CN105776242A - Synthesis method of ZSM-50 molecular sieve - Google Patents
Synthesis method of ZSM-50 molecular sieve Download PDFInfo
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- CN105776242A CN105776242A CN201410805945.0A CN201410805945A CN105776242A CN 105776242 A CN105776242 A CN 105776242A CN 201410805945 A CN201410805945 A CN 201410805945A CN 105776242 A CN105776242 A CN 105776242A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 73
- 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 73
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 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 abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 129
- 239000000377 silicon dioxide Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000013078 crystal Substances 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 238000003786 synthesis reaction Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000010189 synthetic method Methods 0.000 claims description 14
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 238000009415 formwork Methods 0.000 claims description 4
- 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 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 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 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 22
- 230000032683 aging Effects 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 description 42
- 229910052906 cristobalite Inorganic materials 0.000 description 42
- 229910052682 stishovite Inorganic materials 0.000 description 42
- 229910052905 tridymite Inorganic materials 0.000 description 42
- 238000003756 stirring Methods 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 229910052593 corundum Inorganic materials 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 7
- 229910000632 Alusil Inorganic materials 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 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
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009432 framing Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 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 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the technical field of catalysts, and relates to a synthesis method of a ZSM-50 molecular sieve. The preparation process comprises the following steps: firstly, mixing sodium metaaluminate and a silicon source in a reaction kettle, then adding a template agent and a pH regulator, aging, crystallizing at a certain temperature, and finally carrying out suction filtration, washing, drying and roasting to obtain the ZSM-50 molecular sieve. The synthesized ZSM-50 molecular sieve has a silica-alumina ratio of more than 30.0 and an average particle size of not more than 2 microns. The invention has the advantages that: the ZSM-50 molecular sieve synthesized by the method has large specific surface area, good thermal stability and hydrothermal stability, adopts cheap industrial raw materials and has industrial application prospect.
Description
Technical field
The present invention is the preparation method about a kind of ZSM-50 molecular sieve.More specifically, the present invention is about a kind of method using bi-quaternary ammonium salt to prepare ZSM-50 molecular sieve as template.
Background technology
ZSM-50 molecular sieve is a kind of molecular sieve with EUO framing structure, has ten-ring passage and the pore passage structure of twelve-ring side pocket.This structure makes it represent the performance of excellence in this important chemical reaction of toluene disproportionation dimethylbenzene.For the synthesis of ZSM-50 molecular sieve, generally use organic ammonium salt as template.No matter organic formwork agent gained molecular sieve has very big adaptability and motility at the silica alumina ratio of product.From current patent and document, although it is a lot of for the report of ZSM-50 molecular sieve to relate to organic ammonium salt, but the stray crystal of the ZSM-12 of meeting generating section in most building-up process, and also grain size distribution is wider.
Chinese invention patent application CN1840474A, disclose a kind of method synthesizing NaY molecular sieve, the method includes being directed to the Alusil that agent, silicon source, aluminum source and water are formed, mix homogeneously with a kind of organic compound again, then through aging and crystallization process, it is characterised in that described organic compound is X (R) selected from formula3-(CH2)n-N(R)3The organic diammonium compound of X, wherein X is halogen, and R is methyl or ethyl, 6≤n≤18, its addition in mol, account for Al in Alusil2O3Molal quantity 0.5%～20%.
The method is made up of following step:
(1) according to mole composition (9～36) Na2O:Al2O3(8～21) SiO2(100～800) H2O prepares directed agents；
(2) it is directed to agent with silicon source, aluminum source and water mix homogeneously at 40 DEG C～90 DEG C, obtains mole consisting of (2.0～5.0) Na2O:Al2O3(7～20) SiO2: (100～600) H2The Alusil of O, the wherein Al in directed agents2O3Account for the total Al of gained mixture2O31～20 weight % of amount；
(3) adding organic diammonium compound in the Alusil of (2), its addition accounts for Al in Alusil2O3The 0.5%～20% of molal quantity；
(4) by (3) gained Alusil aging 2 hours～50 hours, then crystallization 8 hours～60 hours reclaim product at 90 DEG C～120 DEG C at 0 DEG C～90 DEG C.
