CN105585028A - Synthetic method of small-crystal-grain nano zeolite molecular sieve - Google Patents
Synthetic method of small-crystal-grain nano zeolite molecular sieve Download PDFInfo
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Abstract
The invention belongs to the technical field of synthesizing zeolite molecular sieves, and particularly provides a preparation method for synthesizing a small-crystal-grain nano zeolite molecular sieve with temperature controlled. In the field of synthesizing molecular sieves, particle size control on zeolite crystals is an important factor. In the method, the nano ZSM-5 zeolite is prepared with an accurate-control temperature programming reaction process. The method is simple in process and is low in operation cost. Sample XRD shows that the product is ZSM-5 zeolite and has excellent crystalline degree. SEM shows the zeolite is less in nano particle size.
Description
Technical field
The invention belongs to zeolite molecular sieve synthetic technology field, be specially a kind of little crystal grain molecular sieve of Nano zeolite synthetic method.
Background technology
Zeolite is the alumino-silicate with tetrahedron skeleton structure, owing to having molecule sieving actoion, is commonly referred to zeolite molecular sieve, is one of most widely used material in inorganic material. Wherein ZSM-5 was that template synthesize by the Argauer of Mobil oil company and Landelt with four propylamine in 1972 as the very important artificial synthetic zeolite of one, became first important member of " Pentasil " family.
Nano particle belongs to be situated between sees material, and between cluster and macro object, its crystallite dimension is generally less than hundreds of nanometer. The ratio of the surface atom number of nano particle and body phase total atom number reduces and increases with grain size, has obvious bulk effect, skin effect and quantum size effect, thereby presents unique physicochemical properties.
At present, synthetic preparation methods that adopt synthetic conventional molecular sieve of nano-ZSM-5 molecular sieve, take diverse ways restrain grain growth to obtain the ZSM-5 molecular sieve of little crystal grain more simultaneously in crystallization process. The high activity of nano-ZSM-5 zeolite, high selectivity and the good concern that recycles advantage and be subjected to domestic all kinds of catalyst users, therefore still need constantly research with perfect to the synthetic method of nano-ZSM-5. Explore the change in size of ZSM-5 zeolite molecular sieve crystal, accurately control its particle size, the impact of catalytic performance is had to prior meaning.
CN200910072747.7 has introduced a kind of preparation method of nano-ZSM-5 molecular sieve, pre-crystallization crystal seed is joined in the gel rubber system without template synthesis of nano ZSM-5 molecular sieve, crystallization 24 hours at 160～180 DEG C again, is cooled to room temperature by product centrifugal filtration, washing, dry, roasting. Solve existing synthesis technique and existed and be prone to that stray crystal phase, cost are high, contaminated environment, easily lose the problem of nano material characteristic, made nano-ZSM-5 molecular sieve and be the highly crystal of the nanoscale of gathering, without stray crystal phase. CN200810043970.4 relates to a kind of ZSM-5 molecular sieve with small crystal grains and uses thereof, mainly solves the silica alumina ratio SiO that has ZSM-5 molecular sieve with small crystal grains in conventional art2/Al2O3All be less than 200, and in the past ZSM-5 molecular sieve for preparing propylene from methanol when reaction, its poor catalyst stability, short technical problem of life-span. By adopting molecular sieve crystal diameter to be less than 300 microns, SiO2/Al2O3Mol ratio is >=200 ZSM-5 molecular sieve with small crystal grains, has solved preferably this problem for the technical scheme of preparing propylene from methanol reaction, can be used in the industrial production of preparing propylene from methanol.
CN201110027383.8 provides a kind of preparation method of nano pure silicone ZSM-5 zeolite, comprises organosilicon acid esters with SiO2Meter, with water and hydrolytic reagent according to organosilicon acid esters: after the mol ratio of hydrolytic reagent: water=1: 0.001-0.08: 2-15 is fully uniformly mixed, be under the condition of 20-100 DEG C in temperature, ageing 0.3-48 hour, obtain silicon gel, by after the silicon gel drying of gained, grind to form silica gel particle, by the silica gel particle of gained with SiO2Meter, template are with TPA+Meter, with water according to silica gel particle: the mixed in molar ratio of template: water=1: 0.1-1: 15-40 evenly after, be crystallization 1-7 days at 100-190 DEG C in temperature, and by the calcining of crystallization gained solid product, obtain nano pure silicone ZSM-5 zeolite. The method is that a kind of step is simple, and can synthesize the preparation method that crystal grain is less than the pure silicon ZSM-5 zeolite of 100nm.
