CN103539151B - 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, particularly relate to a kind of preparation method with the high silica alumina ratio y-type zeolite enriching second hole, belong to molecular screen material preparing technical field.
Background technology
In recent years, along with crude oil day by day heaviness, in poor quality and market to the increase day by day of light-end products demand, refinery is for improving the ability of heavy raw oil (long residuum, vacuum residuum, deasphalted oil) catalytic cracking deep processing, the quality of 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 cracking activity of zeolite and selectivity directly affect the product slates of cracking reaction.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 enable zeolite 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 the ratio improving cracking/hydrogen transfer activity, reduce catalysis green coke, improve product slates.In addition, due to heaviness and the in poor quality of crude oil, in order to improve the cracking capability of catalyst towards heavy matter and inferior raw material, the Y zeolite as active centre is needed to have more second hole; In order to reach the object of increasing output of diesel oil, also need more second hole.Visible, high silica alumina ratio, the y-type zeolite (hereinafter referred to as type-Y high silicon zeolite) enriching second hole are very suitable for the catalytic cracking of heavy oil, and it directly affects product slates and the economic benefit of Catalyst Production and catalytic cracking unit.
Traditional method 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 and a kind ofly obtains the NaY zeolite that silica alumina ratio reaches 10 with quaternary ammonium hydroxide, quaternary ammonium salt for template; Chinese patent application 97196809 discloses a kind of preparation method being raw material with a small amount of water and organism, 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 of needs is very long, is unfavorable for large-scale industrial application.Non-template agent method is adopted directly to synthesize y-type zeolite (such as RUP2090502, USP3130007, JP1091013), by adjusting the experiment synthetic method of the proportioning of reactant, crystallization condition and directed agents or 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 the framework si-al ratio improving zeolite further.Hydrothermal dealumination method (such as USP3449370, USP4701313, USP4297335, USP4438178), feature to prepare the USY of silica alumina ratio 6-20, but with the generation of non-framework aluminum, zeolite portion lattice easily occurs and to cave in phenomenon; Chemical dealuminization method (such as USP40493560), feature to prepare the Y-type zeolite molecular sieve of silica alumina ratio 6-15, but can introduce other atom, to cave in phenomenon with zeolite portion lattice.Heteroatoms is introduced in y-type zeolite and form heteroatoms Y-type zeolite molecular sieve, can the acidity, absorption property, oxidation-reduction quality etc. of modulation Y-type zeolite molecular sieve, method disclosed in USP4333859, USP4309313 is incorporated in y-type zeolite by cesium ion, obtained the molecular sieve that silica alumina ratio is 7.
Can find out, although above-mentioned processing method has 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, the crystallization reservation degree of the y-type zeolite obtained is low, pore structure and acidity not ideal enough.So, research and develop and a kind ofly adopt non-template agent method synthetic technology route to prepare to have the Y zeolite simultaneously having again a higher crystalline reservation degree compared with high silica alumina ratio, higher thermostability to 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 adopting simple process directly to synthesize Fe-NaY molecular sieve under non-template agent state and be that raw material adopts the columbite process of " two hand over two hydro-thermals " to obtain a kind ofly having the silica alumina ratio higher than conventional y-type zeolite and the y-type zeolite of abundanter second hole with Fe-NaY molecular sieve.
For achieving the above object, the present invention provide firstly 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 DEG C by silicon source, aluminium source, source of iron and water mixing, stir obtain gel reaction mixture;
Make above-mentioned gel reaction mixture crystallization 24-120h at 90-140 DEG C, obtain former powder molecular sieve Fe-NaY;
According to former powder molecular sieve Fe-NaY: ammonium salt: water=1: the weight ratio of 0.2-2: 5-20, former powder molecular sieve Fe-NaY, ammonium salt solution and water are mixed, pH value be 2.0-10.0, temperature stirs 0.5-4h under being the condition of 20-95 DEG C, after filtration, wash, at 50-120 DEG C dry 5-12h, then at 550-750 DEG C, roasting 0.5-4h in the steam atmosphere of 100%, then repeat above-mentioned ammonium and exchange process and hydrothermal treatment consists once (also comprises filtration, washing step), obtain y-type zeolite (or title Fe-USY zeolite).
