CN104030314A - ZSM-5-based hierarchical porous molecular sieve material and preparation method thereof - Google Patents
ZSM-5-based hierarchical porous molecular sieve material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ZSM-5-based hierarchical porous molecular sieve. The dimension of the ZSM-5-based hierarchical porous molecular sieve material prepared in the invention is 100nm-20[mu]m; when the dimension of the ZSM-5 molecular sieve is greater than 1[mu]m, the ZSM-5 molecular sieve has a cruciate flower morphology, every individual is formed by accumulating nanometer crystals, and a gap among the nanometer crystals forms a mesopore; or when the dimension of the ZSM-5 molecular sieve is not greater than 1mum, the ZSM-5 molecular sieve has a nanometer rod plug self-assembling morphology characteristic, and a gap among nanometer rods forms a mesopore. The ZSM-5-based hierarchical porous molecular sieve is prepared by adopting cheap raw materials through a one step method with tetrapropyl ammonium bromide as a template. The method has the advantages of low cost and simple operation, and the obtained hierarchical porous molecular sieve material has good physical and chemical properties and a catalysis characteristic, and is suitable for the industrial production.
Description
Technical field
The present invention relates to a kind of multi-stage porous molecular screen material, particularly, relate to a kind of have size and pattern controlled, based on the nanocrystalline accumulation of ZSM-5 or grafting and multi-stage porous molecular screen material and preparation method thereof.
Background technology
ZSM-5 molecular sieve belongs to a member of high silicon shape-selective molecular sieve " pentaisl " family, has 3 D pore canal system, is intersected and to be formed, about the 0.54nm of aperture by the straight hole road that is parallel to the axial sinusoidal of a duct (turning is 150 °) and is parallel to b axle.Due to the higher silica alumina ratio of skeleton, cause this molecular sieve to there is higher heat and hydrothermal stability and stronger acidity and hydrophobicity, and it is played an important role because of its unique pore passage structure and higher anti-carbon performance in shape selective catalysis field.Especially aspect propylene enhancing, ZSM-5 is not only widely used in the catalytic pyrolysis field of refining of petroleum, also becomes the important catalyzer of preparing propylene by methanol transformation in Coal Chemical Industry (MTP) technique.
ZSM-5 molecular sieve is by Mobil company, to be developed first the seventies in last century, be to use TPAOH as structure directing agent at first, the mixture of silicon source, aluminium source, alkali source, water and template crystallization 6h-10d under 100-175 ° of C is prepared and obtained.Along with the continuous expansion of its application, its study on the synthesis, also constantly deeply, is expanded to without in template system by initial template system, and realized already suitability for industrialized production.But the industrial goods crystal grain of ZSM-5 molecular sieve is often all larger, conventionally between 3-5 μ m (Fig. 1-2).For micro porous molecular sieve, its active centre is often all inner in duct.Therefore, zeolite crystal size increases molecule at the diffusional resistance of its inside, duct compared with conference, makes target product molecule can not diffuse out in time duct inner and secondary reaction finally occurs generate other molecule compared with long the evolving path.Therefore the yield that, how to shorten the evolving path, reduces diffusional resistance and increase object product has great importance.
In order to realize this purpose, the molecular sieve of synthesis of nano size is an effective approach.Nano molecular sieve is because grain-size reduces greatly, have the outside surface larger than conventional molecular sieve, more expose structure cell, higher surface can and short and regular duct, therefore be conducive to the inner product molecule generating in duct and diffuse out in time duct, avoid the generation of secondary reaction.The method of synthesis of nano molecular sieve mainly contains the several different methods such as " clear liquid-template ", " crystal seed method ", " the spacing method in space ", although can obtain being of a size of several molecular sieve crystals to hundreds of nanometer, the method is had relatively high expectations to synthesis condition conventionally.And for adopting " the spacing method in space ", also need to remove by aftertreatment the second template that crystal growing space is provided, not only cause the raising greatly of synthetic cost, and increased the complicacy of building-up process.The most important is that the molecular sieve of this nano-scale is because structure cell number in crystal is less, so the stability under heat and thermal and hydric environment is very poor, it is coalescent easily to occur, regeneration difficulty after inactivation; And because grain-size reduces, outside surface increases greatly, the active sites number of outside surface is corresponding increasing also, thereby a part of raw molecule is directly reacted on the outer surface, and this need to utilize the reaction of its duct shape selectivity unfavorable on the contrary for some.In addition the filtered and recycled difficulty facing in industrial production, is also to limit its industrialized important factor.
