CN100586855C - Method for preparing perforation type zeolite material with multilevel pore canals - Google Patents
Method for preparing perforation type zeolite material with multilevel pore canals Download PDFInfo
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- CN100586855C CN100586855C CN 200610001331 CN200610001331A CN100586855C CN 100586855 C CN100586855 C CN 100586855C CN 200610001331 CN200610001331 CN 200610001331 CN 200610001331 A CN200610001331 A CN 200610001331A CN 100586855 C CN100586855 C CN 100586855C
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Abstract
This invention discloses a method for preparing multi-level porous cross-flow zeolite material. The method comprises: (1) dispersing zeolite microcrystal in water or inorganic salt solution to form colloidal solution; (2) soaking the multi-level porous cross-flow silica gel material in polyelectrolyte solution so that the surface of the modified backbone is charged; (3) soaking and washing the silica gel material obtained in step 2 in the colloidal solution obtained in step 1 under normal or negative pressure; (4) soaking the silica gel material obtained in step 3in the colloidal solution obtained in step 1 under normal or negative pressure, and performing secondary crystallization by using vapor phase method. The obtained multi-level porous cross-flow property and abundant macropores withhigh uniformity, and can be used in catalysis and adsorption-separation. It has obvious advantages against normal zeolite molecular sieve on catalyst, adsorbent, separating agent and water treatment.
Description
Technical field
The invention relates to a kind of preparation method of zeolitic material, further say so about a kind of preparation method of zeolite material in perforation type of multilevel pore canals.
Background technology
Zeolite has abundant microporous, molecular sieve selection performance and good heat and hydrothermal stability as a kind of inorganic porous material, is widely used in catalysis and separating technology.The general preparation method of zeolite catalyst is at present: the reaction mass gel mixture high temperature crystallization with certain proportioning makes zeolite earlier, then zeolite is combined with the carrier that contains or do not contain binding agent, makes the catalyzer finished product through moulding again.Make its active ingredient zeolite of catalyzer like this and be scattered in catalyst body each position in mutually, and can not high dispersing give full play to its katalysis, and introduced diffusional limitation in catalyst surface.In order to increase the useful area of zeolite, the method that reduces diffusion is the zeolitic material that preparation has multi-stage artery structure.
Mainly be (B.T.Holland, L.Abrams and A.Stein, J.Am.Chem.Soc. such as Holland, 1999,121,4308) and (X.D.Wang, W.L.Yang such as Wang Xingdong, Y.Tang, T.J.Wang, S.K.Fuand Z.Gao, Chem.Commun., 2000 (21), 2126) by form to need on the template zeolite structured after remove template and just can obtain the multi-stage artery structure zeolitic material.But the macroporous structure that this method needs is made of template, and the intensity of material is very poor when removing template, is not easy to prepare moulding, and the loaded down with trivial details repeatability of operation steps is bad, is difficult to practical application.
Recently, after Anderson etc. (M.W.Anderson, S.M.Holmes, N.Hanif and C.S.Cundy, Angew.Chem.Int.Ed., 2000,39,2707) adopted diatomite to be carrier loaded zeolite seed crystal, utilization added the silicon source, diauxic growth is carried out in the aluminium source.
Tang Yi etc. (CN 01126842.5) employing diatomite is carrier, by nano zeolite crystal seed layer lamination assemble method after its surface forms zeolite membrane, diauxic growth under organic amine atmosphere, on diatomite, form the zeolitic material that zeolite membrane makes certain intensity and multi-stage artery structure like this, but not to connect mutually between the diatomaceous duct of zeolitization, will limit diffusion.
People such as Hiroko Shikata use sol-gel method that Silicalit-1 is loaded on perforation type of multilevel pore canals silica gel material (Journal of Sol-Gel Science andTechnology adding under the situation of silicon source, 19,769-773,2000), people (EP 1 934 113 A2) such as Takahashi adopted the vapor phase method that Silicalit-1 and ZSM-5 zeolite original position are loaded on the multistage pore canal silica gel material afterwards, but these two kinds of carrying methods can not make zeolite load on uniformly on the perforation type of multilevel pore canals silica gel material, can not effectively control the size of zeolite grain growth, and in preparation process, destroy the skeleton of part perforation type of multilevel pore canals silica gel material.
Multilevel hierarchy through-flow silica gel material is a kind of large pore material that grows up in high performance liquid phase (HPLC) field at present.1996, Minakuchi etc. have at first prepared the successive monolithic silica column, hydrolysis and polymerization by the silicon source, silica polycondensate product and additive copolymerizing and blending form all miscible system, sol-gel transition takes place and be separated, form the macropore (0.5～10 μ m) of open type like this, very fast hole internal diffusion can be provided, prepare mesoporously by ageing and exchange of solvent, abundant specific surface area (600cm is provided
2g
-1About).With packed column relatively, the flow pressure drop of air-flow in integral post can reduce (less than 6～8 times of packed column) air-flow flow model in integral post and approach air-flow and flow in straight tube.Recently, people such as Takahashi are load aluminium on the multistage pore canal silica gel material, shows that by catalysis the utilization ratio of the interior specific surface of its catalytic material approaches 1.
