CN1281494C - Process for preparing small crystal ZSM-5 zeolite - Google Patents
Process for preparing small crystal ZSM-5 zeolite Download PDFInfo
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- CN1281494C CN1281494C CN 200410048354 CN200410048354A CN1281494C CN 1281494 C CN1281494 C CN 1281494C CN 200410048354 CN200410048354 CN 200410048354 CN 200410048354 A CN200410048354 A CN 200410048354A CN 1281494 C CN1281494 C CN 1281494C
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- China
- Prior art keywords
- zeolite
- zsm
- silica gel
- sio
- alumino silica
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 84
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000010457 zeolite Substances 0.000 title claims abstract description 84
- 239000013078 crystal Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 36
- 229960001866 silicon dioxide Drugs 0.000 claims description 36
- 239000000741 silica gel Substances 0.000 claims description 31
- 229910002027 silica gel Inorganic materials 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000009415 formwork Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 abstract description 27
- 238000001914 filtration Methods 0.000 abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 8
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 230000000887 hydrating effect Effects 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 239000011734 sodium Substances 0.000 description 22
- 229910052708 sodium Inorganic materials 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 238000006703 hydration reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 206010013786 Dry skin Diseases 0.000 description 10
- 238000013019 agitation Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 235000019353 potassium silicate Nutrition 0.000 description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002050 diffraction method Methods 0.000 description 7
- 230000036571 hydration Effects 0.000 description 7
- 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 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 4
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 239000001166 ammonium sulphate Substances 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000012224 working solution Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- -1 tetrapropyl amine bromides Chemical class 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing small crystal particle ZSM-5 zeolite. Silica-alumina granules with the SiO2/Al2O3 molar ratio of 20 to 600 and with the granularity of 20 to 300 meshes are mixed with the water solution of organic templates, the mixture is hydrothermally crystallized with or without ZSM-5 zeolite crystal seeds, and primary filtration, dryness and calcining are carried out. The method can prepare ZSM-5 zeolite with the silica-alumina molar ratio of 15 to 200 and with the primary crystal particle of 0.1 to 0.5 mum. Because the method avoids using raw materials containing sodium ions in synthetic systems, the serial processes of ammonium exchange, filtration and calcining are reduced. Thereby, the yield of zeolite products is improved, production processes are simplified, and the zeolite can obtain a good cyclohexene conversion rate when the zeolite is used for preparing cyclohexanol catalysts by hydrating cyclohexene.
Description
Technical field
The invention relates to a kind of ZSM-5 prepare zeolite method.More particularly, the invention relates to a kind of small-grain ZSM-5 prepare zeolite method that is used for preparing cyclohexanol by cyclohexene hydration reaction.
Background technology
Hexalin is a kind of important chemical product and industrial chemicals, adopts the method for cyclohexene hydration to produce more at large at present.Use therein catalyzer is mineral acid such as sulfuric acid etc. in early days, but product is lumped together with catalyzer and is difficult to separate and reclaim; Exist a large amount of side reactions to cause product to be difficult to purify in the reaction; In case the catalyzer inactivation just is difficult to regeneration.People propose to use solid catalyst instead for this reason, as ion exchange resin.But ion exchange resin bad mechanical strength, heat impedance are poor, have caused that catalyst activity is low, the life-span is low.Another kind of solid catalyst zeolite, because it has water insoluble, physical strength and heat resistanceheat resistant performance preferably, now successfully be applied in the technology of preparing cyclohexanol by cyclohexene hydration reaction, reported zeolite has mordenite, y-type zeolite, zeolite L and ZSM series zeolite.Wherein reporting more is the ZSM-5 zeolite, all is to carry out synthetic in the presence of alkalimetal ion from the synthetic method of this zeolite.
USP4,588,846 to disclose a kind of close grain ZSM-5 zeolite that adopts be the technological process of Preparation of Catalyst hexalin.As can be seen, alkali metallic sodium is contained in the silicon source of adopting in this zeolite synthesis from embodiment.
USP5,268,162 disclose a kind of ZSM-5 prepare zeolite method and the application in preparing cyclohexanol by cyclohexene hydration reaction thereof.Also contain alkali metallic sodium in the wherein synthetic mixed system.
