CN1332759C - Method for preparing ZSM-5 and beta zeolite mixed crystal material - Google Patents
Method for preparing ZSM-5 and beta zeolite mixed crystal material Download PDFInfo
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- CN1332759C CN1332759C CNB2004100009591A CN200410000959A CN1332759C CN 1332759 C CN1332759 C CN 1332759C CN B2004100009591 A CNB2004100009591 A CN B2004100009591A CN 200410000959 A CN200410000959 A CN 200410000959A CN 1332759 C CN1332759 C CN 1332759C
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- 239000013078 crystal Substances 0.000 title claims abstract description 69
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 49
- 239000010457 zeolite Substances 0.000 title claims abstract description 49
- 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 48
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 9
- 150000007522 mineralic acids Chemical class 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- BPLYVSYSBPLDOA-GYOJGHLZSA-N n-[(2r,3r)-1,3-dihydroxyoctadecan-2-yl]tetracosanamide Chemical group CCCCCCCCCCCCCCCCCCCCCCCC(=O)N[C@H](CO)[C@H](O)CCCCCCCCCCCCCCC BPLYVSYSBPLDOA-GYOJGHLZSA-N 0.000 claims description 2
- -1 tetraethyl ammonium halide Chemical class 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
- 239000002808 molecular sieve Substances 0.000 abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 10
- 206010013786 Dry skin Diseases 0.000 description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005899 aromatization reaction Methods 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 239000000320 mechanical mixture Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 238000011068 loading method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000007725 thermal activation Methods 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 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
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- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The present invention discloses a preparation method of a mixed crystal material of ZSM-5 zeolite and beta zeolite, which is characterized in that the mixed crystal material is prepared by that a ZSM-5 molecular sieve as a crystal seed is added to a synthesis reaction mixture of beta zeolite, and then, hydrothermally crystallized. The mixed crystal material synthesized by the method has adjustable mixed crystal ratio and has catalytic performance better than that of a mixed crystal material prepared by the mechanical mix of ZSM-5 zeolite and beta zeolite.
Description
Technical field
The invention relates to a kind of preparation method of mixed crystal material, further say the preparation method who the invention relates to a kind of ZSM-5 and β zeolite mixed crystal material.
Background technology
Along with to the improving constantly of the quality requirement of chemical products, the catalytic performance of zeolite catalysis material is also had higher requirement.People have arrived certain degree of depth for the exploration of single structure zeolite, for the performance that makes the zeolite catalysis material has more improvement, are fit to commercial Application better, and the mixed crystal catalysis material of exploring multiple structure type is a new approach.
In oil refining and petrochemical industry, β zeolite and ZSM-5 are widely used two kinds of catalysis materials, and they itself exist many distinctive advantages and unsurmountable shortcoming.As special pore passage structure of ZSM-5 molecular sieve and good heat and hydrothermal stability, make it have unique catalytic performance, but because its scarce limit on structure and aperture makes heavy ends can not enter this molecular sieve, product produces and is difficult for spreading out in some reaction; The β zeolite is that good heat, hydrothermal stability are arranged, appropriateness acidity and absolute acid stability, unique mesoporous molecular sieve with intersection 12-membered ring channel system, its catalytic reaction shows the characteristics that hydrocarbon reaction is difficult for coking and long service life, and reactant and product there is certain shape feature of selecting, product is distributed with certain influence, but needs strong acid catalytic reaction acid strength not enough those, and its synthetic cost height.
Consider that ZSM-5 and β zeolite microcosmic mix the interaction that may exist, utilize they separately advantage and overcome its shortcoming, may have some characteristic that is beneficial to catalytic reaction.Therefore, synthesizing in oil refining and petrochemical industry of ZSM-5/ β zeolite mixed crystal material has very important significance for theories and practical significance.
Synthetic about the mixed crystal material of different types of structure has following document to report.
At Microporous Mater.1996, reported the synthetic of FAU/MCM-41 mixed crystal catalyst among the 6:287..In Chem.Commun.1997:2281, reported the synthetic of composite catalyst MCM-41/MFI mixed crystal system and characterized.
(Li Fuxiang, Wu Lan, Qin Menggeng etc. such as Li Fuxiang, Wu Lan, Qin Menggeng, mesopore MCM-41 molecular sieve is in the research of micro porous molecular sieve outgrowth on micro-pore zeolite ZSM-5, the chemistry of fuel journal, 1998,26 (2): 102-107) once designed mesopore-micropore molecular sieve composite material that a kind of plan is used for macromolecular reaction, so outgrowth on micro-pore zeolite ZSM-5 is studied to mesopore MCM-41 molecular sieve.
