CN106629765B - A kind of preparation method of high silicon FAU zeolite molecular sieves - Google Patents
A kind of preparation method of high silicon FAU zeolite molecular sieves Download PDFInfo
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- CN106629765B CN106629765B CN201611172305.6A CN201611172305A CN106629765B CN 106629765 B CN106629765 B CN 106629765B CN 201611172305 A CN201611172305 A CN 201611172305A CN 106629765 B CN106629765 B CN 106629765B
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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Abstract
The invention belongs to micropore material technology field, specially a kind of preparation method of silica-rich zeolite material.Column type or spheric granules is made using commodity NaY zeolite molecular sieve powder and amorphous silica as raw material in the present invention after mixing；Then in fixed bed reactors, in the nitrogen stream containing silicon tetrachloride, by four vapour solid phase reaction processes to get to high silicon FAU zeolite molecular sieves, silica alumina ratio（SAR）It is 9 150, relative crystallinity is 105 135%, and yield is 105 140%.The molecular sieve can be used for preparing macropore hydrophobic zeolite adsorbent and hydrocarbon cracking catalyst.
Description
Technical field
The invention belongs to micropore material technology fields, and in particular to a kind of preparation method of silica-rich zeolite material.The material
Have wide application prospects in organic pollution removal, adsorbing separation and catalysis etc..
Background technology
The structure aperture 0.74nm of Y zeolites, pore volume 0.30ml/g belong to large pore molecular sieve.The zeolite is oil refining
System（It FCC catalytic cracking and is hydrocracked）The main active of catalyst processes one ton of crude oil for FCC catalytic cracking
It needs to consume 0.2-0.4 kilograms of Y zeolite.Therefore, which is the maximum catalysis zeolitic material of international and domestic consumption.
Its framework silicon-aluminum molar ratio of the usual Y zeolites of commercial synthesis（SAR）4.5-5.2 range.Lower SAR makes the boiling
The hydrothermal stability of stone does not adapt to the harsh reaction condition of FCC catalysis.The fundamental way for improving its hydrothermal stability is to pass through
The structurally-modified SAR for improving the zeolite.However, the low acid resistance of the zeolite makes it that acid processing dealuminzation can not simply be used to improve
SAR.It is industrially generally exchanged with multiple ammonium and NH is made in NaY4It roasts and is made " super steady Y " or negative under high-temperature vapor again after Y
Rare earth element is carried, to improve its hydrothermal stability.Hydrogenation catalyst cracking needs the high silicon Y of SAR 10-100, can only pass through " dealuminzation
Mend silicon " method modification realization.The catalyst plant of major petro-chemical corporation of China has developed since the beginning of the 1980s with fluosilicic acid and its salt
Class carries out dealumination complement silicon reaction as chemical modifier in water phase, improves the SAR of Y zeolites, and the method is used till today always.
This method is difficult to improve the skeleton SAR of Y to 20 or more by primary first-order equation.Multiple liquid phase processing brings high cost, low
Yield and the environmental problem to dispose waste liquid.
In recent years, home and abroad environment pressure force numerous chemical enterprise an urgent demands reduce and eliminate the VOC in exhaust gas and
TOC discharges in waste water, hydrophobic ZSM-5 can successfully remove the small organic molecule that diameter is less than 0.6nm, but it is straight to remove molecule
The organic matter of diameter bigger can only use hydrophobic Y or hydrophobic Beta molecular sieves, the wherein hydrophobic Y molecular sieve that structure aperture is more than 0.7nm
It is preferred, has the urgent market demand.But in addition to the qualified products that the U.S. and Japanese fewer companies have price high, the country is still
No product supply is used.
Hermann K. Beyer and Ita Belenykaja in 1980 be put forward for the first time using powdery NaY zeolite as raw material containing
In the nitrogen stream of silicon tetrachloride, preparation SAR is reacted under 250-550 degrees Celsius, by dealumination complement silicon>6 high silicon and full Si Y-type point
Method [Studies in Surface Science the and Catalysis, Volume 5,1980, Pages of son sieve
203–210,Catalysis by Zeolites].In the reaction, the aluminium atom in NaY zeolite skeleton is by the silicon of silicon tetrachloride
Atomic component or all substitution generate high silicon Y or full silicon Y-Zeolites.Replaced and be detached from the aluminium atom and silicon tetrachloride of skeleton by silicon
Chlorine atom combines the by-product alchlor generated, can distil at 180 DEG C airborne from principal product by N2.And the sun in NaY zeolite
Ion Na reacts another by-product NaCl of generation with the chlorine in silicon tetrachloride and stays in Y zeolites, and subsequent hot water carrying out washing treatment can
Remove it [Michael W. Anderson and Jacek Klinowski,J. Chem. SOC.F, araday
Trans. I, 1986, 82, 1449-1469]。
Obviously, admittedly silicon tetrachloride vapour-reaction dealumination complement silicon that Beyer is proposed prepares the single step reaction method of high silicon Y or total silicon Y
The above-mentioned other method and processes of More are simple, and by-product NaCl and AlCl3 are easily recycled generation added value in post-processing, more may be used
Exempt the environmental problem brought that disposes waste liquid.It is contemplated that total manufacturing cost of this method is less than other methods.
