CN101077481A - Double-micropore zeolites and method of making thereof - Google Patents
Double-micropore zeolites and method of making thereof Download PDFInfo
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Abstract
The double microporous zeolite and its preparation process belongs to the field of fine chemical technology. The preparation process is one two step crystallizing process including the first step of synthesizing Beta, and the second step of preparing composite zeolite product in BEA/FAU structure with the Beta as material and through replenishing aluminum source, regulating basicity of the system, adding guiding agent, filtering, washing, drying and roasting. The composite zeolite product has strong acidity, and excellent heat and hydrothermal stability, and may be applied as catalyst, co-catalyst and adsorbent in petrochemical industry.
Description
One, technical field
A kind of double-micropore zeolites of the present invention and preparation method thereof belongs to the fine chemical technology field, in particular to a kind of two step of employing crystallization method, two kinds of micro-pore zeolites of Beta and Y are organically combined, thereby formation has the technical scheme of the new zeolite material of two microcellular structures.
Two, technical background
Y zeolite and modifier thereof show excellent catalytic performance (M.A.Saberi in reactions such as catalytic cracking, hydrocracking, hydroisomerization, alkane aromatization, alkylation, R.Le Van Mao, M.Martin, A.W.H.Mak.AppliedCatalysis A:General 214 (2001); I.P.Dzikh, J.M.Lopes, F.Lemos, F.
Ribeiro.CatalysisToday 65 (2001); Wei Ruiping, Wang Jun, Ren Xiaoqian etc. Chinese Journal of Inorganic Chemistry .12 (2004); A.M.Radwan, zhang-GuoZhang, P.Chambrion, et al.Fuel Processing Technology 55 (1998) .), be crucial catalysis material in the petrochemical industry.The Beta zeolite is synthetic first in 1967 by Wadlinger et al (U.S.pat.3308069), and it has unique three-dimensional open-framework, is unique macropore silica-rich zeolite with three-dimensional staggered twelve-ring pore passage structure of finding up to now.The Beta zeolite is in the hydrocarbons hydrogenation cracking, hydroisomerization, and alkane aromatization, aspects such as alkylation and transalkylation reaction show excellent catalytic performance.On the one hand, but because the characteristics such as duct size, hydrophobicity, acidity, heat and hydrothermal stability of its high surface modulation, and showing the characteristics that are difficult for coking and long service life aspect the hydro carbons catalytic reaction, being widely used as acid catalyst at petroleum chemical industry, is a kind of crucial catalysis material; On the other hand, the Beta zeolite has very big using value at aspects such as catalysis, absorption.But owing to fail to solve its structure determination problem for a long time, therefore synthetic the and successful Application of ZSM series zeolite fails to cause enough attention of people, until 1988 (Newsam, J.M in addition; Treacy.M.M.J; Koetsier.W.T et al.Proc R Soc Lond is A.1988) year disclosed its distinctive Three Dimensions Structure, the Beta zeolite causes people's interest heavily again.
When with the two micropores of two or more molecular sieve together, they might show good synergy and excellent catalytic performance.For example, with the two micro porous molecular sieves of MCM-41/ZSM-5 that the two micropores of MCM-41 and ZSM-5 form together, have than they mechanical impurities higher to n-C12 alkane catalytic cracking activity (Huang L M, Guo W P, DengPeng, et al.J Phys Chem B104 (2000)); The RFCC of ZSM-5 (nuclear)/ALPO-5 (shell) binary structure zeolite is better than the mechanical mixture sample of arbitrary component or two components, show higher crude oil conversion and low-carbon alkene and diesel yield (Zhang Zhe, Zong Baoning. catalysis journal .24 (2003)); Y zeolite and Beta zeolite all have important purposes at petrochemical industry just.If can successfully prepare the double microporous material of y-type zeolite and Beta zeolite, organically combine the characteristics of the two, will potential application prospect be arranged in petrochemical industry and field of fine chemical.Our seminar adopts two step crystallization, successful preparation the two micro porous molecular sieves of two micropores that Y and Beta zeolite are organically combined (licenses number: ZL200410012333.2), when it is characterized in that utilizing the synthetic zeolite of the first step to go on foot synthesis material as second, the part clear liquid is toppled in requirement, owing to contain components such as silicon, aluminium, alkali in the clear liquid, the amount that causes in second step adding aluminium source and alkali in synthetic is difficult to grasp, and causes the repeated wayward of synthetic two micro porous molecular sieves.