In aforesaid method provided by the invention, preferably, the temperature of crystallization can control at 90-120 DEG C.
In aforesaid method provided by the invention, preferably, in above-mentioned gel reaction mixture, being added with directed agents, the crystal property of molecular sieve can be improved by adding directed agents, directed agents can mix with silicon source, aluminium source, source of iron etc., is then prepared into gel reaction mixture by stirring.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 add-on of directed agents controls the 5-50% for gel reaction mixture quality.
Directed agents of the present invention can be prepare by the various methods preparing faujusite directed agents in prior art, preferably prepare according to the method preparing directed agents adopted in the customary preparation methods of the industrial i.e. NaY generally adopted at present, such as according to USP3639099, USP3671191, (being introduced here as a reference by the full text of above-mentioned patent application) is prepared by the method preparing directed agents proposed in USP4166099 and CN1081425A, the synthesis technique of existing NaY can not be changed like this and do 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 silicon source, aluminium source and water being uniformly mixed, stirs ageing 2-50h obtained at 10-70 DEG C.According to specific embodiment of the invention scheme, preferably, when preparing directed agents, the silicon source adopted 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 adopted 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 adopted 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 adopted 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 exchanged by ammonium to combine with hydrothermal treatment process and the method process Fe-NaY type zeolite be used alternatingly obtains; This y-type zeolite mixes with matrix can make catalytic cracking catalyst, may be used for process distillate or residual oil.In the process of " two hand over two hydro-thermals ", the process that ammonium exchanges is that Fe-NaY is exchanged into Fe-HY, carrying out hydrothermal treatment consists is subsequently that silicon is mended in dealuminzation deferrization in solid phase, the room stayed after Siliciumatom can be made to occupy dealuminzation deferrization, reach the stabilization of structure, as mentioned above, the ammonium that hockets exchanges and hydrothermal treatment consists, the degree of depth of dealuminzation deferrization can be controlled, the type-Y high silicon zeolite of obtained 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: ammonium salt: water=1: the weight ratio of 0.2-2: 5-20, former powder molecular sieve Fe-NaY, ammonium salt (aqueous solution), water are mixed, pH value be 2.0-10.0, temperature stirs 0.5-4h at being 20-95 DEG C, after filtration, washing, dryly to realize in 50-120 DEG C.In ammonium exchange process, the ammonium salt adopted is preferably one or several the mixture in ammonium chloride, ammonium sulfate and ammonium nitrate etc., is more preferably ammonium chloride; The component molar of former powder molecular sieve Fe-NaY, ammonium salt, water is than being 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 process, the temperature of hydrothermal treatment consists is preferably 500-700 DEG C, and the time of hydrothermal treatment consists is preferably 1-4h.
The preparation method of y-type zeolite provided by the invention first introducing hetero-atoms Fe synthesizes the Fe-NaY zeolite of high-crystallinity, high silica alumina ratio, then exchange in conjunction with ammonium, hydrothermal treatment consists two processes being used alternatingly, process Fe-NaY zeolite, obtain USFeY zeolite, it is a kind of Y zeolite having high silica alumina ratio, enrich second hole.The y-type zeolite degree of crystallinity prepared by method provided by the invention can reach more than 85%, silica alumina ratio (SiO
2/ Al
2o
3) can more than 20 be reached, the percentage ratio that second hole volume accounts for total pore volume is 40-60%, and the USY zeolite facies ratio obtained with adopting same procedure and non-introducing hetero-atoms Fe, silica alumina ratio amplification is more than 40%, and second hole volume amplification is more than 47%.With the USY zeolite facies ratio adopting 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 adopting the synthetic method lower than USY zeolite water thermal treatment temp 100 DEG C, the Fe-USY zeolite prepared 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 preparation and the molecular sieve USY2 of comparative example 2 preparation.
Fig. 3 is the XRD figure spectrum of the y-type zeolite of embodiment 3 preparation and the molecular sieve USY3 of comparative example 3 preparation.
