CN100431958C - Preparation method of beta zeolite containing rare earth - Google Patents

Preparation method of beta zeolite containing rare earth Download PDF

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CN100431958C
CN100431958C CNB2005100474865A CN200510047486A CN100431958C CN 100431958 C CN100431958 C CN 100431958C CN B2005100474865 A CNB2005100474865 A CN B2005100474865A CN 200510047486 A CN200510047486 A CN 200510047486A CN 100431958 C CN100431958 C CN 100431958C
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rare earth
zeolite
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silicon source
aluminium
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CN1951808A (en
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王刚
李�灿
方向晨
谷明镝
韩崇仁
孙万付
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a preparing method of REbeta zeolite, which comprises the following steps: adding RE in the silicon source and aluminium source as synthesizing material of beta zeolite into synthesizing system; making tetraethyl ammonium hydroxide as moulding agent; adopting normal hydrothermal method to synthesize.

Description

The preparation method of beta zeolite containing rare earth
Technical field
The present invention relates to the preparation method of a kind of beta zeolite containing rare earth (RE β), the method for the synthetic RE β zeolite of particularly a kind of original position.
Background technology
The β zeolite is the supersiliceous zeolite (US3 with three-dimensional open-framework that the U.S. succeeds in developing in the Mobil company sixties; 308; 069); the late nineteen eighties; the various countries scholar is to the research Showed Very Brisk of β zeolite; because the pore passage structure of β zeolite uniqueness and excellent catalytic performance are with a wide range of applications at oil and chemical field.Commercial application shows that the β zeolite has higher hydrogenation cracking activity and hydroisomerization performance, can be used for hydrocracking behind modification and loaded metal, hydro-isomerization, hydrofining, Hydrodewaxing, processes such as diesel oil pour point depression.
Natural all is widely used as catalyzer and sorbent material with the synthetic zeolite, and its catalytic performance and absorption property are somewhat dependent upon the pore passage structure of zeolite and the element of composition, the β zeolite has unique pore passage structure and excellent catalytic performance is the zeolite of being paid close attention in recent years, thinks that it has the potential application prospect.
Proved with RE ion-exchange Y zeolite, can improve the hydro-thermal and the thermostability of Y zeolite, suppress zeolite and in use continue dealuminzation, this point is even more important to the β zeolite, because the β zeolite is dealuminzation very easily, be used for hydrocracking catalyst with the Y zeolite of RE ion-exchange and can change its acidity, improve the anti-nitrogen ability of catalyzer, reduce the activity of hydrogen transference, the effect of RE ion pair β zeolite is identical, can suppress to continue dealuminzation in the use of β zeolite, anti-nitrogen performance and stability are provided.
Yet the hydrated ion diameter of RE is 7.9 * 10 -10M, and the linear passageway diameter of β zeolite is 7.5 * 5.7 * 10 -10M is difficult to introduce rare earth ion with conventional switching method to the β zeolite, and the silica alumina ratio of β zeolite is very high in addition, and tradable position seldom; In addition rare earth ion in alkaline medium very easily hydrolysis generate precipitation, therefore can't resemble the compound of adding metallic element in the system of synthetic β zeolite of previous patent report, metallic element is incorporated in the β zeolite, thereby must adopt other method, and be introduced in the β zeolite RE.
US3,308,069 have introduced the synthetic method of β zeolite first, wherein contain transition element, but do not comprise rare earth element.
Though the metal ion when speaking of the β zeolite synthesis in the claim of European patent EP 159846 can be IIA, IIIA, IVA, IB, IIB only has Na in the metal examples such as IIIB +A kind of.