By comparison, another approach---in molecular crystal, introduce mesoporous (macropore), i.e. the molecular screen material of synthetic microporous-composite mesoporous multi-stage artery structure, due to just by introducing the mesoporous diffusional resistance that reduces, accelerate diffusion, become the focus of current research.Synthetic method about the ZSM-5 molecular sieve material of hierarchical porous structure is a lot, modal method, in synthetic system, not only add exactly the micropore template that promotes that ZSM-5 skeleton forms, also add the mesoporous template of inducing mesoporous formation, comprise carbon black pellet as hard template, carbon nanotube, charcoal-aero gel, polysaccharide compound etc. and as the cationic polymers of soft template and amphiphilic organosilane etc.Although two template can access orderly mesoporous distribution, the use of mesoporous template has not only increased cost and has also caused the complicated of synthesis step, and is not suitable for industrial application.Some scholar's research are developed has the effect that bifunctional template molecule is brought into play micropore template and mesoporous template simultaneously.For example, the people such as Choi interacts to obtain ZSM-5 molecular sieve nanometer sheet by compound quaternary ammonium surfactant and silicate anion (Fig. 3 a).Wherein the existence as the ammonium molecule of micropore template is mainly the formation of induction micropore, the afterbody of the tensio-active agent being connected with ammonium molecule is self-assembled into lamellar micelle, in building-up process, will between the microporous crystal of formation, keep apart, thereby obtain the aggregate of nanoscale twins.Although it is regular that this method can arrive pattern, there is the molecular screen material of good mesoporous distribution, this to have bifunctional template molecule preparation process very complicated, is only suitable for laboratory study.
Except utilizing the pore-creating effect of template, synthetic zeolite product is carried out aftertreatment, utilizes the silicon source of special property or aluminium source and add the methods such as crystal seed and some additive and also can obtain the ZSM-5 of multi-stage porous.Although can obtain having the ZSM-5 base multilevel hole material of special appearance, building-up process but has certain complicacy, and need extra aftertreatment to remove Raney Ni.In addition, some investigators adopt the conventional micropore template of ZSM-5 molecular sieve and conventional silicon source, aluminium source, are not adding under the prerequisite of the second template, only by regulating synthesis condition to obtain having the molecular screen material of micro-Jie's composite structure.(the Yang such as Yang, J., et al., Chem.Eng.J., 2011,166,1083) by the synthesis condition of regulation system, control nucleation and crystal growing process, be about to silicon source tetraethoxy and aluminium source aluminum isopropylate and be prepared into gel prior to the fully rear remix of hydrolysis under room temperature, and then coordinate the mode of two sections of crystallization to obtain the nanocrystalline coacervate forming (300-600nm) by 30-50nm, its pattern as shown in Figure 3 b.
There are a variety of route of synthesis in the multi-stage porous molecular screen material based on ZSM-5 at present, but these methods exist certain weak point.As: the raw material of employing special property and template generate when inducing micropore and mesoporous (macropore), conventionally need to carry out pre-treatment or adopt complicated preparation process or in preparing the process of gel, add extra raw material and need aftertreatment to remove raw material, these processes have not only increased synthetic cost, but also increased the complicacy of building-up process, and be unfavorable for industrialized production.By changing crystallization condition, controlling general that the formation of hierarchical porous structure obtains is all nanocrystalline coacervate, nanocrystalline formation generally needs the raw material that character of use is better, price is more expensive, as tetraethoxy, aluminum isopropylate and TBAH etc.Patent application CN101983921A discloses a kind of synthetic multistage pore canal of simple and easy to control, economical rationality, the method for the ZSM-5 molecular sieve that nano microcrystalline is piled up in order, adopt comparatively cheap silicon source, aluminium source and template, by adding seed particles as template in synthetic system and adding a certain amount of additive (KF, Na
2sO
4deng) control formation and the amount of piling up hole, the product of synthesized presents shape characteristic as shown in Figure 3 c.In order to realize industrial application, farthest reduce synthetic cost, the raw material of exploitation based on cheap and the synthetic method of simple operations step are the inevitable course.Given this, special proposition the present invention.
Summary of the invention
The object of the present invention is to provide a kind of ZSM-5 molecular sieve.This molecular sieve is that grain-size is controlled, the molecular screen material of the ZSM-5 base multi-stage artery structure with nanocrystalline stacking pattern.
Another object of the present invention is to provide a kind of preparation method of ZSM-5 molecular sieve, and the method cost is low, simple.
ZSM-5 Quito level porous molecular sieve material, has following feature:
1) ZSM-5 molecular sieve is of a size of 100nm-20 μ m;
2) during described ZSM-5 molecular sieve size > 1 μ m, present cruciate flower pattern, each individuality is to be formed by nanocrystalline accumulation, and the gap of nanocrystalline forms mesoporous; Or
3) during described ZSM-5 molecular sieve size≤1 μ m, present the shape characteristic of nanometer rod grafting self-assembly, the gap between nanometer rod forms mesoporous.