(volume such as Duan Qiwei such as the yellow upright people in 1998, Chen Haiying, the 9th national catalysis academic meeting paper collection, p500) with the organic formwork agent tetrapropyl amine bromide (TPBr) that synthesizes ZSM-5, keep inducing under stable temperature and the certain pH value condition amorphous aluminum silicide in the hole wall to carry out crystalline phase arranges in the mesopore duct, the even mesopore that existing aperture is bigger has the highly acid composite MCM-41/ZSM-5 of microporous crystal structure again.
The catalyst ZSM/AlPO that people such as Chih-Hao Mark Tsang of ABB AB and Pel-shing Eugene Dal are extensively used two discussion
4Be synthesized together (Chih-Hao MarkTsang, Pel-shing Eugene Dal.Binary Molecular Sieves Having A Core andShell of Different Structures and Compositions.USA 5888921,1999).
At J.Mater.Chem, 2001,11 (7), the Beta/MCM-41 synthetic method of 1886-1890. report is to use tetraethyl ammonium hydroxide and softex kw, by two step crystallization hydro-thermal methods.
" (several molecular sieves change the control of brilliant and mixed crystal and the optimization of single crystal is synthesized " (catalysis journal, in July, 2002, Vol.23 (4)) in, reported with hexamethylene imine and done the template agent, under the certain situation of charge ratio, reaction temperature and reaction time, ZSM 5 to MCM 22, the influence of ZSM 35 and mordenite molecular sieve finished product.Simultaneously, this article has also been inquired into the influence of the adding of crystal seed to the product crystalline phase. by the conditioned reaction temperature and time, in specific temperature and time interval, can synthesize the controlled ZSM35/MCM of ratio 22 mixed crystal, ZSM 5/ZSM 35 mixed crystal and ZSM 35/ modenite mixed crystal.
Do not see report so far about ZSM-5 and β zeolite mixed crystal material preparation method.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of ZSM-5 and β zeolite mixed crystal material.
The preparation method of ZSM-5 provided by the invention and β zeolite mixed crystal material is characterized in that the ZSM-5 molecular sieve is added in the synthesis reaction mixture of β zeolite as crystal seed, forms through hydrothermal crystallizing.
More particularly, synthetic method provided by the invention is according to the aluminium source: (15～100) silicon source: (0～100) inorganic base: (1.5～30) template agent: (0～20) fluoride: (270～3200) water: the mole of the β zeolite synthetic reaction system of (0～20) inorganic acid is formed, mix with ZSM-5 as crystal seed, wherein inorganic acid and inorganic base do not use simultaneously, in closed container, synthesize under the conventional hydrothermal crystallizing condition then and the recovery product, wherein, in the mole composition formula, the aluminium source is with Al
2O
3Meter, silicon source are with SiO
2Meter, the weight of said ZSM-5 as crystal seed is 2～100%, preferred 5～80% of β zeolite synthetic reaction system butt weight.
In method provided by the invention, the addition sequence of raw material there is no special requirement, but wherein preferred raw material addition sequence is earlier inorganic base or acid, template agent, fluoride, deionized water to be mixed, and adds ZSM-5, under agitation adds aluminium source, silicon source again.
In method provided by the invention, said aluminium source, silicon source, fluoride, template agent and raw materials such as inorganic base, inorganic acid there is no special requirement, the raw material that can synthesize the β zeolite in the prior art can be applied to the present invention, for example, said aluminium source is selected from least a in the group that boehmite, sodium aluminate or aluminum sulfate forms; Said silicon source is waterglass and/or Ludox; Said fluoride is alkali-metal fluoride or ammonium fluoride or its mixture, and in alkali-metal fluoride, preferred fluorinated sodium; Said inorganic base is selected from least a in the group that NaOH, potassium hydroxide or ammoniacal liquor forms, and said inorganic acid is sulfuric acid or hydrochloric acid; Said template agent is selected from tetraethyl ammonium hydroxide, tetraethyl ammonium halide, TPAOH or its mixture.
In the method provided by the invention, said conventional hydrothermal crystallizing condition generally is 100 ℃～200 ℃ crystallization 3～7 days.
Method provided by the invention has the following advantages:
(1) because ZSM-5 be linear relationship (Fig. 1) as crystal seed adding ratio fashionable and in mixed crystal material substantially, so the ratio of ZSM-5 and β zeolite can be regulated easily by the metering to adding ZSM-5 crystal seed in the mixed crystal material.