Fig. 4 is the XRD figure spectrum of the y-type zeolite of embodiment 4 preparation and the molecular sieve USY4 of comparative example 4 preparation.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
In each embodiment, the secondary pore volume of Fe-NaY molecular sieve and the measuring method of total pore volume as follows: according to RIPP151-90 standard method (" Petrochemical Engineering Analysis method (RIPP test method) ", the Yang Cui volume such as surely, Science Press, nineteen ninety publishes) total pore volume of molecular sieve is determined according to adsorption isothermal line, then determine the micro pore volume of molecular sieve from adsorption isothermal line according to T graphing method, total pore volume is deducted 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 wide by 0.02, adopt area sum (comparing with NaY molecular sieve standard specimen) the calculation sample degree of crystallinity (relative crystallinity) at (331), (511,333), (440), (533), (642), (822,660), (555,751), (664) totally eight peaks.The measuring method of silica alumina ratio according to SH/T0339-92 standard method (see " standard of chemical industry compilation ", China Standards Press, publishes for 2000), 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 formulae discovery y-type zeolite silica alumina ratio:
Si/Al＝(25.858-a)/(a-24.191)
Embodiment 1
Present embodiments provide a kind of preparation method of y-type zeolite, it comprises the following steps:
Take 43.3g water glass, after 30.3g high alkali deflection aluminium acid sodium solution mixes, ageing 5h obtains directed agents under 50 DEG C of whipped states, and the component molar of this directed agents is than being 16.0Na
2o: 1Al
2o
3: 15.1SiO
2: 322.3H
2o;
Take 331.3g water glass and be placed in beaker, under 50 DEG C of stirring in water bath, add 68.3g high alkali deflection aluminium acid sodium solution successively, 63.4g directed agents stirs 3h, then add 173.lg alum liquor and stir 1h, finally add source of iron (iron nitrate solution) and 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), to be loaded in reactor crystallization at 96 DEG C, crystallization time is respectively 30h, 42h, 60h, then through washing, filter, obtain former powder molecular sieve Fe-NaY in 100 DEG C of dry 10h;
Get 50g former powder molecular sieve Fe-NaY, being scattered in 550g concentration is in the aqueous ammonium chloride solution of 9wt% (in weight ammonium chloride), after stirring, the pH value regulating gained slurries with 1mol/L hydrochloric acid soln is 3.3, be warming up to 90 DEG C, 1h is stirred under maintaining the constant condition of pH value, filter, with the deionized water wash of 20 times extremely without acid group, dry, then hydrothermal device is put into, be warming up to 650 DEG C, pass into 100% steam roasting 2h, repeat once above-mentioned ammonium again to exchange, hydrothermal treatment process, obtain y-type zeolite, be designated as Fe-USY, the X-ray diffraction thing phasor (XRD) of products therefrom is shown in Fig. 1, the diffraction peak (331) of Fe-USY, (511, 333), (440), (533), (642), (822, 660), (555, 751), (664) eight characteristic diffraction peak peak shapes keep complete, generate without stray crystal, 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 provided by embodiment 1, just do not add source of iron when preparing gel reaction mixture, the molecular sieve obtained is designated as USY1, the X-ray diffraction thing phasor (XRD) of products therefrom is shown in Fig. 1, eight characteristic diffraction peak peak shapes of the diffraction peak (331) of molecular sieve USY1, (511,333), (440), (533), (642), (822,660), (555,751), (664) keep complete, generate without stray crystal, 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 |
As can be seen from table 1 with the comparative analysis of table 2, compared with the molecular sieve (USY1) adopting hydrothermal dealumination method to prepare with comparative example 1, the second hole volume of Fe-USY prepared by embodiment 1 is all at 0.22cm
3g
-1above, 0.29cm is up to
3g
-1, framework si-al ratio, all more than 19, is up to 27.5.This second hole volume increases mode and significantly drops to cost not with micro pore volume, and the micro pore volume of all Fe-USY samples all still maintains 0.22cm
3g
-1an even above high position.As can be seen here, the y-type zeolite that prepared by embodiment 1 is a kind of Y zeolite having high silica alumina ratio, enrich second hole.
