CN1353087A - Process for preparing ZSM-5 molecular sieve - Google Patents
Process for preparing ZSM-5 molecular sieve Download PDFInfo
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- CN1353087A CN1353087A CN 00133567 CN00133567A CN1353087A CN 1353087 A CN1353087 A CN 1353087A CN 00133567 CN00133567 CN 00133567 CN 00133567 A CN00133567 A CN 00133567A CN 1353087 A CN1353087 A CN 1353087A
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- molecular sieve
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 52
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 18
- 239000011541 reaction mixture Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 229910052681 coesite Inorganic materials 0.000 claims abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract 3
- 239000007791 liquid phase Substances 0.000 claims abstract 3
- 239000000377 silicon dioxide Substances 0.000 claims abstract 3
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052593 corundum Inorganic materials 0.000 claims abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 2
- 238000002425 crystallisation Methods 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 18
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 10
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [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
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005216 hydrothermal crystallization Methods 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 229910008389 Si—Al—Fe Inorganic materials 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 52
- 239000011734 sodium Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229960003753 nitric oxide Drugs 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000012976 tarts Nutrition 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- -1 Fe (III) compound Chemical class 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
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910018619 Si-Fe Inorganic materials 0.000 description 1
- 229910008289 Si—Fe Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019391 nitrogen oxide Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
一种含Fe的ZSM－5分子筛的制备方法,其特征在于该方法包括:首先通过液相离子交换使Y型分子筛含有3～25重量%的Fe2O3得到FeY分子筛;然后将该FeY分子筛与硅源、铝源、有机胺模板剂R和水混合均匀并调整碱度,使所得反应混合物的总的摩尔组成为Na2O∶Al2O3∶SiO2∶R∶H2O=(0.04～0.12)∶(0.006～0.05)∶1∶(0～0.40)∶(5～40);然后将所得反应混合物在水热条件下晶化;其中所说FeY中的SiO2占所说反应混合物总SiO2量的2～40重量%。本发明方法可以在Si－Al－Fe体系中直接水热合成ZSM－5分子筛。A method for preparing Fe-containing ZSM-5 molecular sieve, which is characterized in that the method comprises: first, the Y-type molecular sieve contains 3 to 25% by weight of Fe 2 O 3 through liquid-phase ion exchange to obtain FeY molecular sieve; then, the FeY molecular sieve Mix evenly with silicon source, aluminum source, organic amine template R and water and adjust the alkalinity so that the total molar composition of the resulting reaction mixture is Na2O: Al2O3 : SiO2: R: H2O =( 0.04～0.12):(0.006～0.05):1:(0～0.40):(5～40); then the resulting reaction mixture is crystallized under hydrothermal conditions; wherein the SiO in the FeY accounts for the reaction 2-40% by weight of the total SiO 2 content of the mixture. The method of the invention can directly hydrothermally synthesize ZSM-5 molecular sieve in Si-Al-Fe system.
Description
The present invention relates to a kind of preparation method of ZSM-5 molecular sieve, more particularly relate to a kind of preparation method of ferruginous ZSM-5 molecular sieve.
Metal ion combines with molecular sieve, has produced the catalytic material of many excellent performances.Fe-ZSM-5 is exactly an example wherein.Fe-ZSM-5 for benzene hydrolysis system phenol, xylene isomerization, aromatizing low-carbon paraffin, Fischer-Tropsch reaction, remove reaction such as airborne oxynitride and have good catalytic activity.
At present, the preparation method of Fe-ZSM-5 molecular sieve mainly contains following several: ionic liquid phase exchange process, pickling process, solid ionic exchange process, subliming method, direct hydro-thermal synthetic silicon iron hetero-atom molecular-sieve method.Preceding four kinds of methods all are behind the molecular sieve end of synthesis iron to be introduced by different way, and the 5th kind of method is to introduce iron in sieve synthesis procedure.Therefore, preceding relatively four kinds of the 5th kind of method, wherein the distribution of iron is more even, and state is more single.For different reactions, the different positions that iron is in molecular sieve can produce different catalytic performances.