(2) compare with the resulting mixed crystal material of β zeolite with mechanical mixture ZSM-5, interact because ZSM-5 wherein and β zeolite microcosmic mix or exist.Identical at two kinds of zeolite proportions, for example respectively account under the situation of 50 weight %, the invention provides the synthetic mixed crystal material of method all is better than mechanical mixed crystal material in the isomerization of meta-xylene disproportionation, aromatization of methanol, toluene disproportionation performance evaluation.
Description of drawings
The graph of a relation of ZSM-5 content and the ZSM-5 crystal seed that added in the mixed crystal material that Fig. 1 is synthesized for embodiment 1～4.
Fig. 2 is the XRD spectra of the ZSM-5 molecular sieve DB-2 that synthesizes of synthetic β zeolite DB-1 of embodiment 1～4 mixed crystal material A1, the A2 that add different amount ZSM-5 molecular sieves and synthesize, A3, A4 and Comparative Examples 1 and Comparative Examples 2.
The specific embodiment
Following example will give further instruction to method provided by the invention, but therefore not limit the present invention.
Among the embodiment, synthetic raw materials used middle tetraethyl oxyammonia, Ludox, waterglass are technical grade, and other is SILVER REAGENT.
In the mixed crystal material, the relative amount of ZSM-5 and β zeolite carries out quantitative analysis by XRD spectra.
Earlier respectively preparation to contain the ZSM-5 mass percent be 20%, 40%, 50%, 60%, 80% the mixed ZSM-5/ β zeolite of machinery, it is carried out XRD analysis, be the x axle with the diffracted intensity of its characteristic peak, be the y axle with its mass percent, make working curve.The ZSM-5/ β zeolite mixed crystal that is synthesized is also carried out XRD analysis, to the working curve of being done, find out its corresponding mass percent, can obtain the mass percent of ZSM-5 in the ZSM-5/ β zeolite mixed crystal by its diffracted intensity.
Comparative Examples 1
This Comparative Examples explanation β prepare zeolite.
Sulfuric acid solution and the 13.5mL deionized water of 0.6g sodium fluoride, 29.5g tetraethyl oxyammonia solution (15%, technical grade), 2.2g 20% are mixed, under mechanical agitation, add the 0.5g sodium aluminate again, be stirred to evenly, add 19.7g Ludox (technical grade) again, continue to be stirred to evenly, move into reactor then, in 140 ℃ of crystallization 6 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the β zeolite powder, numbering DB-1.
Comparative Examples 2
The explanation of this Comparative Examples is as the preparation of the ZSM-5 of crystal seed.
26.8g waterglass and 37.4g deionized water are mixed, under mechanical agitation, slowly add the 13.3g aluminum sulfate solution again and become glue, the sulfuric acid solution that adds 4.7g 20% again, the back that stirs fast adds 0.30g NaZSM-5 crystal seed, and is again that its strong agitation is even, move into reactor then, in the cooling rapidly after 48 hours of 165 ℃ of crystallization, after filtration, wash to pH=8～9, in baking oven in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of ZSM-5, numbering DB-2.
Comparative Examples 3
The mixed crystal material of this Comparative Examples obtains through mechanical mixture.
The ZSM-5 molecular sieve mechanical mixture that the β zeolite that Comparative Examples 1 is synthetic and Comparative Examples 2 are synthetic, wherein β zeolite and ZSM-5 respectively account for 50 heavy %, and this contrast material is numbered DB-3.
1.0g ZSM-5 crystal seed, 0.6g sodium fluoride, 29.5g tetraethyl oxyammonia solution, 2.2g sulfuric acid solution and 13.5mL deionized water are mixed, under mechanical agitation, add the 0.5g sodium aluminate again, be stirred to evenly, add the 19.7g Ludox again, continue to stir, move into reactor then, in 140 ℃ of crystallization 6 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal, numbering A1.
2.0g ZSM-5 crystal seed, 0.6g sodium fluoride, 29.5g tetraethyl oxyammonia solution, 2.2g20% sulfuric acid solution and 13.5mL deionized water are mixed, under mechanical agitation, add the 0.5g sodium aluminate again, be stirred to evenly, add the 19.7g Ludox again, continue to be stirred to evenly, move into reactor then, in 140 ℃ of crystallization 6 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal, numbering A2.
Embodiment 3
3.0g ZSM-5 crystal seed, 0.6g sodium fluoride, 29.5g 15% tetraethyl oxyammonia solution, 2.2g 20% sulfuric acid solution and 13.5mL deionized water are mixed, under mechanical agitation, add the 0.5g sodium aluminate again, be stirred to evenly, add the 19.7g Ludox again, continue to be stirred to evenly, move into reactor then, in 140 ℃ of crystallization 6 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal, numbering A3.
