CN103539151A - Preparation method of high silica-alumina ratio Y type zeolite rich in secondary pores - Google Patents
Preparation method of high silica-alumina ratio Y type zeolite rich in secondary pores Download PDFInfo
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Abstract
The invention relates to a preparation method of high silica-alumina ratio Y type zeolite rich in secondary pores. The method comprises the following steps of mixing a silicon resource, an aluminum resource, an iron source and water under 40 to 70 DEG C; agitating to obtain a gel-reaction mixture; crystallizing the gel-reaction mixture for 24 to 120 hours under 90 to 140 DEG C to obtain a raw powder molecular sieve Fe-NaY; uniformly mixing the raw powder molecular sieve Fe-NaY, an ammonium salt solution and water according to the weight ratio of the raw powder molecular sieve Fe-NaY to the ammonium salt solution to water of 1: (0.2-2): (5-20); agitating for 0.5 to 4 hours under pH of 2.0 to 10.0 at the temperature of 20 to 95 DEG C in order to perform ammonium exchange; filtering; washing; drying for 5 to 12 hours under 50 to 120 DEG C; roasting for 0.5 to 4 hours in an 100% water vapor atmosphere under 550 to 750 DEG C; and then performing the ammonium exchange and hydro-thermal treatment once again to obtain Y type zeolite. The Y type zeolite prepared by the method is higher in silica-alumina ratio and richer in the secondary pores.
Description
Technical field
The present invention relates to a kind of preparation method of y-type zeolite, relate in particular to a kind of preparation method with the high silica alumina ratio y-type zeolite that enriches second hole, belong to molecular screen material preparing technical field.
Background technology
In recent years, along with crude oil heaviness, in poor quality and the market increase day by day to light-end products demand day by day, refinery is for improving the ability of heavy raw oil (long residuum, vacuum residuum, deasphalted oil) catalytic cracking deep processing, quality to oil refining catalyst is had higher requirement, and the demand of molecular sieve is also risen gradually.
As everyone knows, y-type zeolite is the main active component of industrial FCC catalyzer, and the product that the cracking activity of zeolite and selectivity directly affect cracking reaction distributes.Framework si-al ratio (the SiO of y-type zeolite structure cell
2/ Al
2o
3) directly affect hydrothermal stability and the acid acceptance of zeolite.When being applied to catalytic cracking catalyst, higher framework si-al ratio can make zeolite can bear reaction regeneration condition harsh in catalytic cracking process, the work-ing life of extending catalyst.In addition, improve the silica alumina ratio of y-type zeolite skeleton, rationally reduce Al center density, improve the relative intensity in acid site, contribute to improve the ratio of cracking/hydrogen transfer activity, reduce catalysis green coke, improve product and distribute.In addition,, due to heaviness and the in poor quality of crude oil, in order to improve the cracking ability of catalyst towards heavy matter and inferior raw material, need to there is as the Y zeolite in active centre more second hole; In order to reach the object of increasing output of diesel oil, also needing has more second hole.Visible, high silica alumina ratio, the y-type zeolite (hereinafter to be referred as type-Y high silicon zeolite) that enriches second hole are very suitable for the catalytic cracking of heavy oil, and the product that it directly affects Catalyst Production and catalytic cracking unit distributes and economic benefit.
Traditional method of preparing type-Y high silicon zeolite can be divided into two kinds: direct synthesis technique and aftertreatment modification method.Wherein direct synthesis technique can be divided into template agent method and non-template agent method.Chinese patent application 96108159 discloses a kind ofly take quaternary ammonium hydroxide, quaternary ammonium salt and reaches 10 NaY zeolite as template makes silica alumina ratio; Chinese patent application 97196809 discloses a kind of preparation method that a small amount of water and organism be raw material of take, the SiO of Y type faujusite prepared by the method
2/ Al
2o
3mol ratio can reach 6-10; But template used dose expensive, the crystallization time needing is very long, is unfavorable for large-scale industrial application.Adopt directly synthetic y-type zeolite (for example RUP2090502, USP3130007, JP1091013) of non-template agent method, by adjusting proportioning, crystallization condition and the directed agents of reactant or the experiment synthetic method of crystal seed, feature is that the silica alumina ratio of zeolite is at 5.6-7.5, shortcoming is that framework si-al ratio is low, hydrothermal stability and acid-resistant stability poor, the work-ing life of catalyzer is short, needs further to improve the framework si-al ratio of zeolite.Hydrothermal dealumination method (for example USP3449370, USP4701313, USP4297335, USP4438178), feature is to prepare the USY of silica alumina ratio 6-20, but with the generation of non-framework aluminum, and the zeolite part lattice phenomenon of caving in easily occurs; Chemical dealuminization method (for example USP40493560), feature is to prepare the y-type zeolite molecular sieve of silica alumina ratio 6-15, but can introduce other atom, follows the zeolite part lattice phenomenon of caving in.Heteroatoms is introduced and in y-type zeolite, formed heteroatoms y-type zeolite molecular sieve, acidity that can modulation y-type zeolite molecular sieve, absorption property, oxidation-reduction quality etc., the disclosed method of USP4333859, USP4309313 is that cesium ion is incorporated in y-type zeolite, the molecular sieve that to have made silica alumina ratio be 7.