Embodiment 2
Present embodiments provide a kind of preparation method of y-type zeolite, it comprises the following steps:
Take 46g water glass, after 28g high alkali deflection aluminium acid sodium solution mixes, ageing 5h obtains directed agents under 50 DEG C of whipped states, and the component molar of this directed agents is than being 16.7Na
2o: 1Al
2o
3: 17.35SiO
2: 350: 4H
2o;
Take 333g water glass and be placed in beaker, under 50 DEG C of stirring in water bath, add 70g high alkali deflection aluminium acid sodium solution successively, 65g directed agents stirs 3h, then add 160g alum liquor and stir 1h, finally add source of iron (iron nitrate solution) and 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), to be loaded in reactor crystallization at 96 DEG C, crystallization time is respectively 35h, 47h, 80h, then through washing, filter, in 100 DEG C of dry 10h, obtain former powder molecular sieve Fe-NaY;
Get 50g former powder molecular sieve Fe-NaY, being scattered in 550g concentration is in the aqueous ammonium chloride solution of 9wt% (in weight ammonium chloride), after stirring, the pH value regulating gained slurries with 1mol/L hydrochloric acid soln is 3.3, be warming up to 90 DEG C, 1h is stirred under maintaining the constant condition of pH value, filter, with the deionized water wash of 20 times extremely without acid group, dry, then hydrothermal device is put into, be warming up to 650 DEG C, pass into 100% steam roasting 2h, repeat once above-mentioned ammonium again to exchange, hydrothermal treatment process, obtain y-type zeolite, be designated as Fe-USY, the X-ray diffraction thing phasor (XRD) of products therefrom is shown in Fig. 2, the diffraction peak (331) of Fe-USY, (511, 333), (440), (533), (642), (822, 660), (555, 751), (664) eight characteristic diffraction peak peak shapes keep complete, generate without stray crystal, 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 provided by embodiment 2, just do not add source of iron when preparing gel reaction mixture, the molecular sieve obtained is designated as USY2, the X-ray diffraction thing phasor (XRD) of products therefrom is shown in Fig. 2, eight characteristic diffraction peak peak shapes of the diffraction peak (331) of molecular sieve USY2, (511,333), (440), (533), (642), (822,660), (555,751), (664) keep complete, generate without stray crystal, 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 |
As can be seen from table 3 with the comparative analysis of table 4, compared with the molecular sieve (USY2) prepared by hydrothermal dealumination method with comparative example 2, the second hole volume of Fe-USY prepared by embodiment 2 is all at 0.23cm
3g
-1above, 0.32cm is up to
3g
-1, framework si-al ratio, all more than 19.9, is up to 26.4.This second hole volume increases mode and significantly drops to cost not with micro pore volume, and the micro pore volume of all Fe-USY samples all still maintains 0.22cm
3.g
-1an even above high position.As can be seen here, the y-type zeolite that prepared by embodiment 2 is a kind of Y zeolite having high silica alumina ratio, enrich second hole.