Summary of the invention
The objective of the invention is provides a kind of preparation method of zeolite material in perforation type of multilevel pore canals at the requirement in above-mentioned the deficiencies in the prior art and the reality.
Therefore, the preparation method of zeolite material in perforation type of multilevel pore canals provided by the invention is characterized in that this method contains following step:
(1) crystallite with zeolite is dispersed in the colloidal solution that forms concentration 1.0～25 heavy %, pH9～14 in water or the inorganic salt solution, and the micelle size is 1.0nm～2.5 μ m;
(2) under normal pressure or the negative pressure perforation type of multilevel pore canals silica gel material being soaked 1min～1h in the polyelectrolyte solution of 1.0～10 heavy %, use deionized water rinsing then 1～5 time, the Skeleton Table after the modification is worn electric charge;
(3) under normal pressure or negative pressure with (2) in silica gel material in the colloidal solution of (1), soak, wash.
In the method provided by the invention, the zeolite of step (1) is selected from one or more in ZSM-5, β, silicalite-1, TS-1, A, X and the y-type zeolite.
The preferred concentration of the said colloidal solution of step (1) is 1.0～15 heavy %, and the pH value is 9～12, and the micelle size is 1～500nm.Inorganic salt solution concentration is 0.01～1.5M.Said inorganic salt are preferably NaC l.
In the method provided by the invention, the perforation type of multilevel pore canals silica gel material of step (2) has the mesoporous of the macropore of 0.5～30 μ m and 3～20nm simultaneously, and is penetrating between the macropore.Said perforation type of multilevel pore canals silica gel material can also loaded metal or metal oxide.Said metal is selected from IIIA, IB or the IIIVB family of the periodic table of elements, wherein preferred Al, Cu or Ni.
Said perforation type of multilevel pore canals silica gel material can be a monolithic silica column.Said monolithic silica column is preferably a kind of diplopore silica gel, this diplopore silica gel and preparation method thereof is disclosed in application number is 200510092073.7 Chinese patent application, be characterised in that its macropore diameter is 0.5～3.0 μ m, mesoporous aperture is 3～10nm, and pore volume is 2.5～3.5cm
3/ g, specific surface area is 250～710m
2/ g, this material highly is being 1cm, when diameter is 0.7cm right cylinder particle shape, crush strength is 180～220N, said diplopore silica gel is to obtain by the method that comprises following process: with polyoxyethylene glycol, water, acid, the silicon source is 1 in molar ratio: (5800～60000): (1～11): mix (300～4000), stir down at 0 ℃, form vitreosol, behind gel, silica obtained post is washed in the alcoholic solution of water successively, aging in the alcoholic solution in silicon source, in surface tension less than the liquid of water or can reduce in the capillary solution and soak, again through super-dry and roasting.
Said polyelectrolyte solution comprises polycation electrolyte and/or polyanion electrolyte in the step (2).The preferably poly-p-sulfonic acid base vinylbenzene of the preferred Poly Dimethyl Diallyl Ammonium Chloride of said polycation electrolyte, polyanion electrolyte.
In the method provided by the invention, can alternately adsorb polyelectrolyte solution and zeolite colloid, repeatedly circulate to obtain the zeolite membrane of different thickness.
In the method provided by the invention, can also proceed step (4), said step (4) is aluminium source, sodium source, template, deionized water to be mixed form the secondary crystallization growth media, make under normal pressure or negative pressure that growth media is full of that step (3) obtains the duct of perforation type of multilevel pore canals silica gel in, under 60～300 ℃ of encloses containers and autogenous pressure 0.5～10 day and reclaim the zeolite product of crystallization.
Said secondary crystallization growth media is made up of aluminium source, sodium source, template and deionized water in the step (4) solution or suspension.Said aluminium source is sodium aluminate or Tai-Ace S 150.Said sodium source is the mixture of sodium aluminate or sodium aluminate and sodium hydroxide.Said template is selected from TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, primary amine, secondary amine, tertiary amine, one or more mixtures in the tensio-active agent.
Method provided by the invention can be used for dissimilar zeolites, can prepare the zeolite material in perforation type of multilevel pore canals that contains various structures (as MFI, BEA, A, structures such as FAU).For example when said zeolite product was the β zeolite, the molar ratio of secondary crystallization growth media was: (0.5～5) Na
2O: Al
2O
3: (10～100) SiO
2: (100～500) H
2O: (1～6) template; When said zeolite product was the ZSM-5 zeolite, the ratio of secondary crystallization growth media was: (0.5～5) Na
2O: Al
2O
3: (50～150) SiO
2: (600～1500) H
2O: (1～6) template.