The pattern of described cruciate flower is as accompanying drawing 5(a) as shown in, present the pattern of nanometer rod grafting self-assembly as accompanying drawing 5(c) as shown in.
Described ZSM-5 molecular sieve has X-ray diffraction spectrogram as shown in Figure 4.
Micron-sized ZSM-5 molecular sieve is uniform " cruciate flower " pattern, and each individuality is again to be formed by a large amount of nanocrystalline self-assemblies, and the space between nanocrystalline is that intergranular is mesoporous.By feed intake silica alumina ratio can obtain the arbitrary size of size within the scope of 1-20 μ m and the product of Acidity in conjunction with the modulation of crystallization condition of change.
The ZSM-5 molecular sieve of submicron order presents the shape characteristic of nanometer rod " grafting ", the particle size that a plurality of nanometer rod form after pegging graft is between 100-1000nm, can effectively regulate and control according to the change of amount of seed and crystallization condition, Acidity can carry out modulation by the change silica alumina ratio that feeds intake.
In order to realize object of the present invention, a kind of preparation method of ZSM-5 molecular sieve, comprises the steps:
By raw material containing the material of IVA element, mix containing material, alkali metal hydroxide, template, the water of IIIA element, gained mixture is first crystallization under 40-120 ° of C in temperature, and then be to continue static crystallization under 130-210 ° of C in temperature, after crystallization completes, solid matter is separated from mother liquor, isolated solid matter is extremely neutral, also dry through deionized water wash, finally by roasting, remove template, obtain micron-sized ZSM-5 molecular sieve, this molecular sieve has multi-stage porous, its size > 1 μ m
Wherein, containing the consumption of the material of IVA element with YO
2count, containing the consumption of the material of IIIA element with X
2o
3count, the consumption of alkali metal hydroxide is with M
2o counts, and template is 4-propyl bromide, and the consumption of 4-propyl bromide is with (TPA)
2o counts; Amount of substance proportioning between raw material (mol ratio, lower same) is M
2o:X
2o
3: YO
2: (TPA)
2o:H
2o=2-40:0-5.0:10-1000:0.3-120:40-10000, preferred proportioning is M
2o:X
2o
3: YO
2: (TPA)
2o:H
2o=4-25:0.2-3.0:25-200:0.6-48:200-5000, preferred proportioning is M
2o:X
2o
3: YO
2: (TPA)
2o:H
2o=6_15:0.5-1.0:35-150:0.75-10:500-2500.
The ZSM-5 molecular sieve of gained presents the pattern of " cruciate flower ".
In described method, the time that is crystallization under 40-120 ° of C in temperature is 8-480 hour, preferably 12-168 hour, more preferably 12-72 hour.
In described method, in temperature, be that the time of continuing static crystallization under 130-210 ° of C is 6-36 hour, preferred 8-24 hour.
In described method, preferably, mixture is first to carry out crystallization under 70-100 ° of C in temperature, and then proceeds crystallization under 160-185 ° of C.
The preparation method of another kind of ZSM-5 molecular sieve, comprises the steps:
After raw material is mixed containing the material of IVA element, containing material, alkali metal hydroxide, template, the water of IIIA element, in mixture, add crystal seed, described crystal seed is ZSM-5 Quito level porous molecular sieve material of the prepared size > of aforesaid method 1 μ m, the mixture of preset crystal seed is carried out to burin-in process 0-360 hour under 5-60 ° of C, mixture after aging is crystallization under temperature 100-200 ° C again, obtain the ZSM-5 molecular sieve of submicron order, this molecular sieve has multi-stage porous, its size≤1 μ m
Wherein, containing the consumption of the material of IVA element with YO
2count, containing the consumption of the material of IIIA element with X
2o
3count, the consumption of alkali metal hydroxide is with M
2o counts, and template is 4-propyl bromide, and the consumption of 4-propyl bromide is with (TPA)
2o counts; Amount of substance proportioning between raw material is M
2o:X
2o
3: YO
2: (TPA)
2o:H
2o=2-40:0-5.0:10-1000:0.1-60:40-10000.
Gained ZSM-5 molecular sieve presents the shape characteristic of nanometer rod " grafting ".
The addition of crystal seed is YO
2and X
2o
3the 0.05-20% of total mass.Preferred 0.5-10%, it is 1%-7% more preferably.
Described burin-in process refers to standing 0-360 hour in the environment of 5-60 ° of C.Preferred burin-in process temperature is 15-25 ° of C, and ageing treatment time is 0-72h.
Mixture after aging is crystallization 4-48 hour under 100-200 ° of C in temperature.Preferred crystallization temperature is 150-180 ° of C, and preferred crystallization time is 6-24h.