USP4,661,639 disclose a kind of cyclohexene hydration method, wherein in the Preparation of catalysts process owing to use water glass to make raw material, also be the system of alkali metal containing sodium therefore.
USP4, employed Preparation of catalysts also uses water glass to do raw material in 879, the 422 hexalin preparations that disclose, and also is the system of alkali metal containing sodium therefore.
Up to now, all about being in the report of cyclohexene hydration catalyzer with the ZSM-5 zeolite, used zeolite synthesis is and contains the sodium system, and the zeolite product primary particle diameter that synthesizes is the close grain of≤0.5 μ m.Because have only close grain could increase near the quantity in active centre, zeolite aperture, also could increase the contact probability of tetrahydrobenzene and catalyzer, thereby reach the purpose that improves the tetrahydrobenzene transformation efficiency.Close grain prepare zeolite process is: synthetic → filtration → drying → roasting → ammonium exchange (purpose is the sodium of removing in the zeolite) → filtration → drying → roasting (purpose is the ammonium of removing in the zeolite) obtains product.Because the crystal grain of zeolite is meticulous, therefore the filtration procedure with zeolite and aqueous phase separation becomes a step the most difficult in the industrial production, and can cause the reduction of product yield in this preparation process, for suitability for industrialized production and application have increased difficulty.
Summary of the invention
Purpose of the present invention is exactly in order to solve the above-mentioned problems in the prior art, and a kind of ZSM-5 prepare zeolite method that is applicable to industrial production and is applicable to the little crystal grain of cyclohexene hydration reaction is provided.
Small-grain ZSM-5 prepare zeolite method provided by the invention is with SiO
2/ Al
2O
3Mol ratio 20～600, granularity are the aqueous solution of 20～300 purpose alumino silica gel particles and organic formwork agent, in the presence of the ZSM-5 zeolite seed crystal, make this mixture carry out hydrothermal crystallizing, promptly obtain the small-grain ZSM-5 zeolite product through once filtration, drying, roasting then.
Wherein said alumino silica gel can be according to the prior art synthetic, also can be the commercially available prod, and its impurity natrium content is with Na
2The O meter should be less than 0.2 weight %, and its pore volume is 0.4-1.0 milliliter/gram.
Wherein said organic formwork agent is selected from quaternary ammonium hydroxide and/or quaternary ammonium salt, for example tetraethyl ammonium hydroxide and/or its salt, TPAOH and/or its salt, its consumption should make in the reaction mixture that the mol ratio of contained silicon-dioxide is 0.01-0.20, preferred 0.05-0.15 in this organic formwork agent and alumino silica gel.
The consumption of water should make in the reaction mixture that the mol ratio of contained silicon-dioxide is H in the water and alumino silica gel in the said reaction mixture
2O/SiO
2=2-15.
The consumption of said ZSM-5 crystal seed should be below 10% of alumino silica gel weight, is preferably 0-5%.
Hydrothermal crystallization process to reaction mixture in the inventive method has no particular limits, and gets final product according to the method for routine.For example, can directly be warming up to 120-180 ℃, thermostatic crystallization 10-40 hour; Also can be earlier at 70-120 ℃ of constant temperature 1-10 hour, be warming up to then 150-180 ℃ constant temperature 10-50 hour again.
Drying, roasting to the final product zeolite do not have special requirement yet, get final product according to the condition of routine.For example, drying can be carried out under 80-130 ℃ 3-8 hour; Roasting can be carried out under 400-600 ℃ 1-5 hour.
It is that 15-200, elementary crystal grain particle are the ZSM-5 zeolite of 0.1-0.5 μ m that preparation method provided by the invention can make silica alumina ratio; Because this method avoids using the raw material that contains sodium ion in synthetic system, thereby ammonium exchange, filtration, a series of processes of roasting have been reduced, thereby improved the yield of zeolite product, simplified Production Flow Chart, make the original production flow process: synthetic → filtration → drying → roasting → ammonium exchange → filtration → drying → roasting, be reduced to: synthetic → filtration → drying → roasting promptly obtains product.
ZSM-5 zeolite provided by the invention can obtain tetrahydrobenzene transformation efficiency preferably as cyclohexene hydration system hexalin catalyzer the time.
