CN1686800A - ZSM-22/ZSM-23 composite molecular sieve and preparation method - Google Patents
ZSM-22/ZSM-23 composite molecular sieve and preparation method Download PDFInfo
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- CN1686800A CN1686800A CN 200510066975 CN200510066975A CN1686800A CN 1686800 A CN1686800 A CN 1686800A CN 200510066975 CN200510066975 CN 200510066975 CN 200510066975 A CN200510066975 A CN 200510066975A CN 1686800 A CN1686800 A CN 1686800A
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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 title claims abstract description 88
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 25
- 239000010703 silicon Substances 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 239000000084 colloidal system Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims abstract description 14
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 239000004411 aluminium Substances 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 206010013786 Dry skin Diseases 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 229910001038 basic metal oxide Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 5
- 229910052681 coesite Inorganic materials 0.000 abstract 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract 4
- 229910052682 stishovite Inorganic materials 0.000 abstract 4
- 229910052905 tridymite Inorganic materials 0.000 abstract 4
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000005216 hydrothermal crystallization Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 description 24
- 239000011734 sodium Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 17
- 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 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- 230000007935 neutral effect Effects 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a ZSM-22/ZSM-23 compound molecular sieve and its synthesis method. The aluminosiica colloid obtained by mixing silicon source, aluminium source, inorganic alkali, water and template agent and ZSM-22 molcular sieve are mixed, then molar composition of said aluminosilica colloid includes SiO2/Al2O3=60-300, R/SiO2=0.05-3, OH-/SiO2=0.05-0.5 and H2O/SiO2=10-65, and the added quantity of ZSM-22 molecular sieve is 0.01-0.6 of weight of silicon dioxide, and the template agent can be one of pyrrolidine, isopropyl amine and isobutyl amine or several kinds of them, and the obtained reaction mixture is undergone the process of hydrothermal crystallization so as to obtain the invented compound molecular sieve.
Description
Technical field
The present invention relates to a kind of composite molecular screen, specifically, relate to a kind of ZSM-22/ZSM-23 composite molecular screen.
The invention still further relates to the preparation method of above-mentioned composite molecular screen.
Background technology
Zeolite molecular sieve material has obtained widespread use and be used as catalytic material, gas delivery and sorbent material, ion-exchanger etc. at oil and natural gas processing, fine chemistry industry, environmental protection and nuclear waste disposal field because of the duct size of its uniform composition, regular structure, adjustable surface acidity and molecular size has special shape selective catalysis performance.The molecular sieve catalytic function also develops into base catalysis, soda acid double-function catalyzing, oxidation-reduction catalysis and metal catalytic etc. by simple acid catalysis effect.The basis of molecular sieve catalytic functionalization and Application Areas expansion is the exploitation of molecular sieve novel material.Therefore the synthetic work of zeolite molecular sieve has crucial meaning, designs the structure of zeolite molecular sieve artificially as required and synthesize the direction that becomes people's effort.
Nineteen seventies, the template during the employing organic amine synthesizes as molecular sieve, obtaining with ZSM-5 is the high silicon 3 D intersection duct novel molecular sieve of representative.The success of the eighties aluminum phosphate series molecular sieve is synthetic, broken the boundary that the molecular sieve component only limits to silicon, aluminium, a large amount of hetero-atom molecular-sieves occurred.These two important breakthroughs are that after this synthetic of molecular screen material novel in a large number, that have unique pore passage structure and surface properties laid a good foundation.The synthetic method of molecular sieve develops into several different methods such as non-aqueous system is synthetic, gas-solid is combined to, height is pressed into, super critical condition synthesizes, below-G conditions synthesizes also by traditional hydrothermal synthesis method, and the novel molecular sieve material continues to bring out.According to international molecular sieve association (IZA) statistics in 2003, the structure sum of molecular sieve has reached 145 kinds.
ZSM-22 molecular sieve and ZSM-23 molecular sieve are the novel high silicon Si-Al zeolite molecular sieves of people's synthetic two classes.About the document of ZSM-22 molecular sieve and ZSM-23 molecular sieve many.US4076842, US4528171 disclose the method for making the synthetic ZSM-23 molecular sieve of template with tetramethyleneimine.US6475464 discloses a kind of method with the synthetic ZSM-23 molecular sieve of ZSM-23 crystal seed.It is the method for the synthetic ZSM-22 molecular sieve of template with the diethylamine hydrochloride that US4556477 discloses a kind of.US4902406, US5707600, US5783168 disclose and have adopted 1, and the 6-hexanediamine is the method for the synthetic ZSM-22 molecular sieve of template.EP220893 has announced a kind of method of synthesizing ZSM-22 molecular sieve and ZSM-23 molecular sieve with the alcohols of organic amine and 1～6 carbon jointly as template respectively.