NaY molecular sieve is equably tiled to be dispersed in silica wool by Chinese patent CN102320621A propositions is put into reaction
Stove, then be passed through N2 and reacted under 300-600 degree with the mixed gas of SiCl4.Obviously, silica wool clast is easy to be mingled in production
In product zeolite.Chinese patent CN101850239A is proposed, molecular sieve is first made to molecular sieve paper and is hot pressed into corrugated shape,
Honeycomb ceramics is further made.The honeycomb ceramics is reacted in closed container with contained silicon tetrachloride steam in nitrogen.This method
The adsorbent of molecular sieve with specific shape can only be made.
It can be encountered in scale industrial production with vapour/solid phase reaction between powdery NaY zeolite and SiCl4 steams following
It is difficult：If using fixed bed reaction, byproduct of reaction NaCl can cause sieve particle to glue link block, influence SiCl4 diffusions,
Cause reaction incomplete, it is uneven to also result in product component.If with fluid bed, the crystallite dimension of commercial goods NaY powder is only
Only 1-2 microns, it is difficult to form stable fluidisation state, and dust loss is more, product yield is low, and engineering is very difficult.
Admittedly it is as follows to propose that the NaY powder listed of reaction principle with silicon tetrachloride vapour-reacts equilibrium equation by above-mentioned document：
Na55(Al55 Si137 O384) + 55 SiCl4192 SiO2+ 55 AlCl3 + 55 NaCl-----（I）
（NaY, SAR=4.98, structure cell formula Na55(Al55 Si137 O384)；192 SiO of total silicon Y structure cells formula2）.
By reaction equation I by simply calculating, it can be deduced that the data of raw material and product amount：With the NaY of 1Kg drying and dehydratings
It for raw material, is at least reacted with 734 g SiCl4, produces 906 g of total silicon Y.In addition, by-product AlCl3 576 g, NaCl
253 g.It can be seen that after vapour-solid phase reaction, AlCl3 distillations carry reaction bed outside by N2, and the NaCl contained by high silicon Y products leads to again
Cross washing removing.The theoretical yield of the high silicon Y of overall process is 90.6%.The present invention proposes NaY zeolite powder and amorphous silica
Compound particles be made up of complicated vapour-solid phase reaction in the nitrogen atmosphere containing silicon tetrachloride.
Invention content
The high silicon FAU zeolites of low, product yield high that the purpose of the present invention is to provide a kind of production costs, good product quality
The preparation method of molecular sieve.
The preparation method of high silicon FAU zeolite molecular sieves provided by the invention, with commodity NaY zeolite molecular sieve powder with it is amorphous
Silica（SiO2）Column type or spheric granules is made in the mixture constituted for raw material, after drying and dehydrating is handled, in fixation
In bed reactor, containing silicon tetrachloride（SiCl4）Nitrogen stream in, by following four vapour-solid phase reaction process：NaY with
The dealumination complement silicon of silicon tetrachloride steam reacts；Amorphous silica surface hydroxyl is reacted with silicon tetrachloride, is generated high activity and is contained
Chlorine Si-O intermediate products；Zeolite surface silicone hydroxyl is reacted with the intermediate product, makes amorphous silica on high-silicon Y-Zeolite surface
Turn crystals growth；Amorphous silica obtains granular disintegration in Y zeolite surface epitaxial growths；Then by the granular disintegration
It is washed through hot water, particle, that is, self-dispersing is powder, then removes soluble NaCl to get to high silicon FAU zeolite molecular sieves（High silicon
Y powder）.
In the present invention, the raw material powdery NaY zeolite molecular sieve silica alumina ratio 4.5-5.2.
In the present invention, the amorphous silica can be used Ludox or White Carbon black, NaY zeolite molecular sieve with it is amorphous
Silica, ratio of the two in compound particles are calculated as NaY/ SiO with butt2=3.0/1-10/1。
In the present invention, when vapour-solid phase reaction, the air velocity of nitrogen is 120-150ml/ points.