The introducing of previous patent report metallic element is the compound that directly adds the containing metal element in synthetic β zeolite alkalescence sial colloidal state system.And rare earth ion can hydrolysis generate precipitation in alkaline medium, the muriate that therefore can't directly add rare earth, for exploring the new approach of in the β zeolite, introducing rare earth element, patent CN1209356A adopts xenocryst guiding method to add REX and REY zeolite in synthetic β zeolite system, synthesizes a kind of β zeolite that contains rare earth.This zeolite not only has the feature and the attribute of general zeolite, but also contains the RE element, is reflected on the X-ray diffraction spectrogram 2 θ angles and three new characteristic peaks occur, and being reflected on the catalytic performance is high anti-nitrogen ability and high stability.But this method has been owing to introduced foreign crystal in β zeolite synthesis process, makes to be easy to generate other crystal in the crystallization process or synthetic β zeolite is impure, contains other crystal.In addition, it is higher to use crystal to introduce its cost of rare earth element.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of new RE β prepare zeolite method, the inventive method can reduce the production cost of RE β.
The building-up process of RE β zeolite of the present invention comprises the steps:
(1), (consumption is with Na with NaOH 2The O meter), (TEA) 2O, aluminium source, silicon source and H 2O is mixed and made into slurries, and the molar ratio of these slurries is: SiO 2/ Al 2O 3=20-60, Na 2O/Al 2O 3=0.5-2.5, (TEA) 2O/Al 2O 3=1.0-5.0, H 2O/Al 2O 3=100-500, RE 2O 3/ Al 2O 3=0.03-0.8.
(2), after said mixture stirs, in autoclave 100～200 ℃, crystallization 2～5 days separates obtaining RE β then.
Wherein part or all of aluminium source in the step (1) and/or silicon source is the material that contains rare earth, and generally can adopt 5～100% of aluminium source and silicon source is aluminium source and the silicon source that contains rare earth, and consumption is with RE 2O 3Content is 0.5～10w% in zeolite, RE 2O 3Content is preferably 1～5w%.All the other are conventional material, as common silica gel, silicon sol, aluminium hydroxide, aluminum oxide, sodium metaaluminate, sodium aluminate etc. or mixture.The silicon source that contains rare earth can be silica gel that contains rare earth etc., and the aluminium source that contains rare earth can be aluminum oxide that contains rare earth etc., also can be amorphous silicon aluminium that contains rare earth etc.Can use various rare earth elements, that the most frequently used is La or Ce.Preparation contains the silicon source of rare earth and/or the method in aluminium source is generally: silicon source and/or aluminium source contact with rare earths salt, flood 1-8 hour drying and roasting then, RE in silicon source that obtains and/or the aluminium source down at 20-90 ℃ 2O 3Content in the 1-30w% scope, 5-20w% preferably.Dry and roast is a usual terms, as descending dry 1～20 hour at 80～180 ℃, 300～650 ℃ of following roastings 1～10 hour.Rare-earth salts is soluble salt, as nitrate, muriate, oxalate etc.
Template (TEA) 2The O tetraethylammonium cation can be by tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide, and tetraethyl ammonium iodide and composition thereof provides.The preparation method of beta zeolite containing rare earth of the present invention, the sodium ion of wherein used sodium hydroxide can be by basic metal or alkaline-earth metal and replace.
After crystallization finishes, slurries can be diluted with water purification, directly make 0.5～2M ammonium nitrate or ammonium chloride solution then, 70～90 ℃ of down exchanges 2～3 hours, filter then, clean, drying, roasting obtain final zeolitic solid powder-product.Also can direct filtration, clean, dry, roasting obtains final zeolitic solid powder-product.Roasting condition is generally 100～550 ℃ of roastings 10～30 hours.Crystallization rare earth β zeolite slurry completely exchanges through ammonium salt, and ammonium salt can be used ammonium nitrate, ammonium chloride, ammonium sulfate.High-temperature roasting removes organic ammonium and can follow these steps to carry out.
The first step: 100～150 ℃ of constant temperature 1-5 hour low temperature dewaterings;
Second step: 250～350 ℃ of warm organic ammoniums in constant temperature 1-5 hour decompose;
The 3rd step: till 500～540 ℃ of high-temperature materials burnt in vain, the pyrolytic decomposition uncombined carbon generally was 10-20 hour.
The RE β zeolite that the inventive method obtains generally has following feature: SiO 2/ Al 2O 3Be 20～40, RE 2O 3Content is 0.5～10w%, RE 2O 3Content is preferably 1～5w%.Infrared acidity is 1.000-1.500mmol/g, is preferably 1.000-1.200mmol/g.