In direct hydrothermal method, because Fe and Al are trivalent elements, but Al forms framework of molecular sieve than easier the combination with silicon of Fe, if therefore synthetic system is the Si-Al-Fe system, be mainly sial in the molecular sieve that generally synthesizes, and Fe content is seldom in molecular sieve.Therefore the synthetic ZSM-5 molecular sieve that contains Fe of hydrothermal method all is not contain aluminium or contain aluminium Si-Fe system (being the synthetic of Ferrisilicate molecular sieve) seldom in the prior art.As USP4,952, the synthetic method of the ZSM-5 molecular sieve of the disclosed Fe of containing is silicon source and aminated compounds and quaternary ammonium compound to be joined in the acidic aqueous solution of Fe (III) compound make mixture in 385, with this mixture crystallization, then with the molecular sieve after the crystallization respectively through the thermal treatment of indifferent gas, air and water vapour atmosphere.It is said that this ZSM-5 molecular sieve that contains Fe contains Fe and the outer Fe of skeleton in the skeleton, and the outer Fe of most of skeleton is at the molecular sieve outer surface good dispersion.This ZSM-5 molecular sieve that contains Fe can be used as the Fischer-Tropsch catalyst for reaction.
The preparation method who the purpose of this invention is to provide a kind of ZSM-5 molecular sieve that contains Fe newly, this method can direct hydro-thermal be synthesized the ZSM-5 molecular sieve in the Si-Al-Fe system.
The preparation method of the ZSM-5 molecular sieve of the Fe of containing provided by the invention is with the Y zeolite that the contains Fe part silicon and aluminum source (or crystal seed) as synthetic ZSM-5 molecular sieve, method by the xenocryst guiding is introduced Fe in the ZSM-5 molecular sieve, make the distribution of Fe in the ZSM-5 molecular sieve that synthesizes better, reactivity worth is more superior.
Specifically, the preparation method of the ZSM-5 molecular sieve of the Fe of containing provided by the invention comprises: at first make Y zeolite contain 3～25 weight %, the Fe of preferred 5～20 weight % by the ionic liquid phase exchange
2O
3Obtain the FeY molecular sieve; Then this FeY molecular sieve and silicon source, aluminium source, organic amine template R (if desired), water etc. are mixed and adjust basicity, make total mole of gained reaction mixture consist of Na
2O:Al
2O
3: SiO
2: R: H
2O=(0.04～0.12): (0.006～0.05): 1: (0～0.40): (5～40) are preferably Na
2O: Al
2O
3: SiO
2: R: H
2O=(0.05～0.10): (0.01～0.05): 1: (0～0.35): (10～35); Then with gained reaction mixture crystallization under hydrothermal condition; SiO among the wherein said FeY
2Account for the total SiO of said reaction mixture
22～40 weight % of amount, preferred 5～20 weight %, and its silicon and aluminium count in total composition of said reaction mixture.Na wherein
2O represents the basicity of reaction mixture, and it does not comprise the part that is neutralized by acid.
Said Y zeolite can be NaY, NH in the method provided by the invention
4Various Y zeolites such as Y, HY, wherein NaY molecular sieve preferably.The exchange of the ionic liquid phase of described Fe is carried out according to the method for prior art, can repeated exchanged once more than, contain the Fe of 3～25 weight % with gained FeY molecular sieve
2O
3Be standard, the present invention has no particular limits it; General give-and-take conditions are room temperature to 95 ℃ exchanges more than 10 minutes, preferred 50～90 ℃ of exchanges 20 minutes to 1 hour.
Said silicon source can be water glass, solid silicone or solid silicon aluminium glue in the method provided by the invention, wherein water glass preferably.
Said aluminium source can be tart aluminium salt such as Tai-Ace S 150, aluminum chloride or aluminum nitrate in the method provided by the invention, also can be the aluminate such as the sodium metaaluminate of alkalescence, but in order to be beneficial to adjustment basicity, and wherein preferably tart aluminium salt, more preferably Tai-Ace S 150.
The organic formwork agent that uses in the method provided by the invention is optional, and the performance of products obtained therefrom is better when using organic formwork agent, but can increase cost.Said organic formwork agent comprises ethamine (EA), TPAOH (TPAOH), 4-propyl bromide (TPABr) etc.
Said hydrothermal crystallizing carries out according to the condition of prior art in the method provided by the invention, and the present invention has no particular limits it; General crystallization condition is a crystallization 10～60 hours under 120～200 ℃ and autogenous pressure, preferably crystallization 20～50 hours under 140～180 ℃ and autogenous pressure.
Fig. 1 is X-ray diffraction (XRD) figure of embodiment 3 gained sieve samples.