Can find out, although above-mentioned processing method has been carried out modification to y-type zeolite molecular sieve character, operational path is loaded down with trivial details, energy consumption is high, problem of environmental pollution is serious, and the crystallization reservation degree of resulting y-type zeolite is low, pore structure and acid not ideal enough.So, research and develop that a kind of to adopt non-template agent method synthetic technology route preparation to have the Y zeolite that has again higher crystalline reservation degree simultaneously compared with high silica alumina ratio, higher thermostability be one of this area problem demanding prompt solution.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of preparation method of y-type zeolite, by adopt simple process under non-template agent state, directly synthetic Fe-NaY molecular sieve the Fe-NaY molecular sieve of take are that raw material adopts the columbite process of " two hand over two hydro-thermals " to obtain a kind ofly having than the y-type zeolite of the higher silica alumina ratio of conventional y-type zeolite and abundanter second hole.
For achieving the above object, first the present invention provides a kind of preparation method of y-type zeolite, and it comprises the following steps:
According to (1-8) Na
2o: 1Al
2o
3: (7-20) SiO
2: (180-250) H
2o: (0.002-0.2) Fe
2o
3mol ratio, at 40-70 ℃, ,Lv source, silicon source, source of iron and water are mixed, stir and obtain gel reaction mixture;
Make above-mentioned gel reaction mixture crystallization 24-120h at 90-140 ℃, obtain former powder molecular sieve Fe-NaY;
According to former powder molecular sieve Fe-NaY: the weight ratio of ammonium salt: water=1: 0.2-2: 5-20, former powder molecular sieve Fe-NaY, ammonium salt solution and water are mixed, in pH value, be that 2.0-10.0, temperature are to stir 0.5-4h under the condition of 20-95 ℃, wash after filtration,, at 50-120 ℃, be dried 5-12h, then roasting 0.5-4h in 550-750 ℃, 100% steam atmosphere, then repeat above-mentioned ammonium exchange processing and hydrothermal treatment consists and once (also comprise filtration, washing step), obtain y-type zeolite (or claiming Fe-USY zeolite).
In aforesaid method provided by the invention, preferably, the temperature of crystallization can be controlled at 90-120 ℃.
In aforesaid method provided by the invention, preferably, in above-mentioned gel reaction mixture, be added with directed agents, by adding directed agents, can improve the crystal property of molecular sieve, directed agents can mix with ,Lv source, silicon source, source of iron etc., then by stirring, is prepared into gel reaction mixture.The add-on of this directed agents is the 1-60% (add-on of directed agents is included among the quality of gel reaction mixture herein) of gel reaction mixture quality; More preferably, the control of the add-on of directed agents is the 5-50% of gel reaction mixture quality.
Directed agents of the present invention can be to prepare by the whole bag of tricks of preparing faujusite directed agents in prior art, preferably what generally adopt is prepared by the method for preparing directed agents adopting in the conventional preparation method of NaY according at present industrial, for example, according to USP3639099, USP3671191, the method of preparing directed agents proposing in USP4166099 and CN1081425A is prepared (full text of above-mentioned patent application is introduced as a reference) here, can not change so the synthesis technique of existing NaY and not need increase equipment, the raw material constitutive molar ratio scope of directed agents may be controlled to (4-40) Na
2o: 1Al
2o
3: (8-40) SiO
2: (100-530) H
2o.