Three, summary of the invention
The purpose of a kind of double-micropore zeolites of the present invention and preparation method thereof is, solve above-mentioned problems of the prior art, the mixture that contain Beta synthetic with the first step synthesizes the raw material of Y as second step, thereby a kind of preparation method of Beta/Y double-micropore zeolites is provided.
The preparation method of a kind of double-micropore zeolites of the present invention, it is characterized in that it being a kind of method of synthesizing the Beta/Y zeolitic material of two microcellular structures, this method adopts two step crystallization methods, the at first synthetic Beta of the first step, then with the raw material of the synthetic reactant mixture that contains Beta as synthetic Y zeolite of second step, by replenishing the aluminium source, adjusting the basicity of system simultaneously, and the directed agents that adds synthetic Y zeolite is reacted crystallization, through filtration, washing, drying, roasting obtains the double-micropore zeolites product of BEA/FAU structure.
The preparation method of above-mentioned a kind of double-micropore zeolites is characterized in that concrete processing step is:
I, utilize tetraethyl ammonium TEA
+Be the template agent, with itself and alkali, ammoniacal liquor, deionized water, aluminium source, silicon source material (2.2-9.5) Na in molar ratio
2O: Al
2O
3: (20-35) SiO
2: (0-5.0) (TEA)
2O: (0-15) (NH
4)
2O: (440-825) H
2After O mixes, move in the stainless steel cauldron, under 135-145 ℃, crystallization 72-312h, cooling obtains containing the solidliquid mixture of Beta zeolite then.
II, in the synthetic solidliquid mixture that contains the Beta zeolite of the first step, add a certain amount of aluminium and regulate basicity, obtain molar ratio ((1.33-4.7) Na
2O: Al
2O
3: (6.01-30.3) SiO
2: (0-4.3) (TEA)
2O: (0-13) (NH
4)
2O: (137-563) H
2O) solidliquid mixture adds the Y directed agents (15Na of 3-5% then by volume
2O: 16SiO
2: Al
2O
3: 320H
2O), after under intense agitation, mixing, move in the stainless steel cauldron, react crystallization 12-36h down at 85-90 ℃, cool off, be washed with distilled water to neutrality, vacuum filtration subsequently, dry 8-12h in the baking oven below 100 ℃ with running water at normal temperatures then, then under 500-550 ℃ in muffle furnace, roasting 4-6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.
The preparation method of above-mentioned a kind of double-micropore zeolites is characterized in that described silicon source is Ludox, white carbon black or waterglass.
The preparation method of above-mentioned a kind of double-micropore zeolites is characterized in that described aluminium source is a sodium aluminate.
The preparation method of above-mentioned a kind of double-micropore zeolites is characterized in that described alkali is NaOH and ammonium hydroxide.
The preparation method of above-mentioned a kind of double-micropore zeolites is characterized in that described TEA
+Be tetraethyl ammonium hydroxide or tetraethylammonium bromide.
The preparation method of above-mentioned a kind of double-micropore zeolites, the percentage by weight that it is characterized in that Y zeolite in the described Beta/Y double-micropore zeolites is 5-95%.
The double-micropore zeolites of the BEA/FAU structure of above-mentioned preparation method's preparation.