The Y zeolite duct is bigger, helps the exchange of the bigger metal ion of radius.The Y zeolite that present method will exchange Fe (III) is dispersed in the alkaline silica-alumina gel system, and under the hydrothermal condition, the Y zeolite recurring structure dissociates, and forms the structure fragment that contains Fe (III).Be the center with this structure fragment again, under hydrothermal synthesizing condition, make the growth around it gradually of silicon oxide, aluminum oxide, the final Fe-ZSM-5 that forms with ZSM-5 structure.Compare with the Fe-ZSM-5 molecular sieve (Comparative Examples 1) of exchange process preparation, the distribution of Fe in molecular sieve structure among the Fe-ZSM-5 of the inventive method preparation is more even, and has better reactivity worth; Fe-ZSM-5 molecular sieve as the inventive method preparation has high reactivity in wideer temperature range in the conversion reaction of NO, this is very favourable for removing of NO in the flue gas.Compare with direct hydrothermal method of the prior art (Comparative Examples 2), the inventive method can directly synthesize the high FeZSM-5 molecular sieve of aluminum content, rather than can only synthesize the Ferrisilicate molecular sieve of pure silicon, and because the increase of aluminium content, reactive behavior improves (Comparative Examples 9) greatly.
The ZSM-5 molecular sieve that contains Fe of the inventive method preparation is applicable to: remove oxynitride and hydro carbons in the exhaust of lean-burn automotive, remove the oxynitride in factory's (nitric plant, fertilizer plant, refinery etc.) tail gas, benzene hydrolysis system phenol reactant, the aromatizing low-carbon paraffin reaction, the Fischer-Tropsch reaction, xylene isomerization reaction etc.
The following examples will the present invention is described further.
Embodiment 1
The present embodiment explanation is as the preparation of the FeY of one of raw material.
Take by weighing 2.16 gram FeCl
36H
2O is dissolved in the deionized water, is made into Fe (III) solution of 400 milliliter of 0.02 mol.20 gram (dry basis) NaY molecular sieves (Chang Ling oil-refining chemical factory catalyst plant product) are joined in above-mentioned Fe (III) solution, regulate about pH=4.0, then these slurries are warming up to 60 ℃ of exchanges 1 hour with ammoniacal liquor.The exchange product after filtration, washing, 120 ℃ of dryings 4 hours, the FeY that makes is designated as Y-1, as the raw material of the synthetic FeZSM-5 in back.
The chemical constitution of Y-1 is as shown in table 1.
Table 1
| ?Na 2O, weight % | Al 2O 3, weight % | SiO 2, weight % | Fe 2O 3, weight % |
| ????8.5 | ????20 | ????64 | ????6.6 |
Embodiment 2
The present embodiment explanation is as the preparation of the FeY of one of raw material.
The Y-1 that embodiment 1 is made by identical step repeated exchanged once obtains the higher FeY zeolite of Fe content, is designated as Y-2, as the raw material of the synthetic FeZSM-5 in back.
The chemical constitution of Y-2 is as shown in table 2.
Table 2
| ?Na 2O, weight % | Al 2O 3, weight % | SiO 2, weight % | Fe 2O 3, weight % |
| ????4.2 | ????20 | ????63 | ????12 |
Embodiment 3
Take by weighing the Y-2 that 0.45 gram embodiment 2 makes, it is scattered in 36 ml water glass (Na
2O 77.6 grams per liters, SiO
2250.5 grams per liter, density 1.250 grams per milliliters) in, stir system A.Other takes by weighing 1.0 gram Al
2(SO
4)
318H
2O is with 3.0 gram H
2SO
4With 68 gram deionized water wiring solution-forming B.Under the stirring action, solution B is slowly added among the system A, and stir, get system C.
Take by weighing ethylamine solution (30 weight %) 4.5 grams, add among the system C, stir.
This mixed system is transferred in the autoclave, and crystallization is 30 hours under 175 ℃ and autogenous pressure.Crystallization product after filtration, washing, dry, 550 ℃ of roastings 3 hours, promptly get Na type Fe-ZSM-5.Again with NH
4 +NH is promptly made in ion-exchange
4 +Type Fe-ZSM-5.550 ℃ of roastings 3 hours, H type Fe-ZSM-5.