According to specific embodiment of the invention scheme, preferably, directed agents of the present invention is according to (4-40) Na
2o: 1Al
2o
3: (8-40) SiO
2: (100-530) H
2the mol ratio of O, after ,Lv source, silicon source and water are uniformly mixed, stirs at 10-70 ℃ that ageing 2-50h makes.According to specific embodiment of the invention scheme, preferably, when preparation directed agents, the silicon source adopting is water glass, and aluminium source is high alkali deflection aluminium acid sodium.
According to specific embodiment of the invention scheme, preferably, when preparing gel reaction mixture, the silicon source adopting is one or several the mixture in water glass, water glass, solid silicone and white carbon black etc.
According to specific embodiment of the invention scheme, preferably, when preparing gel reaction mixture, the aluminium source adopting is one or several the mixture in pseudo-boehmite, high alkali deflection aluminium acid sodium, Tai-Ace S 150, aluminum nitrate and aluminum chloride etc.
According to specific embodiment of the invention scheme, preferably, when preparing gel reaction mixture, the source of iron adopting is one or several the mixture in ferric sulfate, iron nitrate and iron(ic) chloride etc.
In aforesaid method provided by the invention, the synthesis technique of " two hand over two hydro-thermals " can carry out according to the flow process shown in formula (1):
Fe-NaY → ammonium exchange → hydrothermal treatment consists → ammonium exchange → hydrothermal treatment consists (1)
Y-type zeolite provided by the invention is by ammonium, to exchange the method processing Fe-NaY type zeolite that combines with hydrothermal treatment consists process and be used alternatingly to obtain; This y-type zeolite mixes and can make catalytic cracking catalyst with matrix, can be for the treatment of distillate or residual oil.In the process of " two hand over two hydro-thermals ", the process of ammonium exchange is that Fe-NaY is exchanged into Fe-HY, carrying out subsequently hydrothermal treatment consists is that silicon is mended in dealuminzation deferrization in solid phase, can make Siliciumatom occupy the room staying after dealuminzation deferrization, reach the stabilization of structure, as mentioned above, the ammonium that hockets exchange and hydrothermal treatment consists, can control the degree of depth of dealuminzation deferrization, make the type-Y high silicon zeolite of required silica alumina ratio.
According to specific embodiment of the invention scheme, preferably, ammonium exchange process of the present invention is according to former powder molecular sieve Fe-NaY: the weight ratio of ammonium salt: water=1: 0.2-2: 5-20, former powder molecular sieve Fe-NaY, ammonium salt (aqueous solution), water are mixed, in pH value, be that 2.0-10.0, temperature are at 20-95 ℃, to stir 0.5-4h, after filtration, washing, in 50-120 ℃ of dry realize.In ammonium exchange process, the ammonium salt adopting is preferably one or several the mixture in ammonium chloride, ammonium sulfate and ammonium nitrate etc., more preferably ammonium chloride; The component mol ratio of former powder molecular sieve Fe-NaY, ammonium salt, water is preferably 1: 0.8-1.5: 8-12; PH value is preferably 2.5-5.0, and general available ammoniacal liquor or hydrochloric acid regulate.In hydrothermal treatment consists process, the temperature of hydrothermal treatment consists is preferably 500-700 ℃, and the time of hydrothermal treatment consists is preferably 1-4h.
The preparation method of y-type zeolite provided by the invention is the Fe-NaY zeolite of the synthetic high-crystallinity of introducing hetero-atoms Fe, high silica alumina ratio first, then in conjunction with ammonium exchange, two processes of hydrothermal treatment consists and be used alternatingly, process Fe-NaY zeolite, obtain USFeY zeolite, it is a kind of Y zeolite that has high silica alumina ratio, enriches second hole.The y-type zeolite degree of crystallinity of preparing by method provided by the invention can reach more than 85%, silica alumina ratio (SiO
2/ Al
2o
3) can reach more than 20, the percentage ratio that second hole volume accounts for total pore volume is 40-60%, the USY zeolite facies ratio that introducing hetero-atoms Fe does not make with adopting same procedure, and silica alumina ratio amplification is more than 40%, and second hole volume amplification is more than 47%.With the USY zeolite facies ratio that adopts identical hydro-thermal treatment method to prepare, Fe-USY zeolite prepared by the present invention has higher silica alumina ratio, more flourishing second hole; When adopt lower than 100 ℃ of USY zeolite water thermal treatment temps synthetic method time, the Fe-USY zeolite preparing and USY zeolite have the silica alumina ratio of formed objects.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the y-type zeolite of embodiment 1 preparation and the molecular sieve USY1 of comparative example 1 preparation.