The ZSM-22 molecular sieve belongs to the TON topological framework, one-dimensional tunnel structure with ten-ring, port size 4.4 * 5.5 , its X-ray diffraction spectra data are as shown in table 1, also have KZ-2, NU-10, Theta-1, ISI-1 with the ZSM-22 molecular sieve belongs to the TON topological framework; The ZSM-23 molecular sieve belongs to the MTT topological framework, has the one-dimensional tunnel structure of ten-ring, port size 4.5 * 5.2 .Its X-ray diffraction spectra data are as shown in table 2, also have KZ-1, ISI-4, SSZ-32 with the ZSM-23 molecular sieve belongs to the MTT topological framework.
The X-ray diffraction spectra data of table 1, ZSM-22 molecular sieve
d/nm I/I
0
10.73 M-S
8.64 W
6.89 W
5.41 VW
4.56 VW
4.35 VS
3.66 VS
3.61 S
3.46 M
3.34 VW
2.90 VW
2.74 VW
2.52 W
2.43 VW
2.36 VW
Intensity in the table: VS-80～100%, S-60～80%, M-40～60%, W-20～40%, VW-＜20%
The X-ray diffraction spectra data of table 2, ZSM-23 molecular sieve
d/nm I/I
0
10.74 S-VS
9.88 W
7.79 M
6.07 VW
5.57 VW
5.39 W
4.90 VW
4.48 M-S
4.22 M
3.87 M
3.68 S
3.59 M-S
3.51 W
3.41 W
3.14 VW
2.82 VW
2.52 W
2.44 VW
2.38 VW
2.32 VW
Intensity in the table: VS-80～100%, S-60～80%, M-40～60%, W-20～40%, VW-＜20%
Have benefited from having the most suitable pore passage structure and stronger surface acid characteristic, this two molecular sieve analog shows very high catalytic activity and selectivity in alkene and alkane isomerization reaction, have the incomparable superiority of other catalyzer, good prospects for application is arranged.But because the nuance of pore passage structure and physico-chemical property such as surface acid intensity and acid amount etc., the effect that this two molecular sieve analog is applied to isomerization dewaxing is not quite similar again.
Simultaneously, for some reactions, lubricating oil distillate for example, owing to wherein contain very complicated component, not that identical molecule is participated in reaction, so some adaptability problems will appear for the molecular sieve with homogeneous structural, to a kind of molecule can fine coupling catalytic material, just may not be very desirable for other component.
For the normal paraffin in the lubricating oil distillate, because its condensation point is higher, cause the lubricating oil low temperature flowability poor, if only by isomerization reaction, often can not make its condensation point reach the ideal effect, and may cause viscosity index to reduce, therefore, base oil character is done the trick taking place isomerizedly simultaneously some normal paraffin components that are difficult for taking place isomerization reactions to be carried out suitable cracking.So just wish that a catalyzer has the shape of selecting cracking and isomerized multi-functional simultaneously, if adopt single molecular sieve then do not reach good effect.
Summary of the invention
The object of the present invention is to provide a kind of ZSM-22/ZSM-23 composite molecular screen.
The present invention also aims to provide the preparation method of above-mentioned ZSM-22/ZSM-23 composite molecular screen.
ZSM-22/ZSM-23 composite molecular screen provided by the invention is different from ZSM-22 and ZSM-23 molecular sieve simple physical blended composite molecular sieve, composite molecular screen has the pore passage structure characteristics and the acidic character of ZSM-23 and two kinds of molecular sieves of ZSM-22 concurrently, and so near adjacent of the different pore passage structure of two kinds of molecular sieves with different acid sites, closely to having only several nanometers, synergy between them will the most effective performance like this, and embody good synergistic, thereby embody unique catalytic performance.The two-phase proportion and the silica alumina ratio that change in the composite molecular screen by the optimising and adjustment synthesis condition obtain having the optimum pore passage structure and the composite molecular screen of proper acidic, be used for lube oil hydrotreating process, can make normal paraffin select shape cracking-isomerization reaction simultaneously, have lubricant base yield height, viscosity index height and the low characteristics of pour point.
ZSM-22/ZSM-23 composite molecular screen provided by the invention is expressed as by oxide mol ratio:
(3～450) R: (60～300) SiO
2: 1Al
2O
3: (600～7500) H
2The sial colloid of O and the reaction mixture of ZSM-22 molecular sieve, wherein the ZSM-22 molecular sieve is 0.01～0.6 of a silica weight, R is an organic amine.