The advantage of a kind of double-micropore zeolites of the present invention and preparation method thereof is: adopt two step crystallization methods, contain the whole system of Beta mixture as the raw material that synthesizes Y with what the first step was synthesized, by adding the aluminium source, the basicity of regulation system, the two micro porous molecular sieves of Beta/Y have successfully been synthesized, successfully having solved the patent No. is ZL200410012333.2, when the zeolite raw material that utilizes the first step to synthesize, need topple over the part clear liquid and contain silicon owing in the clear liquid, aluminium, components such as alkali, the amount that causes adding aluminium source and alkali in synthetic is difficult to grasp, the uppity problem of its product repeatability.Can be used as multiple catalyst, catalyst promoter and adsorbent after Beta/Y double-micropore zeolites that the present invention synthesizes and the modification thereof; Stronger acidity is arranged after ion-exchange, and good heat and hydrothermal stability have potential using value at aspects such as the catalytic cracking of petrochemical industry, hydrocracking.The Beta/Y double-micropore zeolites is through behind the roasting removed template method, through roasting and be transformed into Hydrogen again after the ammonia exchange.To make it to become the zeolite that contains different metal in various metals or the two micro porous molecular sieves of its compound introducing by ion-exchange, dipping or additive method; Can also be by method dealuminzations such as pickling, chemical extracting and steam, to improve the Si/Al ratio of Beta/Y double-micropore zeolites.
Four, description of drawings
Fig. 1 is the XRD diffraction pattern of Beta/Y double-micropore zeolites sample.
Five, the specific embodiment
Embodiment 1:
The first step: with 17.4gTEABr (tetraethylammonium bromide), the 6ml concentrated ammonia liquor, 2.26g sodium metaaluminate, 0.5g NaOH, 31ml Ludox, 34ml distilled water are mixed into even white jelly, in the 100ml stainless steel cauldron of packing into, stand-by in the taking-up in 10 days of 140 ℃ of following crystallization, the initial material mol ratio of Beta zeolite is: 2.2Na
2O: 20SiO
2: Al
2O
3: 4.6 (TEA)
2O: 4.6 (NH
4)
2O: 440H
2O.
Second step: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add the 2.35g sodium metaaluminate, 1.31g NaOH, the 2.5mlY directed agents, total molar ratio of material is: 2.62Na
2O: Al
2O
3: 9.7SiO
2: 2.32 (TEA)
2O: 2.32 (NH
4)
2O: 215H
2O.Mixing and stirring then, pack in the 100ml stainless steel cauldron, take out in 85 ℃ of following crystallization 24h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 8h in 100 ℃ baking oven, then under 500 ℃ in muffle furnace, roasting 4h under the condition of blowing air, the plate agent is touched in removal, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 50%, accompanying drawing 1.
Embodiment 2:
The first step: with 17.4gTEABr (tetraethylammonium bromide), the 6ml concentrated ammonia liquor, 2.26g sodium metaaluminate, 0.5g NaOH, 31ml Ludox, 34ml distilled water are mixed into even white jelly, in the 100ml stainless steel cauldron of packing into, stand-by in the taking-up in 8 days of 145 ℃ of following crystallization, the initial material mol ratio of Beta zeolite is: 2.2Na
2O: 20SiO
2: Al
2O
3: 4.6 (TEA)
2O: 4.6 (NH
4)
2O: 440H
2O.
Second step: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add 2.97g sodium metaaluminate 1.31g NaOH, the 3.5mlY directed agents, total molar ratio of material is: 2.47Na
2O: Al
2O
3: 8.55SiO
2: 2.04 (TEA)
2O: 2.04 (NH
4)
2O: 190H
2O.Be mixed in the 100ml stainless steel cauldron of packing into behind the even white thing, take out in 90 ℃ of following crystallization 24h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 65%.
Embodiment 3:
The first step: with 17.4gTEABr (tetraethylammonium bromide), the 6ml concentrated ammonia liquor, 2.26g sodium metaaluminate, 0.5g NaOH, 31ml Ludox, 34ml distilled water are mixed into even white jelly, in the 100ml stainless steel cauldron of packing into, stand-by in the taking-up in 13 days of 135 ℃ of following crystallization, the initial material mol ratio of Beta zeolite is: 2.2Na
2O: 20SiO
2: Al
2O
3: 4.6 (TEA)
2O: 4.6 (NH
4)
2O: 440H
2O.