The method of synthesis NaY molecular sieve that this application for a patent for invention provides, when not changing other physico-chemical parameter, synthesized by the product molecule sifter device that obtains have the feature of little crystal grain.
This application for a patent for invention is disclosed that a kind of method synthesizing NaY molecular sieve, the framing structure of NaY is (FAU, the pore passage structure of 3 D stereo, there is the supercage structure of twelve-ring), and the skeleton structure type of ZSM-50 (EU-1, the structure of the subsidiary twelve-ring side pocket in one-dimensional ten-ring duct).The ZSM-50 Zeolite synthesis method of present patent application, although there is similar part with the kind of template with above-mentioned patent in raw material, but technically there is this qualitative difference: (1) NaY and ZSM-5 architectural difference is big, the formula of Zeolite synthesis and condition are unique, do not have mutual reference；(2) synthesis of NaY needs to adopt directed agents, and the synthesis of ZSM-50 molecular sieve have employed crystal seed in conjunction with specific hydrothermal condition., there is, in existing bibliographical information, the problem that stray crystal is more in the synthesis of ZSM-50, the technology of this patent can realize high-crystallinity and the molecular sieve without stray crystal.
Summary of the invention
The technical scheme is that for the shortcoming that the molecular sieve stray crystal overcoming the synthesis existed in prior art is more, and a kind of process introducing crystal seed induction Hydrothermal Synthesis is provided, it is adaptable to the preparation method producing degree of crystallinity height, even grain size and the ZSM-50 molecular sieve without stray crystal.
Technical scheme:
The synthetic method of a kind of ZSM-50 molecular sieve, the method specifically comprises the following steps that
The first step: with bi-quaternary ammonium salt [(CH3)3N(CH2)nN(CH3)3]Br2(n=5～7) are template, after a certain proportion of silicon source, aluminum source, sodium hydroxide, template and water being mixed by a certain percentage, by introducing crystal seed, adopt hydrothermal crystallization method synthesis ZSM-50 molecular sieve；
Second step: filter, reclaim molecular sieve；
3rd step: ammonium exchange removes the sodium on molecular sieve；
4th step: filtration, dry, roasting.
Described silicon source is one or more in silochrom, gas-phase silica, tetraethyl orthosilicate, Ludox, waterglass, solid silicone or amorphous silica.
The described preferred Ludox in silicon source.
Described aluminum source is one or more in sodium aluminate, aluminum nitrate, aluminum sulfate, aluminium hydroxide or boehmite.
The described preferred sodium aluminate in aluminum source.
Described crystal seed is ZSM-50 molecular sieve, and the mass ratio of its consumption and silicon dioxide is 0.01～0.1.
The mol ratio of described organic formwork agent and silicon dioxide is 0.05～0.20.
The consumption of described sodium hydroxide should make the mol ratio of sodium oxide and silicon dioxide be 0.02～0.2.
The consumption of described water should make the mol ratio of water and silicon dioxide in reactant mixture be 10～50.
Described hydrothermal crystallizing synthesis temperature is 150 DEG C～200 DEG C, crystallization time 1～7 day.
Beneficial effects of the present invention:
The present invention compared with prior art has the feature that
(1) skeleton structure type (EU-1 of ZSM-50, the one-dimensional ten-ring duct structure with twelve-ring side pocket), and the framing structure of NaY is (FAU, the pore passage structure of 3 D stereo, there is the supercage structure of twelve-ring), there is this qualitative difference in formula and the condition of two kinds of great Zeolite synthesis of architectural difference；
(2) NaY cannot change into ZSM-50, the synthesizing formula of NaY molecular sieve and synthesis condition are the synthesis not being suitable for ZSM-50, and at present academic and industrial quarters was never reported the synthesizing formula utilizing a certain molecular sieves and method and then developed the example of molecular sieve of another kind of new structure on this basis；
(3) Zeolite synthesis condition uniqueness and what specificity was well recognized as；
(4) synthesis of NaY needs to adopt directed agents；And the synthesis of ZSM-50 molecular sieve needs crystal seed, then in conjunction with specific hydrothermal condition, here it is the most significant technical difference；
(5), there is the problem that stray crystal is more in the synthetic method of existing ZSM-50, the technology of this patent can realize high-crystallinity and the molecular sieve without stray crystal from bibliographical information.
