CN100429148C - Method for mesoporous molecular sieve overgrowth on microporous molecular sieve surface - Google Patents
Method for mesoporous molecular sieve overgrowth on microporous molecular sieve surface Download PDFInfo
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- CN100429148C CN100429148C CNB2004100840994A CN200410084099A CN100429148C CN 100429148 C CN100429148 C CN 100429148C CN B2004100840994 A CNB2004100840994 A CN B2004100840994A CN 200410084099 A CN200410084099 A CN 200410084099A CN 100429148 C CN100429148 C CN 100429148C
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 77
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 208000012868 Overgrowth Diseases 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000010457 zeolite Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- -1 silicon ester Chemical class 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 1
- 239000013335 mesoporous material Substances 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 10
- 229910052736 halogen Inorganic materials 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 8
- 239000010935 stainless steel Substances 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 150000002366 halogen compounds Chemical class 0.000 abstract description 2
- 239000012229 microporous material Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 9
- 239000013543 active substance Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 206010010356 Congenital anomaly Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- 229910002800 Si–O–Al Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- MAZPIOPHRNWBNG-UHFFFAOYSA-N [Cl-].Cl[NH3+].[Na] Chemical compound [Cl-].Cl[NH3+].[Na] MAZPIOPHRNWBNG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a method of the overgrowth of a mesoporous molecular sieve on the surface of a microporous molecular sieve. The method comprises the following steps: a silicon source and an aluminum source are used as raw materials, and the raw materials, a template agent, a halogen compound and water are mixed, stirred evenly and crystallized at a certain temperature so that a microporous molecular sieve containing halogen is prepared; the microporous molecular sieve containing halogen is strongly stirred, and at a room temperature, the prepared microporous molecular sieve containing halogen is added into an activation solution containing a surface active agent, alkali (acid) and distilled water, and the mixture is stirred for 0.5 to 3.0 hours; then a certain number of template agents, silicon sources and aluminum sources are supplemented orderly into the mixture, stirred for 0.5 to 3.0 hours, sealed in a stainless steel reaction kettle and crystallized at a temperature of 80 to 120 DEG C for 12 to 72 hours; and the crystallized product is processed by filtration, washing, drying and roasting at a temperature of 550 DEG C for 6 hours, and a finished product is obtained. The preparation method is especially suitable to be used for preparing microporous zeolites with a low surface Na<+> content and high ratio of Si to Al; the advantages of both microporous materials and mesoporous materials are integrated with the preparation method so that the advantages of the two materials are developed, the disadvantages of the two materials are avoid, and the two materials have a synergistic effect.
Description
Technical field
The invention belongs to inorganic materials and catalytic field, specifically, relate to the preparation method of microporous-mesoporous composite molecular sieve, i.e. a kind of method of mesoporous molecular sieve overgrowth on microporous molecular sieve surface.
Technical background
As everyone knows, the micro-pore zeolite molecular sieve is a shape-selective catalyst important in the modern petrochemical complex, have good molecule shape selectivity and acid catalysis performance, but its narrow and small pore passage structure has hindered entering of high boiling point (＞400 ℃) vacuum residuum, the rapid diffusion that also influences reacted product molecule is overflowed, thereby causes the increase of secondary cracking and green coke amount.Heaviness gradually along with oil, the aperture limitation of micro porous molecular sieve shows extraordinarily outstandingly, resolving heavy oil, the macromolecular reaction of residual oil and diffusion problem becomes one of most important technical problem of world oil manufacture field, and break through this technology be to develop stable, that have homogeneous, larger aperture at all with the tart molecular sieve.Under this industrial background, the Mobil oil company of the U.S. has developed the M41S mesoporous material in report in 1992, wins the great attention (Nature, 359:710,1992) of industry member and scientific circles with its outstanding porous.Yet this class material exists poor, the acid low congenital drawback of hydrothermal stability, has hindered its application in refining of petroleum.Trace it to its cause, be because the unbodied feature of its hole wall reaches and the existence of the exhibiting high surface silicon hydroxyl of its association, be easy to and water and other medium effect, cause collapsing of skeleton, and from another side, aluminium in the mesoporous material occurs with the form of hexa-coordinate in many cases, can not provide reaction required acidity.Thereby make this class aspect porous, quite have the material of characteristics to be difficult to be applied in industrial production.