Second step: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add 3.15g sodium metaaluminate 1.07g NaOH, the 3.5mlY directed agents, total molar ratio of material is: 2.30Na
2O: Al
2O
3: 8.27SiO
2: 1.98 (TEA)
2O: 1.98 (NH
4)
2O: 184H
2O.Be mixed in the 100ml stainless steel cauldron of packing into behind the even white thing, take out in 90 ℃ of following crystallization 24h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 80%.
Embodiment 4:
The first step: with 17.4gTEABr (tetraethylammonium bromide), the 6ml concentrated ammonia liquor, 2.26g sodium metaaluminate, 0.5g NaOH, 31ml Ludox, 34ml distilled water are mixed into even white jelly, in the 100ml stainless steel cauldron of packing into, stand-by in the taking-up in 9 days of 140 ℃ of following crystallization, the initial material mol ratio of Beta zeolite is: 2.2Na
2O: 20SiO
2: Al
2O
3: 4.6 (TEA)
2O: 4.6 (NH
4)
2O: 440H
2O.
Second step: add 4.99g sodium metaaluminate 1.71g NaOH in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, total molar ratio of material is: 3.13Na
2O: Al
2O
3: 6.17SiO
2: 1.47 (TEA)
2O: 1.47 (NH
4)
2O: 137H
2O.Be mixed in the 100ml stainless steel cauldron of packing into behind the even white thing, take out in 88 ℃ of following crystallization 20h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 85%.
Embodiment 5:
The first step: with 17.7gTEABr (tetraethylammonium bromide), the 6ml concentrated ammonia liquor, 2.26g sodium metaaluminate, 0.5g NaOH, 31ml Ludox, 34ml distilled water are mixed into even white jelly, in the 100ml stainless steel cauldron of packing into, stand-by in the taking-up in 10 days of 140 ℃ of following crystallization, the initial material mol ratio of Beta zeolite is: 2.2Na
2O: 20SiO
2: Al
2O
3: 4.6 (TEA)
2O: 4.6 (NH
4)
2O: 440H
2O.
Second step: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add 4.52g sodium metaaluminate 1.6g NaOH, the 3.2mlY directed agents, total molar ratio of material is: 2.36Na
2O: Al
2O
3: 6.59SiO
2: 1.57 (TEA)
2O: 1.57 (NH
4)
2O: 147H
2O.Be mixed in the 100ml stainless steel cauldron of packing into behind the even white thing, take out in 90 ℃ of following crystallization 24h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 75%.。
Embodiment 6:
The first step: with 17.7gTEABr (tetraethylammonium bromide), the 6ml concentrated ammonia liquor, 2.26g sodium metaaluminate, 0.5g NaOH, 31ml Ludox, 34ml distilled water are mixed into even white jelly, in the 100ml stainless steel cauldron of packing into, stand-by in the taking-up in 10 days of 140 ℃ of following crystallization, the initial material mol ratio of Beta zeolite is: 2.2Na
2O: 20SiO
2: Al
2O
3: 4.6 (TEA)
2O: 4.6 (NH
4)
2O: 440H
2O.
Second step: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add 3.24g sodium metaaluminate 1.59g NaOH, the 3.5mlY directed agents, total molar ratio of material is: 2.58Na
2O: Al
2O
3: 8.1SiO
2: 1.94 (TEA)
2O: 1.94 (NH
4)
2O: 180H
2O.Be mixed in the 100ml stainless steel cauldron of packing into behind the even white thing, take out in 90 ℃ of following crystallization 36h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 65%.
