous material; These methods roughly can be divided into two types: the first kind is that the hole wall to unbodied mesoporous material carries out some modifications; Comprise the thickness that increases hole wall, hole wall surface is carried out chemical modification, increases the condensation level of mesoporous material skeleton etc.; These methods have improved the stability of mesoporous material to a certain extent; But shortcoming is the specific surface area and the pore volume of the mesoporous material after the process modification bigger loss is arranged, and complex process, step is various; Second class methods are in the mesoporous material hole wall, to introduce secondary zeolite structured unit or unbodied mesoporous material is carried out the crystallization aftertreatment, and what utilize that these class methods obtain is the micropore-mesopore grading structure material.The hole wall of this type material has crystallization to a certain degree, and its hydrothermal stability also is greatly improved than the mesoporous material of hole wall modification.But in essence, the hole wall of these materials still is unbodied, and the hydrothermal stability test result is unsatisfactory for a long time.Therefore still be difficult to satisfy advantages of high catalytic activity in the industrial application, the reaction times and the harsh requirements such as reaction conditions of length.Like: publication number be in the Chinese patent of CN1393403 be with ordinary method earlier synthetic microporous zeolite (like Y; ZSM-5, reaction mixture gel β) is carried out the crystallization of fs under certain condition; Behind the crystallization certain hour; Adjust the potential of hydrogen of reaction mixture, and add the template of synthesising mesoporous molecular sieve, also can add the silicon source and/or the aluminium source of needs in case of necessity; And then under certain temperature and pressure, carry out the crystallization of subordinate phase, obtain micropore-mesopore behind the crystallization certain hour and meet combination of molecular sieve.This method is complex steps not only, has used the template of more synthesising mesoporous molecular sieve in the preparation process simultaneously, and cost is higher.Therefore, this area is badly in need of simple, the lower-cost method of a kind of process and is used for the good micropore-mesopore grading structure material of processability.
In the prior art; The auxiliary method of steam has been successfully applied to the preparation of micro-pore zeolite molecular sieve; Zeolite molecular sieve uniform particles, the crystallization of utilizing this method to prepare are good, also do not appear in the newspapers but combine this technology that unbodied mesoporous material is carried out the method that the back crystallization handles the micropore-mesopore grading structure material for preparing crystallization of pore wall.
Summary of the invention
The purpose of this invention is to provide a kind of micropore-mesopore grading structure material and preparation method thereof.
The microscopic particles of micropore-mesopore grading structure material of the present invention has the three-dimensional meso-hole structure that connects, and the hole wall of said meso-hole structure is that crystallization is zeolite structured.
Preferably, the chemical formula of said micropore-mesopore grading structure material is M
xSiO
(2+nx/2), wherein, M is selected from Ti, Zr, Al or Fe; X is the mol ratio of M and Si, and the span of x is 0.001～0.1; N is the valency of M, and the value of n is 3 or 4.
Preferably, when M was Ti or Zr, n was 4; When M was Al or Fe, n was 3.
Preferably, the specific surface area of said micropore-mesopore grading structure material is 390～450m
2/ g, more preferably 390～442m
2/ g.
Preferably, the particle diameter of the microscopic particles of said micropore-mesopore grading structure material is 1～5 μ m.
Preferably, the aperture of said meso-hole structure is 8～12nm.
Preferably, said crystallization is zeolite structured to be rhombic system, and pore passage structure is { [100] 105.1 * 5.5} → { [010] 105.3 * 5.6}.
The preparation method of micropore-mesopore grading structure material of the present invention comprises the steps:
1) preparation of solid gel: the precursor of the precursor of silicon, trolamine, metallic element and deionized water are mixed and stir, and then add TPAOH solution, continue to be stirred to the formation solid gel; Wherein, the mol ratio of the precursor of said silicon, trolamine, TPAOH and deionized water is 1: (0.05～0.3): (0.5～2): (5～20); The mol ratio of the element silicon in the metallic element in the precursor of said metallic element and the precursor of silicon is 1: 10～1000.