Fig. 2 is the XRD figure spectrum of the y-type zeolite of embodiment 2 preparations and the molecular sieve USY2 of comparative example 2 preparations.
Fig. 3 is the XRD figure spectrum of the y-type zeolite of embodiment 3 preparations and the molecular sieve USY3 of comparative example 3 preparations.
Fig. 4 is the XRD figure spectrum of the y-type zeolite of embodiment 4 preparations and the molecular sieve USY4 of comparative example 4 preparations.
Embodiment
For technical characterictic of the present invention, object and beneficial effect being had more clearly, understand, existing technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
In each embodiment, the secondary pore volume of Fe-NaY molecular sieve and the measuring method of total pore volume are as follows: according to RIPP151-90 standard method (< < Petrochemical Engineering Analysis method (RIPP test method) > >, Yang Cui is the volume such as surely, Science Press, nineteen ninety publication) according to adsorption isothermal line, determine the total pore volume of molecular sieve, then from adsorption isothermal line, according to T graphing method, determine the micro pore volume of molecular sieve, total pore volume is deducted to micro pore volume and obtain second hole volume.The mensuration of relative crystallinity and silica alumina ratio all adopts Japanese Shimadzu XRD6000 type x-ray powder diffraction instrument, test condition is: CuK α radiation, Ni filtering, tube voltage 30KV, tube current 40Ma, walk widely by 0.02, adopt (331), (511,333), (440), (533), (642), (822,660), (555,751), (664) the area sum at totally eight peaks (with the comparison of NaY molecular sieve standard specimen) calculation sample degree of crystallinity (relative crystallinity).The measuring method of silica alumina ratio according to SH/T0339-92 standard method (referring to < < standard of chemical industry compilation > >, China Standard Press, within 2000, publish), and according to following formula:
Calculate lattice constant a
In formula, a-lattice constant
λ-Cu-K α
1wavelength
(h
2+ k
2+ l
2)-X-ray diffraction index sum of squares.
According to Breck-Flanigen formula, calculate y-type zeolite silica alumina ratio:
Si/Al＝(25.858-a)/(a-24.191)
Embodiment 1
The present embodiment provides a kind of preparation method of y-type zeolite, and it comprises the following steps:
After taking 43.3g water glass, 30.3g high alkali deflection aluminium acid sodium solution and mixing, under 50 ℃ of whipped states, ageing 5h makes directed agents, and the component mol ratio of this directed agents is 16.0Na
2o: 1Al
2o
3: 15.1SiO
2: 322.3H
2o;
Take 331.3g water glass and be placed in beaker, under 50 ℃ of stirring in water bath, add successively 68.3g high alkali deflection aluminium acid sodium solution, 63.4g directed agents to stir 3h, then add 173.lg alum liquor to stir 1h, finally add source of iron (iron nitrate solution) to stir 0.5h, after stirring, obtain gel reaction mixture, in this gel reaction mixture, the mol ratio of each component is 2.45Na
2o: 1Al
2o
3: 8.08SiO
2: 181.9H
2o: xFe
2o
3(x is respectively 0.002,0.01,0.03), is packed in reactor into crystallization at 96 ℃, and crystallization time is respectively 30h, 42h, 60h, then through washing, filter, in 100 ℃ of dry 10h, obtain former powder molecular sieve Fe-NaY;
Get the former powder molecular sieve of 50g Fe-NaY, be scattered in the aqueous ammonium chloride solution that 550g concentration is 9wt% (in weight ammonium chloride), after stirring, with 1mol/L hydrochloric acid soln, regulating the pH value of gained slurries is 3.3, be warming up to 90 ℃, maintain under the condition that pH value is constant and stir 1h, filter, with the deionized water wash of 20 times to without acid group, dry, then put into hydrothermal device, be warming up to 650 ℃, pass into 100% steam roasting 2h, repeat again once above-mentioned ammonium exchange, hydrothermal treatment consists process, obtain y-type zeolite, be designated as Fe-USY, the X-ray diffraction phase figure (XRD) of products therefrom is shown in Fig. 1, the diffraction peak of Fe-USY (331), (511, 333), (440), (533), (642), (822, 660), (555, 751), (664) eight characteristic diffraction peak peak shapes keep complete, without stray crystal, generate, be indicated as Y zeolite structure.The chemical composition and structure parameter of above-mentioned y-type zeolite is in Table 1.