The raw material that the inventive method will contain RE joins in the material of synthetic β zeolite, synthetic zeolite under the required condition of synthetic β zeolite, thus the RE element is incorporated in the β zeolite lattice.Owing to adopt the amorphous thing to introduce rare earth element, therefore synthetic cost is low, zeolite product purity height.
Embodiment
Further specify detailed process of the present invention and effect below by embodiment.
Embodiment 1
At first preparation contains the synthesis material of RE element, takes by weighing water glass and (contains SiO 240.67w%) 482.34g is measured the RE (NO of 0.1M 3) 3Solution 80ml mixes, and adds the HNO of 10w% then 3Amount 200ml filters, and washs 3 times, and the filter cake that obtains 110 ℃ of dryings 8 hours, 450 ℃ of roastings 3 hours, is obtained containing RE element silica gel as the silicon source, and wherein RE is La.
Take by weighing sodium aluminate (Al 2O 342.28w%, Na 2O 34.26w%) 19.6g, place the 250ml beaker, add 4.3gNaOH, add the 45g water purification, and then add 294.5g tetraethyl-oxyammonia (weight concentration 20%), stirred respectively again 15 minutes, as working solution, in room temperature the silica gel that contains the RE element for preparing is previously all added in the working solution at leisure as the silicon source then, till adding, the mole of mixture consists of: (Na 2O) 2.0[(TEA 2O)] 2.5 (SiO 2) 40 (Al 2O 3) 1.0 (H 2O) 200, continued high-speed stirring again 15 minutes, make this material uniform mixing, in the stainless cylinder of steel of packing into then, will cover screwing hermetic, put into muffle furnace and took out filtration, 2 times, 110 ℃ dryings of washing 3 hours in 165 ℃ of crystallization 3 days (72 hours).Obtain β zeolite A.
Embodiment 2
At first preparation contains the synthesis material of RE element, takes by weighing silica gel and (contains SiO 298.20w%) 196.23g is measured the RE (NO of 0.1M 3) 3Solution 80ml mixes, and floods 3 hours, and 3 hours, 550 ℃ roastings of 100 ℃ of dryings are 2 hours then, obtain containing RE element silica gel as the silicon source.RE is La.
Except that with this silicon source, all the other are identical with embodiment 1, synthetic β zeolite B.
Embodiment 3
At first preparation contains the synthesis material of RE element, takes by weighing amorphous aluminum silicide and (contains SiO 233.45w%, Al 2O 340.53%) 20.40g is measured the RE (NO of 0.1M 3) 3Solution 80ml mixes, and floods 3 hours, and 2 hours, 500 ℃ roastings of 140 ℃ of dryings are 5 hours then, as containing RE element raw material.RE is Ce.
Take by weighing silica gel and (contain SiO 298.20w%) 189.20g, add 4.3gNaOH, the 35g water purification, and then adding 294.5g tetraethyl-oxyammonia (concentration 20%), stirred respectively again 15 minutes, as working solution, then room temperature with the sial that contains the RE element for preparing previously as all adding in the working solution at leisure, till adding, the mole of mixture consists of: (Na 2O) 2.0[(TEA 2O)] 2.5 (SiO 2) 40 (Al 2O 3) 1.0 (H 2O) 200, continued high-speed stirring again 15 minutes, make this material uniform mixing, in the stainless cylinder of steel of packing into then, will cover screwing hermetic, put into muffle furnace and take out filtration, washing 2 times, 140 dryings 3 hours in 185 ℃ of crystallization 2 days (48 hours), obtain β zeolite C.
Embodiment 4
At first preparation contains the synthesis material of RE element, takes by weighing aluminum oxide and (contains Al 2O 396w%) 3g is measured the RE (NO of 0.2M 3) 3Solution 296ml mixes, and floods 3 hours, and 5 hours, 450 ℃ roastings of 100 ℃ of dryings are 4 hours then, as containing RE element raw material.