Embodiment 3
Present embodiments provide a kind of preparation method of y-type zeolite, it comprises the following steps:
Take 50g water glass, after 25g high alkali deflection aluminium acid sodium solution mixes, ageing 5h obtains directed agents under 50 DEG C of whipped states, and the component molar of this directed agents is than being 18Na
2o: 1Al
2o
3: 21.12SiO
2: 397.1H
2o;
Take 335g water glass and be placed in beaker, under 50 DEG C of stirring in water bath, add 40g high alkali deflection aluminium acid sodium solution successively, 67g directed agents stirs 3h, then add 164g alum liquor and stir 1h, finally add source of iron (iron nitrate solution) and stir 0.5h, after stirring, obtain gel reaction mixture, the mol ratio of each component of this 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), to be loaded in reactor crystallization at 96 DEG C, crystallization time is respectively 55h, 72h, 99h, then through washing, filter, in 100 DEG C of dry 10h, obtain former powder molecular sieve Fe-NaY;
Get 50g former powder molecular sieve Fe-NaY, being scattered in 550g concentration is in the aqueous ammonium chloride solution of 9wt% (in weight ammonium chloride), after stirring, the pH value regulating gained slurries with 1mol/L hydrochloric acid soln is 3.3, be warming up to 90 DEG C, 1h is stirred under maintaining the constant condition of pH value, filter, with the deionized water wash of 20 times extremely without acid group, dry, then hydrothermal device is put into, be warming up to 650 DEG C, pass into 100% steam roasting 2h, repeat once above-mentioned ammonium again to exchange, hydrothermal treatment process, obtain y-type zeolite, be designated as Fe-USY, the X-ray diffraction thing phasor (XRD) of products therefrom is shown in Fig. 3, the diffraction peak (331) of Fe-USY, (511, 333), (440), (533), (642), (822, 660), (555, 751), (664) eight characteristic diffraction peak peak shapes keep complete, generate without stray crystal, 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 provided by embodiment 3, just do not add source of iron when preparing gel reaction mixture, the molecular sieve obtained is designated as USY3, the X-ray diffraction thing phasor (XRD) of products therefrom is shown in Fig. 3, eight characteristic diffraction peak peak shapes of the diffraction peak (331) of USY3, (511,333), (440), (533), (642), (822,660), (555,751), (664) keep complete, generate without stray crystal, 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 |
As can be seen from table 5 with the comparative analysis of table 6, compared with the molecular sieve (USY3) that the hydrothermal dealumination method provided with comparative example 3 prepares, the second hole volume of Fe-USY prepared by embodiment 3 is all at 0.23cm
3g
-1above, 0.28cm is up to
3g
-1, framework si-al ratio, all more than 23.2, is up to 27.4.This second hole volume increases mode and significantly drops to cost not with micro pore volume, and the micro pore volume of all Fe-USY sample crystalline substances all still maintains 0.21cm
3g
-1an even above high position.As can be seen here, the y-type zeolite that prepared by embodiment 3 is a kind of Y zeolite having high silica alumina ratio, enrich second hole.
Embodiment 4
Present embodiments provide a kind of preparation method of y-type zeolite, it comprises the following steps:
Take 60g water glass, after 28g high alkali deflection aluminium acid sodium solution mixes, ageing 5h obtains directed agents under 50 DEG C of whipped states, and the component molar of this directed agents is than being 18.5Na
2o: 1Al
2o
3: 22.6SiO
2:: 415.8H
2o;
Take 337g water glass and be placed in beaker, under 50 DEG C of stirring in water bath, add 46g high alkali deflection aluminium acid sodium solution successively, 55g directed agents stirs 3h, then add 130g alum liquor and stir 1h, finally add source of iron (iron nitrate solution) and stir 0.5h, after stirring, obtain gel reaction mixture, the mol ratio of each component of this 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), to be loaded in reactor crystallization at 96 DEG C, crystallization time is respectively 70h, 110h, 130h, then through washing, filter, in 100 DEG C of dry 10h, obtain former powder molecular sieve Fe-NaY;
Get 50g former powder molecular sieve Fe-NaY, being scattered in 550g concentration is in the aqueous ammonium chloride solution of 9wt% (in weight ammonium chloride), after stirring, the pH value regulating gained slurries with 1mol/L hydrochloric acid soln is 3.3, be warming up to 90 DEG C, 1h is stirred under keeping the constant condition of pH value, filter, with the deionized water wash of 20 times extremely without acid group, dry, then hydrothermal device is put into, be warming up to 650 DEG C, pass into 100% steam roasting 2h, repeat once above-mentioned ammonium again to exchange, hydrothermal treatment process, obtain y-type zeolite, be designated as Fe-USY, the X-ray diffraction thing phasor (XRD) of products therefrom is shown in Fig. 4, the diffraction peak (331) of Fe-USY, (511, 333), (440), (533), (642), (822, 660), (555, 751), (664) eight characteristic diffraction peak peak shapes keep complete, generate without stray crystal, 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 provided by embodiment 4, just do not add source of iron when preparing gel reaction mixture, the molecular sieve obtained is designated as USY4, the X-ray diffraction thing phasor (XRD) of products therefrom is shown in Fig. 4, eight characteristic diffraction peak peak shapes of the diffraction peak (331) of Fe-USY, (511,333), (440), (533), (642), (822,660), (555,751), (664) keep complete, generate without stray crystal, be indicated as Y zeolite structure.