The zeolite material in perforation type of multilevel pore canals that the inventive method obtains has the evenly abundant macroporous structure of high zeolite content and through-flow characteristic, can have a clear superiority in the same type of material than single zeolite molecular sieve aspect catalyzer, sorbent material, separating agent and the water treatment in fields such as catalysis, fractionation by adsorption performance important application.
The zeolite that method provided by the present invention obtains is compared with additive method, has the specific surface area height of finished product, and the macropore duct connects, and zeolite content is adjustable, the characteristics that zeolite type can be controlled in advance.Layer laminate of the present invention and secondary crystallization method are implemented simple, and be not high to matching requirements, and deposition process is easy to external control.And secondary crystallization can be converted into zeolite with unformed silicon-dioxide under the condition of not destroying the silica gel skeleton structure, and this method is an eco-friendly mode, can be used for catalytic separation industry.
Description of drawings
Fig. 1 is the perforation type of multilevel pore canals monolithic silica column sample A of embodiment 1
1SEM figure.
Fig. 2 is the perforation type of multilevel pore canals monolithic silica column sample B of embodiment 2
1SEM figure.
Fig. 3 is the perforation type of multilevel pore canals monolithic silica gel material sample C of embodiment 3
1SEM figure.
Fig. 4 is the perforation type of multilevel pore canals monolithic silica gel material sample D of the load Al of embodiment 4
1SEM figure.
Fig. 5 is the perforation type of multilevel pore canals monolithic silica gel material sample E of the loaded Cu of embodiment 5
1SEM figure.
Fig. 6 is the perforation type of multilevel pore canals monolithic silica gel material sample F of the load Ni of embodiment 6
1SEM figure.
Fig. 7 is the zeolite material in perforation type of multilevel pore canals sample A of embodiment 30
26SEM figure.
Fig. 8 is the zeolite material in perforation type of multilevel pore canals sample A of embodiment 33
29SEM figure.
Fig. 9 is the zeolite material in perforation type of multilevel pore canals sample A of embodiment 39
35SEM figure.
Figure 10 is the zeolite material in perforation type of multilevel pore canals sample A of embodiment 40
36SEM figure.
Figure 11 is perforation type of multilevel pore canals material sample A
26, A
29, A
35, A
36XRD figure.
Figure 12 is a perforation type of multilevel pore canals monolithic silica gel materials A
1And C
1N
2The adsorption-desorption isothermal curve.
Figure 13 is zeolite material in perforation type of multilevel pore canals sample A
26, A
29, A
35, A
36N
2The adsorption-desorption isothermal curve.
Figure 14 is zeolite material in perforation type of multilevel pore canals sample A
26, A
29, A
35, A
36Pore distribution figure.
Embodiment
Below by embodiment the present invention is further described, but content not thereby limiting the invention.
Agents useful for same is analytical pure among the embodiment, wherein, tetraethyl ammonium hydroxide (〉=20%, go in in a big way emerging good fortune fine chemistry industry institute), TPAOH (〉=20%, go in in a big way emerging good fortune fine chemistry industry institute), Poly Dimethyl Diallyl Ammonium Chloride and p-sulfonic acid base vinylbenzene produced by Aldrich company, other reagent are common agents.
Used sign instrument parameter among the embodiment: XRD-7000, the ZDJ strength test trier of Dalian Device Diagnostic factory and the Autosorb-1-MP type physical adsorption appearance of U.S. Quantachrome company in JSM-35C type scanning electron microscope sem, day island proper Tianjin.
The preparation process of embodiment 1-6 explanation perforation type of multilevel pore canals silica gel material.
The present embodiment explanation has the process of perforation type of multilevel pore canals monolithic silica column with the tetramethoxysilance for the preparation of silicon source.
The 0.01mol/L acetic acid solution of tetramethoxysilance, 6g polyoxyethylene glycol and the 30ml of 30ml is stirred, after the sealing, stir 50min down at 0 ℃.In gained colloidal sol impouring tetrafluoroethylene test tube or Glass tubing, ageing is one day in 30 ℃ of water-baths, obtains wet silicagel column.Soak silicagel column with 0.01mol/L ammoniacal liquor then, with the preparation mesopore.Use the ethanolic soln and the tween 80 of 0.1mol/L salpeter solution, distilled water, 30% ethanol/water to soak cylinder 6h more respectively.Final drying, roasting obtain perforation type of multilevel pore canals monolithic silica gel materials A
1
A
1SEM figure see Fig. 1, N
2The adsorption-desorption curve is seen Figure 12.
Embodiment 2
The present embodiment explanation has the process of perforation type of multilevel pore canals monolithic silica column with the water glass solution for the preparation of silicon source.