Table 1
Comparative example 1
The method preparation contrast molecular sieve providing by embodiment 1, just when preparing gel reaction mixture, do not add source of iron, the molecular sieve obtaining is designated as USY1, the X-ray diffraction phase figure (XRD) of products therefrom is shown in Fig. 1, eight characteristic diffraction peak peak shapes of the diffraction peak of molecular sieve USY1 (331), (511,333), (440), (533), (642), (822,660), (555,751), (664) keep complete, without stray crystal, generate, be indicated as Y zeolite structure.
The chemical composition and structure parameter of this molecular sieve USY1 is in Table 2.
Table 2
| USY1 | |
| Relative crystallinity, % | 90 |
| Framework si-al ratio | 16.1 |
| Specific surface area, m 2/g | 637.9 |
| Total pore volume, ml/g | 0.39 |
| Micro pore volume, ml/g | 0.24 |
| Second hole volume, ml/g | 0.15 |
| Second hole volume/total pore volume, % | 38.4 |
| Chemical constitution, % by weight | |
| Na 2O | 0.17 |
| Al 2O 3 | 23.3 |
| SiO 2 | 63.4 |
From the comparative analysis of table 1 and table 2, can find out, compare with the molecular sieve (USY1) that comparative example 1 adopts hydrothermal dealumination method to prepare, the second hole volume of the Fe-USY of embodiment 1 preparation is all at 0.22cm
3g
-1above, be up to 0.29cm
3g
-1, framework si-al ratio all, more than 19, is up to 27.5.This second hole volume increase mode not with micro pore volume significantly drop to cost, the micro pore volume of all Fe-USY samples all still maintains 0.22cm
3g
-1a high position even.As can be seen here, the y-type zeolite of embodiment 1 preparation is a kind of Y zeolite that has high silica alumina ratio, enriches second hole.
The present embodiment provides a kind of preparation method of y-type zeolite, and it comprises the following steps:
After taking 46g water glass, 28g high alkali deflection aluminium acid sodium solution and mixing, under 50 ℃ of whipped states, ageing 5h makes directed agents, and the component mol ratio of this directed agents is 16.7Na
2o: 1Al
2o
3: 17.35SiO
2: 350: 4H
2o;
Take 333g water glass and be placed in beaker, under 50 ℃ of stirring in water bath, add successively 70g high alkali deflection aluminium acid sodium solution, 65g directed agents to stir 3h, then add 160g alum liquor to stir 1h, finally add source of iron (iron nitrate solution) to stir 0.5h, after stirring, obtain gel reaction mixture, in this gel reaction mixture, the mol ratio of each component is 2.85Na
2o: 1Al
2o
3: 8.7SiO
2: 190.4H
2o: xFe
2o
3(x is respectively 0.006,0.02,0.05), is packed in reactor into crystallization at 96 ℃, and crystallization time is respectively 35h, 47h, 80h, then through washing, filter, in 100 ℃ of dry 10h, obtain former powder molecular sieve Fe-NaY;
Get the former powder molecular sieve of 50g Fe-NaY, be scattered in the aqueous ammonium chloride solution that 550g concentration is 9wt% (in weight ammonium chloride), after stirring, with 1mol/L hydrochloric acid soln, regulating the pH value of gained slurries is 3.3, be warming up to 90 ℃, maintain under the condition that pH value is constant and stir 1h, filter, with the deionized water wash of 20 times to without acid group, dry, then put into hydrothermal device, be warming up to 650 ℃, pass into 100% steam roasting 2h, repeat again once above-mentioned ammonium exchange, hydrothermal treatment consists process, obtain y-type zeolite, be designated as Fe-USY, the X-ray diffraction phase figure (XRD) of products therefrom is shown in Fig. 2, the diffraction peak of Fe-USY (331), (511, 333), (440), (533), (642), (822, 660), (555, 751), (664) eight characteristic diffraction peak peak shapes keep complete, without stray crystal, generate, be indicated as Y zeolite structure.The chemical composition and structure parameter of above-mentioned y-type zeolite is in Table 3.