But if the duct advantage of mesoporous material can be combined with the strongly-acid of micro porous molecular sieve and the advantage of stability, develop a kind of micropore-mesopore matrix material, wherein two kinds of material advantage complementations, synergy, this class material will certainly become the hydrogenation catalyst novel material of a class potentialization so.
Up to the present, realize that micropore and composite mesoporous pattern have: (1) overgrowth, at micro-pore zeolite surface overgrowth mesoporous material, the method for employing is mainly template ion exchange method (MicroporousMaterials, 6:287,1996); (2) crystallization of pore wall, the investigator of Fudan University adopts two directed agents methods by two step crystallization methods, first synthesize meso-porous material, then the amorphous crystallization of pore wall of mesoporous material is become micro porous molecular sieve (J.Phy.Chem.B, 2000,104,2817-2823).
Carrier of hydrocracking catalyst is from amorphous Si O
2-Al
2O
3, zeolite molecules is sieved to amorphous Si O
2-Al
2O
3Add the evolution of a small amount of zeolite molecular sieve.At present used molecular sieve is substantially based on Y, USY and β type, these molecular sieves are being brought into play important effect aspect raising hydrocracking catalyst activity, the selectivity, its weak point is that the duct of molecular sieve is narrow, and the macromole in the cracking stock is difficult to enter in the duct of molecular sieve and reacts.And the appearing as to address this problem possibility is provided of micro-pore zeolite molecular sieve surface overgrowth mesopore molecular sieve novel method.
Goal of the invention
The object of the present invention is to provide a kind of method of mesoporous molecular sieve overgrowth on microporous molecular sieve surface, i.e. static coupling synthesis method.At micro-pore zeolite molecular sieve surface overgrowth mesopore molecular sieve, integrate by the advantage of poromerics and mesoporous material on the one hand, the two is maximized favourable factors and minimized unfavourable ones, synergy; On the other hand, mesoporous material has improved the hydrothermal stability of matrix material by transition layer and poromerics surface formation interconnection chemically, has produced new acid active sites simultaneously.With above-mentioned synthetic matrix material is the preparing carriers hydrocracking catalyst, helps improving the acid catalysis function of cracking catalyst.
The present invention proposes a kind of method for preparing composite molecular screen, promptly makes the method for mesoporous material in poromerics surface overgrowth by the static coupling, is intended to integrate the advantage of poromerics and mesoporous material, the two is maximized favourable factors and minimized unfavourable ones, synergy.
The present invention is achieved in that
The mesoporous material that the present invention proposes is that mesoporous material is by transition layer and poromerics surface formation interconnection chemically in one of feature of the overgrowth method on poromerics surface.At transition layer, the four-coordination aluminium and the silicon of mesoporous material active silicon hydroxyl in surface and zeolite surface end group form Si-O-Si or Si-O-Al condensation, therefore reduce to influence the hidden danger of mesoporous material stability, improved hydrothermal stability, produced acid active sites simultaneously.Be subjected to the influence of interfacial effect, the degree of order that mesoporous material is arranged increases, and has also promoted the raising of hydrothermal stability from another side.
The mesoporous material that the present invention proposes is based on the X that the applicant proposes in one of feature of the overgrowth on poromerics surface
-S
+I
-The static assembly model, X in the formula
-Be the halide-ions of zeolite surface, S
+Be the positively charged ion of tensio-active agent, I
-Be silicate anion.What control this static composition mechanism is electrostatic interaction between tensio-active agent polar head and the mineral ion, and halide-ions plays important bridging effect therein.Generally, under the effect of zeolite surface halogen anion, be electropositive tensio-active agent positively charged ion and assemble, form electrostatic double layer (X to it
-S
+).Silicon source after the hydrolysis attracted near the orderly micella arrangement that forms the electrostatic double layer to be electronegative anionic form under alkaline condition, forms X
-S
+I
-Three electricity layers of form, and then be piled into the hole wall of mesopore molecular sieve.Thus, form from group process itself, S with regard to finishing mesoporous material
+With I
-Between electrostatic interaction be main drive, causing can then be classical surface energy between halogen anion and the tensio-active agent in the major cause of zeolite surface overgrowth, comprises hydrogen bond.