The concentrated nitric acid of water glass solution, 2g polyvinyl alcohol and the 15ml of 20g is mixed, gained colloidal sol poured in the test tube seal, place 40 ℃ of water-bath ageing 40h, soaked 4 days with deionized water again, change water one time every 24h, final drying, roasting get perforation type of multilevel pore canals structure monolithic silica gel material B
1
B
1SEM figure see Fig. 2.
Embodiment 3
Present embodiment explanation prepares the process of diplopore silica gel according to the method for Chinese patent application numbers 200510073092.7.
Take by weighing the 4.9737g polyoxyethylene glycol and pour in the Erlenmeyer flask, add the acetate of 52ml 0.01mol/L, be stirred to dissolving fully.Measure 28.4ml TMOS and join in the Erlenmeyer flask, Erlenmeyer flask is placed ice-water bath vigorous stirring 30min after, gained colloidal sol poured in the Glass tubing seal, place water-bath gel 1～2h of 40 ℃.Then wet silicagel column is immersed in the ethanolic soln of water, keeps 24h down at 60 ℃.Then be immersed in the ethanolic soln of TMOS, keep 72h down at 70 ℃.Again respectively with ethanol, normal heptane at 50 ℃ of each 24h of washing silicagel column down, the strengthened diplopore silica gel sample C of hardness of final drying, roasting
1C
1Highly for 1cm, when diameter is 0.7cm right cylinder particle shape, crush strength is 190N.
C
1SEM figure see Fig. 3.N
2The adsorption-desorption isothermal curve is seen Figure 12.
N from Figure 12
2The sign of adsorption-desorption can find that after hardness was strengthened, obvious variation had taken place the monolithic silica column pore structure, and specific surface area reduces to 286m
2G
-1, this hardening that has also proved monolithic silica column realizes with degree of connection by increasing skeleton thickness.
N
2The adsorption-desorption isothermal curve shows that monolithic silica column is typical IV curve, and the hysteresis loop with H1 type.Isothermal adsorption-desorption the curve of general mesoporous material is the IV curve, and the monolayer adsorption that takes place at low pressure area capillary condensation takes place to pressure when enough, and performance has a hop on curve, and the pressure of mesoporous big more generation capillary condensation is high more.Simultaneously at the high pressure area curve tip-tilted trend is arranged, also explanation has the existence of macropore.The formation of the hysteresis loop of H1 type is that it is by forming by finite concentration ammonia solvent silicon skeleton in the monolithic silica column preparation process owing to have evenly size and regular hole.The isothermal adsorption of monolithic silica column-desorption curve becomes I type curve and has H3 type hysteresis loop simultaneously after the hardening.I type curve also can occur in mesoporous material except occurring in pore material, but the aperture scope is approached in mesoporous aperture, occurs wide mesoporous distribution simultaneously; The hysteresis loop of H3 is owing to the existence in uneven slit-shaped duct, may be because the slit that forms during tabular build-up of particles.This be since on the former silica gel skeleton bigger mesoporous for dissolve-precipitin reaction provides reaction compartment, and being deposited in around it of not lacking of silicon source, so just reduced mesoporous aperture.
Embodiment 4
Take by weighing concentrated nitric acid 1.15g, tetraethoxy (TEOS) 9.31g, nine water aluminum nitrate 2.21g, PEG1.15g, distilled water 7.5g.PEG, aluminum nitrate and distilled water are joined in the nitric acid, again TEOS is joined in the above-mentioned mixing solutions, and constantly stir.After mixing solutions becomes uniform solution, be sealed in the test tube, keep 24h down at 50 ℃.Watch-glass is put in taking-up, 50 ℃ of following dry weeks.At 600 ℃ of following roasting 2h, obtain the perforation type of multilevel pore canals monolithic silica gel material D of load Al at last
1D
1SEM figure see Fig. 4.
Embodiment 5-6
With embodiment 4 identical methods, but use cupric nitrate, obtain the perforation type of multilevel pore canals monolithic silica gel material E of loaded Cu
1, use nickelous nitrate, obtain the perforation type of multilevel pore canals monolithic silica gel material F of load Ni
1E
1SEM figure see Fig. 5, F
1SEM figure see Fig. 6.