In the present invention, vapour-solid phase reaction temperature is 270-500 DEG C, and the reaction time is 15-100 minutes.
FAU zeolite molecular sieves prepared by the present invention, silica alumina ratio（SAR）For 9-150, relative crystallinity is 105-
135%, yield is 105-140%.
The molecular sieve can be used for preparing macropore hydrophobic zeolite adsorbent and hydrocarbon cracking catalyst.
Description of the drawings
Fig. 1 is vapour-solid phase reaction apparatus structure diagram.
Figure label：1 is steel cylinder, and 2 be flowmeter, and 3 be pressure gauge, and 4 be drying tube, and 5 be reaction liquid container, and 6 be reaction
Device, 7 be alchlor collecting pipe, and 8 be tail gas absorption pipe, and 9 be thermocouple, and 10,11,12 be three-way valve, and 13,14,15 be two
Port valve door.
Specific implementation mode
The vapour that the present invention uses-solid phase reaction device, as shown in Fig. 1.It reacts in liquid container 5 and is reacted equipped with silicon tetrachloride
Liquid, NaY powder are placed on amorphous silica compound particles in reactor 6.Nitrogen is from steel cylinder 1 with certain flow through dry
After dry pipe 4 by react liquid container 5 be saturated by silicon tetrachloride after enter reactor 6, at a certain temperature with after drying and dehydrating
Compound particles react.The distillation that the tail gas that reactor 6 flows out is taken out of is that gaseous alchlor is collected in pipeline 7
In, the acids such as the complete silicon tetrachloride of contained unreacted and HCl are by the solid CaO or NaOH in tail gas absorption pipe in tail gas
It is absorbed, prevents from entering atmosphere pollution environment.The electric tube furnace of outside of reactor 6（It does not draw）Heating, is built in reaction tube
In thermocouple 9 be used to measure reaction temperature and control the heating temperature of electric tube furnace.
In the present invention, four reaction process are respectively：
Process 1, raw material NaY powder and SiCl4Steam carries out vapour/solid phase dealumination complement silicon reaction, improves the SAR of zeolite；
；
Process 2, amorphous silica surface hydroxyl and silicon tetrachloride vapour-solid phase reaction generate Si-O of the high activity containing chlorine
Intermediate product；
；
Process 3, zeolite surface silicone hydroxyl are reacted with the Si-O intermediate products containing chlorine realizes amorphous silica in height
Silicon Y-Zeolite surface turns crystals growth；
；
Process 4, Y zeolite surfaces silicone hydroxyl and the silicone hydroxyl on amorphous silica surface and SiCl4Reaction is realized high
Epitaxial growth on silicon Y-Zeolite
。
It is raw materials used：
NaY powder-Shanghai Xin Nian petrochemical industry auxiliary reagent factory, SAR=4.7；Silicon tetrachloride-is anhydrous, and the bright cutting edge of a knife or a sword chemical industry in Zhejiang Quzhou is limited
Company；Ludox（SiO2-30%）Haiyang Chemical Plant, Qingdao；White Carbon black-Shandong Weifang Long Gang silicon industry.
Product detection instrument and method
Instrument：Chemical analysis-X-ray Fluorescence Spectrometer；Relative crystallinity-XRD powder diffractometers；BET- cryogenic absorptions surface
Product analyzer；Water and n-hexane adsorbance-micro vapor sorption balance.
Test method：
Relative crystallinity：With the XRD of raw material NaY powder in 5-35oOn the basis of the total mark intensity of the characteristic diffraction peak of/2 θ,
Characteristic diffraction peak total mark intensity ratio number, that is, relative crystallinity in contrast of the product to be measured in same angle of diffraction。
Hydrophobic property coefficient Hn=Sn/Sw：Sn- zeolites to be measured are 7 torr in pressure（Mm Hg columns）N-hexane under vapour pressure
Adsorb weight；Sw- zeolites to be measured are 5 torr in pressure（Mm Hg columns）Water vapour in absorption weight.Hn is less than 1, indicates
The molecular screen material is hydrophily；Hn is more than 1, indicates that the molecular screen material is hydrophobicity.
Calculation of yield：Yield (%) Gu=vapour/high-silicon Y-Zeolite yield after reaction/is put into the dehydration NaY amounts in reaction tube.
