CN102557071A - ZSM-11 molecular sieve with hierarchical porous structure and preparation method thereof - Google Patents
ZSM-11 molecular sieve with hierarchical porous structure and preparation method thereof Download PDFInfo
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Abstract
A ZSM-11 molecular sieve with a hierarchical porous structure is characterized in that X-X-ray diffraction spectrum of the molecular sieve is as shown in Figure 1(a)/table 1; the molecular sieve has an even spherical appearance, each ball is formed through self assembly of rod-shaped crystallites (Figure 2), the molecular sieve is formed by evenly mixing raw materials of substance containing IVA elements, substance containing IIIA element, alkali metal hydroxide, template and water, and then through two stages of crystallization processes, the molecular sieve product has pure crystalling phase, is relatively high in degree of crystallinity, and has an excellent heat and water heat stability, namely, the method is relatively low in cost, the performance of the ZSM-11 molecular sieve is excellent, and the method is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of ZSM-11 molecular sieve, particularly, relate to a kind of hierarchical porous structure ZSM-11 molecular sieve and preparation method thereof.
Background technology
ZSM-11 (MEL) is synthetic first by Mobil company the seventies in 20th century, is a member of high-silicon ZSM-5 series molecular sieve, and tetragonal system belongs to Pentasil type zeolite (five-element circular type zeolite) with ZSM-5.ZSM-11 has similar structure and chemical constitution with ZSM-5 (MFI), is the right-angled intersection pore passage structure that ten-ring constitutes, and difference is that ZSM-11 is two-dimentional straight hole road, and the duct is of a size of 0.53*0.54nm; And the ZSM-5 duct constitutes aperture 0.51*0.56nm by straight tubular and sinusoidal intersection.The basic structural unit of the two skeleton connects into [5 by silicon (aluminium) oxygen tetrahedron
8] unit; Through share the limit and with single aggressiveness silicon (aluminium) oxygen tetrahedron through simply becomes-scission of link after formation be parallel to the five silicon chains (Pentasil chain) of c axle, these five silicon chains have the ten-ring hole and are the wavy stratum reticulare that is parallel to the ac face with the formation that connects together of crystal face symmetrical manner.Adjacent stratum reticulare is with different symmetric modes---and symmetry centre is relevant or minute surface is relevant, forms ZSM-5 and ZSM-11 three-dimensional framework respectively.
Pentasil type molecular sieve has obtained using very widely at catalytic field because of its special skeleton structure makes it, also receive much concern for its synthetic research, but research mainly concentrates on MFI type molecular sieve always; And MEL type molecular sieve very easily produces the ZSM-11/ZSM-5 mixed crystal in building-up process because of its skeleton high symmetry causes; Synthetic pure mutually needed raw material and crystallization condition require relatively harsher, need to use a large amount of special template agent with strong guide function to improve the purity of product crystalline phase.Kokotailo in 1973, Pochen Chu etc. use R
4(wherein R is C to the organic cpds of X-shaped formula
1-C
7Alkyl or aryl, X is a periodic table of elements VA element) under hydrothermal condition, synthesize the ZSM-11 molecular sieve as structure directing agent, common template mainly contains tetrabutylphosphonium chloride and Tetrabutyl amonium bromide etc., Rollmann etc. adopts C subsequently
8-C
9Diamine replace the TBuA positively charged ion also to obtain ZSM-11.But there are some researches show soon and use product reality that the TBuA positively charged ion synthesizes as structure directing agent eutectic mixture, and the ZSM-11 of pure phase is difficult to be synthesized as ZSM-11/5.In recent years, along with the optimization to synthesis condition and material proportion, ZSM-11's was synthetic main still at TBuA positively charged ion (TBA
+) inducing under accomplish.In order to improve the crystalline phase purity of product ZSM-11, investigators adopt usually and increase the template consumption, add second template, add crystal seed and adopt dynamically or microwave is synthetic etc. that method realizes.In addition, for the effectively mass transfer and the heat transfer of raising system, the throwing water yield of synthetic system is usually than higher, thereby causes single-autoclave yield rate to descend.