Embodiment
Following example will the present invention is further illustrated, but not thereby limiting the invention.
Comparative Examples 1
This Comparative Examples is according to USP4, and 588,846 methods that provided prepare close grain ZSM-5 zeolite.
Under agitation, prepare following two kinds of working solutions respectively:
Solution A: 111 gram water glass (contain 28.8%SiO
2And 8.9%Na
2O)+138 restrain water.
Solution B: the 3.2 gram Tai-Ace S 150+32.8 gram sodium-chlor+9.3 gram vitriol oils+13.9 gram 4-propyl bromides+189 gram water.
Under agitation, solution B is added in the solution A, mix in the rearmounted autoclave, be warming up to 160 ℃ of constant temperature then 5 hours in 120 ℃ of constant temperature 72 hours.In whole crystallization process, stirring velocity is 600 rev/mins.
Crystallization finishes after the zeolite that the whizzer filtration obtains, carries out ammonium with ammoniumsulphate soln in 90 ℃ and exchanges twice after 3 hours through 5 hours, 550 ℃ roastings of 110 ℃ of dryings, exchanges 0.5 hour at every turn, and the liquid-solid ratio during exchange is 10: 1.Zeolite after the filtration promptly gets the hydration zeolite catalyst that prior art provides through 5 hours, 550 ℃ roastings of 110 ℃ of dryings 3 hours.
This zeolite product note is made D1.Through its structure of X diffraction analysis is ZSM-5 zeolite, its SiO
2/ Al
2O
3=50, its degree of crystallinity is decided to be 100%; Recording its elementary crystal grain particle dia with scanning electron microscope is 0.2 μ m.
Embodiment 1
This example illustrates small-grain ZSM-5 prepare zeolite process provided by the invention.
(1) preparation of alumino silica gel
Get 100 gram water glass and (contain 28.8%SiO
2And 8.9%Na
2O) add 10 gram sodium aluminate solutions and (contain 7.9%Al
2O
3And 12.3%Na
2O) in, stir, under agitation be added dropwise to 25% sulphuric acid soln then, to the pH value of solution be 6.With the gel of gained wash, drying, use ammonium nitrate according to silica gel again: ammonium nitrate: the weight ratio of water=1: 0.5: 10 is carried out ion-exchange, the gel after the exchange promptly obtains the required alumino silica gel of synthetic zeolite through washing, dry, 500 ℃ of roastings.
The analytical results of this alumino silica gel is: Na
2O＜0.2m%; SO
4 =＜0.1m%; SiO
2/ Al
2O
3=60; Pore volume is 0.8ml/g.
(2) small-grain ZSM-5 prepare zeolite process
The above-mentioned 80-120 purpose alumino silica gel of preparing of 40 grams is mixed with the solution of being made up of 47 gram tetrapropyl oxyammonias (concentration is 22%) and 76 gram water, stir, the mole of gained mixture consists of: SiO
2/ Al
2O
3=60, tetrapropyl oxyammonia/SiO
2=0.082, H
2O/SiO
2=10
The said mixture reactor of packing into was carried out crystallization in 30 hours in 150 ℃ of constant temperature, and crystallization is cooled to room temperature with it after finishing, after filtration, 5 hours, 550 ℃ roastings of 110 ℃ of dryings promptly got the small-grain ZSM-5 zeolite that the inventive method makes in 3 hours.
This zeolite product note is made S11.Through its structure of X diffraction analysis is ZSM-5 zeolite, its SiO
2/ Al
2O
3=51, its degree of crystallinity is 101%; Recording its elementary crystal grain particle dia with scanning electron microscope is 0.2 μ m.
Embodiment 2
This example illustrates small-grain ZSM-5 prepare zeolite process provided by the invention.
(1) preparation of alumino silica gel
Get 100 gram water glass and (contain 28.8%SiO
2And 8.9%Na
2O) add 10 gram sodium aluminate solutions and (contain 7.9%Al
2O
3And 12.3%Na
2O) in, stir, under agitation be added dropwise to 25% sulphuric acid soln then, to the pH value of solution be 9, be warming up to 80 ℃ of constant temperature 1 hour.With the gel of gained wash, drying, use ammonium nitrate according to silica gel again: ammonium nitrate: the weight ratio of water=1: 0.5: 10 is carried out ion-exchange, the gel after the exchange promptly obtains the required alumino silica gel of synthetic zeolite through washing, dry, 500 ℃ of roastings.