Table 3
Comparative example 2
The method preparation contrast molecular sieve providing by embodiment 2, just when preparing gel reaction mixture, do not add source of iron, the molecular sieve obtaining is designated as USY2, the X-ray diffraction phase figure (XRD) of products therefrom is shown in Fig. 2, eight characteristic diffraction peak peak shapes of the diffraction peak of molecular sieve USY2 (331), (511,333), (440), (533), (642), (822,660), (555,751), (664) keep complete, without stray crystal, generate, be indicated as Y zeolite structure.
The chemical composition and structure parameter of this molecular sieve USY2 is in Table 4.
Table 4
| USY2 | |
| Relative crystallinity, % | 89 |
| Framework si-al ratio | 15.4 |
| Specific surface area, m 2/g | 634.7 |
| Total pore volume, ml/g | 0.38 |
| Micro pore volume, ml/g | 0.25 |
| Second hole volume, ml/g | 0.13 |
| Second hole volume/total pore volume, % | 34.2 |
| Chemical constitution, % by weight | |
| Na 2O | 0.16 |
| Al 2O 3 | 24.3 |
| SiO 2 | 63.7 |
From the comparative analysis of table 3 and table 4, can find out, the molecular sieve (USY2) preparing by hydrothermal dealumination method with comparative example 2 is compared, and the second hole volume of the Fe-USY of embodiment 2 preparations is all at 0.23cm
3g
-1above, be up to 0.32cm
3g
-1, framework si-al ratio all, more than 19.9, is up to 26.4.This second hole volume increase mode not with micro pore volume significantly drop to cost, the micro pore volume of all Fe-USY samples all still maintains 0.22cm
3.g
-1a high position even.As can be seen here, the y-type zeolite of embodiment 2 preparations is a kind of Y zeolites that have high silica alumina ratio, enrich second hole.
Embodiment 3
The present embodiment provides a kind of preparation method of y-type zeolite, and it comprises the following steps:
After taking 50g water glass, 25g high alkali deflection aluminium acid sodium solution and mixing, under 50 ℃ of whipped states, ageing 5h makes directed agents, and the component mol ratio of this directed agents is 18Na
2o: 1Al
2o
3: 21.12SiO
2: 397.1H
2o;
Take 335g water glass and be placed in beaker, under 50 ℃ of stirring in water bath, add successively 40g high alkali deflection aluminium acid sodium solution, 67g directed agents to stir 3h, then add 164g alum liquor to stir 1h, finally add source of iron (iron nitrate solution) to stir 0.5h, after stirring, obtain gel reaction mixture, the mol ratio of this each component of gel reaction mixture is 2.17Na
2o: 1Al
2o
3: 9.34SiO
2: 194.8H
2o: xFe
2o
3(x is respectively 0.02,0.04,0.07), is packed in reactor into crystallization at 96 ℃, and crystallization time is respectively 55h, 72h, 99h, then through washing, filter, in 100 ℃ of dry 10h, obtain former powder molecular sieve Fe-NaY;
Get the former powder molecular sieve of 50g Fe-NaY, be scattered in the aqueous ammonium chloride solution that 550g concentration is 9wt% (in weight ammonium chloride), after stirring, with 1mol/L hydrochloric acid soln, regulating the pH value of gained slurries is 3.3, be warming up to 90 ℃, maintain under the condition that pH value is constant and stir 1h, filter, with the deionized water wash of 20 times to without acid group, dry, then put into hydrothermal device, be warming up to 650 ℃, pass into 100% steam roasting 2h, repeat again once above-mentioned ammonium exchange, hydrothermal treatment consists process, obtain y-type zeolite, be designated as Fe-USY, the X-ray diffraction phase figure (XRD) of products therefrom is shown in Fig. 3, the diffraction peak of Fe-USY (331), (511, 333), (440), (533), (642), (822, 660), (555, 751), (664) eight characteristic diffraction peak peak shapes keep complete, without stray crystal, generate, be indicated as Y zeolite structure.The chemical composition and structure parameter of above-mentioned y-type zeolite is in Table 5.