The ZSM-11 molecular sieve that conventional hydrothermal synthesis method obtains mainly presents the shape characteristic of monocrystalline, therefore has flourishing microvoid structure; But because the micro porous molecular sieve aperture is less, it is inner that the bigger or molecule close with the aperture just is difficult to get into the duct of molecular sieve than its aperture, and its effective rate of utilization is reduced greatly, will have influence on its catalytic activity if be applied to heavy oil conversion.Simultaneously, the long duct diffusional limitation of conventional molecular sieve is more serious, makes it in catalyzed reaction, be easy to receive the influence of carbon distribution and inactivation reduces work-ing life greatly.In order to overcome the defective of conventional micro porous molecular sieve, reduce the zeolite crystal size and in molecular sieve crystal, introduce mesoporously all can effectively improve its diffusion.Wherein, The nano molecular sieve of grain-size＜100nm is because crystal grain is little; Have the outside surface bigger, more expose structure cell, higher surface energy and short and regular duct than conventional molecular sieve; Therefore have higher intracrystalline rate of diffusion, in macromolecular catalyzed conversion, demonstrate unique catalytic activity.But when using as catalytic material, nano molecular sieve is easy to coalescence, and heat is poor with hydrothermal stability, regeneration difficulty, and filtered and recycled etc. all is difficult to realize industriallization, all is the major reason that nano molecular sieve can't be realized its industrial application value.In addition, nano molecular sieve has reduced it to some product selectivity because grain-size reduces greatly, has also influenced its using value.
The multistage pore canal molecular sieve is the effective way that another kind reduces the molecular diffusion resistance.Because it has combined the advantage of zeolite molecular sieve and mesopore orbit; The advantage that not only has stronger acidity of zeolite molecular sieve and hydrothermal stability; And, mesoporous introducing possessed the diffusion more excellent more than conventional zeolite molecular sieve because of making it; Make title product rapidly from the active site be diffused into body mutually, prevent further secondary reaction; Carbon distribution is burn off more easily, helps the regeneration of catalyzer.Therefore, the multistage pore canal zeolite molecular sieve of this integrated zeolite molecular sieve and ordered mesoporous material advantage is considered to potential catalytic material of future generation.
Summary of the invention
The purpose of this invention is to provide a kind of ZSM-11 zeolite molecular sieve, this ZSM-11 zeolite molecular sieve has performances such as good heat, hydrothermal stability, crystalline phase are pure, percent crystallinity height.
Another object of the present invention provides a kind of preparation method of ZSM-11 zeolite molecular sieve, and this method is simple, and cost is low, and the ZSM-11 zeolite molecular sieve that makes has performances such as good heat, hydrothermal stability, crystalline phase are pure, percent crystallinity height.
A kind of ZSM-11 zeolite molecular sieve has following characteristic:
1) the X-ray diffraction spectrogram of this molecular sieve is:
2) this molecular sieve has the uniform spherical pattern, and each ball is to be formed by bar-shaped crystallite self-assembly.
Be realization the object of the invention, a kind of preparation method of ZSM-11 zeolite molecular sieve, adopt following technical scheme:
Raw material is contained the material of IVA element, the material that contains the IIIA element, alkali metal hydroxide, template, water to mix; The gained mixture is a 60-120 ℃ of following crystallization in temperature earlier, and then under temperature is 150-200 ℃, continues static crystallization, after the crystallization; Solid matter is separated from mother liquor; Isolated solid matter to neutral, also dry, after template is removed in roasting, promptly gets the ZSM-11 zeolite molecular sieve through deionized water wash;
Wherein, the consumption of material that contains the IVA element is with YO
2Count, the consumption of material that contains the IIIA element is with W
2O
3Count, the consumption of alkali metal hydroxide is with M
2O counts, and template is a Tetrabutyl amonium bromide, and the consumption of Tetrabutyl amonium bromide is with (TBA)
2O counts; Amount of substance proportioning between the raw material is M
2O: W
2O
3: YO
2: (TBA)
2O: H
2O=5-18: 0.5-2.0: 17.5-200: 0.45-6: 350-8000.