The mesoporous material that the present invention proposes also is the absorption of halide-ions in one of feature of the overgrowth on poromerics surface.Because the outside surface of micro-pore zeolite is rich aluminium state, easy and its reaction of halide-ions is as F
-The Yi Yuqi reaction generates (AlF
6)
3-, and be present in the outside surface that zeolite is examined, thus electrostatic field produced.The halogen ion of present method indication at first is meant the F that electronegativity is strong
-, be followed successively by Cl
-, Br
-, and I
-Because of its electronegativity difference, not as the scope of present method indication.
The mesoporous material that the present invention proposes is that in one of feature of the overgrowth on poromerics surface this preparation method is particularly useful for surperficial Na
+The high silica alumina ratio micro-pore zeolite that content is low.Kloetstra etc. had once carried out report first to the overgrowth of MCM-41 on the faujusite Y molecular sieve, because the y-type zeolite silica alumina ratio is low, and the Na that surface enrichment is a large amount of
+, they make its surperficial Na by ion-exchange in water-tensio-active agent-y-type zeolite-alkali-silicate system
+Thereby replaced in zeolite Y surface overgrowth the MCM-41 mesopore material by tensio-active agent.Yet high and surperficial Na for silica alumina ratio
+The zeolite that content is low, only to reach the purpose of the overgrowth of mesoporous material be infeasible to the form by ion-exchange.For this reason, the present invention has designed by changing zeolite surface electric field performance, makes its surperficial overgrowth mesoporous material be easy to the route that carries out.
The preparation method of microporous-mesoporous composite molecular sieve of the present invention comprises two basic steps:
(1) at first the halogen-containing micro porous molecular sieve of preparing according to ordinary method is carried out activation treatment,, be convenient to the overgrowth of mesopore molecular sieve to change the surface field of micro porous molecular sieve.
(2) mesoporous molecular sieve overgrowth on microporous molecular sieve surface after activation treatment.
Specifically be stated as: with silicon source, aluminium source is raw material, stir with template, halogen compounds, water, crystallization makes the micro porous molecular sieve that contains halogen at a certain temperature, preparation details and proportioning raw materials can be referring to the documents of existing micro porous molecular sieve preparation, synthetic method can adopt hydrothermal crystallization method, also can adopt solid phase method.The silica alumina ratio scope of product is not limit.Under the condition of violent stirring and room temperature, the halogen-containing micro porous molecular sieve for preparing is joined in the activated solution that contains tensio-active agent, alkali (acid) and distilled water, continue to stir 0.5～3.0 hour.Then, to wherein adding a certain amount of template, silicon source and aluminium source restir 0.5～3.0 hour successively, enclose in the stainless steel cauldron, in 80～120 ℃ of following crystallization 12～72 hours, after finishing, crystallization, made finished product in 6 hours 550 ℃ of following roastings through filtration, washing, drying.
Employed micro porous molecular sieve can be ZSM-35, ZSM-5, Beta, TS-1, silicalite-1 in the method provided by the present invention; Mesopore molecular sieve can be MCM-41, MCM-48, SBA-2.The silicon source can be silicon sol, water glass, tetraethoxy, positive silicic acid propyl ester or butyl silicate etc., and the ratio in the reaction mother liquor of preparation is 5～80%; The aluminium source can be Tai-Ace S 150, sodium metaaluminate, aluminum isopropylate etc., and its ratio in reaction mother liquor is 0.01～30%, is preferably 0.01～15%.Wherein the halide-ions of Yin Ruing at first is meant the F that electronegativity is strong
-, be followed successively by Cl
-, Br
-, the material of interpolation can be Sodium Fluoride, Neutral ammonium fluoride, sodium-chlor, ammonium chloride and Organohalogen compounds.
In the mesopore molecular sieve overgrowth process, use sodium hydroxide solution or hydrochloric acid conditioning solution potential of hydrogen among the present invention, used tensio-active agent is long chain alkyl ammonium salt and bipolarity head surface promoting agent.The micro porous molecular sieve quality accounts for 1～90% of reaction mother liquor total solid content in the reaction mixture, is preferably 20～50%.
Specific embodiments
The technical characterstic that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.
Embodiment 1
The typical method of overgrowth mesopore molecular sieve MCM-41 on micro porous molecular sieve ZSM-35.
(1) activation treatment of F-ZSM-35
0.15g sodium hydroxide and 5.6g cetyl trimethylammonium bromide are dissolved in the 29.3ml distilled water, under violent stirring, add 1.0g F-ZSM-35 that prepare in advance, porphyrize, stirred at ambient temperature 1.0 hours, form white suspension liquid.