Embodiment 4
4.5g ZSM-5 crystal seed, 0.6g sodium fluoride, 29.5g 15% tetraethyl oxyammonia solution, 2.2 g, 20% sulfuric acid solution and 13.5mL deionized water are mixed, under mechanical agitation, add the 0.5g sodium aluminate again, be stirred to evenly, add the 19.7g Ludox again, continue to be stirred to evenly, move into reactor then, in 140 ℃ of crystallization 6 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal, numbering A4.
1.0g ZSM-5 crystal seed, 0.4g ammonium fluoride, 19.6g 15% tetraethyl oxyammonia solution, 7.6mL concentrated ammonia liquor and 6.2mL deionized water are mixed, under mechanical agitation, add the 0.7g sodium aluminate again, be stirred to evenly, add the 19.7g Ludox again, continue to be stirred to evenly, move into reactor then, in 120 ℃ of crystallization 7 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal, be numbered A5.
Embodiment 6
0.5g ZSM-5 crystal seed, 15.7g 15% tetraethyl oxyammonia solution and 5.4mL deionized water are mixed, under mechanical agitation, add 0.7g aluminum sulfate again, be stirred to evenly, add the 19.7g Ludox again, continue to be stirred to evenly, move into reactor then, in 155 ℃ of crystallization 5 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal, be numbered A6.
Embodiment 7
3.0g ZSM-5 crystal seed, 0.5g sodium fluoride, 22.7g 15% tetraethyl oxyammonia solution and 12.7mL deionized water are mixed, under mechanical agitation, add the 0.7g sodium aluminate again, be stirred to evenly, add the 15.7g Ludox again, continue to be stirred to evenly, move into reactor then, in 145 ℃ of crystallization 5 days, crystallization finished back cooling rapidly, washing after filtration, put into baking oven again in 100～110 ℃ of dryings 3～4 hours, promptly get the former powder of mixed crystal, be numbered A7.
The catalytic perfomance of the mixed crystal material that embodiment 8～10 explanations method provided by the invention is synthesized.
Embodiment 8
The dimethylbenzene disproportionated reaction pulse micro-inverse evaluation result of present embodiment explanation mixed crystal material.
Sample loading amount 0.1g is at 450 ℃ of down logical N
2Pre-thermal activation was a probe molecule with meta-xylene after 30 minutes, pulse sample introduction 0.3 μ L.
Chromatograph is the HP5890II type, is furnished with fid detector.The product analysis condition: (chromatogram column temperature is from 40 ℃ of temperature programmings to 250 ℃, 300 ℃ of detector temperatures for the capillary column of 50m * 0.2mm), 280 ℃ of injector temperatures to select OV-1 for use.
The sodium type is converted into the process of Hydrogen: take off amine under the first temperature programming condition, take by weighing a certain amount of mixed crystal that has taken off amine then, add the NH of 1mol/L
4Cl solution (15mL/g zeolite) heats in 96～100 ℃ of water-baths, and constantly stirring makes it exchange evenly, need to keep exchange 1h, finish back suction filtration and be washed to no chlorine, twice of repeated exchanged of exchange at every turn, oven dry is put into muffle furnace at last and was kept 4 hours down in 540 ℃.
Dimethylbenzene disproportionated reaction activity and product distribute and see Table 1.
Table 1
| Catalyst | Conversion ratio/% | Benzene/% | Toluene/% | Meta-xylene/% | Paraxylene/% | Ortho-xylene/% | (benzene+toluene)/% | The dimethylbenzene total amount |
| A4 | 89.90 | 6.00 | 34.80 | 10.10 | 28.79 | 11.13 | 40.8 | 50.02 |
| DB-3 | 94.91 | 28.19 | 47.16 | 5.09 | 15.93 | 2.32 | 75.35 | 23.34 |
| DB-2 | 80.10 | 2.62 | 23.85 | 19.86 | 49.90 | 0.67 | 26.47 | 70.43 |
| DB-1 | 92.36 | 15.34 | 37.71 | 7.64 | 24.57 | 7.54 | 53.05 | 39.79 |
As shown in Table 1, when 450 ℃ of reaction temperatures, the inventive method preparation ZSM-5 and β zeolite mixed crystal (A4) ortho-xylene is had good selectivity through ZSM-5 and β zeolite (DB-3), pure β zeolite (DB-1), the pure ZSM-5 (DB-2) of mechanical mixture.
Embodiment 9
The reactivity worth of mixed crystal material in the aromatization of methanol pulse micro-inverse is estimated of present embodiment explanation the inventive method preparation.