In the described method, be that time of 60-120 ℃ of following crystallization is 12-384 hour in temperature, its preferred 24-240 hour, more preferably 24-48 hour.
In the described method, be that 150-200 ℃ of time of continuing static crystallization down is 8-48 hour in temperature, preferred 12-28 hour.
In the described method, preferred, mixture is to carry out crystallization under 80-110 ℃ in temperature earlier; Under 150-180 ℃, carry out crystallization then.
The material of the described IVA of containing element comprises the material that contains element silicon.
The said material that contains element silicon comprises one or more the mixing in silicon sol, water glass, tetraethoxy, WHITE CARBON BLACK, the silica gel bead.
The material of the described IIIA of containing element comprises the material that contains aluminium element.
The described material that contains aluminium element comprises one or more mixing of Tai-Ace S 150, sodium aluminate, aluminum nitrate, aluminum chloride, aluminum isopropylate.
Described alkali metal hydrogen oxidation comprises in Lithium Hydroxide MonoHydrate, sodium hydroxide, the Pottasium Hydroxide one or more mixing.
Preferably, in the described method, the amount of substance proportioning between the raw material is M
2O: W
2O
3: YO
2: (TBA)
2O: H
2O=6-12: 0.8-1.8: 25-100: 0.75-3: 1000-4000.
Preferred, the amount of substance proportioning between the raw material is M
2O: W
2O
3: YO
2: (TBA)
2O: H
2O=8-10: 1.0: 40-65: 0.75-2: 1000-2000.
In raw materials mix, preferred, material, template and the water that will contain the IVA element earlier mix; Be mixture I; The material, alkali metal hydroxide and the water that contain the IIIA element mix, and are mixtures II, then mixture I and mixtures II are under agitation mixed.
The ZSM-11 zeolite molecular sieve of method for preparing has X-ray diffraction spectrogram as shown in Figure 1, and has crystal morphology shown in Figure 2.The ZSM-11 molecular sieve major part of gained of the present invention is uniform spherical pattern (micron order), and each bead is to be formed by a large amount of bar-shaped crystallite self-assemblies, and it is mesoporous that crystallite piles up the intergranular that space that the back produces just formed molecular sieve each other.Carry out modulation through changing crystallization condition, the grain-size of molecular sieve can change in the 1-20 mu m range.
Resulting ZSM-11 zeolite molecular sieve has good heat and hydrothermal stability, and crystalline phase is pure, and percent crystallinity is high, has multi-stage artery structure, can improve the diffusion of molecular sieve greatly.Grain-size controlled (1-20 μ m), and, still have good heat and hydrothermal stability along with the decline of grain-size.
Zeolite molecular sieve ZSM-11 provided by the invention changes into through conventional ammonium ion exchange and can be used as active ingredient after the Hydrogen and prepare the heavy oil catalytic pyrolysis catalyst applications in heavy oil conversion, and can realize producing more propylene and the dp that reduces benzene content in gasoline simultaneously.
Described method also further comprises the steps, mixes at the material that raw material is contained the IVA element, the material that contains the IIIA element, alkali metal hydroxide, template, water; In mixture, add crystal seed; Described crystal seed is the ZSM-11 zeolite molecular sieve of method for preparing, and the mixture that presets crystal seed was carried out burin-in process 0-240 hour, and the mixture after wearing out is a 120-180 ℃ of following crystallization in temperature; Promptly get fine grain ZSM-5-11 zeolite molecular sieve
Wherein, the consumption of material that contains the IVA element is with YO
2Count, the consumption of material that contains the IIIA element is with W
2O
3Count, the consumption of alkali metal hydroxide is with M
2O counts, and template is a Tetrabutyl amonium bromide, and the consumption of Tetrabutyl amonium bromide is with (TBA)
2O counts; Amount of substance proportioning between the raw material is M
2O: W
2O
3: YO
2: (TBA)
2O: H
2O=5-18: 0.5-2.0: 17.5-200: 0.45-6: 350-8000.
The addition of crystal seed is YO
2And W
2O
3The 0.1-20% of total mass; Its preferred 1-10%; It is 4%-6% more preferably.