In the preparation method of two kinds of described ZSM-5 molecular sieves, the material that contains IVA element comprises the material containing element silicon.The described material containing element silicon comprises one or more the mixing in silicon sol, water glass, tetraethoxy, white carbon black, silica gel bead.The described material containing IIIA element comprises the material containing aluminium element.Containing the material of aluminium element, comprise one or more mixing of Tai-Ace S 150, sodium aluminate, aluminum nitrate, aluminum chloride, aluminum isopropylate.The oxidation of described alkali metal hydrogen comprises in lithium hydroxide, sodium hydroxide, potassium hydroxide one or more mixing.
Compared with prior art, the outstanding advantage of ZSM-5 of the present invention Quito level porous molecular sieve material is:
ZSM-5 molecular sieve of the present invention has the granule-morphology feature of " cruciate flower ", and each particle is again to be formed by a large amount of nanocrystalline mutual stacking self-assemblies.This special pattern not only makes material possess good micropore distribution (ZSM-5 is nanocrystalline), and formed a large amount of gaps due to nanocrystalline after stacking each other, therefore embody good mesoporous distribution, in addition, when this special self-assembly pattern has also solved nano molecular sieve industrial production and the separation problem of mother liquor, and guaranteed that material has good heat and hydrothermal stability; This molecular sieve can also present the shape characteristic of nanometer rod " grafting ", not only has larger outside surface and good micro-mesoporous distribution, and makes it have good heat and hydrothermal stability because of its special pattern.
ZSM-5 molecular sieve of the present invention is the micropore template that adopts cheap silicon source, aluminium source and relatively small amount, do not adding under the prerequisite of mesoporous template, crystal seed and extra additive, static hydrothermal synthetic method one step by two sections of crystallization prepares the ZSM-5 based molecular sieve material with multi-stage artery structure.On the basis of synthesizing micron-grade ZSM-5 Quito level porous molecular sieve, the ZSM-5 molecular sieve of " cruciate flower " pattern that further reduces micropore template consumption and add above-mentioned synthetic size > 1 μ m is as crystal seed, by the synthetic ZSM-5 Quito level porous molecular sieve material that just obtains size≤1 μ m of simple static hydrothermal, the ZSM-5 molecular sieve size obtaining can be effectively controlled by add-on, seed sized and the modulation crystallization condition of modulation crystal seed.; by feed intake silica alumina ratio in conjunction with the modulation of crystallization condition and corresponding amount of seed and size of change; can obtain the ZSM-5 based molecular sieve of the multi-stage porous character of arbitrary size and Acidity within the scope of size 100nm-20 μ m; for meeting needs of production, have great importance; and this preparation method is simple; and cost is low, the ZSM-5 Quito level porous molecular sieve excellent property obtaining, is applicable to suitability for industrialized production.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of Fig. 1 business ZSM-5 molecular sieve;
The N of Fig. 2 business ZSM-5 molecular sieve
2adsorption desorption curve and mesoporous distribution;
The scanning electron microscope (SEM) photograph of the ZSM-5 molecular sieve material of the hierarchical porous structure of Fig. 3 prior art;
The XRD spectra of ZSM-5 Quito level porous molecular sieve material prepared by Fig. 4 the present invention;
The scanning electron microscope (SEM) photograph of ZSM-5 Quito level porous molecular sieve material prepared by Fig. 5 the present invention;
The N of ZSM-5 Quito level porous molecular sieve material prepared by Fig. 6 the present invention (> 1 μ m)
2adsorption desorption curve and Jie (greatly) pore distribution;
The N of ZSM-5 Quito level porous molecular sieve material (≤1 μ m) prepared by Fig. 7 the present invention
2adsorption desorption curve and Jie (greatly) pore distribution.
Embodiment
Combination experimental example below will be described further technical scheme of the present invention, but protection domain not thereby limiting the invention.
Embodiment 1
Under the condition stirring, prepare respectively following two kinds of working solutions:
Mixture I: by the homogeneous solution of 1.39g Tai-Ace S 150,1.57g sodium hydroxide and the preparation of 10g deionized water;
Mixtures II: by 17.27g silicon sol (40%SiO
2, 60%H
2o, as follows), 0.92g 4-propyl bromide (99%), 10g deionization adds in beaker and mixes.
Under constantly stirring, two kinds of mixtures are mixed, continue to stir by force to evenly, the amount of substance of the reaction mixture obtaining is than being Na
2o:Al
2o
3: SiO
2: (TPA)
2o:H
2o=9.0:1.0:55:0.82:825, is transferred to the initial gel obtaining in the reactor with polytetrafluoro liner, inserts in the baking oven of Hydrothermal Synthesis after sealing, prior to 80 ℃ of constant temperature 24h, is then warming up to 175 ° of C and continues constant temperature 24h.After reactor is cooling, solid is separated with mother liquor, and solid to neutral, after 120 ° of C are dried in air, is removed template through 550 ° of C roasting 3h through deionized water wash, obtains the former powder of molecular screen material.