The analytical results of this alumino silica gel is: Na
2O＜0.2m%; SO
4 =＜0.1m%; SiO
2/ Al
2O
3=60; Pore volume is 0.52ml/g.
(2) small-grain ZSM-5 prepare zeolite process
The above-mentioned 130-250 purpose alumino silica gel of preparing of 40 grams is mixed with the solution of being made up of 47 gram tetrapropyl oxyammonias (concentration is 22%) and 76 gram water, stir, the mole of gained mixture consists of: SiO
2/ Al
2O
3=60, tetrapropyl oxyammonia/SiO
2=0.082, H
2O/SiO
2=10
The said mixture reactor of packing into was carried out crystallization in 20 hours in 5 hours, 160 ℃ constant temperature of 120 ℃ of constant temperature, after crystallization finishes it is cooled to room temperature, after filtration, 5 hours, 550 ℃ roastings of 110 ℃ of dryings promptly got the small-grain ZSM-5 zeolite that the inventive method makes in 3 hours.
This zeolite product note is made S12.Through its structure of X diffraction analysis is ZSM-5 zeolite, its SiO
2/ Al
2O
3=50, its degree of crystallinity is 98%; Recording its elementary crystal grain particle dia with scanning electron microscope is 0.22 μ m.
Comparative Examples 2
This Comparative Examples also is according to USP4, and 588,846 methods that provided prepare close grain ZSM-5 zeolite.
Under agitation, prepare following two kinds of working solutions respectively:
Solution A: 220 gram water glass (contain 28.8%SiO
2And 8.9%Na
2O)+138 restrain water.
Solution B: the 3.2 gram Tai-Ace S 150+32.8 gram sodium-chlor+9.3 gram vitriol oils+13.9 gram 4-propyl bromides+189 gram water.
Under agitation, solution B is added in the solution A, mix in the rearmounted autoclave, be warming up to 160 ℃ of constant temperature then 5 hours in 120 ℃ of constant temperature 72 hours.In whole crystallization process, stirring velocity is 600 rev/mins.
Crystallization finishes after the zeolite that the whizzer filtration obtains, carries out ammonium with ammoniumsulphate soln in 90 ℃ and exchanges twice after 3 hours through 5 hours, 550 ℃ roastings of 110 ℃ of dryings, exchanges 0.5 hour at every turn, and the liquid-solid ratio during exchange is 10: 1.Zeolite after the filtration promptly gets the hydration zeolite catalyst that prior art provides through 5 hours, 550 ℃ roastings of 110 ℃ of dryings 3 hours.
This zeolite product note is made D2.Through its structure of X diffraction analysis is ZSM-5 zeolite, its SiO
2/ Al
2O
3=98, its degree of crystallinity is decided to be 100%; Recording its elementary crystal grain particle dia with scanning electron microscope is 0.25 μ m.
Embodiment 3
This example illustrates small-grain ZSM-5 prepare zeolite process provided by the invention.
(2) preparation of alumino silica gel
Get 100 gram water glass and (contain 28.8%SiO
2And 8.9%Na
2O) add 4.7 gram sodium aluminate solutions and (contain 7.9%Al
2O
3And 12.3%Na
2O) in, stir, under agitation be added dropwise to 25% sulphuric acid soln then, to the pH value of solution be 8.With the gel of gained wash, drying, use ammonium nitrate according to silica gel again: ammonium nitrate: the weight ratio of water=1: 0.5: 10 is carried out ion-exchange, the gel after the exchange promptly obtains the required alumino silica gel of synthetic zeolite through washing, dry, 500 ℃ of roastings.
The analytical results of this alumino silica gel is: Na
2O＜0.2m%; SO
4 =＜0.1m%; SiO
2/ Al
2O
3=120; Pore volume is 0.68ml/g.