Table 5
Comparative example 3
The method preparation contrast molecular sieve providing by embodiment 3, just when preparing gel reaction mixture, do not add source of iron, the molecular sieve obtaining is designated as USY3, the X-ray diffraction phase figure (XRD) of products therefrom is shown in Fig. 3, eight characteristic diffraction peak peak shapes of the diffraction peak of USY3 (331), (511,333), (440), (533), (642), (822,660), (555,751), (664) keep complete, without stray crystal, generate, be indicated as Y zeolite structure.
The chemical composition and structure parameter of gained molecular sieve is in Table 6.
Table 6
| USY3 | |
| Relative crystallinity, % | 81 |
| Framework si-al ratio | 14.2 |
| Specific surface area, m 2/g | 631.9 |
| Total pore volume, ml/g | 0.36 |
| Micro pore volume, ml/g | 0.24 |
| Second hole volume, ml/g | 0.12 |
| Second hole volume/total pore volume, % | 33.3 |
| Chemical constitution, % by weight | |
| Na 2O | 0.14 |
| Al 2O 3 | 22.7 |
| SiO 2 | 64.4 |
From the comparative analysis of table 5 and table 6, can find out, the molecular sieve (USY3) that the hydrothermal dealumination method providing with comparative example 3 prepares is compared, and the second hole volume of the Fe-USY of embodiment 3 preparations is all at 0.23cm
3g
-1above, be up to 0.28cm
3g
-1, framework si-al ratio all, more than 23.2, is up to 27.4.This second hole volume increase mode not with micro pore volume significantly drop to cost, the micro pore volume of all Fe-USY sample crystalline substances all still maintains 0.21cm
3g
-1a high position even.As can be seen here, the y-type zeolite of embodiment 3 preparations is a kind of Y zeolites that have high silica alumina ratio, enrich second hole.
Embodiment 4
The present embodiment provides a kind of preparation method of y-type zeolite, and it comprises the following steps:
After taking 60g water glass, 28g high alkali deflection aluminium acid sodium solution and mixing, under 50 ℃ of whipped states, ageing 5h makes directed agents, and the component mol ratio of this directed agents is 18.5Na
2o: 1Al
2o
3: 22.6SiO
2:: 415.8H
2o;
Take 337g water glass and be placed in beaker, under 50 ℃ of stirring in water bath, add successively 46g high alkali deflection aluminium acid sodium solution, 55g directed agents to stir 3h, then add 130g alum liquor to stir 1h, finally add source of iron (iron nitrate solution) to stir 0.5h, after stirring, obtain gel reaction mixture, the mol ratio of this each component of gel reaction mixture is 2.47Na
2o: 1Al
2o
3: 10.56SiO
2: 208.90H
2o: xFe
2o
3(x is respectively 0.9,0.12,0.20), is packed in reactor into crystallization at 96 ℃, and crystallization time is respectively 70h, 110h, 130h, then through washing, filter, in 100 ℃ of dry 10h, obtain former powder molecular sieve Fe-NaY;
Get the former powder molecular sieve of 50g Fe-NaY, be scattered in the aqueous ammonium chloride solution that 550g concentration is 9wt% (in weight ammonium chloride), after stirring, with 1mol/L hydrochloric acid soln, regulating the pH value of gained slurries is 3.3, be warming up to 90 ℃, keep stirring 1h under condition that pH value is constant, filter, with the deionized water wash of 20 times to without acid group, dry, then put into hydrothermal device, be warming up to 650 ℃, pass into 100% steam roasting 2h, repeat again once above-mentioned ammonium exchange, hydrothermal treatment consists process, obtain y-type zeolite, be designated as Fe-USY, the X-ray diffraction phase figure (XRD) of products therefrom is shown in Fig. 4, the diffraction peak of Fe-USY (331), (511, 333), (440), (533), (642), (822, 660), (555, 751), (664) eight characteristic diffraction peak peak shapes keep complete, without stray crystal, generate, be indicated as Y zeolite structure.
The chemical composition and structure parameter of above-mentioned y-type zeolite is in Table 7.
Table 7
Comparative example 4
The method preparation contrast molecular sieve providing by embodiment 4, just when preparing gel reaction mixture, do not add source of iron, the molecular sieve obtaining is designated as USY4, the X-ray diffraction phase figure (XRD) of products therefrom is shown in Fig. 4, eight characteristic diffraction peak peak shapes of the diffraction peak of Fe-USY (331), (511,333), (440), (533), (642), (822,660), (555,751), (664) keep complete, without stray crystal, generate, be indicated as Y zeolite structure.