(2) overgrowth of mesopore molecular sieve MCM-41
In above-mentioned white suspension liquid, add a certain amount of cetyl trimethylammonium bromide again, add 10ml silicon sol (SiO then
2Content is 5.88mol/L) continue to stir 1.0 hours, enclose in the stainless steel cauldron, crystallization is 24 hours under 373K, through filtration, washing, drying, makes finished product in 6 hours 550 ℃ of following roastings after crystallization is finished.
The XRD of synthetic sample and SEM characterize and illustrate that this composite molecular screen has degree of crystallinity preferably, and mesopore molecular sieve MCM-41 is grown in micro porous molecular sieve ZSM-35 surface, by transition layer two kinds of molecular sieves is combined, and form microporous-mesoporous composite molecular sieve.
Embodiment 2
The typical method of overgrowth mesoporous material SBA-2 on micro porous molecular sieve ZSM-5.
(1) bipolarity head surface promoting agent 16-12-16 or the 18-3-1 with 0.6mol is dissolved in the 30ml distilled water, be 1.0～2.0 with dilute hydrochloric acid regulator solution pH then, under violent stirring, add 1.0g Cl-ZSM-5 that prepare in advance, porphyrize, continue at ambient temperature to stir 0.5～1.0 hour, form white suspension liquid.
(2) overgrowth of mesopore molecular sieve SBA-2
In above-mentioned white suspension liquid, add a certain amount of bipolarity head surface promoting agent again, adding the 8.64g tetraethoxy then continues to stir 0.5～2.0 hour, enclose in the stainless steel cauldron at last, in 80 ℃ of following crystallization 24 hours, after crystallization is finished through filtration, washing, drying, made finished product in 6 hours 550 ℃ of following roastings, identify to have SBA-2 characteristic peak and ZSM-5 crystal phase structure through XRD.
Embodiment 3
The typical method of overgrowth mesopore molecular sieve MCM-48 on micro porous molecular sieve Mordenite.
(1) activation treatment of Br-Mordenite
The 18-3-1 of 0.32g sodium hydroxide and 0.001mol is dissolved in the 27.0ml distilled water, fully stir, regulating the pH value with sodium hydroxide solution is 9.0～10.0, under violent stirring, add Br-Mordenite that 1.5g prepares in advance, porphyrize again, continue at ambient temperature to stir 1.0 hours, form white suspension liquid.
(2) overgrowth of mesopore molecular sieve MCM-48
In above-mentioned white suspension liquid, add the 0.001mol octadecyl trimethyl ammonium chloride again, add 5.0ml water glass (SiO then
2Weigh 26%, modulus 3.2, proportion 1.384), after fully stirring, enclose in the stainless steel cauldron, crystallization is 72 hours under 373K, and above-mentioned pH value of solution value to 9～10 were regulated at wherein every interval in 12 hours.After reaction finished, product was through filtration, washing, drying.For improving the degree of crystallinity of product, the said products is mixed with deionized water with 1:20 (weight ratio), heating is 10 days under 373K, and product identifies to have MCM-48 characteristic peak and Mordenite crystal phase structure through XRD.
Embodiment 4
The typical method of overgrowth mesoporous material MCM-41 on micro porous molecular sieve Beta.
With the 5.6g cetyl trimethylammonium bromide, 0.15g sodium hydroxide is dissolved in the 29.3ml distilled water, under violent stirring, adds 1.0g F-Beta zeolite that prepare in advance, porphyrize, stirs at ambient temperature 1.0 hours, forms white suspension liquid.In above-mentioned white suspension liquid, add a certain amount of cetyl trimethylammonium bromide then, add 10ml silicon sol (SiO then successively
2Content is 5.88mol/L), 5% sodium aluminate solution 5.0g, continue to stir 1.0 hours, reaction mixture is enclosed in the stainless steel cauldron, crystallization certain hour under 373K, through filtration, washing, drying, made finished product in 6 hours after crystallization is finished, identify to have MCM-41 characteristic peak and Beta crystal phase structure through XRD 550 ℃ of following roastings.
Embodiment 5
The typical method of overgrowth MCM-48 on silicalite-1.