Preparation method provided by the invention can prepare silica alumina ratio more than 30, the ZSM-50 molecular sieve that product degree of crystallinity is higher.Compared with prior art, the inventive method owing to introducing crystal seed in synthetic system, thus avoids the generation of stray crystal, and molecular sieve product yield is high, even grain size.
Accompanying drawing explanation
This specification has 3 width accompanying drawings.
Fig. 1. for the X-ray diffractogram of the ZSM-50 molecular sieve of embodiment 1 preparation；
Fig. 2. for the scanning electron microscope (SEM) photograph of the ZSM-50 molecular sieve of embodiment 1 preparation；
Fig. 3. for the synthetic method block diagram of the ZSM-50 molecular sieve of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are further described:
As it is shown on figure 3, the preparation method of ZSM-50 molecular sieve provided by the invention is:
The first step: with bi-quaternary ammonium salt [(CH3)3N(CH2)nN(CH3)3]Br2(n=5～7) are template, after a certain proportion of silicon source, aluminum source, sodium hydroxide, template and water being mixed by a certain percentage, by introducing crystal seed, adopt hydrothermal crystallization method synthesis ZSM-50 molecular sieve；
Second step: filter, reclaim molecular sieve；
3rd step: ammonium exchange removes the sodium on molecular sieve；
4th step: filtration, dry, roasting.
Silicon source described in offer method of the present invention is one or more in silochrom, gas-phase silica, tetraethyl orthosilicate, Ludox, waterglass, solid silicone or amorphous silica, wherein preferred Ludox.
Aluminum source described in offer method of the present invention is one or more in sodium aluminate, aluminum nitrate, aluminum sulfate, aluminium hydroxide or boehmite, wherein preferred sodium aluminate.
Crystal seed described in offer method of the present invention is ZSM-50 molecular sieve, and the mass ratio of its consumption and silicon dioxide is 0.01～0.1.
The mol ratio of organic formwork agent described in offer method of the present invention and silicon dioxide is 0.05～0.20.
The consumption of sodium hydroxide described in offer method of the present invention should make the mol ratio of sodium oxide and silicon dioxide be 0.02～0.2.
The consumption of water described in offer method of the present invention should make the mol ratio of water and silicon dioxide in reactant mixture be 10～50.
Hydrothermal crystallizing synthesis temperature described in offer method of the present invention is 150 DEG C～200℃, crystallization time 1～7 day.
In the inventive method, the ammonium exchange process for molecular sieve has no particular limits, and conventionally carries out.Such as, the ammonium salt of use can select ammonium nitrate, ammonium chloride, ammonium acetate etc., according to molecular sieve: ammonium salt: the weight ratio of water=1:0.2～1:5～10 exchanges 1～2 time, exchanges 0.5～1 hour at 80 DEG C every time.
Drying end product, roasting is also without special requirement, and condition conventionally carries out.Such as, dry and can carry out 3～8 hours at 80 DEG C～120 DEG C；Roasting can carry out 1～5 hour at 400 DEG C～600 DEG C.
Below by way of specific embodiment, the present invention will be described in detail, but the present invention is not limited only to following embodiment.