(2) small-grain ZSM-5 prepare zeolite process
The above-mentioned 50-100 purpose alumino silica gel of preparing of 40 grams is mixed with solution of being made up of 10.7 gram tetrapropyl oxyammonias (concentration is 22%), 78 gram tetraethyl-oxyammonias (concentration is 10%) and 50 gram water and 2 gram ZSM-5 crystal seeds, stir, the mole of gained mixture consists of: SiO
2/ Al
2O
3=120, tetrapropyl oxyammonia/SiO
2=0.018, tetraethyl-oxyammonia/SiO
2=0.082, H
2O/SiO
2=11
The said mixture reactor of packing into was carried out crystallization in 35 hours in 5 hours, 150 ℃ constant temperature of 120 ℃ of constant temperature, after crystallization finishes it is cooled to room temperature, after filtration, 5 hours, 550 ℃ roastings of 110 ℃ of dryings promptly got the small-grain ZSM-5 zeolite that the inventive method makes in 3 hours.
This zeolite product note is made S21.Through its structure of X diffraction analysis is ZSM-5 zeolite, its SiO
2/ Al
2O
3=100, its degree of crystallinity is 100%; Recording its elementary crystal grain particle dia with scanning electron microscope is 0.22 μ m.
Comparative Examples 3
This Comparative Examples also is according to USP4, and 588,846 methods that provided prepare close grain ZSM-5 zeolite.
Under agitation, prepare following two kinds of working solutions respectively:
Solution A: 330 gram water glass (contain 28.8%SiO
2And 8.9%Na
2O)+138 restrain water.
Solution B: the 3.2 gram Tai-Ace S 150+31.5 gram sodium-chlor+9.2 gram vitriol oils+15.2 gram 4-propyl bromides+189 gram water.
Under agitation, solution B is added in the solution A, mix in the rearmounted autoclave, be warming up to 160 ℃ of constant temperature then 5 hours in 120 ℃ of constant temperature 72 hours.In whole crystallization process, stirring velocity is 600 rev/mins.
Crystallization finishes after the zeolite that the whizzer filtration obtains, carries out ammonium with ammoniumsulphate soln in 90 ℃ and exchanges twice after 3 hours through 5 hours, 550 ℃ roastings of 110 ℃ of dryings, exchanges 0.5 hour at every turn, and the liquid-solid ratio during exchange is 10: 1.Zeolite after the filtration promptly gets the hydration zeolite catalyst that prior art provides through 5 hours, 550 ℃ roastings of 110 ℃ of dryings 3 hours.
This zeolite product note is made D3.Through its structure of X diffraction analysis is ZSM-5 zeolite, its SiO
2/ Al
2O
3=145, its degree of crystallinity is decided to be 100%; Recording its elementary crystal grain particle dia with scanning electron microscope is 0.21 μ m.
Embodiment 4
This example illustrates small-grain ZSM-5 prepare zeolite process provided by the invention.
(3) preparation of alumino silica gel
Get 10O gram water glass and (contain 28.8%SiO
2And 8.9%Na
2O) add 3.0 gram sodium aluminate solutions and (contain 7.9%Al
2O
3And 12.3%Na
2O) in, stir, under agitation be added dropwise to 25% sulphuric acid soln then, to the pH value of solution be 6.2.With the gel of gained wash, drying, use ammonium nitrate according to silica gel again: ammonium nitrate: the weight ratio of water=1: 0.5: 10 is carried out ion-exchange, the gel after the exchange promptly obtains the required alumino silica gel of synthetic zeolite through washing, dry, 500 ℃ of roastings.
The analytical results of this alumino silica gel is: Na
2O＜0.2m%; SO
4 =＜O.1m%; SiO
2/ Al
2O
3=174; Pore volume is 0.79ml/g.
(2) small-grain ZSM-5 prepare zeolite process
The above-mentioned 40-80 purpose alumino silica gel of preparing of 40 grams is mixed with solution of being made up of 5.2 gram tetrapropyl amine bromides, 114 gram tetraethyl-oxyammonias (concentration is 10%) and 26 gram water and 1 gram ZSM-5 crystal seed, stir, the mole of gained mixture consists of: SiO
2/ Al
2O
3=174, tetrapropyl amine bromide/SiO
2=0.03, tetraethyl-oxyammonia/SiO
2=0.12, H
2O/SiO
2=11
The said mixture reactor of packing into was carried out crystallization in 45 hours in 10 hours, 150 ℃ constant temperature of 110 ℃ of constant temperature, after crystallization finishes it is cooled to room temperature, after filtration, 5 hours, 550 ℃ roastings of 110 ℃ of dryings promptly got the small-grain ZSM-5 zeolite that the inventive method makes in 3 hours.