Except that with this aluminium source, add aluminum oxide 5.5g again, all the other are identical with embodiment 1, synthetic β zeolite D.
Comparative example 1
Take by weighing silicon sol and (contain SiO 240.67w%) 128.34g, sodium metaaluminate (Al 2O 333.28w%, Na 2O21.57w%) 9.2g, place the 250ml beaker respectively, add the 12.86g water purification in the silicon sol, add 1.28gNaOH in the sodium metaaluminate, stirring and dissolving in the 70-80 ℃ of aqueous solution, stirred respectively 15 minutes, and then add 44.12ml tetraethyl-oxyammonia (concentration 0.85M) respectively, and stirring respectively again 15 minutes, room temperature adds sodium metaaluminate in the silicon sol at leisure, till adding, the mole of mixture consists of: (Na 2O) 1.6[(TEA 2O)] 2.5 (SiO 2) 29 (Al 2O 3) 1.0 (H 2O) 300, continued high-speed stirring again 15 minutes, and made this material uniform mixing, in the stainless cylinder of steel of packing into then (band teflon lined), to cover screwing hermetic, and put into muffle furnace and took out filtration, 2 times, 120 ℃ dryings of washing 3 hours in 165 ℃ of crystallization 3 days (72 hours).Obtain β zeolite E.
Comparative example 2～3
At first prepare REX and REY zeolite, get each 500g of X and Y zeolite, the oven dry porphyrize is placed on 3%RE (NO 3) 3In the aqueous solution, exchange is 2 times in 70 ℃ of aqueous solution, and each 1 hour, and the pH value of control slurries filters then 4.0, washing, 110 ℃ of dryings 6 hours down, butt 80w%, 550 ℃ of following roastings 2 hours, at this moment, RE in REX and the REY zeolite 2O 3Content be respectively 23.42w% and 19.15w%.RE is La.
With the silicon sol (SiO that contains 36.65w% 2) sodium aluminate (Al that contains 24.93w% 2O 3, 21.43 Na 2O), the tetraethyl ammonium hydroxide aqueous solution (strength of solution 0.85M), the fine powder of REX or REY (certain proportion by synthetic solid phase amount adds), the sodium hydroxide mixture stirs and is added in the reactor, in certain temperature, crystallization in the certain hour.Obtain RE β zeolite F and G.
Figure C20051004748600081
Example 5
Get above-mentioned product 1M NH 4NO 3Solution, 80 ℃ of down exchanges 1 time, 2 hours, filter then, washing, 110 ℃ dry 6 hours down.Dry sample removes organic ammonium 540 ℃ of following roastings 20 hours, and material all burns white.Analyze all round properties, the result is as follows:
Specimen coding Embodiment 1 A Embodiment 2 B Embodiment 3 C Embodiment 4 D Comparative example 1 E Comparative example 2 F Comparative example 3 G
SiO 2/Al 2O 3 24.80 24.59 24.56 25.10 25.43 22.67 23.07
Na 2O％ 1.21 1.12 1.14 1.18 1.32 1.16 1.20
RE 2O 3％ 1.12 1.08 1.10 8.15 / 1.02 0.52
Form REβ REβ REβ REβ β REβ RE β+stray crystal
Infrared acidity mmol/g
B acid 0.764 0.747 0.732 0.703 0.72 0.743 0.626
L acid 0.295 0.302 0.320 0.340 0.27 0.326 0.394
Total acid 1.059 1.049 1.052 1.043 0.99 1.069 1.020
The total M of S 2/g 653 660 649 645 539 637 657
V ml/g 0.349 0.348 0.354 0.365 0.338 0.356 0.362
This shows that RE β has higher acidity, pore volume and specific surface.