Final product powder presents the spectrum peak of standard ZSM-5 molecular sieve through X-ray diffraction analysis, and (Fig. 4 a), selecting it is standard specimen to establish its degree of crystallinity be 100%.By scanning electron microscope, recording its pattern is " cruciate flower " pattern as shown in Figure 5 a, and particle size is 6 μ m left and right.Individual particle surface presents nanocrystalline stacking pattern (Fig. 5 b) after amplifying.The Adsorption and desorption isotherms of product present similar H4 type hysteresis winding (Fig. 6 a), illustrate nanocrystalline between orderly accumulation formed a large amount of holes of slit-shaped uniformly, and be mainly distributed in the mesoporous scope of 2-50nm (Fig. 6 b).In addition, this special shape characteristic also makes sample have the outside surface (table 1) larger than conventional micropore ZSM-5 molecular sieve.
Embodiment 2
Under the condition stirring, prepare respectively following two kinds of working solutions:
Solution I: by the homogeneous solution of 1.27g Tai-Ace S 150,1.91g sodium hydroxide and the preparation of 10g deionized water;
Solution II: by 8.61g silicon sol, 0.23g 4-propyl bromide, 10g deionization adds in beaker and mixes.
Under constantly stirring, two kinds of mixtures are mixed, continue to stir by force to evenly.The mol ratio of initial gel is Na
2o:Al
2o
3: SiO
2: (TPA)
2o:H
2o=12.0:1.0:30:0.23:750.The initial gel obtaining is transferred in the reactor with polytetrafluoro liner, after sealing, inserts in the baking oven of Hydrothermal Synthesis, prior to 80 ° of C constant temperature 24h, be then warming up to 175 ° of C and continue constant temperature 30h.After reactor is cooling, solid is separated with mother liquor, and solid to neutral, after 120 ° of C are dried in air, is removed template through 550 ° of C roasting 3h through deionized water wash, obtains the former powder of ZSM-5 based molecular sieve material.Product presents " cruciate flower " pattern, degree of crystallinity 95.23%, granularity 8 μ m left and right.
Embodiment 3
Under the condition stirring, prepare respectively following two kinds of working solutions:
Solution I: by the homogeneous solution of 0.25g Tai-Ace S 150,0.25g sodium hydroxide and the preparation of 10g deionized water;
Solution II: by 11.20g silicon sol, 0.40g 4-propyl bromide, 10g deionization adds in beaker and mixes.
Under constantly stirring, two kinds of mixtures are mixed, continue to stir by force to evenly.The mol ratio of initial gel is Na
2o:Al
2o
3: SiO
2: (TPA)
2o:H
2o=8.2:1.0:200:2.0:4000.The initial gel obtaining is transferred in the reactor with polytetrafluoro liner, after sealing, inserts in the baking oven of Hydrothermal Synthesis, prior to 80 ° of C constant temperature 12h, be then warming up to 170 ° of C and continue constant temperature 16h.After reactor is cooling, solid is separated with mother liquor, and solid to neutral, after 120 ° of C are dried in air, is removed template through 550 ° of C roasting 3h through deionized water wash, obtains the former powder of ZSM-5 based molecular sieve material.Product presents " cruciate flower " pattern, degree of crystallinity 110.25%, granularity 2.5 μ m left and right.
Embodiment 4
Under the condition stirring, prepare respectively following two kinds of working solutions:
Solution I: by the homogeneous solution of 0.33g sodium hydroxide and the preparation of 10g deionized water;
Solution II: by 12.94g silicon sol, 0.69g 4-propyl bromide, 10g deionization adds in beaker and mixes.
Under constantly stirring, two kinds of mixtures are mixed, continue to stir by force to evenly.The mol ratio of initial gel is Na
2o:Al
2o
3: SiO
2: (TPA)
2o:H
2o=9.3:0:200:3.0:3600.The initial gel obtaining is transferred in the reactor with polytetrafluoro liner, after sealing, inserts in the baking oven of Hydrothermal Synthesis, prior to 80 ° of C constant temperature 8h, be then warming up to 170 ° of C and continue constant temperature 12h.After reactor is cooling, solid is separated with mother liquor, solid through deionized water wash to neutral, in air 120 ℃ dry after, through 550 ° of C roasting 3h, remove template, obtain the former powder of ZSM-5 based molecular sieve material.Product presents " cruciate flower " pattern, degree of crystallinity 122.86%, granularity 2.0 μ m left and right.