The method of the above-mentioned ZSM-22/ZSM-23 composite molecular screen of preparation provided by the invention the steps include:
A) silicon source, aluminium source, mineral alkali, water and template are mixed the sial colloid that obtains, its mole consists of: SiO
2/ Al
2O
3=60～300, R/SiO
2=0.05～3, OH
-/ SiO
2=0.05～0.5, H
2O/SiO
2=10～65, R is a template;
B) add the ZSM-22 molecular sieve in the sial colloid of step a, the add-on of this molecular sieve is 0.01～0.6 of a silica weight, crystallization obtains described ZSM-22/ZSM-23 composite molecular screen under the power hydrothermal condition that boosts, wherein crystallization temperature is 100～220 ℃, crystallization time is 8～120 hours, preferred crystallization temperature is 150～180 ℃, and crystallization time is 48～96 hours;
C) after the crystallization of step b finishes, with the reaction mixture cool to room temperature, filter, get powdery product, water or organic solvent wash this powdery product, and 100～150 ℃ of dryings obtain target product.
Used template is one or more in tetramethyleneimine, Isopropylamine, the isobutylamine.
Used silicon source is gas-phase silica, silicon sol, water glass, solid silicone or amorphous silica, preferred silicon sol.
Used aluminium source is sodium aluminate, aluminum chloride, aluminum nitrate, Tai-Ace S 150, aluminium hydroxide or pseudo-boehmite, preferred sodium aluminate.
Used mineral alkali is basic metal or alkaline earth metal hydroxides, preferred sodium hydroxide.
Wherein the ZSM-22 molecular sieve of Jia Ruing is to contain the molecular screen primary powder of template or through molecular sieve or the ammonium type molecular sieve or the hydrogen type molecular sieve of roasting removed template method.
Description of drawings
Fig. 1 is the x-ray diffraction spectra (XRD) of ZSM-22/ZSM-23 composite molecular screen of the present invention.
Embodiment
The following examples will be further specified the present invention, but the present invention is not limited among the following embodiment.
Comparative Examples
Synthesizing of ZSM-22 molecular sieve
3.24 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.9 gram NaOH and 548 gram water, stirred 4 hours, add 106 gram diethyl triamine, stirred 1 hour, the silicon sol that adds 270 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=117, R/SiO
2=0.8, OH
-/ SiO
2=0.1, H
2O/SiO
2=30.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 180 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained sodium type ZSM-22 molecular sieve in 24 hours in 110 ℃ of dryings then.The X-ray diffraction data of product is as shown in table 1.
With the 80 ℃ 1M NHs of above-mentioned sodium type ZSM-22 molecular sieve 10 times of volume ratios
4Stirred 3 hours in the Cl solution, filter, wash, obtained ammonium type ZSM-22 molecular sieve in 24 hours in 110 ℃ of dryings then.
Above-mentioned ammonium type ZSM-22 molecular sieve 350 ℃ of roastings 3 hours, and is continued to obtain Hydrogen ZSM-22 molecular sieve 550 ℃ of roastings 8 hours.
Embodiment 1
4.4 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 474 gram water, stirred 4 hours, add the 15 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves then, stirred 3 hours, add 66 gram tetramethyleneimine, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, R/SiO
2=0.7, OH
-/ SiO
2=0.08, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.2 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.The X-ray diffraction spectra of product as shown in Figure 1.
Embodiment 2
6.1 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 1232 gram water, stirred 4 hours, add the 45 gram Comparative Examples synthetic Hydrogen ZSM-22 of institute molecular sieves then, stirred 3 hours, add 283 gram tetramethyleneimine, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=60, R/SiO
2=3, OH
-/ SiO
2=0.08, H
2O/SiO
2=65, the add-on of ZSM-22 molecular sieve is 0.6 of a silica weight.Stir in the autoclave of transferring to 2000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Embodiment 3
1.2 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 25.6 gram NaOH and 474 gram water, stirred 4 hours, add the 0.75 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieve then, stirred 3 hours, add 4.7 gram tetramethyleneimine, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=300, R/SiO
2=0.05, OH
-/ SiO
2=0.5, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.01 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Embodiment 4
2.1 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 474 gram water, stirred 4 hours, add the 45 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves then, stirred 3 hours, add 66 gram tetramethyleneimine, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, R/SiO
2=0.7, OH
-/ SiO
2=0.08, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.6 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 220 ℃ in 4 hours, hydrothermal crystallizing 8 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Embodiment 5
4.4 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 1 060 gram water, stirred 3 hours, add 66 gram tetramethyleneimine, stirred 4 hours, add the 15 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves then, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, R/SiO
2=0.7, OH
-/ SiO
2=0.08, H
2O/SiO
2=50, the add-on of ZSM-22 molecular sieve is 0.2 of a silica weight.Stir in the autoclave of transferring to 2000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Embodiment 6