Embodiment 7
With silica gel, tetraethyl ammonium hydroxide and sodium aluminate according to n (TEAOH)/(SiO
2)=0.2, n (SiO
2)/(Al
2O
3)=30, n (H
2O)/(SiO
2)=6～7, n (Na)/(SiO
2The mole proportioning of)=0.12 is mixed, violent stirring at room temperature, put into crystallizing kettle 120 ℃ of crystallization 1 day, then 150 ℃ of crystallization 2 days, obtain nanometer β zeolite colloid,, be dispersed in again after the washing in the NaCl solution of 0.5mol/L again with the colloid centrifugation repeatedly that obtains, obtaining pH is 9.5, and mass percent is 1% β zeolite colloid.Be that 0.5% polycation electrolyte Poly Dimethyl Diallyl Ammonium Chloride (brief note is PDDA) is to perforation type of multilevel pore canals silica gel material A earlier before the deposition with mass concentration
1Show and carry out pre-treatment, adsorb 1h under negative pressure, the absorption back is fully soaked, is washed with deionized water.Perforation type of multilevel pore canals silica gel material after the modification is immersed in mass percent under negative pressure be in 1% the nanometer β zeolite colloidal solution, soak time is 1h, taking-up is washed 4 times with ammonia soln, and being drying to obtain with the perforation type of multilevel pore canals silica gel material is the zeolitic material sample A of the perforation type of multilevel pore canals of skeleton
2
Embodiment 8-10
With the method identical, but change the mass percent concentration of zeolite colloidal solution, be respectively 0.5%, 5%, 10% nanometer β zeolite colloidal solution, obtain the zeolitic material sample A of perforation type of multilevel pore canals with embodiment 7
3, A
4, A
5
Embodiment 11-12
With the method identical, but change the salt concn of zeolite colloidal solution, when being respectively 0.1M and 1M, obtain the zeolitic material sample A of perforation type of multilevel pore canals with embodiment 7
6, A
7
Embodiment 13
With the method identical with embodiment 7, but the pH value that changes zeolite colloidal solution is 4, obtains the zeolite sample A of perforation type of multilevel pore canals
9
Embodiment 14-15
With the method identical with embodiment 7, but using the zeolite of different-grain diameter to be building block, is 60nm with particle diameter respectively, and the nanometer Beta zeolite colloidal solution of 300nm obtains the zeolitic material sample A of perforation type of multilevel pore canals
10, A
11
Embodiment 16-19
With the method identical with embodiment 7, but change the thickness of sedimentary zeolite membrane, alternately adsorb the zeolite membrane that polycation electrolyte and nano zeolite colloidal cycle index obtain different thickness by changing, respectively through 2,5,10,15 circulation absorption obtain the zeolitic material sample A of perforation type of multilevel pore canals
12, A
13, A
14, A
15
With the method identical, but select for use polyanion electrolyte to gather p-sulfonic acid base vinylbenzene in the test, obtain the zeolitic material sample A of perforation type of multilevel pore canals with embodiment 7
16
Embodiment 21-22
With the method identical with embodiment 20, but changing the pH of zeolite colloidal solution, is respectively 1,4 nanometer β zeolite colloidal solution with pH, obtains the zeolitic material sample A of perforation type of multilevel pore canals
17, A
18
Embodiment 23-28
With the method identical, but change the type of colloidal solution mesolite, use ZSM-5 respectively with embodiment 7, silicalite-1, TS-1, A, X, nano zeolites such as Y obtain the zeolitic material sample A of perforation type of multilevel pore canals
19, A
20, A
21, A
22, A
23, A
24
With the method identical, but alternately change the type of nano zeolite,, obtain the zeolitic material sample A of perforation type of multilevel pore canals by ZSM-5 and the alternately absorption of Beta nano zeolite colloidal solution with embodiment 7
25
Embodiment 30
With among the embodiment 7 to sample A
2Roasting at 300 ℃ of following roasting 2h, then at 400 ℃ of following roasting 2h, at 560 ℃ of following roasting 6h, is removed organic molecule at last, obtains the zeolitic material sample A of perforation type of multilevel pore canals
26Its SEM figure sees Fig. 7.
A
26SEM figure see Fig. 7, XRD spectra is seen Figure 11, N
2Adsorption-desorption figure sees Figure 13, from A
26N
2Adsorption-desorption characterizes can find A
26N
2The adsorption-desorption isothermal curve becomes I type curve simultaneously, by the existence that the t method is calculated micropore, finds A
26Have certain micropore and exist, specific surface area is 264m
2G
-1, the micropore pore volume is 0.00211m
3G
-1, the hole area of micropore is 15.8m
2G
-1
A
26Pore distribution figure see Figure 14.