The flow of preparation is as follows：
1, compound particles are prepared：NaY powder is mixed with Ludox or White Carbon black, ratio（It is calculated by butt）NaY/ silicon
Silica=3.0/1-10/1 in colloidal sol or White Carbon black（I.e.（3-10）：1）, it is kneaded into " dough " after adding suitable water, with granulation
The spherical compound particles of 2 millimeters of diameter, 3-4 millimeters of long 5-10 millimeters of strip or diameter are made in machine；
2, it dehydrates：This compound particles is heated 10-24 hours in 300 DEG C of baking oven, removes contained big portion
Divide moisture；
3, depth drying：200 grams of compound particles after dry are put into reaction tube 6 and are heated to scheduled reaction temperature
Keep constant temperature.Nitrogen after abundant drying is passed through in reaction tube and is kept for 2-3 hours, by the thorough drying and dehydrating of compound particles；
Gu 4, vapour/reaction：Nitrogen is passed through equipped with SiCl4Gu reaction liquid container 5 in carry out vapour/reaction, air velocity
120-150ml/ points.Initial reaction stage, temperature in reactor then stop rising because the release of reaction heat can rise 20-50 DEG C
And it is gradually reduced.At this time it is believed that reaction has been basically completed；
5, it purges：The air-flow for entering reactor is switched to the nitrogen of pure drying, reactor is kept to maintain the anti-of former setting
Temperature is answered 2 hours, to purge the cleared silicon tetrachloride steam remained in space reactor and compound particles；
6, washing and roasting：Compound particles are taken out after cooling reaction tube, to remove byproduct of reaction NaCl and amorphous
Particle after reaction is immersed in boiling water by silica, at this point, particle, that is, self-dispersing is powder.
This powder is after deionized water is fully washed into water without chlorion, drying, is roasted 3-5 hours at 350-550 DEG C,
It is placed in drier and is cooled to room temperature, take out.Its weight i.e. products weight is weighed, for calculating reaction yield.Then, it is tested
Ingredient, relative crystallinity, BET surface area, water and n-hexane steam adsorption capacity, to calculate hydrophobic coefficient.
The specific example of preparation：
Amorphous silica raw material used in each secondary response（Silicon source）Gu and its proportion, vapour-reaction temperature and time,
The chemical composition of product, relative crystallinity, yield, adsorption property（BET surface area, water and n-hexane steam adsorption capacity, hydrophobicity
Coefficient）See following table：
* No7 products are through pickling, and after 600 DEG C of steam treatments 4 hours.
Claims (2)
1. a kind of preparation method of high silicon FAU zeolite molecular sieves, which is characterized in that with commodity NaY zeolite molecular sieve powder and without fixed
Shape silica（SiO2）For raw material, column type or spheric granules are made after mixing, it is anti-in fixed bed after drying and dehydrating is handled
It answers in device, is containing silicon tetrachloride（SiCl4）Nitrogen stream in, by following four vapour-solid phase reaction process：NaY and tetrachloro
The dealumination complement silicon of SiClx steam reacts；Amorphous silica surface hydroxyl is reacted with silicon tetrachloride, generates high activity Si- containing chlorine
O intermediate products；Zeolite surface silicone hydroxyl is reacted with the intermediate product, and amorphous silica is made to turn crystalline substance on high-silicon Y-Zeolite surface
Growth；Amorphous silica obtains granular disintegration in Y zeolite surface epitaxial growths；Then by the granular disintegration through heat
Water washing, particle, that is, self-dispersing are powder, then remove soluble NaCl to get to high silicon FAU zeolite molecular sieves；Wherein：
The NaY zeolite molecular sieve silica alumina ratio 4.5-5.2；The amorphous silica is Ludox or White Carbon black；
NaY zeolite molecular sieve and amorphous silica, ratio of the two in compound particles are calculated as NaY/ SiO with butt2=
3.0/1-10/1；
When vapour-solid phase reaction, the air velocity of nitrogen is 120-150ml/ points；
The vapour-solid phase reaction temperature is 270-500 DEG C, and the reaction time is 15-100 minutes.
2. the preparation method of high silicon FAU zeolite molecular sieves according to claim 1, which is characterized in that the FAU zeolites of preparation
Molecular sieve, silica alumina ratio 9-150, relative crystallinity 105-135%, yield 105-140%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194941A (en) * | 1997-03-31 | 1998-10-07 | 中国石油化工总公司 | Process for preparation of catylist composition containing silicon-rich ultrastable Y zeolite |
| CN102452661A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194941A (en) * | 1997-03-31 | 1998-10-07 | 中国石油化工总公司 | Process for preparation of catylist composition containing silicon-rich ultrastable Y zeolite |
| CN102452661A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing molecular sieve |
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