The chemical composition and structure parameter of this molecular sieve USY4 is in Table 8.
From the comparative analysis of table 7 and table 8, can find out, compare with the molecular sieve (USY4) that comparative example 4 hydrothermal dealumination methods prepare, the second hole volume of the Fe-USY of embodiment 4 preparations is all at 0.20cm
3g
-1above, be up to 0.28cm
3g
-1, framework si-al ratio all, more than 18.7, is up to 25.4.This second hole volume increase mode not with micro pore volume significantly drop to cost, the micro pore volume of all Fe-USY samples all still maintains 0.23cm
3g
-1a high position even.As can be seen here, the y-type zeolite of embodiment 4 preparations is a kind of Y zeolites that have high silica alumina ratio, enrich second hole.
Table 8
| USY4 | |
| Relative crystallinity, % | 77 |
| Framework si-al ratio | 14.1 |
| Specific surface area, m 2/g | 627.1 |
| Total pore volume, ml/g | 0.38 |
| Micro pore volume, ml/g | 0.24 |
| Second hole volume, ml/g | 0.14 |
| Second hole volume/total pore volume, % | 36.8 |
| Chemical constitution, % by weight | |
| Na 2O | 0.13 |
| Al 2O 3 | 23.7 |
| SiO 2 | 65.4 |
Claims (10)
1. a preparation method for y-type zeolite, it comprises the following steps:
According to (1-8) Na
2o: 1Al
2o
3: (7-20) SiO
2: (180-250) H
2o: (0.002-0.2) Fe
2o
3mol ratio, at 40-70 ℃, ,Lv source, silicon source, source of iron and water are mixed, stir and obtain gel reaction mixture;
Make above-mentioned gel reaction mixture crystallization 24-120h at 90-140 ℃, obtain former powder molecular sieve Fe-NaY;
According to former powder molecular sieve Fe-NaY: the weight ratio of ammonium salt: water=1: 0.2-2: 5-20, former powder molecular sieve Fe-NaY, ammonium salt solution and water are mixed, in pH value, be that 2.0-10.0, temperature are under the condition of 20-95 ℃, to stir 0.5-4h to carry out ammonium exchange and process, wash after filtration,, at 50-120 ℃, be dried 5-12h, then roasting 0.5-4h in 400-800 ℃, 100% steam atmosphere, then repeat above-mentioned ammonium exchange processing and hydrothermal treatment consists respectively once, obtain described y-type zeolite.
2. method according to claim 1, wherein, is added with directed agents in described gel reaction mixture, and the add-on of this directed agents is the 1-60% of gel reaction mixture quality; Preferably, described directed agents is according to (4-40) Na
2o: 1Al
2o
3: (8-40) SiO
2: (100-530) H
2the mol ratio of O, after ,Lv source, silicon source and water are uniformly mixed, stirs at 10-70 ℃ that 2-50h obtains.
3. method according to claim 2, wherein, the add-on of described directed agents is the 5-50% of gel reaction mixture quality.
4. method according to claim 1, wherein, the temperature of described crystallization is controlled at 90-120 ℃.
5. method according to claim 2, wherein, preparation directed agents silicon source used is water glass, aluminium source is high alkali deflection aluminium acid sodium.
6. method according to claim 1, wherein, the silicon source of preparing gel reaction mixture is one or several the mixture in water glass, water glass, solid silicone and white carbon black.
7. method according to claim 1, wherein, the aluminium source of preparing gel reaction mixture is one or several the mixture in pseudo-boehmite, high alkali deflection aluminium acid sodium, Tai-Ace S 150, aluminum nitrate and aluminum chloride.
8. method according to claim 1, wherein, the source of iron of preparing gel reaction mixture is one or several the mixture in ferric sulfate, iron nitrate and iron(ic) chloride.
9. method according to claim 1, wherein, described ammonium salt is one or several the mixture in ammonium chloride, ammonium sulfate and ammonium nitrate.
10. method according to claim 1, wherein, the weight ratio of described former powder molecular sieve Fe-NaY, ammonium salt, water is 1: 0.8-1.5: 8-12, pH value is 2.5-5.
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