The chemical composition and structure parameter of this molecular sieve USY4 is in table 8.
As can be seen from table 7 with the comparative analysis of table 8, compared with the molecular sieve (USY4) prepared with comparative example 4 hydrothermal dealumination method, the second hole volume of Fe-USY prepared by embodiment 4 is all at 0.20cm
3g
-1above, 0.28cm is up to
3g
-1, framework si-al ratio, all more than 18.7, is up to 25.4.This second hole volume increases mode and significantly drops to cost not with micro pore volume, and the micro pore volume of all Fe-USY samples all still maintains 0.23cm
3g
-1an even above high position.As can be seen here, the y-type zeolite that prepared by embodiment 4 is a kind of Y zeolite having 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 (11)
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 DEG C by silicon source, aluminium source, source of iron and water mixing, stir obtain gel reaction mixture;
Make above-mentioned gel reaction mixture crystallization 24-120h at 90-140 DEG C, obtain former powder molecular sieve Fe-NaY;
According to former powder molecular sieve Fe-NaY: ammonium salt: the weight ratio of water=1:0.2-2:5-20, former powder molecular sieve Fe-NaY, ammonium salt solution and water are mixed, pH value be 2.0-10.0, temperature stir under being the condition of 20-95 DEG C 0.5-4h carry out ammonium exchange process, after filtration, wash, at 50-120 DEG C dry 5-12h, then at 400-800 DEG C, roasting 0.5-4h in the steam atmosphere of 100%, then repeat above-mentioned ammonium and exchange process and hydrothermal treatment consists respectively once, obtain described y-type zeolite.
2. method according to claim 1, wherein, be added with directed agents in described gel reaction mixture, the add-on of this directed agents is the 1-60% of gel reaction mixture quality.
3. method according to claim 2, wherein, 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 silicon source, aluminium source and water being uniformly mixed, stirs at 10-70 DEG C that 2-50h obtains.
4. according to the method in claim 2 or 3, wherein, the add-on of described directed agents is the 5-50% of gel reaction mixture quality.
5. method according to claim 1, wherein, the temperature of described crystallization controls at 90-120 DEG C.
6. according to the method in claim 2 or 3, wherein, the silicon source of preparing directed agents used is water glass, and aluminium source is high alkali deflection aluminium acid sodium.
7. 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.
8. 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.
9. method according to claim 1, wherein, the source of iron preparing gel reaction mixture is one or several the mixture in ferric sulfate, iron nitrate and iron(ic) chloride.
10. method according to claim 1, wherein, described ammonium salt is one or several the mixture in ammonium chloride, ammonium sulfate and ammonium nitrate.
11. methods 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, and pH value is 2.5-5.
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| CN105819465B (en) * | 2016-03-16 | 2018-08-10 | 中国石油天然气集团公司 | A kind of USY molecular sieve and preparation method thereof and catalyst prepared therefrom |
| CN108238613B (en) * | 2016-12-27 | 2020-04-10 | 中国石油天然气集团公司 | Small mesoporous ultrastable Y-type zeolite and preparation method and application thereof |
| CN110316741B (en) * | 2019-05-09 | 2022-08-05 | 山东齐鲁华信高科有限公司 | Preparation method of low-sodium high-silicon Y-type molecular sieve |
| CN111410206A (en) * | 2020-04-13 | 2020-07-14 | 邹凌峰 | Preparation method of Y-type molecular sieve with high silica-alumina ratio |
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| CN112939013B (en) * | 2021-03-10 | 2022-11-01 | 中国石油大学(北京) | High-silicon small-grain Y-type molecular sieve and preparation method and application of template-free molecular sieve |
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