Embodiment 31-32
With the method roasting identical with embodiment 30, but the sample of institute's roasting changes A into
12, A
13, obtain the zeolitic material sample A of perforation type of multilevel pore canals
27, A
28
Embodiment 33
Will be with sample A under negative pressure
2Be immersed in 0.5h in the secondary crystallization liquid, secondary-cleaned liquid is according to Na by sodium hydroxide, tetraethyl ammonium hydroxide, sodium aluminate
2O: H
2O=0.01, H
2O: Al
2O
3=300, TEAOH: H
2The mixed in molar ratio of O=0.0107, be positioned over porous plate top in the reactor then.Inject the deionized water of 10ml to the reactor bottom with syringe, 120 ℃ of crystallization 2 days, take out and use the deionized water wash after drying, then at 300 ℃ of following roasting 2h, then at 400 ℃ of following roasting 2h, at 560 ℃ of following roasting 6h, obtain the zeolitic material sample A of the perforation type of multilevel pore canals of secondary crystallization at last
29
A
29SEM figure see Fig. 8, XRD spectra is seen Figure 11, N
2The adsorption-desorption isothermal curve is seen Figure 13, passes through N
2The sign of adsorption-desorption can be found A
29N
2The adsorption-desorption isothermal curve becomes I type curve, and specific surface area is 191m
2G
-1,, find A by the existence that the t method is calculated micropore
29Have certain micropore and exist, the micropore pore volume is 0.0369m
3G
-1, the hole area of micropore is 82.47m
2G
-1
A
29Pore distribution figure sees Figure 14.
Embodiment 34-37
Be used for the identical method of embodiment 33, but change crystallization temperature, at 80 ℃, 140 ℃, 160 ℃, 180 ℃ of crystallization obtain the zeolitic material sample A of the perforation type of multilevel pore canals of secondary crystallization
30, A
31, A
32, A
33
Embodiment 38-41
Be used for embodiment 33 identical methods and test, but change crystallization time, at 1 day, 3 days, 4 days, 8 days crystallization obtained the zeolitic material sample A of the perforation type of multilevel pore canals of secondary crystallization
34, A
35, A
36, A
37
A
35SEM figure see Fig. 9, A
36SEM figure see Figure 10.
A
35, A
36XRD figure see Figure 11.
A
35And A
36N
2The adsorption-desorption isothermal curve is seen Figure 13.Pass through N
2The sign of adsorption-desorption can be found A
35Isothermal adsorption-desorption curve become I type curve, by the existence that the t method is calculated micropore, find A
35Have certain micropore and exist, specific surface area is 479m
2G
-1, the micropore pore volume is 0.163m
3G
-1, the hole area of micropore is 358.2m
2G
-1A
36Isothermal adsorption-desorption curve become I type curve, by the existence that the t method is calculated micropore, find A
36Have certain micropore and exist, specific surface area is 541m
2G
-1, the micropore pore volume is 0.184m
3G
-1, the hole area of micropore is 406.4m
2G
-1
A
35And A
36Pore distribution figure see Figure 14.
Embodiment 42
With silica gel, tetraethyl ammonium hydroxide and sodium aluminate according to n (TEAOH)/(SiO
2)=0.2, n (SiO
2)/(Al
2O
3)=30, n (H
2O)/(SiO
2)=6～7, n (Na)/(SiO
2The mole proportioning of)=0.12 is mixed, violent stirring at room temperature, put into crystallizing kettle 120 ℃ of crystallization 1 day, then 150 ℃ of crystallization 2 days, obtain nanometer Beta zeolite colloid,, be dispersed in again after the washing in the NaCl solution of 0.5mol/L again with the colloid centrifugation repeatedly that obtains, obtaining pH is 9.5, and mass percent is 1% Be ta zeolite colloid.Be the perforation type of multilevel pore canals silica gel material C that 0.5% polycation electrolyte PDDA prepares embodiment 3 earlier before the deposition with mass concentration
1Show and carry out pre-treatment, adsorb 1h under negative pressure, the absorption back is fully soaked, is washed with deionized water.Perforation type of multilevel pore canals silica gel material after the modification is immersed in mass percent under negative pressure be in 1% the nanometer Beta zeolite colloidal solution, soak time is 1h, taking-up is washed 4 times with ammonia soln, and being drying to obtain with the perforation type of multilevel pore canals silica gel material is the zeolitic material sample C of the perforation type of multilevel pore canals of skeleton
2
C
2Has A
2Constructional feature.