Embodiment 5
Under the condition constantly stirring, to being equipped with in the beaker of 32.05g silicon sol, add successively 1.42g 4-propyl bromide, 1.69g sodium hydroxide and 1.42g Tai-Ace S 150.Continue to stir by force to evenly.The mol ratio of initial gel is Na
2o:Al
2o
3: SiO
2: (TPA)
2o:H
2o=9.5:1.0:100:1.25:519.The initial gel obtaining is transferred in the reactor with polytetrafluoro liner, after sealing, inserts in the baking oven of Hydrothermal Synthesis, prior to 80 ° of C constant temperature 24h, be then warming up to 170 ℃ and continue constant temperature 24h.After reactor is cooling, solid is separated with mother liquor, and solid to neutral, after 120 ° of C are dried in air, is removed template through 550 ° of C roasting 3h through deionized water wash, obtains the former powder of ZSM-5 based molecular sieve material.Product presents " cruciate flower " pattern, degree of crystallinity 112.61%, granularity 3.2 μ m left and right.
Embodiment 6
The raw material of the present embodiment, composition and technical process are as embodiment 1, different: after raw material thing mixes, be transferred in the reactor with polytetrafluoro liner, after sealing, prior to 80 ℃ of constant temperature 360h, be then warming up to 175
°c continues constant temperature 12h.Product is ZSM-5 based molecular sieve material, presents " cruciate flower " pattern, and degree of crystallinity is 97.86%, and granularity is 1.3 μ m left and right.
Embodiment 7
The raw material of the present embodiment, composition and technical process are as embodiment 1, different: after raw material thing mixes, be transferred in the reactor with polytetrafluoro liner, after sealing, prior to 80 ° of C constant temperature 6h, be then warming up to 175 ° of C and continue constant temperature 36h.Product is ZSM-5 based molecular sieve material, presents " cruciate flower " pattern, and degree of crystallinity is 91.33%, and granularity is 10.5 μ m left and right.
Embodiment 8
The raw material of the present embodiment, composition and technical process are as embodiment 1, different: after raw material thing mixes, be transferred in the reactor with polytetrafluoro liner, after sealing, prior to 110 ° of C constant temperature 24h, be then warming up to 150 ° of C and continue constant temperature 48h.Product is ZSM-5 based molecular sieve material, presents " cruciate flower " pattern, and degree of crystallinity is 95.37%, and granularity is 4.0 μ m left and right.
Embodiment 9
The raw material of the present embodiment, composition and technical process are as embodiment 1, different: after raw material thing mixes, be transferred in the reactor with polytetrafluoro liner, after sealing, prior to 60 ° of C constant temperature 24h, be then warming up to 190 ° of C and continue constant temperature 20h.Product is ZSM-5 based molecular sieve material, presents " cruciate flower " pattern, and degree of crystallinity is 105.28%, and granularity is 5.3 μ m left and right.
Embodiment 10
Other raw materials, composition and the technical process of the present embodiment are as embodiment 1, different: to change silicon sol into water glass, feed molar proportioning is constant, after initial gel mixes, is transferred in the reactor with polytetrafluoro liner, inserts in the baking oven of Hydrothermal Synthesis after sealing, prior to 105 ° of C constant temperature 12h, then be warming up to 180 ° of C and continue constant temperature 15h, product is ZSM-5 based molecular sieve material, presents " cruciate flower " pattern, degree of crystallinity is 103.49%, and granularity is 2.7 μ m left and right.
Embodiment 11
Other raw materials, composition and the technical process of the present embodiment are as embodiment 1, different: to change sodium hydroxide into potassium hydroxide, feed molar proportioning is constant, after mixing, initial gel is transferred in the reactor with polytetrafluoro liner, after sealing, insert in the baking oven of Hydrothermal Synthesis, prior to 90 ° of C constant temperature 24h, be then warming up to 170 ° of C and continue constant temperature 28h.Product is ZSM-5 based molecular sieve material, presents " cruciate flower " pattern, and degree of crystallinity is 92.57%, and granularity is 14.7 μ m.
Embodiment 12
Other raw materials, composition and the technical process of the present embodiment are as embodiment 1, different: to change sodium hydroxide into lithium hydroxide, feed molar proportioning is constant, after mixing, initial gel is transferred in the reactor with polytetrafluoro liner, after sealing, insert in the baking oven of Hydrothermal Synthesis, prior to 90 ° of C constant temperature 24h, be then warming up to 170 ° of C and continue constant temperature 24h.Product is ZSM-5 based molecular sieve material, presents " cruciate flower " pattern, and degree of crystallinity is 90.65%, and granularity is 5.5 μ m.