Embodiment 1:
10.0gNaOH fully dissolve with 400.0g deionized water, it is added thereto to 4.8g crystal seed (NaZSM-50 molecular sieve), is stirred vigorously 4h and obtains seed-solution A；
10.0gNaOH be dissolved in 320.0g deionized water, add 145.0g template [(CH3)3N(CH2)6N(CH3)3]Br2And 10.1gNaAlO2, stirring, to being completely dissolved, obtains solution B；
Solution B is under agitation slowly added dropwise in solution A, stirs 3h under room temperature, obtain mixed liquor C；
Being slowly added dropwise with vigorous stirring in mixed liquor C by 400.0g Ludox, obtain silica-alumina gel, gel mol ratio is: SiO2/Al2O3=60, H2O/SiO2=20, SDA/SiO2=0.15, Na2O/SiO2=0.11, wherein the consumption of crystal seed is SiO2The 3.0wt.% of consumption, loads after ageing 12h in 1L reactor under room temperature, at 180 DEG C of temperature, and static crystallization 5d.
After crystallization terminates, cold water is quenched to room temperature, with deionized water wash sucking filtration to neutral, dry at 120 DEG C, obtains ZSM-50 molecular sieve powder.
As shown in Figure 1, product SEM schemes as shown in Figure 2 product X RD spectrogram.
Embodiment 2:
10.0gNaOH fully dissolve with 400.0g deionized water, it is added thereto to 4.8g crystal seed (NaZSM-50 molecular sieve), is stirred vigorously 4h and obtains seed-solution A；
14.4gNaOH be dissolved in 800.0g deionized water, add 145.0g template [(CH3)3N(CH2)6N(CH3)3]Br2And 10.1gNaAlO2, stirring, to being completely dissolved, obtains solution B；
Solution B is under agitation slowly added dropwise in solution A, stirs 3h under room temperature, obtain mixed liquor C；
Being slowly added dropwise with vigorous stirring in mixed liquor C by 160.0g silochrom, obtain silica-alumina gel, gel mol ratio is: SiO2/Al2O3=60, H2O/SiO2=25, SDA/SiO2=0.15, Na2O/SiO2=0.15, wherein the consumption of crystal seed is SiO2The 3.0wt.% of consumption, loads after ageing 12h in 1L reactor under room temperature, at 180 DEG C of temperature, and static crystallization 7d.
After crystallization terminates, cold water is quenched to room temperature, with deionized water wash sucking filtration to neutral, dry at 120 DEG C, obtains ZSM-50 molecular sieve powder.
Embodiment 3:
10.0gNaOH fully dissolve with 400.0g deionized water, it is added thereto to 4.8g crystal seed (NaZSM-50 molecular sieve), is stirred vigorously 4h and obtains seed-solution A；
14.4gNaOH be dissolved in 800.0g deionized water, add 145.0g template [(CH3)3N(CH2)6N(CH3)3]Br2And 10.1gNaAlO2, stirring, to being completely dissolved, obtains solution B；
Solution B is under agitation slowly added dropwise in solution A, stirs 3h under room temperature, obtain mixed liquor C；
Being slowly added dropwise with vigorous stirring in mixed liquor C by 160.0g gas-phase silica, obtain silica-alumina gel, gel mol ratio is: SiO2/Al2O3=60, H2O/SiO2=25, SDA/SiO2=0.15, Na2O/SiO2=0.15, wherein the consumption of crystal seed is SiO2The 3.0wt.% of consumption, loads after ageing 12h in 1L reactor under room temperature, at 180 DEG C of temperature, and static crystallization 5d.
After crystallization terminates, cold water is quenched to room temperature, with deionized water wash sucking filtration to neutral, dry at 120 DEG C, obtains ZSM-50 molecular sieve powder.
Embodiment 4:
10.0gNaOH fully dissolve with 400.0g deionized water, it is added thereto to 4.8g crystal seed (NaZSM-50 molecular sieve), is stirred vigorously 4h and obtains seed-solution A；
14.4gNaOH be dissolved in 320.0g deionized water, it is separately added into 77.2g template [(CH3)3N(CH2)6N(CH3)3]Br2And 10.1gNaAlO2, stirring, to being completely dissolved, obtains solution B；
Solution B is under agitation slowly added dropwise in solution A, stirs 3h under room temperature, obtain mixed liquor C；
Being slowly added dropwise with vigorous stirring in mixed liquor C by 400.0g Ludox, obtain silica-alumina gel, gel mol ratio is: SiO2/Al2O3=60, H2O/SiO2=25, SDA/SiO2=0.08/0.13/0.20, Na2O/SiO2=0.11, wherein the consumption of crystal seed is SiO2The 3.0wt.% of consumption, loads after ageing 12h in 1L reactor under room temperature, at 180 DEG C of temperature, and static crystallization 5d.