Described burin-in process is meant and at room temperature leaves standstill 0-240 hour.
Preferably, described burin-in process is meant and at room temperature leaves standstill 24-48 hour.
Mixture after aging is 120-180 ℃ of following crystallization 4-48 hour in temperature.
The above-mentioned fine grain ZSM-5 that obtains-11 zeolite molecular sieve has kept the shape characteristic of the micron order ZSM-11 of the present invention's preparation; But grain-size is a submicron order; And can control the size of zeolite crystal size through changing crystal seed amount and modulation crystallization condition, the molecular sieve size is changed between 100-1000nm.
Compared with prior art, the outstanding advantage of ZSM-11 zeolite molecular sieve preparation method of the present invention is:
Adopt cheap silicon source, aluminium source and less relatively micropore template, under the prerequisite of not adding mesoporous template, go out to have the ZSM-11 molecular sieve of multi-stage artery structure through the static hydrothermal compound method one-step synthesis of two sections crystallization.The zeolite product crystalline phase that this method obtains is pure, and relative crystallinity is high, has good heat and hydrothermal stability, and promptly this method cost is low, and the performance of the ZSM-11 molecular sieve that obtains is good, is fit to industrialized production.
Under the condition that further reduces micropore template consumption, add the ZSM-11 that ZSM-11 molecular sieve crystal seed static hydrothermal synthesizes submicron order.Institute's synthetic small crystal grain molecular sieve has not only kept the shape characteristic of micron order ZSM-11, and grain-size can be effectively controlled through the add-on and the crystallization condition of modulation crystal seed.The fine grain ZSM-5 that this method obtains-11 has good heat and hydrothermal stability because of its special pattern makes it.
Description of drawings
X-ray diffraction pattern before and after the ZSM-11 zeolite molecular sieve hydrothermal treatment consists of Fig. 1 the present invention preparation
The sem photograph of the ZSM-11 zeolite molecular sieve of Fig. 2 the present invention preparation
Embodiment
Following combination experimental example will be done further explanation to technical scheme of the present invention, but therefore not limit protection scope of the present invention.
Embodiment 1
Under stirring condition, prepare following two kinds of working solutions respectively:
Mixture I: with 15g silicon sol (40%SiO
2, 60%H
2O, as follows), 0.97g four butyl bromation amine (99%), the 11.3g de-ionized adds in the beaker and mixes;
Mixtures II: the homogeneous solution of 1.33g Tai-Ace S 150,1.50g sodium hydroxide and the preparation of 15g deionized water;
Constantly stirring down, mixtures II is slowly added among the mixture I, continue to stir by force to evenly, the amount of substance of the reaction mixture that obtains is than being Na
2O: Al
2O
3: SiO
2: (TBA)
2O: H
2O=9.0: 1.0: 50: 0.75: 1000, the initial gel that obtains is transferred to has in the reaction kettle that gathers the tetrafluoro liner, seal in the baking oven of rearmounted entry thermal synthesis, prior to 90 ℃ of constant temperature 24h, be warming up to 150 ℃ then and continue constant temperature 24h.After the reaction kettle cooling, solid is separated with mother liquor, solid to neutral, after 120 ℃ of dryings, is removed template through 550 ℃ of roasting 4h through deionized water wash in air, obtain the ZSM-11 molecular screen primary powder.
Final product powder is through X-ray diffraction analysis, and shown in Fig. 1 (a), the percent crystallinity of choosing the sample of high temperature section crystallization 24h is 100%, records its pattern such as Fig. 2 (a) with ESEM, and to survey its grain-size be 6.7 μ m.
Embodiment 2
Under stirring condition, prepare following two kinds of working solutions respectively:
Solution I:, mix in the 40.2g de-ionized adding beaker with 15g silicon sol, 3.23g four butyl bromation amine.
Solution II: the homogeneous solution of 1.33g Tai-Ace S 150,2.00g sodium hydroxide and the preparation of 40g deionized water
Constantly stirring down, solution II is slowly added in the solution I, continuation is stirred by force to evenly.The mol ratio of initial gel is Na
2O: Al
2O
3: SiO
2: (TBA)
2O: H
2O=12.0: 1.0: 50: 2.5: 2500.Crystallization condition is identical with embodiment 1.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (a) are identical basically, records its pattern and Fig. 2 (a) matches with ESEM.