The x-ray diffraction pattern of gained Na type Fe-ZSM-5 is seen Fig. 1.ZSM-5 is unique crystalline phase as shown in Figure 1, and relative crystallinity is 100% (this relative crystallinity is that the H type ZSM-5 molecular sieve Industrial products with Chang Ling oil-refining chemical factory catalyst plant are 100% benchmark).The Fe of X fluorescence spectrum method for measuring gained H type Fe-ZSM-5
2O
3Content is 0.62 weight %, SiO
2/ Al
2O
3Mol ratio is 45.
Embodiment 4
Y-2 sample 1.80 grams
36 milliliters of water glass
Al
2(SO
4) 18H
2O 1.0 grams
H
2SO
43.0 gram
Deionized water 65 grams
Ethamine 9 grams
The reaction mixture that to make by above-mentioned prescription prepares the ZSM-5 molecular sieve of the Fe of containing of the present invention according to the same procedure among the embodiment 3, and crystallization condition is 120 ℃ of crystallization that different is are after 12 hours, again in 175 ℃ of crystallization 45 hours.All the other operations are with embodiment 3.
The x-ray diffraction pattern of gained Na type Fe-ZSM-5 is identical with Fig. 1, and relative crystallinity is 85%.The Fe of X fluorescence spectrum method for measuring gained H type Fe-ZSM-5
2O
3Content is 1.7 weight %, SiO
2/ Al
2O
3Mol ratio is 28, Fe
2O
3/ Al
2O
3Mol ratio is 0.20.
Repeat the step of embodiment 3, that different is the Y-1 that used FeY raw material adopts 0.45 gram embodiment, 1 preparation.
The x-ray diffraction pattern of gained Na type Fe-ZSM-5 is identical with Fig. 1, and relative crystallinity is 100%.The Fe of X fluorescence spectrum method for measuring gained H type Fe-ZSM-5
2O
3Content is 0.38 weight %, SiO
2/ Al
2O
3Mol ratio is 44.
Embodiment 6
Y-2 0.18 gram
36 milliliters of water glass
H
2SO
43.45 gram
Deionized water 65 grams
Ethamine 9 grams
The reaction mixture that to make by above-mentioned prescription prepares the ZSM-5 molecular sieve of the Fe of containing of the present invention according to the same procedure among the embodiment 3, and different is that crystallization condition is 175 ℃ of crystallization 60 hours.
The x-ray diffraction pattern of gained Na type Fe-ZSM-5 is identical with Fig. 1, and relative crystallinity is 94%.The Fe of X fluorescence spectrum method for measuring gained H type Fe-ZSM-5
2O
3Content is 0.36 weight %, SiO
2/ Al
2O
3Mol ratio is 84.
Embodiment 7
Y-1 0.45 gram.
36 milliliters of water glass
Al
2(SO
4) 18H
2O 1.0 grams
H
2SO
43.0 gram
Deionized water 50 grams
TPAOH (21-23 weight %) 26.5 grams
The reaction mixture that to make by above-mentioned prescription prepares the ZSM-5 molecular sieve of the Fe of containing of the present invention according to the same procedure among the embodiment 3, and different is that crystallization condition is 175 ℃ of crystallization 27 hours.
The x-ray diffraction pattern of gained Na type Fe-ZSM-5 is identical with Fig. 1, and relative crystallinity is 100%.The Fe of X fluorescence spectrum method for measuring gained H type Fe-ZSM-5
2O
3Content is 0.64 weight %, SiO
2/ Al
2O
3Mol ratio is 44.
Embodiment 8
Y-2 0.84 gram.
CS-1 silica gel 20.2 grams
NaOH 2.53 grams
Deionized water 75 grams
Wherein CS-1 is the solid silicon aluminium glue product that Chang Ling oil-refining chemical factory catalyst plant is produced, and its chemical constitution is: Al
2O
33.16 weight %, SiO
291.98 weight %, Na
2O 0.94 weight %.
The reaction mixture that to make by above-mentioned prescription is in 175 ℃ of crystallization 18 hours, in 145 ℃ of crystallization 6 hours, presses method filtration, washing, drying and roasting among the embodiment 3 then again, makes the ZSM-5 molecular sieve of the Fe of containing of the present invention.
The x-ray diffraction pattern of gained Na type Fe-ZSM-5 is identical with Fig. 1, and relative crystallinity is 85%.The Fe of X fluorescence spectrum method for measuring gained H type Fe-ZSM-5
2O
3Content is 0.56 weight %, SiO
2/ Al
2O
3Mol ratio is 40.