Experimental technique: sample loading amount 0.1g, at 450 ℃ of down logical N
2Behind the pre-thermal activation 30min, be probe molecule with methyl alcohol, pulse sample introduction 0.3 μ L.
The product analysis condition: (chromatogram column temperature is from 40 ℃ of temperature programmings to 250 ℃, 300 ℃ of detector temperatures for the capillary column of 50m * 0.2mm), 280 ℃ of injector temperatures to select OV-1 for use.
Aromatization of methanol reactivity and product distribute and see Table 2.
Table 2
| Catalyst | Conversion ratio/% | Benzene/% | Toluene/% | Meta-xylene/% | Paraxylene/% | Ortho-xylene/% | (benzene+toluene) % | Dimethylbenzene total amount % | The aromatic hydrocarbons total amount |
| A4 | 56.16 | 0.65 | 4.20 | 4.20 | 5.69 | 5.03 | 4.85 | 14.92 | 19.77 |
| DB-3 | 69.78 | 2.97 | 0.99 | - | - | - | 3.96 | 0 | 3.96 |
As shown in Table 2, the ZSM-5 of the inventive method preparation and β zeolite mixed crystal ZSM-5 and the β zeolite mixed than machine has the aromatisation performance of getting well, and the selectivity of toluene, dimethylbenzene is good.
The reactivity worth of mixed crystal material in the toluene disproportionation pulse micro-inverse is estimated of the inventive method preparation.
Experimental technique: sample loading amount 0.1g, at 400 ℃ of down logical N
2Behind the pre-thermal activation 30min, be probe molecule with toluene, pulse sample introduction 0.3 μ L.
The product analysis condition: (chromatogram column temperature is from 40 ℃ of temperature programmings to 250 ℃, 300 ℃ of detector temperatures for the capillary column of 50m * 0.2mm), 280 ℃ of injector temperatures to select OV-1 for use.
Toluene disproportionation process activity and product distribute and see Table 3.
Table 3
| Catalyst | Conversion ratio/% | Benzene/% | Toluene/% | Meta-xylene/% | Paraxylene/% | Ortho-xylene/% | (benzene+toluene)/% | Dimethylbenzene total amount/% |
| A4 | 27.26 | 13.30 | 72.74 | 3.67 | 9.20 | 0.61 | 86.04 | 13.48 |
| DB-3 | 32.92 | 20.72 | 67.08 | 3.05 | 8.22 | 0.43 | 87.8 | 11.7 |
As shown in Table 3, when 400 ℃ of reaction temperatures, the inventive method preparation ZSM-5 and β zeolite mixed crystal ZSM-5 and the β zeolite paraxylene mixed than machine the selectivity of getting well is arranged, and the amount of benzene is few.
Claims (10)
1, the preparation method of a kind of ZSM-5 and β zeolite mixed crystal material, it is characterized in that according to the aluminium source: silicon source: inorganic base: template agent: fluoride: deionized water: inorganic acid=1: (15～100): (0～100): (1.5～30): (0～20): (270～3200): the mole of the β zeolite synthetic reaction system of (0～20) is formed, mix with ZSM-5 as crystal seed, wherein inorganic acid and inorganic base do not use simultaneously, in closed container, synthesized crystallization 3～7 days and reclaimed product under 100 ℃～200 ℃ conditions then, wherein, in the mole composition formula, the aluminium source is with Al
2O
3Meter, silicon source are with SiO
2Meter, the weight of said ZSM-5 as crystal seed is 2～100% of β zeolite synthetic reaction system butt weight.
2, according to the method for claim 1, be earlier inorganic base or inorganic acid, template agent, fluoride, deionized water to be mixed, add ZSM-5, under agitation add aluminium source, silicon source again.
3, according to the method for claim 1, said aluminium source is selected from least a in the group that boehmite, sodium aluminate and aluminum sulfate forms.
4, according to the method for claim 1, described silicon source is waterglass and/or Ludox.
5, according to the method for claim 1, described fluoride is alkali-metal fluoride or ammonium fluoride or its mixture.
6, according to the method for claim 5, wherein alkali-metal fluoride is a sodium fluoride.
7, according to the method for claim 1, said inorganic base is selected from least a in the group that NaOH, potassium hydroxide and ammoniacal liquor forms.
8, according to the method for claim 1, said inorganic acid is sulfuric acid or hydrochloric acid.
9, according to the method for claim 1, said template agent is selected from tetraethyl ammonium hydroxide, tetraethyl ammonium halide, TPAOH or its mixture.
10, according to the method for claim 1, the addition of said ZSM-5 is 5～80% of a β zeolite synthetic reaction system butt weight.
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