Embodiment 3
The raw material of present embodiment, composition and technical process are as embodiment 1, and different is: after the raw material thing mixes, be transferred to and have in the reaction kettle that gathers the tetrafluoro liner, the sealing back is warming up to 180 ℃ then and continues constant temperature 8h prior to 90 ℃ of constant temperature 384h.Product is the ZSM-11 molecular sieve, and percent crystallinity is 98.39%, and granularity is 1.5 μ m.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (a) are identical basically, records its pattern and Fig. 2 (a) matches with ESEM.
Embodiment 4
Under stirring condition, prepare following two kinds of working solutions respectively:
Mixture I:, mix in the 11.3g de-ionized adding beaker with 15g silicon sol, 0.97g four butyl bromation amine;
Mixtures II: the homogeneous solution of 2.66g Tai-Ace S 150,1.71g sodium hydroxide and the preparation of 15g deionized water;
Constantly stirring down, mixtures II is slowly added among the mixture I, continue to stir by force to evenly, the amount of substance of reaction mixture is than being Na
2O: Al
2O
3: SiO
2: (TBA)
2O: H
2O=10.3: 2.0: 50: 0.75: 1000.Initial gel places reaction kettle, prior to 90 ℃ of constant temperature 24h, is warming up to 150 ℃ then and continues constant temperature 48h; After the reaction kettle cooling, solid is separated with mother liquor, solid is extremely neutral through deionized water wash; In air, after 120 ℃ of dryings, remove template through 550 ℃ of roasting 4h, obtaining product is the ZSM-11 molecular sieve; Relative crystallinity is 92.86%, and granularity is 10.0 μ m.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (a) are identical basically, records its pattern and Fig. 2 (a) matches with ESEM.
Under stirring condition, prepare following two kinds of working solutions respectively:
Mixture I:, mix in the 11.3g de-ionized adding beaker with 15g silicon sol, 0.97g four butyl bromation amine;
Mixtures II: the homogeneous solution of 0.33g Tai-Ace S 150,1.00g sodium hydroxide and the preparation of 15g deionized water;
Constantly stirring down, mixtures II is slowly added among the mixture I, continue to stir by force to evenly, the amount of substance of reaction mixture is than being Na
2O: Al
2O
3: SiO
2: (TBA)
2O: H
2O=6.0: 0.25: 50: 0.75: 1000, initial gel places reaction kettle, prior to 90 ℃ of constant temperature 24h; Be warming up to 150 ℃ then and continue constant temperature 20h, after the reaction kettle cooling, solid is separated with mother liquor; Solid to neutral, after 120 ℃ of dryings, is removed template through 550 ℃ of roasting 4h through deionized water wash in air; Obtaining product is the ZSM-11 molecular sieve, and relative crystallinity is 110.75%, and granularity is 2.0 μ m.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (a) are identical basically, records its pattern and Fig. 2 (a) matches with ESEM.
Embodiment 6
Other raw materials, composition and the technical process of present embodiment are as embodiment 1, and different is: change silicon sol into water glass, the feed molar proportioning is constant; Be transferred to after initial gel mixes and have in the reaction kettle that gathers the tetrafluoro liner, seal in the baking oven of rearmounted entry thermal synthesis, prior to 120 ℃ of constant temperature 12h; Be warming up to 180 ℃ then and continue constant temperature 18h; The product that obtains is the ZSM-11 molecular sieve, and percent crystallinity is 97.38%, and granularity is 4.0 μ m.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (a) are identical basically, records its pattern and Fig. 2 (a) matches with ESEM.
Other raw materials, composition and the technical process of present embodiment are as embodiment 1; Different is: change Tai-Ace S 150 into sodium aluminate; The feed molar proportioning is constant, is transferred to after initial gel mixes to have in the reaction kettle that gathers the tetrafluoro liner, seals in the baking oven of rearmounted entry thermal synthesis; Prior to 60 ℃ of constant temperature 24h, be warming up to 150 ℃ then and continue constant temperature 48h.The product that obtains is the ZSM-11 molecular sieve, and percent crystallinity is 93.24%, and granularity is 5.5 μ m.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (a) are identical basically, records its pattern and Fig. 2 (a) matches with ESEM.