After crystallization terminates, cold water is quenched to room temperature, with deionized water wash sucking filtration to neutral, dry at 120 DEG C, obtains ZSM-50 molecular sieve powder.
Embodiment 5:
10.0gNaOH fully dissolve with 400.0g deionized water, it is added thereto to 4.8g crystal seed (NaZSM-50 molecular sieve), is stirred vigorously 4h and obtains seed-solution A；
14.4gNaOH be dissolved in 320.0g deionized water, it is separately added into 125.5g template [(CH3)3N(CH2)6N(CH3)3]Br2And 10.1gNaAlO2, stirring, to being completely dissolved, obtains solution B；
Solution B is under agitation slowly added dropwise in solution A, stirs 3h under room temperature, obtain mixed liquor C；
Being slowly added dropwise with vigorous stirring in mixed liquor C by 400.0g Ludox, obtain silica-alumina gel, gel mol ratio is: SiO2/Al2O3=60, H2O/SiO2=25, SDA/SiO2=0.08/0.13/0.20, Na2O/SiO2=0.11, wherein the consumption of crystal seed is SiO2The 3.0wt.% of consumption, loads after ageing 12h in 1L reactor under room temperature, at 180 DEG C of temperature, and static crystallization 5d.
After crystallization terminates, cold water is quenched to room temperature, with deionized water wash sucking filtration to neutral, dry at 120 DEG C, obtains ZSM-50 molecular sieve powder.
Embodiment 6:
10.0gNaOH fully dissolve with 400.0g deionized water, it is added thereto to 4.8g crystal seed (NaZSM-50 molecular sieve), is stirred vigorously 4h and obtains seed-solution A；
14.4gNaOH be dissolved in 320.0g deionized water, it is separately added into 193.1g template [(CH3)3N(CH2)6N(CH3)3]Br2And 10.1gNaAlO2, stirring, to being completely dissolved, obtains solution B；
Solution B is under agitation slowly added dropwise in solution A, stirs 3h under room temperature, obtain mixed liquor C；
Being slowly added dropwise with vigorous stirring in mixed liquor C by 400.0g Ludox, obtain silica-alumina gel, gel mol ratio is: SiO2/Al2O3=60, H2O/SiO2=25, SDA/SiO2=0.08/0.13/0.20, Na2O/SiO2=0.11, wherein the consumption of crystal seed is SiO2The 3.0wt.% of consumption, loads after ageing 12h in 1L reactor under room temperature, at 180 DEG C of temperature, and static crystallization 5d.
After crystallization terminates, cold water is quenched to room temperature, with deionized water wash sucking filtration to neutral, dry at 120 DEG C, obtains ZSM-50 molecular sieve powder.
Embodiment 7:
15.0gNaOH fully dissolve with 400.0g deionized water, it is added thereto to 8.0g crystal seed (NaZSM-50 molecular sieve), is stirred vigorously 4h and obtains seed-solution A；
14.9gNaOH be dissolved in 320.0g deionized water, add 144.8g template [(CH3)3N(CH2)6N(CH3)3]Br2And 6.0gNaAlO2, stirring, to being completely dissolved, obtains solution B；
Solution B is under agitation slowly added dropwise in solution A, stirs 3h under room temperature, obtain mixed liquor C；
Being slowly added dropwise with vigorous stirring in mixed liquor C by 400.0g Ludox, obtain silica-alumina gel, gel mol ratio is: SiO2/Al2O3=100, H2O/SiO2=20, SDA/SiO2=0.15, Na2O/SiO2=0.15, wherein the consumption of crystal seed is SiO2The 5.0wt.% of consumption, loads after ageing 12h in 1L reactor under room temperature, at 180 DEG C of temperature, and static crystallization 3d.