Embodiment 7:
The first step: with 19.45gTEABr (tetraethylammonium bromide), 19.3ml concentrated ammonia liquor, 2.3g sodium metaaluminate, 1.25g NaOH, 55.7ml Ludox, 33ml distilled water are mixed into even white jelly, in the 150ml stainless steel cauldron of packing into, stand-by in the taking-up in 8 days of 140 ℃ of following crystallization, the initial material mol ratio of Beta zeolite is: 3.1Na
2O: 35SiO
2: Al
2O
3: 5.0 (TEA)
2O: 15 (NH
4)
2O: 650H
2O.
Second step: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add the 9.65g sodium metaaluminate, 1.76g NaOH, the 3mlY directed agents, the 45ml distilled water, the mol ratio of total material is: 2.18Na
2O: Al
2O
3: 6.7SiO
2: 0.96 (TEA)
2O: 2.88 (NH
4)
2O: 174H
2O.Be mixed in the 200ml stainless steel cauldron of packing into behind the even white thing, take out in 90 ℃ of following crystallization 28h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 35%.
Embodiment 8:
The first step: with 19.45gTEABr (tetraethylammonium bromide), 19.3ml concentrated ammonia liquor, 2.3g sodium metaaluminate, 1.25g NaOH, 55.7ml Ludox, 33ml distilled water are mixed into even white jelly, in the 150ml stainless steel cauldron of packing into, stand-by in the taking-up in 6 days of 145 ℃ of following crystallization, the initial material mol ratio of Beta zeolite is: 3.1Na
2O: 35SiO
2: Al
2O
3: 5.0 (TEA)
2O: 15 (NH
4)
2O: 650H
2O.
Second step: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add the 0.35g sodium metaaluminate, 1.76g NaOH, the 3mlY directed agents, total molar ratio of material is: 4.7Na
2O: Al
2O
3: 30.3SiO
2: 4.3 (TEA)
2O: 13 (NH
4)
2O: 563H
2O.Be mixed in the 250ml stainless steel cauldron of packing into behind the even white thing, take out in 90 ℃ of following crystallization 28h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 5%.
Embodiment 9:
The first step, the preparation of Beta directed agents: with 19.5mlTEAOH (tetraethyl ammonium hydroxide), 0.29g sodium metaaluminate, 0.0939gNaOH, 5.66g white carbon black (Deguss, AE-200), 3ml distilled water is mixed into even white jelly, in the stainless steel cauldron of the 30ml teflon lined of packing into, treat in 140 ℃ of following crystallization 4-5h taking-ups.The initial material mol ratio of Beta guiding agent for zeolite is: 2.5Na
2O: 80SiO
2: Al
2O
3: 11 (TEA)
2O: 850H
2O; The Beta zeolite synthetic: with the 2.11g sodium metaaluminate, 5.42g NaOH, the white carbon black (Deguss of 15.3g, AE-200), 126ml distilled water and 8ml Beta directed agents are mixed into even white jelly, in the 150ml stainless steel cauldron of packing into, take out stand-by in 140 ℃ of following crystallization 3d.The initial material mol ratio of Beta zeolite is: 9.5Na
2O: 30SiO
2: Al
2O
3: 825H
2O;
Second step, the two micro porous molecular sieves of the two micropores of Beta/Y synthetic: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add the 8.44g sodium metaaluminate, 1.9ml 98% concentrated sulfuric acid, the 4mlY directed agents, total molar ratio of material is 1.33Na
2O: Al
2O
3: 6.01SiO
2: 165H
2O, be mixed in the 150ml stainless steel cauldron of packing into behind the even white thing, take out in 90 ℃ of following crystallization 12h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air, the plate agent is touched in removal, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 95%.