Embodiment 8
Other raw materials, composition and the technical process of present embodiment are as embodiment 1; Different is: change sodium hydroxide into Lithium Hydroxide MonoHydrate; The feed molar proportioning is constant, is transferred to after initial gel mixes to have in the reaction kettle that gathers the tetrafluoro liner, seals in the baking oven of rearmounted entry thermal synthesis; Prior to 90 ℃ of constant temperature 24h, be warming up to 150 ℃ then and continue constant temperature 26h.The product that obtains is the ZSM-11 molecular sieve, and percent crystallinity is 88.83%, and granularity is 6.5 μ m.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (a) are identical basically, records its pattern and Fig. 2 (a) matches with ESEM.
Embodiment 9
Other raw materials, composition and the technical process of present embodiment are as embodiment 1; Different is: change sodium hydroxide into Pottasium Hydroxide; The feed molar proportioning is constant, is transferred to after initial gel mixes to have in the reaction kettle that gathers the tetrafluoro liner, seals in the baking oven of rearmounted entry thermal synthesis; Prior to 90 ℃ of constant temperature 24h, be warming up to 150 ℃ then and continue constant temperature 26h.The product that obtains is the ZSM-11 molecular sieve, and percent crystallinity is 90.43%, and granularity is 15.8 μ m.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (a) are identical basically, records its pattern and Fig. 2 (a) matches with ESEM.
Under stirring condition, prepare following two kinds of working solutions respectively:
Mixture I: with 15g silicon sol, 0.32g four butyl bromation amine, the 11.5g de-ionized adds in the beaker and mixes, and adds synthetic ZSM-11 among 0.4g (account for raw silicon al oxide total mass the 5%) embodiment 1 then, as crystal seed, and violent stirring 0.5h;
Mixtures II: with the homogeneous solution of 0.83g Tai-Ace S 150,1.54g sodium hydroxide and the preparation of 15g deionized water;
Under continuous stirring condition, mixtures II is slowly added among the mixture I, continue to stir by force to evenly.The amount of substance of the reaction mixture that obtains is than being Na
2O: Al
2O
3: SiO
2: (TBA)
2O: H
2O=14.8: 1.0: 80: 0.4: 1600, the initial gel that obtains is transferred to has in the reaction kettle that gathers the tetrafluoro liner, sealing back room temperature leaves standstill aging 48h, places baking oven through 140 ℃ of static crystallization 16h then.Product is the ZSM-11 molecular sieve, and percent crystallinity is 99.39%, and granularity is 400nm.Its XRD spectra is shown in Fig. 1 (c), and ESEM records its pattern such as Fig. 2 (b).
Embodiment 11
Other proportioning raw materials of present embodiment and technical process are with embodiment 10, and different is: with the crystal seed quantitative change is 0.008g (account for raw silicon al oxide total mass 0.1%).In 140 ℃ of static crystallization 36h, the product that obtains is the ZSM-11 molecular sieve to initial gel behind aged at room temperature 48h, and percent crystallinity is 89.42%, and granularity is 950nm.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (c) are identical basically.
Embodiment 12
Other proportioning raw materials of present embodiment and technical process are with embodiment 10, and different is: with the crystal seed quantitative change is 0.8g (account for raw silicon al oxide total mass 10%).The product that obtains is the ZSM-11 molecular sieve, and percent crystallinity is 91.68%, and granularity is 250nm.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (c) are identical basically.
Embodiment 13
Other proportioning raw materials of present embodiment and technical process are with embodiment 10, and different is: after the raw material thing mixes, be transferred to and have in the reaction kettle that gathers the tetrafluoro liner, sealing back room temperature leaves standstill aging 48h, places baking oven through 180 ℃ of static crystallization 4h then.Product is the ZSM-11 molecular sieve, and percent crystallinity is 99.92%, and granularity is 300nm.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (c) are identical basically.