Embodiment 43-46
With with embodiment 7 same procedure, but use the perforation type of multilevel pore canals silica gel material of modification, change into B respectively
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
2, D
2, E
2, F
2
Embodiment 47
With the method identical, but change the mass percent concentration of zeolite colloidal solution, be respectively 5% nanometer β zeolite colloidal solution, obtain the zeolitic material sample C of perforation type of multilevel pore canals with embodiment 42
3
Embodiment 48-51
Be used for the identical method of embodiment 9, but use the perforation type of multilevel pore canals silica gel material of modification, change B respectively into
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
3, D
3, E
3, F
3
Embodiment 52
With the method identical with embodiment 42, but the salt concn that changes zeolite colloidal solution obtains the zeolitic material sample C of perforation type of multilevel pore canals when being 0.1M
4
Embodiment 53-56
Be used for the identical method of embodiment 11, but use the perforation type of multilevel pore canals silica gel material of modification, be respectively B
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
4, D
4, E
4, F
4
Embodiment 57
With the method identical with embodiment 42, but using the zeolite of different-grain diameter to be building block, is the nanometer β zeolite colloidal solution of 60nm with particle diameter, obtains the zeolitic material sample C of perforation type of multilevel pore canals
5
Embodiment 58-61
Be used for embodiment 18 identical layer laminate and test, but the perforation type of multilevel pore canals silica gel material of use modification is respectively B
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
5, D
5, E
5, F
5
Embodiment 62
With the method identical with embodiment 42, but selecting for use polyanion electrolyte to gather p-sulfonic acid base vinylbenzene, and change the pH of zeolite colloidal solution, is respectively 1 nanometer β zeolite colloidal solution with pH, obtains the zeolitic material sample C of perforation type of multilevel pore canals
6
Embodiment 63-66
Be used for the identical method of embodiment 21, but use the perforation type of multilevel pore canals silica gel material of modification, be respectively B
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
6, D
6, E
6, F
6
Embodiment 67
With the method identical, but change the type of nano zeolite, use ZSM-5 respectively with embodiment 42, silicalite-1, TS-1, A, X, nano zeolites such as Y obtain the zeolitic material sample C of perforation type of multilevel pore canals
7, C
8, C
9, C
10, C
11And C
12
Embodiment 68-71
With the method identical, but use the perforation type of multilevel pore canals silica gel material of modification, be respectively B with embodiment 23
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
7, D
7, E
7, F
7
Embodiment 72-75
With the method identical, but use the perforation type of multilevel pore canals silica gel material of modification, be respectively B with embodiment 24
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
8, D
8, E
8, F
8
Embodiment 76-80
With the method identical, but use the perforation type of multilevel pore canals silica gel material of modification, be respectively B with embodiment 28
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
9, D
9, E
9, F
9
Embodiment 81
With the method identical, but alternately change the type of nano zeolite,, obtain the zeolitic material sample C of perforation type of multilevel pore canals by ZSM-5 and the absorption of Beta nano zeolite colloid with embodiment 42
13
Embodiment 82-85
With the method identical, but use the perforation type of multilevel pore canals silica gel material of modification, be respectively B with embodiment 29
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
10, D
10, E
10, F
10
Embodiment 86
With among the embodiment 7 to sample A
2Roasting at 300 ℃ of following roasting 2h, then at 400 ℃ of following roasting 2h, at 560 ℃ of following roasting 6h, is removed organic molecule at last, obtains the zeolitic material sample C of perforation type of multilevel pore canals
14
Embodiment 87-90
Be used for the identical method of embodiment 30, but use the perforation type of multilevel pore canals silica gel material of modification, be respectively B
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
11, D
11, E
11, F
11
Embodiment 91
Will be with sample C under negative pressure
2Be immersed in 0.5h in the secondary crystallization liquid, secondary-cleaned liquid is according to Na by sodium hydroxide, tetraethyl ammonium hydroxide, sodium aluminate
2O: H
2O=0.01, H
2O: Al
2O
3=300, TEAOH: H
2The mixed in molar ratio of O=0.0107, be positioned over porous plate top in the reactor then.Inject the deionized water of 10ml to the reactor bottom with syringe, 120 ℃ of crystallization 2 days, take out and use the deionized water wash after drying, then at 300 ℃ of following roasting 2h, then at 400 ℃ of following roasting 2h, at 560 ℃ of following roasting 6h, obtain the zeolitic material sample C of the perforation type of multilevel pore canals of secondary crystallization at last
15
Embodiment 92-95
Be used for the identical method of embodiment 91, but use the perforation type of multilevel pore canals silica gel material of modification, be respectively B
1, D
1, E
1, F
1, obtain the zeolitic material sample B of perforation type of multilevel pore canals
12, D
12, E
12, F
12
Claims (21)
1. the preparation method of a zeolite material in perforation type of multilevel pore canals is characterized in that this method contains following step:
(1) crystallite with zeolite is dispersed in the colloidal solution that forms concentration 1.0～25 heavy %, pH9～14 in water or the inorganic salt solution, and the micelle size is 1.0nm～2.5 μ m;
(2) under normal pressure or the negative pressure perforation type of multilevel pore canals silica gel material being soaked 1min～1h in the polyelectrolyte solution of 1.0～10 heavy %, use deionized water rinsing then 1～5 time, the Skeleton Table after the modification is worn electric charge;
(3) under normal pressure or negative pressure with (2) in silica gel material in the colloidal solution of (1), soak, wash.
2. according to the method for claim 1, the zeolite that it is characterized in that step (1) is selected from one or more in ZSM-5, β, silicalite-1, TS-1, A, X and the y-type zeolite.
3. according to the method for claim 1, the concentration that it is characterized in that the said colloidal solution of step (1) is 1.0～15 heavy %, and the pH value is 9～12, and the micelle size is 1～500nm.