4.4 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 20.5 gram NaOH and 474 gram water, stirred 3 hours, add 66 gram tetramethyleneimine, stirred 1 hour, and then add 261.1 grams, 30% silicon sol, and stirred 4 hours, add 15 at last and restrain the Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves and obtain initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, R/SiO
2=0.7, OH
-/ SiO
2=0.4, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.2 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Embodiment 7
4.4 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 474 gram water, stirred 4 hours, add the 15 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves then, stirred 3 hours, add 52 gram Isopropylamines, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, R/SiO
2=0.7, OH
-/ SiO
2=0.08, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.2 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Embodiment 8
4.4 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 474 gram water, stirred 4 hours, add the 15 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves then, stirred 3 hours, add 66 gram isobutylamines, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, R/SiO
2=0.7, OH
-/ SiO
2=0.08, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.2 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 180 ℃ in 4 hours, hydrothermal crystallizing 60 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Embodiment 9
4.4 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 474 gram water, stirred 4 hours, add the 15 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves then, stirred 3 hours, add 33 gram tetramethyleneimine and 27 gram Isopropylamines, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, (R1+R2)/SiO
2=0.7, OH
-/ SiO
2=0.08, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.2 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
4.4 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 474 gram water, stirred 4 hours, add the 15 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves then, stirred 3 hours, add 33 gram tetramethyleneimine and 33 gram isobutylamines, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, (R1+R2)/SiO
2=0.7, OH
-/ SiO
2=0.08, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.2 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Embodiment 11
4.4 gram NaAlO
2(Al
2O
336.3%, Na
2O32.5%) be added in the mixture of 4.1 gram NaOH and 474 gram water, stirred 4 hours, add the 15 gram Comparative Examples synthetic sodium type ZSM-22 of institute molecular sieves then, stirred 3 hours, add 33 gram isobutylamines and 27 gram Isopropylamines, stirred 1 hour, the silicon sol that adds 261.1 grams 30% at last again obtains initial colloid.Initial colloidal mole consists of: SiO
2/ Al
2O
3=83, (R1+R2)/SiO
2=0.7, OH
-/ SiO
2=0.08, H
2O/SiO
2=25, the add-on of ZSM-22 molecular sieve is 0.2 of a silica weight.Stir in the autoclave of transferring to 1000 milliliters after 12 hours, 300 rev/mins of stirring velocitys are regulated in the sealing back, begin to heat up, and are warming up to 165 ℃ in 4 hours, hydrothermal crystallizing 72 hours.After crystallization finishes, autoclave is placed the water chilling, product after filtration, wash pH to filtrate to neutral, obtained the ZSM-22/ZSM-23 composite molecular screen in 24 hours in 110 ℃ of dryings then.
Claims (8)
1. ZSM-22/ZSM-23 composite molecular screen is expressed as by oxide mol ratio:
(3～450) R: (60～300) SiO
2: 1Al
2O
3: (600～7500) H
2The sial colloid of O and the reaction mixture of ZSM-22 molecular sieve, wherein the ZSM-22 molecular sieve is 0.01～0.6 of a silica weight, R is an organic amine.
2. the method for preparing the described ZSM-22/ZSM-23 composite molecular screen of claim 1, step is:
A) silicon source, aluminium source, mineral alkali, water and template are mixed the sial colloid that obtains, its mole consists of: SiO
2/ Al
2O
3=60～300, R/SiO
2=0.05～3, OH
-/ SiO
2=0.05～0.5, H
2O/SiO
2=10～65, R is a template;
B) add the ZSM-22 molecular sieve in the sial colloid of step a, the add-on of this molecular sieve is 0.01～0.6 of a silica weight, crystallization obtains described ZSM-22/ZSM-23 composite molecular screen under the power hydrothermal condition that boosts, and wherein crystallization temperature is 100～220 ℃, and crystallization time is 8～120 hours;
C) after the crystallization of step b finishes, with the reaction mixture cool to room temperature, filter, get powdery product, 100～150 ℃ of dryings obtain target product;
Used template is one or more in tetramethyleneimine, Isopropylamine, the isobutylamine;
Used silicon source is gas-phase silica, silicon sol, water glass, solid silicone or amorphous silica;
Used aluminium source is sodium aluminate, aluminum chloride, aluminum nitrate, Tai-Ace S 150, aluminium hydroxide or pseudo-boehmite;
Used mineral alkali is basic metal or alkaline earth metal hydroxides.
3. method according to claim 2 is characterized in that, the ZSM-22 molecular sieve of adding is to contain the molecular screen primary powder of template or through molecular sieve or the ammonium type molecular sieve or the hydrogen type molecular sieve of roasting removed template method.
4. method according to claim 2 is characterized in that, the silicon source is a silicon sol.
5. method according to claim 2 is characterized in that, the aluminium source is a sodium aluminate.
6. method according to claim 2 is characterized in that, mineral alkali is a sodium hydroxide.
7. method according to claim 2 is characterized in that, the crystallization temperature of step b is 150～180 ℃, crystallization time 48～96 hours.
8. method according to claim 2 is characterized in that, powdery product water or organic solvent after filtering among the step c wash.
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