Embodiment 10:
The first step, the preparation of Beta directed agents: with 19.5mlTEAOH (tetraethyl ammonium hydroxide), 0.29g sodium metaaluminate, 0.0939gNaOH, 5.66g white carbon black (Deguss, AE-200), 3ml distilled water is mixed into even white jelly, in the stainless steel cauldron of the 30ml teflon lined of packing into, take out stand-by in 140 ℃ of following crystallization 4-5h.The initial material mol ratio of Beta guiding agent for zeolite is: 2.5Na
2O: 80SiO
2: Al
2O
3: 11 (TEA)
2O: 850H
2O; The Beta zeolite synthetic: with the 2.11g sodium metaaluminate, 5.42g NaOH, the white carbon black (Deguss of 15.3g, AE-200), 126ml distilled water and 8ml Beta directed agents are mixed into even white jelly, in the 150ml stainless steel cauldron of packing into, take out stand-by in 140 ℃ of following crystallization 3d.The initial material mol ratio of Beta zeolite is: 9.5Na
2O: 30SiO
2: Al
2O
3: 825H
2O;
Second step, the two micro porous molecular sieves of the two micropores of Beta/Y synthetic: in the above-mentioned synthetic solidliquid mixture that contains the Beta zeolite, add the 5.81g sodium metaaluminate, 1ml 98% concentrated sulfuric acid, the 4mlY directed agents, total molar ratio of material is 3.4Na
2O: Al
2O
3: 8.01SiO
2: 220H
2O, be mixed in the 150ml stainless steel cauldron of packing into behind the even white thing, take out in 90 ℃ of following crystallization 12h, cool off, be washed with distilled water to subsequently neutrality, vacuum filtration with running water at normal temperatures then, dry 12h in 90 ℃ baking oven, then under 550 ℃ in muffle furnace, roasting 6h under the condition of blowing air, the plate agent is touched in removal, obtains Beta/Y double-micropore zeolites sample at last.Obtain the double-micropore zeolites sieve sample that crystalline phase is the Beta/Y type through XRD analysis, Y content is 70%.
Claims (8)
1. the preparation method of a double-micropore zeolites, it is characterized in that it being a kind of method of synthesizing the Beta/Y double-micropore zeolites material of two microcellular structures, this method adopts two step crystallization methods, the at first synthetic Beta of the first step, then with the raw material of the synthetic reactant mixture that contains the Beta zeolite as synthetic Y zeolite of second step, by replenishing the aluminium source, adjusting the basicity of system simultaneously, and the directed agents that adds synthetic Y zeolite is reacted crystallization, through filtration, washing, drying, roasting obtains the double-micropore zeolites product of BEA/FAU structure.
2. according to the preparation method of the described a kind of double-micropore zeolites of claim 1, it is characterized in that concrete processing step is:
I, utilize tetraethyl ammonium TEA
+Be the template agent, with itself and alkali, ammoniacal liquor, deionized water, aluminium source, silicon source material (2.2-9.5) Na in molar ratio
2O: Al
2O
3: (20-35) SiO
2: (0-5.0) (TEA)
2O: (0-15) (NH
4)
2O: (440-825) H
2After O mixes, move in the stainless steel cauldron, under 135-145 ℃, crystallization 72-312h, cooling obtains containing Beta zeolite solidliquid mixture then.
II, add a certain amount of aluminium in the Beta zeolite solidliquid mixture and regulate basicity, obtain molar ratio ((1.33-4.7) Na in synthetic the containing of the first step
2O: Al
2O
3: (6.01-30.3) SiO
2: (0-4.3) (TEA)
2O: (0-13) (NH
4)
2O: (137-563) H
2O) solidliquid mixture adds the Y directed agents (15Na of 3-5% then by volume
2O: 16SiO
2: Al
2O
3: 320H
2O), after under intense agitation, mixing, move in the stainless steel cauldron, react crystallization 12-36h down at 85-90 ℃, cool off, be washed with distilled water to neutrality, vacuum filtration subsequently, dry 8-12h in the baking oven below 100 ℃ with running water at normal temperatures then, then under 500-550 ℃ in muffle furnace, roasting 4-6h under the condition of blowing air removes and touches the plate agent, obtains Beta/Y double-micropore zeolites sample at last.