Embodiment 13
Under the condition stirring, prepare respectively following two kinds of working solutions:
Mixture I: by 11.36g silicon sol, 0.20g tetrapropyl amine bromide, 10g deionization adds in beaker and mixes, then add 0.33g(account for raw silicon aluminum oxide total mass 5%) synthetic ZSM-5 in embodiment 1, as crystal seed, violent stirring 0.5h;
Mixtures II: by the homogeneous solution of 0.84g Tai-Ace S 150,1.20g sodium hydroxide and the preparation of 10g deionized water.
Under the condition constantly stirring, mixture II is slowly added in mixture I, continue to stir by force to evenly.The amount of substance of the reaction mixture obtaining is than being Na
2o:Al
2o
3: SiO
2: (TPA)
2o:H
2o=11.4:1.0:60:0.3:1200, is transferred to the initial gel obtaining in the reactor with polytetrafluoro liner, seals the standing aging 48h of rear 25 ° of C, is then placed in baking oven through 135 ° of C static crystallization 24h.Product is ZSM-5 molecular sieve, and degree of crystallinity is 98.67%, and granularity is 500nm left and right.As shown in Figure 4 b, it is " grafting " pattern shown in Fig. 5 c that scanning electron microscope records its pattern to its XRD spectra, causes therefrom sample to present being different from the N of " cruciate flower " pattern sample in example 1-12
2(Fig. 7 a) for Adsorption and desorption isotherms.That is, except there is being similar to the hysteresis winding (P/P of representative " slit pore "
0=0.4-0.9), also at high pressure area (P/P
0=0.9-1.0) there is representing the higher adsorptive capacity of macropore.Illustrate that formed intergranular is mesoporous after not only having nanometer rod in product pegs graft, also comprised a large amount of large pore distribution (> 50nm) (Fig. 7 b), can belong to individual small-particle space each other.Except the difference of (greatly) character that is situated between, the product obtaining in this example, because grain-size reduces greatly, presents the larger outside surface (table 1) of " cruciate flower " product than > 1 μ m.
Embodiment 14
Other proportioning raw materials of the present embodiment and technical process are with embodiment 13, different: by crystal seed quantitative change be 0.02g(account for raw silicon aluminum oxide total mass 0.3%).Initial gel after 25 ° of standing aging 48h of C in 135 ° of C static crystallization 36h.Product is ZSM-5 based molecular sieve material, presents " grafting " pattern, and degree of crystallinity is 89.42%, and granularity is 915nm left and right.
Embodiment 15
Other proportioning raw materials of the present embodiment and technical process are with embodiment 13, different: by crystal seed quantitative change be 0.65g(account for raw silicon aluminum oxide total mass 10%).Initial gel after 25 ° of standing aging 48h of C in 135 ° of C static crystallization 20h.Product is ZSM-5 based molecular sieve material, presents " grafting " pattern, and degree of crystallinity is 92.42%, and granularity is 300nm left and right.
Embodiment 16
Other proportioning raw materials of the present embodiment and technical process are with embodiment 13, different: initial gel after 25 ° of standing aging 480h of C in 150 ° of C static crystallization 12h.Product is ZSM-5 based molecular sieve material, presents " grafting " pattern, and degree of crystallinity is 93.65%, and granularity is 150nm left and right.
Embodiment 17
Other proportioning raw materials of the present embodiment and technical process are with embodiment 13, different: after raw material thing mixes, be transferred in the reactor with polytetrafluoro liner, directly in 180 ° of C static crystallization 8h.Product is ZSM-5 based molecular sieve material, presents " grafting " pattern, and degree of crystallinity is 97.41%, and granularity is 985nm left and right.
Embodiment 18
Other proportioning raw materials of the present embodiment and technical process are with embodiment 13, different: initial gel in 5 ° of C environment after standing aging 48h in 175 ° of C static crystallization 15h.Product is ZSM-5 based molecular sieve material, presents " grafting " pattern, and degree of crystallinity is 93.65%, and granularity is 740nm left and right.
Embodiment 19
Other proportioning raw materials of the present embodiment and technical process are with embodiment 13, different: initial gel in 50 ° of C environment after standing aging 48h in 175 ° of C static crystallization 12h.Product is ZSM-5 based molecular sieve material, presents " grafting " pattern, and degree of crystallinity is 98.73%, and granularity is 350nm left and right.
Embodiment 20-24
The technical process of embodiment 20-24 is referring to embodiment 1, and raw material and consumption thereof see the following form:
Embodiment 25-29
The proportioning of embodiment 25-29 and technical process are referring to embodiment 13, and the kind of silicon source, aluminium source and alkali source, crystal seed kind and consumption and synthesis condition see the following form:
Table 1
Claims (10)
1. a ZSM-5 molecular sieve, has following feature: ZSM-5 Quito level porous molecular sieve material that the present invention is prepared,
1) ZSM-5 molecular sieve is of a size of 100nm-20 μ m;
2) during described ZSM-5 molecular sieve size > 1 μ m, present cruciate flower pattern, each individuality is to be formed by nanocrystalline accumulation, and the gap of nanocrystalline forms mesoporous; Or
3) during described ZSM-5 molecular sieve size≤1 μ m, present the shape characteristic of nanometer rod grafting self-assembly, the gap between nanometer rod forms mesoporous.