This zeolite product note is made S31.Through its structure of X diffraction analysis is ZSM-5 zeolite, its SiO
2/ Al
2O
3=150, its degree of crystallinity is 97%; Recording its elementary crystal grain particle dia with scanning electron microscope is 0.22 μ m.
Embodiment 5
This example explanation the invention provides the small-grain ZSM-5 zeolite that method makes and have catalytic performance preferably in cyclohexene hydration reaction.
Get zeolite sample D1, S11, S12 that top each embodiment and Comparative Examples make; D2, S21; Each 20 gram of D3, S31 place 300 milliliters autoclave with 60 gram water, 30 gram tetrahydrobenzene respectively, and stirring with the system cooling, is carried out gas chromatographic analysis with the organic phase on upper strata down 120 ℃ of reactions 1 hour after the reaction.Gained the results are shown in following table.
| The zeolite numbering | The tetrahydrobenzene transformation efficiency, weight % |
| D1 | 7.3 |
| S11 | 7.4 |
| S12 | 7.2 |
| D2 | 6.5 |
| S21 | 6.6 |
| D3 | 5.2 |
| S31 | 5.3 |
Claims (10)
1, a kind of small-grain ZSM-5 prepare zeolite method is with SiO
2/ Al
2O
3Mol ratio 20～600, granularity are the aqueous solution of 20～300 purpose alumino silica gel particles and organic formwork agent, make this mixture carry out hydrothermal crystallizing in the presence of the ZSM-5 zeolite seed crystal having or do not have, then through once filter, dry, roasting.
2, according to the process of claim 1 wherein that impurity natrium content is with Na in the said alumino silica gel
2The O meter should be less than 0.2 weight %, and its pore volume is 0.4-1.0 milliliter/gram.
3, according to the process of claim 1 wherein that said organic formwork agent is selected from quaternary ammonium hydroxide and/or quaternary ammonium salt, its consumption should make in the reaction mixture that the mol ratio of contained silicon-dioxide is 0.01-0.20 in this organic formwork agent and alumino silica gel.
4, according to the method for claim 3, wherein said organic formwork agent is selected from tetraethyl ammonium hydroxide and/or its salt, TPAOH and/or its salt, and its consumption should make in the reaction mixture that the mol ratio of contained silicon-dioxide is 0.05-0.15 in this organic formwork agent and alumino silica gel.
5, according to the process of claim 1 wherein that the consumption of water in the said reaction mixture should make in the reaction mixture that the mol ratio of contained silicon-dioxide is H in the water and alumino silica gel
2O/SiO
2=2-15.
6, according to the process of claim 1 wherein that the consumption of said ZSM-5 crystal seed is the 0-5% of alumino silica gel weight.
7, according to the process of claim 1 wherein that said hydrothermal crystallization process is at 120-180 ℃, finished in thermostatic crystallization 10-40 hour.
8, according to the process of claim 1 wherein that said hydrothermal crystallization process is earlier at 70-120 ℃ of constant temperature 1-10 hour, be warming up to 150-180 ℃ then and finished in constant temperature 10-50 hour again.
9, according to the process of claim 1 wherein that said drying carried out 3-8 hour under 80-130 ℃.
10, according to the process of claim 1 wherein that said roasting carried out 1-5 hour under 400-600 ℃.
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| CN101514015B (en) * | 2008-02-20 | 2011-04-27 | 中国石油化工股份有限公司 | ZSM-5/beta zeolite/MCM-23 triphase coexisting molecular sieve and method for synthesizing same |
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| CN101514015B (en) * | 2008-02-20 | 2011-04-27 | 中国石油化工股份有限公司 | ZSM-5/beta zeolite/MCM-23 triphase coexisting molecular sieve and method for synthesizing same |
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