3. according to the preparation method of the described a kind of double-micropore zeolites of claim 2, it is characterized in that described silicon source is Ludox, white carbon black or waterglass.
4. according to the preparation method of the described a kind of double-micropore zeolites of claim 2, it is characterized in that described aluminium source is a sodium aluminate.
5. according to the preparation method of the described a kind of double-micropore zeolites of claim 2, it is characterized in that described alkali is NaOH and ammonium hydroxide.
6. according to the preparation method of the described a kind of double-micropore zeolites of claim 2, it is characterized in that described TEA
+Be tetraethyl ammonium hydroxide or tetraethylammonium bromide.
7. according to the preparation method of the described a kind of double-micropore zeolites of claim 2, the percentage by weight that it is characterized in that Y zeolite in the described Beta/Y double-micropore zeolites is 5-95%.
8. the double-micropore zeolites of the BEA/FAU structure of the preparation method of a claim 1 preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100622531A CN100551530C (en) | 2007-07-04 | 2007-07-04 | A kind of double-micropore zeolites and preparation method thereof |
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| CN101514007B (en) * | 2008-02-20 | 2011-04-27 | 中国石油化工股份有限公司 | Beta zeolite/Y zeolite coexisting molecular sieve and method for synthesizing same |
| CN101514009B (en) * | 2008-02-20 | 2011-07-13 | 中国石油化工股份有限公司 | Mordenite/beta zeolite/Y zeolite coexisting material and method for synthesizing same |
| CN102050467B (en) * | 2009-10-27 | 2012-08-29 | 中国石油化工股份有限公司 | Double-grain superposed in-situ synthesized Y-type molecular sieve and preparation method thereof |
| CN102049277B (en) * | 2009-10-27 | 2013-03-20 | 中国石油化工股份有限公司 | Hydrocracking catalyst for producing naphtha and raw material for preparing ethylene |
| CN106669808A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing low-condensation-point hydrocracking tail oil |
| CN107226474A (en) * | 2016-03-23 | 2017-10-03 | 中国石化扬子石油化工有限公司 | Mend aluminium method of modifying in a kind of ZSM-5 original positions |
| CN107344110A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Catalyst for producing low linear paraffin content hydrocracking tail oil and its preparation method and application |
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| CN107344111A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst of maximum production low-coagulation diesel oil and its preparation method and application |
| CN108472635A (en) * | 2016-05-25 | 2018-08-31 | 环球油品公司 | High charge density metal alumino-phospho-silicate molecular sieve MeAPSO-83 |
| CN109529921A (en) * | 2018-11-15 | 2019-03-29 | 太原理工大学 | Hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve, Ni type method for preparing catalyst |
| CN112188928A (en) * | 2018-05-24 | 2021-01-05 | Ifp新能源公司 | Method for synthesizing a composite material consisting of a mixture of AFX and BEA structure zeolites in the presence of an organic nitrogen-containing structuring agent |
| CN114212800A (en) * | 2022-01-13 | 2022-03-22 | 万华化学（宁波）有限公司 | Novel high-silicon Y-type zeolite and preparation method and application thereof |
| CN115504483A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Mesoporous Beta-USY type composite molecular sieve and preparation method and application thereof |
| CN115646539A (en) * | 2022-07-13 | 2023-01-31 | 中国科学院山西煤炭化学研究所 | Solid acid catalyst synthesized from long-chain alkylbenzene and preparation method thereof |
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- 2007-07-04 CN CNB2007100622531A patent/CN100551530C/en not_active Expired - Fee Related
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| CN101514009B (en) * | 2008-02-20 | 2011-07-13 | 中国石油化工股份有限公司 | Mordenite/beta zeolite/Y zeolite coexisting material and method for synthesizing same |