Embodiment 14
Other proportioning raw materials of present embodiment and technical process are with embodiment 10, and different is: after the raw material thing mixes, be transferred to and have in the reaction kettle that gathers the tetrafluoro liner, sealing back room temperature leaves standstill aging 24h, places baking oven through 140 ℃ of static crystallization 24h then.Product is the ZSM-11 molecular sieve, and percent crystallinity is 87.96%, and granularity is 800nm.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (c) are identical basically.
Embodiment 15
Other proportioning raw materials of present embodiment and technical process are with embodiment 10; Different is: after the raw material thing mixes; Be transferred to and have in the reaction kettle that gathers the tetrafluoro liner, sealing back room temperature leaves standstill aging 240h, places baking oven through 120 ℃ of static crystallization 12h then.Product is the ZSM-11 molecular sieve, and percent crystallinity is 93.66%, and granularity is 200nm.Final product powder is through X-ray diffraction analysis, and its result and Fig. 1 (c) are identical basically.
Embodiment 16-22
The technical process of embodiment 16-22 is referring to embodiment 1, and raw material and consumption thereof are as seeing the following form:
Experimental example 1
This experimental example explanation ZSM-11 zeolite with multi-stage artery structure provided by the invention has good hydrothermal stability.
With the micron order of preparation in embodiment 1 and 7 and the zeolite sample of submicron order, be designated as Z1 and Z2 respectively.With it under the condition that 800 ℃, 100% water vapour exist, hydrothermal treatment consists 4h, the flooding quantity that feeds in the aging pipe is every gram sample 15-25 milliliter per hour.
Each sample before and after the hydrothermal treatment consists is characterized the stability of its skeleton respectively with X-ray diffraction.XRD spectra after molecular sieve is aging such as Fig. 1 (b, d) shown in.
(Fig. 1 (b, d)) shows that the ZSM-11 of the hierarchical porous structure of various grain sizes provided by the invention all has higher acidity and hydrothermal stability to the XRD spectra of aging back molecular sieve.This has great industrial utility value for the catalytic process that relates to hydrothermal treatment consists.
ZSM-11 zeolite molecular sieve to other embodiment preparations carries out this experiment, obtains identical result.
Experimental example 2
This experimental example is the application of ZSM-11 zeolite molecular sieve provided by the invention in the catalytic conversion of heavy oil process.With the zeolite sample of crystallization 24h among the embodiment 1 NH through 1.0M
4NO
3Solution is in 80 ℃ of following IXs three times, each 2h, the zeolite after the exchange through deionized water wash to there not being free NO
3 -, filter the back just obtains sodium content＜0.05wt.% after 120 ℃ of dryings ammonium type sample, behind 550 ℃ of roasting 2h, change Hydrogen into.With the Hydrogen sample as active constituent loading on inerts e, mix making beating after, in 700 ℃ of high-temperature roasting 2h, make the fresh lysate catalyzer, after 800 ℃ of hydrothermal agings, become aging agent, note is made Cat-11.Catalyzer as a comparison is to be the catalyst for cracking of active ingredient preparation with industrial HZSM-5.Catalyst preparation process and burin-in process are identical with the former, and note is made Cat-5.
Catalyst sample 250g after the above-mentioned hydrothermal treatment consists of in small-sized fixed fluidized bed reaction unit, packing into carries out heavy oil catalytic pyrolysis.Raw oil is the normal slag of grand celebration, 520 ℃ of temperature of reaction, and reaction pressure 0.1Mpa, agent-oil ratio are 7.Reaction result such as table 1.Wherein the heavy oil conversion rate is 83.25wt%, and propene yield is 10.49wt%, propylene/liquefied gas selectivity 41.33wt%, benzene content 0.33wt% in the gasoline.
Table 2 different activities component catalyst products distribution
Other embodiment products are also carried out as above contrast experiment, and the result and the The above results that obtain match.
Claims (10)
1. ZSM-11 zeolite molecular sieve has following characteristic:
1) the X-ray diffraction spectral data of this molecular sieve is:
2) this molecular sieve has the uniform spherical pattern, and each ball is to be formed by bar-shaped crystallite self-assembly.