2) ageing: with carrying out heat treated after the solid gel ageing that makes in the step 1);
3) utilize the auxiliary back of steam crystallization to handle: with step 2) in the solid gel that makes under steam, heat-treat; Wherein, The said concrete steps of utilizing the auxiliary back of steam crystallization to handle are: will under steam, heat-treat through the solid gel that obtains after Chen Hua and the heat treated; And in the said heat treatment process, the mass ratio of solid gel and water vapor is 1～50: 1; Said heat treated temperature is 140～200 ℃, and heat treatment time is 12～240h.
4) dry and calcining: with in the step 3) through after be warming up to calcining temperature after the product drying that makes after the crystallization processing and calcine.
Preferred, in the solid gel in the said step 1), the mol ratio of the precursor of silicon, trolamine, TPAOH and deionized water is 1: 0.1: 1: 11; The mol ratio of the element silicon in the metallic element in the precursor of said metallic element and the precursor of silicon is 1: 30～200.
Preferably, in the said step 1), the precursor of silicon is selected from: tetraethoxy, silicate or silica gel xerogel.
Preferred, said silicate is water glass, and its component is Na
2SiO
3
The component of said silica gel xerogel is SiO
2
Preferably, in the said step 1), the precursor of metallic element is selected from: the alkoxide of metal, vitriol or nitrate salt are representative with the precursor of aluminium and titanium, and it is aluminum isopropylate or tetrabutyl titanate more preferably.
Preferably, in the said step 1), metallic element is selected from: Ti element, Zr element, Al element or Fe element.
Preferably, in the said step 1), the preparation of solid gel is at room temperature carried out.
Preferably, said step 2) in, ageing is at room temperature carried out, and digestion time is 3-48h.
Preferably, said step 2) in, heat treated is the condition lower open mouth heating 3～45h at 50～150 ℃.
Preferred; The concrete steps of utilizing the auxiliary back of steam crystallization to handle in the said step 3) are: with step 2) in the solid gel that makes be transferred in the polytetrafluoroethylcontainer container; Then said polytetrafluoroethylcontainer container is inserted in the tetrafluoroethylene water heating kettle; And between said polytetrafluoroethylcontainer container periphery and said tetrafluoroethylene water heating kettle, drip deionized water, with after the sealing of tetrafluoroethylene water heating kettle, heated 12～240 hours down then at 140～200 ℃.
Preferably, in the said step 4), drying temperature is 60～200 ℃, and be 1～10 hour time of drying; Temperature rise rate is 0.1～10 ℃/min; Calcining temperature is 500～700 ℃, and calcination time is 2～20h.
The concrete grammar of the hydrothermally stable property testing described in the present invention is: under 100 ℃, sample is carried out hydrothermal treatment consists, the hydrothermal treatment consists time is 50 hours.
Micropore-mesopore grading structure material of the present invention has good hydro-thermal performance; And the preparation method of this micropore-mesopore grading structure material compares with traditional method; Mesoporous tensio-active agent and the microvoid structure directed agents used greatly reduce; Characteristics such as it is simple to have technology, and the cycle is shorter, and easy to implement and cost is lower.The hole wall of micropore-mesopore grading structure material of the present invention is the zeolite structured of crystallization, therefore can be applicable to catalyzer and support of the catalyst field, in particular as the sorbent material of bulky molecular catalysis catalyst for reaction and petroleum chemical industry.The present invention carries out the back crystallization through the method for utilizing steam heat to unbodied mesoporous material and handles, and has obtained a kind of micropore-mesopore grading structure material with good hydrothermal stability.
Description of drawings
Fig. 1: the setting drawing of the auxiliary back of steam crystallization facture.
Fig. 2: XRD figure spectrum with micropore-mesopore grading structure material (silica alumina ratio is 30: 1) and associated materials of high hydrothermal stability.
Fig. 3: transmission electron microscope photo (silica alumina ratio is 30: 1) with micropore-mesopore grading structure material of high hydrothermal stability.