After crystallization terminates, cold water is quenched to room temperature, with deionized water wash sucking filtration to neutral, dry at 120 DEG C, obtains ZSM-50 molecular sieve powder.
Embodiment 8:
15.0gNaOH fully dissolve with 500g deionized water, it is added thereto to 12.0g crystal seed (NaZSM-50), after being stirred vigorously 4h, obtains seed-solution A；
14.9gNaOH be dissolved in 580g deionized water, add 217.2g template [(CH3)3N(CH2)6N(CH3)3]Br2And 15.1gNaAlO2, stirring, to being completely dissolved, obtains solution B；
Solution B is under agitation slowly added dropwise in solution A, stirs 5h under room temperature, obtain mixed liquor C；
Being slowly added dropwise with vigorous stirring in mixed liquor C by 600.0g Ludox, obtain silica-alumina gel, gel mol ratio is: SiO2/Al2O3=60, H2O/SiO2=20, SDA/SiO2=0.15, Na2O/SiO2=0.11, wherein the consumption of crystal seed is SiO2The 5.0wt.% of consumption, loads 2L with in churned mechanically reactor under room temperature after being stirred vigorously 12h, regulating rotating speed is 80 revs/min, is warming up to 180 DEG C in 1h, crystallization 5.5d under stirring at 180 DEG C.
After crystallization terminates, cold water is quenched to room temperature, with deionized water wash sucking filtration to neutral, dry at 120 DEG C, obtains ZSM-50 molecular sieve powder.
Can being drawn by above-described embodiment, preparation method provided by the invention can prepare silica alumina ratio more than 30, the ZSM-50 molecular sieve that product degree of crystallinity is higher.Compared with prior art, the inventive method owing to introducing crystal seed in synthetic system, thus avoids the generation of stray crystal, and molecular sieve product yield is high, even grain size.
Claims (10)
1. the synthetic method of a ZSM-50 molecular sieve, it is characterised in that: the method specifically comprises the following steps that
The first step: with bi-quaternary ammonium salt [(CH3)3N(CH2)nN(CH3)3]Br2, wherein n=5～7 are template, after a certain proportion of silicon source, aluminum source, sodium hydroxide, template and water being mixed by a certain percentage, by introducing crystal seed, adopt hydrothermal crystallization method synthesis ZSM-50 molecular sieve；
Second step: filter, reclaim molecular sieve；
3rd step: ammonium exchange removes the sodium on molecular sieve；
4th step: filtration, dry, roasting.
2. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: described silicon source is one or more in silochrom, gas-phase silica, tetraethyl orthosilicate, Ludox, waterglass, solid silicone or amorphous silica.
3. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: the described preferred Ludox in silicon source.
4. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: described aluminum source is one or more in sodium aluminate, aluminum nitrate, aluminum sulfate, aluminium hydroxide or boehmite.
5. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: the described preferred sodium aluminate in aluminum source.
6. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: described crystal seed is ZSM-50 molecular sieve, and the mass ratio of its consumption and silicon dioxide is 0.01～0.1.
7. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: the mol ratio of described organic formwork agent and silicon dioxide is 0.05～0.20.
8. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: the consumption of described sodium hydroxide should make the mol ratio of sodium oxide and silicon dioxide be 0.02～0.2.
9. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: the consumption of described water should make the mol ratio of water and silicon dioxide in reactant mixture be 10～50.
10. the synthetic method of a kind of ZSM-50 molecular sieve according to claim 1, it is characterised in that: described hydrothermal crystallizing synthesis temperature is 150 DEG C～200 DEG C, crystallization time 1～7 day.
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| CN108996517A (en) * | 2018-08-20 | 2018-12-14 | 中触媒新材料股份有限公司 | A kind of multi-stage porous and wide silica alumina ratio EU-1 molecular sieve and preparation method thereof |
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