| CN101514007B (en) * | 2008-02-20 | 2011-04-27 | 中国石油化工股份有限公司 | Beta zeolite/Y zeolite coexisting molecular sieve and method for synthesizing same |
| CN102050467B (en) * | 2009-10-27 | 2012-08-29 | 中国石油化工股份有限公司 | Double-grain superposed in-situ synthesized Y-type molecular sieve and preparation method thereof |
| CN102049277B (en) * | 2009-10-27 | 2013-03-20 | 中国石油化工股份有限公司 | Hydrocracking catalyst for producing naphtha and raw material for preparing ethylene |
| CN106669808B (en) * | 2015-11-09 | 2020-02-14 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing low-freezing-point hydrocracking tail oil |
| CN106669808A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing low-condensation-point hydrocracking tail oil |
| CN107226474A (en) * | 2016-03-23 | 2017-10-03 | 中国石化扬子石油化工有限公司 | Mend aluminium method of modifying in a kind of ZSM-5 original positions |
| CN107344112B (en) * | 2016-05-05 | 2020-02-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst for producing high-quality catalytic reforming raw material and preparation method and application thereof |
| CN107344110B (en) * | 2016-05-05 | 2020-04-10 | 中国石油化工股份有限公司 | Catalyst for producing hydrocracking tail oil with low straight-chain alkane content and preparation method and application thereof |
| CN107344111A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst of maximum production low-coagulation diesel oil and its preparation method and application |
| CN107344111B (en) * | 2016-05-05 | 2020-04-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst for maximum production of low-freezing diesel oil and preparation method and application thereof |
| CN107344112A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst for producing high-quality catalytic reforming raw material and its preparation method and application |
| CN107344110A (en) * | 2016-05-05 | 2017-11-14 | 中国石油化工股份有限公司 | Catalyst for producing low linear paraffin content hydrocracking tail oil and its preparation method and application |
| CN108472635B (en) * | 2016-05-25 | 2021-09-07 | 环球油品公司 | High charge density metalloaluminophosphate silicate molecular sieve MeAPSO-83 |
| CN108472635A (en) * | 2016-05-25 | 2018-08-31 | 环球油品公司 | High charge density metal alumino-phospho-silicate molecular sieve MeAPSO-83 |
| CN112188928A (en) * | 2018-05-24 | 2021-01-05 | Ifp新能源公司 | Method for synthesizing a composite material consisting of a mixture of AFX and BEA structure zeolites in the presence of an organic nitrogen-containing structuring agent |
| CN112188928B (en) * | 2018-05-24 | 2023-12-05 | Ifp新能源公司 | Method for synthesizing composite material composed of AFX and BEA structure zeolite mixture in presence of organic nitrogen-containing structuring agent |
| CN109529921A (en) * | 2018-11-15 | 2019-03-29 | 太原理工大学 | Hydrogen production by ethanol steam reforming multi-stage porous Beta molecular sieve, Ni type method for preparing catalyst |
| CN109529921B (en) * | 2018-11-15 | 2021-12-07 | 太原理工大学 | Preparation method of hierarchical pore Beta molecular sieve and Ni type catalyst for hydrogen production by ethanol steam reforming |
| CN115504483A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Mesoporous Beta-USY type composite molecular sieve and preparation method and application thereof |
| CN115504483B (en) * | 2021-06-23 | 2024-02-02 | 中国石油化工股份有限公司 | Mesoporous Beta-USY type composite molecular sieve and preparation method and application thereof |
| CN114212800A (en) * | 2022-01-13 | 2022-03-22 | 万华化学（宁波）有限公司 | Novel high-silicon Y-type zeolite and preparation method and application thereof |
| CN115646539A (en) * | 2022-07-13 | 2023-01-31 | 中国科学院山西煤炭化学研究所 | Solid acid catalyst synthesized from long-chain alkylbenzene and preparation method thereof |
| CN115646539B (en) * | 2022-07-13 | 2024-04-23 | 中国科学院山西煤炭化学研究所 | Solid acid catalyst for synthesizing long-chain alkylbenzene and preparation method thereof |
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