Fig. 4: the transmission electron microscope photo of the higher multiple in edge among Fig. 3 (silica alumina ratio is 30: 1).
Fig. 5: the stereoscan photograph of micropore-mesopore grading structure material (silica alumina ratio is 30: 1).
Fig. 6: the nitrogen adsorption of micropore-mesopore grading structure material/desorption curve.
Fig. 7: the micropore-mesopore grading structure material is through the nitrogen adsorption/desorption curve of gained sample after the hydrothermally stable property testing.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1
Getting 0.66 gram aluminum isopropylate, 20.8 gram tetraethoxys, 1.49 gram trolamines and 19.8 gram deionized waters respectively mixes; And vigorous stirring to add 82 gram mass marks after 1 hour again be 25% TPAOH solution, continue to be stirred to the formation solid gel.The mole proportioning of various precursors is in the raw material: aluminum isopropylate: tetraethoxy: trolamine: TPAOH: deionized water=1: 30: 3: 30: 330.With ageing under the prepared gel room temperature after 24 hours, 98 ℃ of heating in the open 12 hours.To heat the back products therefrom then is transferred in the polytetrafluoroethylcontainer container; Then this container is inserted in the bigger tetrafluoroethylene water heating kettle (as shown in Figure 1); And between container periphery and water heating kettle, drip 1 gram deionized water, after the water heating kettle sealing, 160 ℃ were heated 24 hours.100 ℃ of dryings of sample after steam heat handled are put into 600 ℃ of calcinings of retort furnace 8 hours after 3 hours again, and wherein the temperature rise rate by room temperature to 600 ℃ is 2 ℃/min.The powder of the resulting white in calcining back is the micropore-mesopore grading structure material with high hydrothermal stability, and the ratio (silica alumina ratio) of its contained elemental silicon and aluminium is 30: 1.Transmission electron microscope photo in the present embodiment is by Fig. 3 and shown in Figure 4, and stereoscan photograph can be known by Fig. 5 that by shown in Figure 5 the particle diameter of the micropore-mesopore grading structure material that makes in the present embodiment is 1～5 μ m.Get the sample that makes among the part embodiment 1 then and carry out the hydrothermally stable property testing, be specially and under 100 ℃, carry out hydrothermal treatment consists, the treatment time is 50 hours.
Embodiment 2
Method according to embodiment 1; But the mole proportioning of various precursors in the raw material is adjusted into: aluminum isopropylate: tetraethoxy: trolamine: TPAOH: deionized water=1: 200: 20: 200: 2200, obtain silica alumina ratio and be 200: 1 sample.Get the sample that makes among the part embodiment 2 then and carry out the hydrothermally stable property testing, be specially and under 100 ℃, carry out hydrothermal treatment consists, the treatment time is 50 hours.
Embodiment 3
According to the method for embodiment 1, but the mole proportioning of various precursors in the raw material is adjusted into: tetrabutyl titanate: tetraethoxy: trolamine: TPAOH: deionized water=1: 50: 5: 50: 550.Obtain silicon titanium ratio and be 50: 1 sample.Get the sample that makes among the part embodiment 3 then and carry out the hydrothermally stable property testing, be specially and under 100 ℃, carry out hydrothermal treatment consists, the treatment time is 50 hours.
Embodiment 4 (Comparative Examples)
Get 0.66 gram aluminum isopropylate, 20.8 gram tetraethoxys, 1.49 gram trolamines and 19.8 gram deionized waters respectively and mix, and vigorous stirring to add 82 gram mass marks after 1 hour again be 25% TPAOH, continue to be stirred to form the solid gel.The mole proportioning of various precursors is in the raw material: aluminum isopropylate: tetraethoxy: trolamine: TPAOH: deionized water=1: 30: 3: 30: 330.With ageing under the prepared gel room temperature after 24 hours, 98 ℃ of heating in the open are 12 hours again, removing most water in the gel, and make the trolamine polymerization in the gel, form and gather trolamine.Without VT, be placed in the water heating kettle 160 ℃ of heating 24 hours but will heat xerogel that the back forms, put into 600 ℃ of calcinings of retort furnace 8 hours again, wherein the temperature rise rate by room temperature to 600 ℃ is 1 ℃/min, its silica alumina ratio is 30: 1.Get the sample that makes among the part embodiment 4 then and carry out the hydrothermally stable property testing, be specially and under 100 ℃, carry out hydrothermal treatment consists, the treatment time is 50 hours.