With 0.32g sodium hydroxide, 0.001mol the 18-3-1 tensio-active agent is dissolved in the 27.0ml distilled water, fully stir, regulating the pH value with dilute NaOH solution is 9～10, add F-silicalite-1 that 1.3g prepares in advance, porphyrize then, stirred at ambient temperature 1.0 hours, and formed white suspension liquid.In above-mentioned white suspension liquid, add 0.001molCTAB then, add 5.0ml water glass (SiO at last
2Weigh 26%, modulus 3.2, proportion 1.384) fully stir in the back inclosure stainless steel cauldron, crystallization is 72 hours under 373K, and above-mentioned pH value of solution value to 9.0～10.0 were regulated at wherein every interval in 12 hours.After reaction finishes, product, mixes the said products for improving the degree of crystallinity of product through filtration, washing, drying with 1: 20 (weight ratio) deionized water, heating is 10 days under 373K, and product identifies to have MCM-48 characteristic peak and silicalite-1 crystal phase structure through XRD.
Embodiment 6
The typical method of overgrowth SBA-2 on micro porous molecular sieve TS-1.
At first 0.6mol (16-12-16 or 18-3-1) bipolarity head surface promoting agent is dissolved in the 30ml distilled water, with dilute hydrochloric acid regulator solution pH is 1.0～2.0, add the F-TS-1 that 1.0g prepares in advance then, stirred at ambient temperature 0.5～1.0 hour, form white suspension liquid.In above-mentioned white suspension liquid, add a certain amount of bipolarity head surface promoting agent (16-12-16 or 18-3-1), add the 8.64g tetraethoxy then, continue to stir 0.5～1.0 hour, reaction mixture is enclosed in the stainless steel cauldron, in 80 ℃ of following crystallization 24 hours, through filtration, washing, drying, made finished product in 6 hours after crystallization is finished, identify to have SBA-2 characteristic peak and TS-1 crystal phase structure through XRD 550 ℃ of following roastings.
Claims (6)
1, a kind of method of mesoporous molecular sieve overgrowth on microporous molecular sieve surface, it is characterized in that with the long chain alkyl ammonium salt being template, with water glass, silicon sol or silicon ester is the silicon source, with Tai-Ace S 150, sodium metaaluminate or aluminum isopropylate is the aluminium source, with sodium hydroxide solution or hydrochloric acid is the solution acid-base modifier, based on X
-S
+I
-The static assembly model by two steps of activation treatment and overgrowth, has realized mesoporous poromerics at the interface chemistry interconnection, and its concrete steps are:
(1) micro porous molecular sieve that will contain F, Cl or Br joined in the activated solution stirring at room 0.5～3.0 hour, formed white suspension liquid; Activated solution is formulated by template, hydrochloric acid or sodium hydroxide and distilled water, and when wherein using hydrochloric acid, the pH value of activated solution is 1.0～2.0, and when using sodium hydroxide, the pH value of activated solution is 9.0～10.0
(2) overgrowth: add into template in the white suspension liquid that forms after activation treatment, aluminium source and silicon source are then 80～120 ℃ of following crystallization 12～72 hours.
2, the method for a kind of mesoporous molecular sieve overgrowth on microporous molecular sieve surface according to claim 1, it is characterized in that micro porous molecular sieve is molecular sieve, pure silicon molecular sieve or the molecular sieve TS-1 of middle high silica alumina ratio, wherein micro porous molecular sieve accounts for 1～90% of reaction mother liquor total solid content.
3, the method for a kind of mesoporous molecular sieve overgrowth on microporous molecular sieve surface according to claim 2 is characterized in that, wherein the high silica alumina ratio molecular sieve is ZSM-5, ZSM-35, mordenite or Beta zeolite, and the pure silicon molecular sieve is a silicon zeolite-1.
4, the method for a kind of mesoporous molecular sieve overgrowth on microporous molecular sieve surface according to claim 1 is characterized in that template used dose is cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, C
18H
37N (CH
3)
2(CH
2)
3N (CH
3)
3Or C
16H
33N (CH
3)
2(CH
2)
12N (CH
3)
2C
16H
33
5, the method for a kind of mesoporous molecular sieve overgrowth on microporous molecular sieve surface according to claim 1 is characterized in that silicon ester is tetraethoxy, positive silicic acid propyl ester or butyl silicate, and the ratio in the reaction mother liquor of preparation is 5～80%.
6, the method for a kind of mesoporous molecular sieve overgrowth on microporous molecular sieve surface according to claim 1 is characterized in that the ratio of aluminium source in the reaction mother liquor of preparation is 0.01～30%.
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