4. according to the method for claim 1, it is characterized in that inorganic salt solution concentration is 0.01～1.5M.
5. according to the method for claim 1, it is characterized in that said inorganic salt are NaCl.
6. according to the method for claim 1, the perforation type of multilevel pore canals silica gel material that it is characterized in that step (2) has the mesoporous of the macropore of 0.5～30 μ m and 3～20nm simultaneously, and is penetrating between the macropore.
7. according to the method for claim 1, it is characterized in that said perforation type of multilevel pore canals silica gel material is metal oxide-loaded.
8. according to the method for claim 7, it is characterized in that said metal is selected from the IIIA of the periodic table of elements, IB family.
9. according to the method for claim 7, it is characterized in that said metal is selected from Al, Cu or Ni.
10. according to the method for one of claim 1 or 6～9, it is characterized in that said perforation type of multilevel pore canals silica gel material is a monolithic silica column.
11. according to the method for claim 10, it is characterized in that said monolithic silica column is a diplopore silica gel, its macropore diameter is 0.5～3.0 μ m, mesoporous aperture is 3～10nm, and pore volume is 2.5～3.5cm
3/ g, specific surface area is 250～710m
2/ g, this material highly for 1cm, when diameter is 0.7cm right cylinder particle shape, crush strength is 180～220N.
12. method according to claim 11, it is characterized in that said diplopore silica gel, be to obtain by the method that comprises following process: with polyoxyethylene glycol, water, acid, silicon source is 1 in molar ratio: (5800～60000): (1～11): mix (300～4000), stir down at 0 ℃, form vitreosol, behind gel, with silica obtained post washing in the alcoholic solution of water successively, aging in the alcoholic solution in silicon source, in surface tension less than the liquid of water or can reduce in the capillary solution and soak, again through super-dry and roasting.
13., it is characterized in that the said polyelectrolyte solution of step (2) is polycation electrolyte or polyanion electrolyte according to the method for claim 1.
14. according to the method for claim 13, it is characterized in that said polycation electrolyte is a Poly Dimethyl Diallyl Ammonium Chloride, polyanion electrolyte is poly-p-sulfonic acid base vinylbenzene.
15. according to the method for claim 1, it is characterized in that alternately adsorbing polyelectrolyte solution and zeolite colloidal solution, repeatedly circulate to obtain the zeolite membrane of different thickness.
16. method according to claim 1, it is characterized in that proceeding step (4), step (4) is aluminium source, sodium source, template, deionized water to be mixed form the secondary crystallization growth media, make under normal pressure or negative pressure that growth media is full of that step (3) obtains the duct of perforation type of multilevel pore canals silica gel material in, under 60～300 ℃ of encloses containers and autogenous pressure, reacted 0.5～10 day and reclaimed the zeolite product of crystallization.
17., it is characterized in that the said secondary crystallization growth media of step (4) is solution or suspension according to the method for claim 16.
18., it is characterized in that said aluminium source is sodium aluminate or Tai-Ace S 150 according to the method for claim 16.
19., it is characterized in that said sodium source is the mixture of sodium aluminate or sodium aluminate and sodium hydroxide according to the method for claim 16.
20., it is characterized in that said template is a TPAOH, tetraethyl ammonium hydroxide, one or more mixtures in the Tetramethylammonium hydroxide according to the method for claim 16.
21. the zeolite material in perforation type of multilevel pore canals of one of claim 1-20 method preparation.
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| CN103172847A (en) * | 2013-03-19 | 2013-06-26 | 岳阳蓬诚科技发展有限公司 | Method for preparing alkyl naphthalene polycondensation catalyst |
| CN107954443B (en) * | 2016-10-14 | 2021-03-30 | 中国石油化工股份有限公司 | Method for synthesizing hierarchical pore ZSM-5 molecular sieve |
| WO2019010700A1 (en) * | 2017-07-14 | 2019-01-17 | 北京大学深圳研究生院 | Multi-pore zeolite having layered structure and preparation method therefor |
| US10272418B2 (en) * | 2017-08-07 | 2019-04-30 | Saudi Arabian Oil Company | Mesoporous zeolites and methods for the synthesis thereof |
| CN109304141A (en) * | 2018-12-13 | 2019-02-05 | 吉林大学 | It is a kind of for adsorbing diatomite/molecular sieves compound material preparation method of volatile organic contaminant |
| CN111377461B (en) * | 2018-12-28 | 2022-07-12 | 中国石油化工股份有限公司 | Multi-stage hole HZSM-5 zeolite molecular sieve |
| CN109879317B (en) * | 2019-04-15 | 2021-04-09 | 陕西科技大学 | Hierarchical hole ZrO2Solid material, preparation method and application thereof |
| CN115448324B (en) * | 2022-09-27 | 2023-06-27 | 吉林大学 | MFI structure molecular sieve hierarchical pore material and preparation method thereof |
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