The XRD figure spectrum of sample and the standard ZSM-5 zeolitic material of the micropore-mesopore grading structure material that makes among the micropore-mesopore grading structure material that makes among embodiment 1 and the embodiment 4, the embodiment 1 after hydrothermal treatment consists is as shown in Figure 2; In Fig. 2; From top to bottom, micropore-mesopore grading structure material that makes among the micropore-mesopore grading structure material that makes among the sample of the micropore-mesopore grading structure material that makes among the corresponding respectively embodiment 1 after hydrothermal treatment consists, the embodiment 1, the embodiment 4 and the XRD figure of standard ZSM-5 zeolitic material spectrum.Can know by Fig. 2; The microscopic particles of the micropore-mesopore grading structure material that makes among the present invention has the three-dimensional meso-hole structure that connects; The hole wall of this meso-hole structure is that crystallization is zeolite structured, and the micropore-mesopore grading structure material among the present invention has good hydro-thermal performance.
Structural parameter to the micropore-mesopore grading structure material that makes among the embodiment 1 ~ 4 detect, and the detected result of the micropore-mesopore grading structure material structural parameter that make among the embodiment 1 ~ 4 (comprising: specific surface area, aperture and pore volume) is seen shown in the table 1.
Structural parameter table behind table 1. Different Silicon aluminum ratio and the hydrothermally stable property testing
| ? | Specific surface area (BET)/(m 2/g) | BET a/ (m 2/g) | Aperture (pore diameter)/(nm) | pore diameter a /(nm) | Pore volume (pore volume)/(cm 3/g) | pore volume a/ (cm 3/g) |
| Embodiment 1 | 442 | 398 | 11 | 10 | 1.19 | 1.06 |
| Embodiment 2 | 443 | 361 | 8 | 8 | 0.93 | 0.82 |
| Embodiment 3 | 390 | 360 | 12 | 11 | 1.21 | 1.09 |
| Embodiment 4 | 390 | 239 | 9 | 14 | 0.96 | 1.01 |
* BET
a, pore diameter
a, pore volume
aThe specific surface area, aperture and the pore volume that refer to sample behind the hydrothermally stable property testing respectively
Can find out by the content in the table 1, among the embodiment 4 (Comparative Examples) owing to do not pass through VT in the preparation process, therefore after carrying out the hydrothermally stable property testing, the altering a great deal of specific surface area (by 390m
2/ g is changed to 239m
2/ g); And correlatedly with it be; Among the embodiment 1～3 through the micropore-mesopore grading structure material that makes after the VT after through the hydrothermally stable property testing; The variation of its specific surface area and pore volume is very little, therefore can know, has very good hydrothermal stability through the micropore-mesopore grading structure material that makes after the VT.
The nitrogen adsorption of the micropore-mesopore grading structure material that makes among the embodiment 1～4/desorption curve is as shown in Figure 6.Wherein, figure A is volume adsorption-relative pressure graphic representation, in figure A, from top to bottom, the nitrogen adsorption/desorption curve of the prepared sample of the corresponding embodiment 1-4 of difference; Figure B is volume adsorption-aperture graphic representation, in figure B, from top to bottom, the nitrogen adsorption/desorption curve of the prepared sample of the corresponding embodiment 1-4 of difference.
