CN1121979C - Process for preparing ZSM-5 molecular sieve - Google Patents

Process for preparing ZSM-5 molecular sieve Download PDF

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CN1121979C
CN1121979C CN 00133567 CN00133567A CN1121979C CN 1121979 C CN1121979 C CN 1121979C CN 00133567 CN00133567 CN 00133567 CN 00133567 A CN00133567 A CN 00133567A CN 1121979 C CN1121979 C CN 1121979C
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molecular sieve
zsm
fey
reaction mixture
sio
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CN1353087A (en
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杨翼
何鸣元
宋家庆
宗保宁
王一萌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The present invention relates to a method for preparing a ZSM-5 molecular sieve, which is characterized in that the method comprises the following steps: firstly, a FeY molecular sieve is obtained by making Y type molecular sieves contain 3 to 25 wt% of Fe2O3 by a liquid phase ion exchange; then the FeY molecular sieve, a silicon source, an aluminum source, an organic amine template R and water are uniformly mixed, and the alkalinity of the mixture is adjusted so that the obtained reaction mixture comprises the components of the following proportion: 0.04 to 0.12 of Na2O, 0.006 to 0.05 of Al2O3, 1 of SiO2, 0 to 0.40 of R and 5 to 40 of H2O; the obtained reaction mixture is crystallized under a hydrothermal condition, wherein the SiO2 quantity of the FeY moleculer sieve accounts for 2 to 40 wt% of the total SiO2 quantity of the reaction mixture. With the method of the present invention, the ZSM-5 molecular sieve can be directly hydrothermally synthesized in a Si-Al-Fe system.

Description

A kind of preparation of ZSM-5 molecular sieve
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 larger, is conducive to the exchange of the larger metal ion of radius. The Y zeolite that this method will exchange Fe (III) is dispersed in the alkaline silica-alumina gel system, and under the hydrothermal condition, Y type molecular sieve recurring structure dissociates, and forms the structure fragment that contains Fe (III). Centered by this structure fragment, under hydrothermal synthesizing condition, make the gradually growth around it of silica, aluminium oxide again, the final Fe-ZSM-5 with ZSM-5 structure that forms. 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 such as the inventive method preparation has high activity in wider 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, reactivity improves (Comparative Examples 9) greatly.
The ZSM-5 molecular sieve that contains Fe of the inventive method preparation is applicable to: remove nitrogen oxide and hydro carbons in the exhaust of lean-burn automotive, remove the nitrogen oxide in factory's (nitric plant, chemical fertilizer factory, oil plant etc.) tail gas, benzene hydrolysis phenol reactant processed, 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.
Embodiment 5
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 2O 1.08 grams are 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
Figure C0013356700111
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)

1, a kind of preparation method who contains the ZSM-5 molecular sieve of Fe is characterized in that this method comprises: at first make Y zeolite contain the Fe of 3～25 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 and water 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); 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.
2, according to the process of claim 1 wherein that said Y zeolite is the NaY molecular sieve.
3, according to the process of claim 1 wherein that the condition of described Y zeolite ionic liquid phase exchange is 50～90 ℃ of exchanges 20 minutes to 1 hour.
4, according to the process of claim 1 wherein the Fe of said FeY 2O 3Content is 5～20 weight %.
5, according to the process of claim 1 wherein that said silicon source is water glass, solid silicone or solid silicon aluminium glue.
6, according to the process of claim 1 wherein that said aluminium source is the aluminate of tart aluminium salt or alkalescence.
7, according to the method for claim 6, wherein said aluminium source is a Tai-Ace S 150.
8, according to the process of claim 1 wherein that said organic formwork agent is ethamine, TPAOH or 4-propyl bromide.
9, according to the process of claim 1 wherein that total mole of said reaction mixture consists of Na 2O: Al 2O 3: SiO 2: R: H 2O=(0.05～0.10): (0.01～0.05): 1: (0～0.35): (10～35).
10, according to the SiO that the process of claim 1 wherein among the said FeY 2Account for the total SiO of said reaction mixture 25～20 weight % of amount.
11, according to the process of claim 1 wherein that the condition of said hydrothermal crystallizing is a crystallization 10～60 hours under 120～200 ℃ and autogenous pressure.
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