2. the preparation method of one kind ZSM-11 zeolite molecular sieve,
Raw material is contained the material of IVA element, the material that contains the IIIA element, alkali metal hydroxide, template, water to mix; The gained mixture is a 60-120 ℃ of following crystallization in temperature earlier, and then under temperature is 150-200 ℃, continues static crystallization, after the crystallization; Solid matter is separated from mother liquor; Isolated solid matter to neutral, also dry, after template is removed in roasting, promptly gets the ZSM-11 zeolite molecular sieve through deionized water wash;
Wherein, the consumption of material that contains the IVA element is with YO
2Count, the consumption of material that contains the IIIA element is with W
2O
3Count, the consumption of alkali metal hydroxide is with M
2O counts, and template is a Tetrabutyl amonium bromide, and the consumption of Tetrabutyl amonium bromide is with (TBA)
2O counts; Amount of substance proportioning between the raw material is M
2O: W
2O
3: YO
2: (TBA)
2O: H
2O=5-18: 0.5-2.0: 17.5-200: 0.45-6: 350-8000;
Preferably, the amount of substance proportioning between the raw material is M
2O: W
2O
3: YO
2: (TBA)
2O: H
2O=6-12: 0.8-1.8: 25-100: 0.75-3: 1000-4000.
3. preparation method according to claim 2 is characterized in that, is that time of 60-120 ℃ of following crystallization is 12-384 hour in temperature, its preferred 24-240 hour, and more preferably 24-48 hour.
4. according to claim 2 or 3 described preparing methods, it is characterized in that, is that 150-200 ℃ of time of continuing static crystallization down is 8-48 hour in temperature, preferred 12-28 hour.
5. preparation method according to claim 3 is characterized in that, mixture is a 80-110 ℃ of following crystallization in temperature earlier.
6. according to each described preparation method of claim 2-5, it is characterized in that the material of the described IVA of containing element comprises the material that contains element silicon; The material of the described IIIA of containing element comprises the material that contains aluminium element.
7. preparation method according to claim 6 is characterized in that, the described material that contains element silicon comprises one or more the mixing in silicon sol and, water glass, tetraethoxy, WHITE CARBON BLACK, the silica gel bead; The described material that contains aluminium element comprises one or more the mixing in Tai-Ace S 150, sodium aluminate, aluminum nitrate, aluminum chloride, the aluminum isopropylate; Described alkali metal hydrogen oxidation comprises in Lithium Hydroxide MonoHydrate, sodium hydroxide, the Pottasium Hydroxide one or more mixing.
8. preparation method according to claim 2; It is characterized in that, also further comprise the steps, mix at the material that raw material is contained the IVA element, the material that contains the IIIA element, alkali metal hydroxide, template, water; In mixture, add crystal seed; Described crystal seed is the ZSM-11 zeolite molecular sieve of claim 1 preparation, and the mixture that presets crystal seed was carried out burin-in process 0-240 hour, and the mixture after wearing out is a 120-180 ℃ of following crystallization in temperature; Promptly get fine grain ZSM-5-11 zeolite molecular sieve
Wherein, the consumption of material that contains the IVA element is with YO
2Count, the consumption of material that contains the IIIA element is with W
2O
3Count, the consumption of alkali metal hydroxide is with M
2O counts, and template is a Tetrabutyl amonium bromide, and the consumption of Tetrabutyl amonium bromide is with (TBA)
2O counts; Amount of substance proportioning between the raw material is M
2O: W
2O
3: YO
2: (TBA)
2O: H
2O=5-18: 0.5-2.0: 17.5-200: 0.45-6: 350-8000.
9. will go 8 described preparing methods according to right, it is characterized in that, the addition of crystal seed is YO
2And W
2O
3The 0.1-20% of total mass; Its preferred 1%-10%; More preferably 4%-6%.
10. will go 8 described preparing methods according to right, it is characterized in that, described burin-in process is meant and at room temperature leaves standstill 0-240 hour; Mixture after aging is 120-180 ℃ of following crystallization 4-48 hour in temperature.
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