Example 6
With super steady zeolite with contain the β zeolite that rare-earth ultra-steady zeolite, β zeolite and synthetic contain rare earth, on micro-reactor, be that raw material (nitrogen content is 2000 μ g/g in the raw material) carries out the test of anti-nitrogen ability respectively with the normal heptane that contains pyridine, along with the zeolite lytic activity that carries out that reacts descends, but drop to and to a certain degree will keep stable no longer reduction, the lytic activity that keeps with this moment is represented the anti-nitrogen ability of zeolite, its result such as following table:
Zeolite type Remaining activity %
Overstable gamma zeolite (USY) 26.6
Hyperastable Y-type RE zeolite (REUSY) 46.0
Conventional β zeolite E 36.0
Comparative example synthesizing rare-earth β zeolite F 52.0
Present method synthesizing rare-earth β zeolite A 53.0
The result shows because the introducing of rare earth ion makes the anti-nitrogen ability of β zeolite that by a relatively large margin raising be arranged.

Claims (6)

1, a kind of β prepare zeolite method that contains rare earth, building-up process comprises the steps:
(1), with NaOH, (TEA) 2O, aluminium source, silicon source and H 2O is mixed and made into slurries, and the molar ratio of these slurries is: SiO 2/ Al 2O 3=20-60, Na 2O/Al 2O 3=0.5-2.5, (TEA) 2O/Al 2O 3=1.0-5.0, H 2O/Al 2O 3=100-500, RE 2O 3/ Al 2O 3=0.03-0.8;
(2), after said mixture stirs, in autoclave 100～200 ℃, crystallization 2～5 days separates obtaining RE β then;
Wherein part or all of aluminium source in the step (1) and/or silicon source is the material that contains rare earth, and consumption is with RE 2O 3Content is 0.5～10w% in zeolite; The silicon source that contains rare earth is the silica gel that contains rare earth, and the aluminium source that contains rare earth is the aluminum oxide that contains rare earth, or contains the amorphous silicon aluminium of rare earth; Containing the silicon source of rare earth and/or the preparation method in aluminium source is: silicon source and/or aluminium source contact with rare earths salt, then drying and roasting.
2, in accordance with the method for claim 1, it is characterized in that adopting 5%～100% of aluminium source and silicon source is aluminium source and the silicon source material that contains rare earth.
3, in accordance with the method for claim 1, it is characterized in that RE 2O 3Content is 1～5w% in zeolite.
4, in accordance with the method for claim 1, it is characterized in that described silicon source and/or aluminium source and rare earths salt contact conditions are for flooding 1～8 hour down at 20～90 ℃, dry and roasting condition is following dry 1～20 hour at 80～180 ℃, at 300～650 ℃ of following roastings 1～10 hour, RE in silicon source that obtains and/or the aluminium source 2O 3Content is in 1～30w% scope.
5, in accordance with the method for claim 1, it is characterized in that described template (TEA) 2O is tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide, tetraethyl ammonium iodide or its mixture.
6, in accordance with the method for claim 1, it is characterized in that crystallization finishes after, directly with 0.5～2M ammonium nitrate or ammonium chloride solution 70～90 ℃ of exchanges 2～3 hours down, filter then, clean, drying, roasting obtain final zeolitic solid powder-product; Or direct filtration, clean, dry, roasting obtains final zeolitic solid powder-product; Roasting condition is 100～550 ℃ of roastings 10～30 hours.
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CN101723394B (en) * 2008-10-28 2012-06-27 中国石油化工股份有限公司 Nano-beta molecular sieve with low Si/Al ratio and preparation method thereof
CN103204519B (en) * 2013-04-15 2015-06-03 珠海市吉昌稀土有限公司 Synthetic method of rare-earth silicon-aluminum molecular sieve
CN112371079A (en) * 2020-11-02 2021-02-19 江苏方天电力技术有限公司 Deteriorated oil regeneration treatment adsorbent and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0159846A2 (en) * 1984-04-16 1985-10-30 Mobil Oil Corporation Preparation of zeolite beta
CN1209356A (en) * 1997-08-27 1999-03-03 中国石油化工总公司 Beta zeolite containing rare-earth and preparation method therefor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0159846A2 (en) * 1984-04-16 1985-10-30 Mobil Oil Corporation Preparation of zeolite beta
CN1209356A (en) * 1997-08-27 1999-03-03 中国石油化工总公司 Beta zeolite containing rare-earth and preparation method therefor

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