Comparative Examples 1
This Comparative Examples explanation exchange process contains the preparation of the ZSM-5 molecular sieve of Fe.
Take by weighing FeCl
36H
2The O1.08 gram is dissolved in Fe (III) solution that is made into 400 milliliter of 0.01 mol in the deionized water.
Take by weighing H type ZSM-5 molecular sieve (Chang Ling oil-refining chemical factory catalyst plant Industrial products) 20 grams, add in above-mentioned Fe (III) solution, regulate about pH=4 with ammoniacal liquor.The gained slurries are exchanged 1 hour under 80 ℃ of water bath condition.The exchange product after filtration, washing, 120 ℃ of dryings 4 hours, 550 ℃ of roastings are 3 hours in muffle furnace, obtain the contrast molecular sieve that contains Fe of exchange process preparation.Record the Fe of this contrast molecular sieve
2O
3Content is 2.0 weight %, SiO
2/ Al
2O
3Mol ratio is 25, Fe
2O
3/ Al
2O
3Mol ratio is 0.20, and relative crystallinity is 100%.
Comparative Examples 2
The explanation of this Comparative Examples does not adopt the conventional hydrothermal method of FeY xenocryst guiding to contain the preparation of the ZSM-5 molecular sieve of Fe.
Take by weighing Fe
2(SO
4)
3XH
2O (commercial reagent contains the Fe of 22 weight %) 2.55 grams are dissolved in and contain 4.8 gram H
2SO
4100 ml deionized water in, stirred 1 hour, solution A.
In solution A, drip 72 ml water glass under the vigorous stirring, continue to stir 1 hour.Add ethylamine solution 30 grams again.After stirring, move in the autoclave, under autogenous pressure, divide two sections crystallization: prior to 175 ℃ of crystallization 16 hours, again in 160 ℃ of crystallization 48 hours.Crystallization product carries out aftertreatment according to the same procedure among the embodiment 3, obtains Na type, NH respectively
4 +Type and H type Fe-silicalite molecular sieve (the pure silicon ZSM-5 molecular sieve that promptly contains Fe).
The x-ray diffraction pattern of gained Na type Fe-silicalite molecular sieve is identical with Fig. 1, and relative crystallinity is 87%.The Al of X fluorescence spectrum method for measuring gained H type Fe-silicalite molecular sieve
2O
3Content is 0.89%, SiO
2/ Fe
2O
3Mol ratio is 34.
Embodiment 9
Present embodiment explanation molecular sieve of the present invention and contrast molecular sieve remove the activity rating of oxynitride.
Reaction conditions:
Reaction gas is formed nitrogen protoxide 700ppm (volumetric concentration)
Ammonia 700ppm (volumetric concentration)
Oxygen 1% (volumetric concentration)
Argon balance gas
Total gas flow rate 400 per minute standard cubic centimeters
The reaction pressure normal pressure
100 milligrams of molecular sieve loadings
H type ZSM-5 molecular sieve is anticipated the order into 20-40, and the internal diameter of packing into is in 6 millimeters the crystal reaction tube.Embodiment 4, Comparative Examples 1, Comparative Examples 2 gained H type ZSM-5 molecular sieves remove nitric oxide production activity and see Table 3 under differing temps.Wherein
Nitric oxide concentration is analyzed with QGS-08B type nitrogen-oxide analyzer, (Beijing Analytical Instrument Factory's product).
Table 3
The NO transformation efficiency, %
250 ℃ of 350 ℃ 450 ℃ 550 ℃ 650 ℃ of 750 ℃ of embodiment, 4 11.1 61.3 89.3 90.7 84.3 63 Comparative Examples, 1 9.2 62.9 90.6 86.5 69.4 51.8 Comparative Examples 2 2.3 24.5 53.2 61.3 28.9 0
As can be seen from Table 3, the Fe-ZSM-5 that the present invention makes has the nitric oxide production activity of good catalytic eliminating at the middle high-temperature zone of wide temperature range (350-750 ℃), and is better than other two kinds of Fe-ZSM-5 that method is made.
Claims (11)
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| CN101117730B (en) * | 2007-06-28 | 2011-08-31 | 复旦大学 | Multi-stage orderedly arranged ZSM-5 nano rod bundle and preparation method thereof |
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