The micropore-mesopore grading structure material that makes among the embodiment 1～4 is as shown in Figure 7 through the nitrogen adsorption/desorption curve of gained sample after the hydrothermally stable property testing.Wherein, figure A is volume adsorption-relative pressure graphic representation, in figure A, from top to bottom, the result after the sample water heat stability testing of corresponding embodiment 1～4 gained of difference; Figure B is volume adsorption-aperture graphic representation, in figure B, from top to bottom, the result after the sample water heat stability testing of corresponding embodiment 1～4 gained of difference.Can know that by Fig. 6 and Fig. 7 micropore-mesopore grading structure material of the present invention has good hydrothermal stability and absorption property.
Embodiment 5
Method according to embodiment 1; But the mole proportioning of various precursors in the raw material is adjusted into: aluminum isopropylate: tetraethoxy: trolamine: TPAOH: deionized water=1: 1000: 50: 500: 5000, obtain silica alumina ratio and be 1000: 1 sample.Through detecting, the specific surface area of the micropore-mesopore grading structure material that makes in the present embodiment is 390m
2/ g, the particle diameter of microscopic particles are 1～5 μ m, and the aperture is 11nm.
Embodiment 6
Method according to embodiment 1; But the mole proportioning of various precursors in the raw material is adjusted into: aluminum isopropylate: tetraethoxy: trolamine: TPAOH: deionized water=1: 10: 0.6: 20: 100, obtain silica alumina ratio and be 10: 1 sample.Through detecting, the specific surface area of the micropore-mesopore grading structure material that makes in the present embodiment is 450m
2/ g, the particle diameter of microscopic particles are 1～5 μ m, and the aperture is 10nm.
Embodiment 7
Get Tai-Ace S 150, water glass, trolamine and deionized water respectively and mix, and vigorous stirring to add massfraction after 1 hour again be 25% TPAOH solution, at room temperature continue to be stirred to the formation solid gel.The mole proportioning of various precursors is in the raw material: Tai-Ace S 150: water glass: trolamine: TPAOH: deionized water=1: 1000: 50: 500: 11000.With ageing under the prepared gel room temperature after 3 hours, 50 ℃ of heating in the open 45 hours.To heat the back products therefrom then is transferred in the polytetrafluoroethylcontainer container; Then this container is inserted in the bigger tetrafluoroethylene water heating kettle (as shown in Figure 1); And between container periphery and water heating kettle, drip deionized water (wherein the mass ratio of solid gel and deionized water is 1: 1); After the water heating kettle sealing, 140 ℃ were heated 240 hours.60 ℃ of dryings of sample after steam heat handled are put into 500 ℃ of calcinings of retort furnace 20 hours after 10 hours again, and wherein the temperature rise rate by room temperature to 500 ℃ is 0.1 ℃/min.The powder of the resulting white in calcining back is the novel microporous-mesoporous grading structure material with high hydrothermal stability, and the ratio (silica alumina ratio) of its contained elemental silicon and aluminium is 1000: 1.Through detecting, the specific surface area of the micropore-mesopore grading structure material that makes in the present embodiment is 442m
2/ g, the particle diameter of microscopic particles are 1～5 μ m, and the aperture is 12nm.
Embodiment 8
Get Zr (NO respectively
3)
4, silica gel xerogel, trolamine and deionized water mix, and vigorous stirring to add massfraction after 1 hour again be 25% TPAOH solution, at room temperature continue to be stirred to the formation solid gel.The mole proportioning of various precursors is in the raw material: Zr (NO
3)
4: the Si element in the silica gel xerogel: trolamine: TPAOH: deionized water=1: 100: 30: 200: 2000.With ageing under the prepared gel room temperature after 48 hours, 150 ℃ of heating in the open 3 hours.To heat the back products therefrom then is transferred in the polytetrafluoroethylcontainer container; Then this container is inserted in the bigger tetrafluoroethylene water heating kettle (as shown in Figure 1); And between container periphery and water heating kettle, drip deionized water (wherein the mass ratio of solid gel and deionized water is 50: 1); After the water heating kettle sealing, 200 ℃ were heated 12 hours.200 ℃ of dryings of sample after steam heat handled are put into 700 ℃ of calcinings of retort furnace 2 hours after 1 hour again, and wherein the temperature rise rate by room temperature to 700 ℃ is 10 ℃/min.The powder of the resulting white in calcining back is the novel microporous-mesoporous grading structure material with high hydrothermal stability, and the ratio of its contained elemental silicon and zirconium (silicon zirconium ratio) is 100: 1.Through detecting, the specific surface area of the micropore-mesopore grading structure material that makes in the present embodiment is 450m
2/ g, the particle diameter of microscopic particles are 1～5 μ m, and the aperture is 12nm.