2. ZSM-5 molecular sieve according to claim 1, is characterized in that, described ZSM-5 molecular sieve has X-ray diffraction spectrogram as shown in Figure 4.
3. a preparation method for ZSM-5 molecular sieve, comprises the steps:
By raw material containing the material of IVA element, mix containing material, alkali metal hydroxide, template, the water of IIIA element, gained mixture is first crystallization under 40-120 ° of C in temperature, and then be to continue static crystallization under 130-210 ° of C in temperature, after crystallization completes, solid matter is separated from mother liquor, isolated solid matter is extremely neutral, also dry through deionized water wash, finally by roasting, remove template, obtain micron-sized ZSM-5 molecular sieve, this molecular sieve has multi-stage porous, its size > 1 μ m
Wherein, containing the consumption of the material of IVA element with YO
2count, containing the consumption of the material of IIIA element with X
2o
3count, the consumption of alkali metal hydroxide is with M
2o counts, and template is 4-propyl bromide, and the consumption of 4-propyl bromide is with (TPA)
2o counts; Amount of substance proportioning between raw material (mol ratio, lower same) is M
2o:X
2o
3: YO
2: (TPA)
2o:H
2o=2-40:0-5.0:10-1000:0.3-120:40-10000, preferred proportioning is M
2o:X
2o
3: YO
2: (TPA)
2o:H
2o=4-25:0.2-3.0:25-200:0.6-48:200-5000, preferred proportioning is M
2o:X
2o
3: YO
2: (TPA)
2o:H
2o=6_15:0.5-1.0:35-150:0.75-10:500-2500.
4. in method according to claim 3, it is characterized in that, the time that is crystallization under 40-120 ° of C in temperature is 8-480 hour, preferably 12-168 hour, more preferably 12-72 hour.
5. according in the method described in claim 3 or 4, it is characterized in that, is that the time of continuing static crystallization under 130-210 ° of C is 6-36 hour in temperature, preferably 8-24 hour.
6. in method according to claim 3, it is characterized in that, mixture is first to carry out crystallization under 70-100 ° of C in temperature, and then proceeds crystallization under 160-185 ° of C.
7. a preparation method for ZSM-5 molecular sieve, comprises the steps:
After raw material is mixed containing the material of IVA element, containing material, alkali metal hydroxide, template, the water of IIIA element, in mixture, add crystal seed, described crystal seed is ZSM-5 Quito level porous molecular sieve material of the prepared size > of method claimed in claim 31 μ m, the mixture of preset crystal seed is carried out to burin-in process 0-360 hour under 5-60 ° of C, mixture after aging is crystallization under temperature 100-200 ° C again, obtain the ZSM-5 molecular sieve of submicron order, this molecular sieve has multi-stage porous, its size≤1 μ m
Wherein, containing the consumption of the material of IVA element with YO
2count, containing the consumption of the material of IIIA element with X
2o
3count, the consumption of alkali metal hydroxide is with M
2o counts, and template is 4-propyl bromide, and the consumption of 4-propyl bromide is with (TPA)
2o counts; Amount of substance proportioning between raw material is M
2o:X
2o
3: YO
2: (TPA)
2o:H
2o=2-40:0-5.0:10-1000:0.1-60:40-10000.
8. method according to claim 7, is characterized in that, the addition of crystal seed is YO
2and X
2o
3the 0.05-20% of total mass.Preferred 0.5-10%, it is 1%-7% more preferably.
9. according to the method described in claim 7 or 8, it is characterized in that, described burin-in process temperature is 15-25 ° of C, and ageing treatment time is 0-72h; Mixture after aging is crystallization 4-48 hour under 100-200 ° of C in temperature, and its preferred crystallization temperature is 150-180 ° of C, and crystallization time is 6-24h.
10. the method described in a claim 3 or 7, it is characterized in that, containing the material of IVA element, comprise the material containing element silicon, the described material containing element silicon comprises one or more the mixing in silicon sol, water glass, tetraethoxy, white carbon black, silica gel bead; The described material containing IIIA element comprises the material containing aluminium element, comprises one or more mixing of Tai-Ace S 150, sodium aluminate, aluminum nitrate, aluminum chloride, aluminum isopropylate containing the material of aluminium element; The oxidation of described alkali metal hydrogen comprises in lithium hydroxide, sodium hydroxide, potassium hydroxide one or more mixing.
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