Embodiment 9
Get Fe (NO respectively
3)
3, silica gel xerogel, trolamine and deionized water mix, and vigorous stirring adds TPAOH solution again after 1 hour, at room temperature continue to be stirred to the formation solid gel.The mole proportioning of various precursors is in the raw material: Fe (NO
3)
3: the Si in the silica gel xerogel: trolamine: TPAOH: deionized water=1: 100: 20: 100: 1500.With ageing under the prepared gel room temperature after 24 hours, 50 ℃ of heating in the open 3 hours.To heat the back products therefrom then is transferred in the polytetrafluoroethylcontainer container; Then this container is inserted in the bigger tetrafluoroethylene water heating kettle (as shown in Figure 1); And between container periphery and water heating kettle, drip deionized water (wherein the mass ratio of solid gel and deionized water is 20: 1); After the water heating kettle sealing, 140 ℃ were heated 12 hours.200 ℃ of dryings of sample after steam heat handled are put into 700 ℃ of calcinings of retort furnace 20 hours after 10 hours again, and wherein the temperature rise rate by room temperature to 600 ℃ is 2 ℃/min.The powder of the resulting white in calcining back is the novel microporous-mesoporous grading structure material with high hydrothermal stability, and the ratio (ferrosilicon ratio) of its contained elemental silicon and iron is 100: 1.Through detecting, the specific surface area of the micropore-mesopore grading structure material that makes in the present embodiment is 442m
2/ g, the particle diameter of microscopic particles are 1～5 μ m, and the aperture is 12nm.
Claims (3)
1. the preparation method of a micropore-mesopore grading structure material comprises the steps:
1) preparation of solid gel: the precursor of precursor, trolamine, deionized water and the metallic element of silicon is mixed and stirs, and then add TPAOH solution, continue to be stirred to the formation solid gel; Wherein, the mol ratio of the precursor of said silicon, trolamine, TPAOH and deionized water is 1: (0.05～0.3): (0.5～2): (5～20); The mol ratio of the element silicon in the metallic element in the precursor of said metallic element and the precursor of silicon is 1: 10～1000;
2) ageing: with carrying out heat treated after the solid gel ageing that makes in the step 1);
3) utilize the auxiliary back of steam crystallization to handle: with step 2) in the solid gel that makes under steam, heat-treat; Wherein, The said concrete steps of utilizing the auxiliary back of steam crystallization to handle are: will under steam, heat-treat through the solid gel that obtains after ageing and the heat treated; And in the said heat treatment process, the mass ratio of solid gel and water vapor is 1～50: 1; Said heat treated temperature is 140～200 ℃, and heat treatment period is 12～240h.
4) dry and calcining: with in the step 3) through after be warming up to calcining temperature after the product drying that makes after the crystallization processing and calcine.
2. the preparation method of micropore-mesopore grading structure material described in claim 1 is characterized in that, in the said step 1), the precursor of silicon is selected from tetraethoxy, silicate or silica gel xerogel; The precursor of said metallic element is selected from the alkoxide of metal, the vitriol of metal or the nitrate salt of metal; Said metallic element is selected from Ti element, Zr element, Al element or Fe element.
3. the preparation method of micropore-mesopore grading structure material described in claim 1 is characterized in that, in the said step 4), drying temperature is 60～200 ℃, and be 1～10 hour time of drying; Temperature rise rate is 0.1～10 ℃/min; Calcining temperature is 500～700 ℃, and calcination time is 2～20h.
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