Described in above patent, in method, seldom use the standby nanoscale ZSM-5 zeolite uniformly of the meticulous control legal system of the present invention's temperature used, and be static crystallization substantially, crystallization process does not stir. Crystallization temperature has a great impact the synthetic tool of zeolite, and the present invention, by changing crystallization temperature-rise period, controls zeolite nucleation and crystallization time and distributes, and is stirred and obtain nanometer small crystal grain ZSM-5 zeolite molecular sieve in crystallization process.
Summary of the invention
Key technical problem to be solved by this invention is that prior art obtains the preparation process of nanoscale ZSM-5 and loaded down with trivial details, and gained sample degree of crystallinity is low, easily has dephasign, and is not easy to industrialization. The invention provides a kind of new nano-ZSM-5 molecular sieve preparation method, the method while preparing, has synthesis step easy for ZSM-5, controls meticulously, and can obtain evenly and the feature of the nano-ZSM-5 that degree of crystallinity is high.
For solving the problems of the technologies described above, technical solution of the present invention is as follows:
By material proportion be:
SiO2：(5-200)H2O：(0.01-20)R1：(0.002-0.05)Al：(0-10)F-：(0-20)OH-, take template R1, mineralizer sodium fluoride, silicon source, aluminium source, sodium hydroxide solution, add in reactor, stir, the aging 5-36h of gel, controls certain crystallization temperature, and 100-300rpm stirs lower crystallization 1-15 days; Be cooled to after room temperature, product is centrifugal with deionized water washing, more than 80 DEG C of oven dry 12h, obtain end product;
Controlling crystallizing temperature is: room temperature is through 0.1-2 DEG C/min temperature programming to 50-90 DEG C, and after crystallization 12-48h, 0.1-2 DEG C/min temperature programming is to 100-150 DEG C, and after crystallization 36-60h, 0.1-2 DEG C/min temperature programming is to 160-200 DEG C, crystallization 72-120h.
Controlling crystallizing temperature preferable range is: 0.5-1.5 DEG C/min of room temperature process temperature programming is to 60-80 DEG C, after crystallization 24-48h, 0.5-1.5 DEG C/min temperature programming is to 100-130 DEG C, after crystallization 36-48h, 0.5-1.5 DEG C/min temperature programming is to 160-180 DEG C, crystallization 72-120h.
Template R1 is at least one in hydroxylation tetramethyl-ammonium, hydroxylation tetraethyl ammonium, hydroxylation tetrapropyl ammonium, bromination tetrapropyl ammonium, tetraethylammonium bromide.
Described silicon source is at least one in Ludox, ethyl orthosilicate, amorphous silicon oxide powder, silicate, and aluminium source is at least one in Patent alum, aluminium isopropoxide or meta-aluminate, aluminate. Hydroxide used is NaOH.
H2O/SiO2Preferable range is 5-100, R1/SiO2Preferable range is 0.2-10. Si/Al preferable range is 100-400.
The main serviceability temperature exact controllability of the present invention synthesizes granule nano-ZSM-5 zeolite molecular sieve, and sample is characterized with XRD and SEM.
Product of the present invention is ZSM-5 molecular sieve, and by regulating temperature, control program temperature-rise period, can effectively regulate sample crystallite dimension. Meanwhile, this synthetic method can improve combined coefficient, reduces synthetic cost, also has the features such as good collimation, repeatability, operability, has better practicality and validity. Application of temperature control method simultaneously, energy-saving and emission-reduction, easy and simple to handle, there is good prospects for commercial application.
Example below will be described further nano-ZSM-5 molecular sieve synthetic method provided by the invention.
Detailed description of the invention
Embodiment 1
Synthetic method: 10g water 0.1g Patent alum, the sodium hydroxide solution of 2g mass fraction 30%, 4g sodium fluoride, 13g 4-propyl bromide are added in reactor, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 0.83 DEG C/min temperature programming to 60 DEG C, and crystallization is after 1 day, 0.83 DEG C/min temperature programming to 100 DEG C, and crystallization is after 2 days, 0.83 DEG C/min temperature programming to 180 DEG C, crystallization 3 days. Be cooled to after room temperature, deionized water is washed centrifugal 3 times, dries 12h, obtains final products for 80 DEG C.
Products therefrom has the characteristic diffraction peak of ZSM-5, and has higher degree of crystallinity. The SEM photo of products obtained therefrom different amplification can see that sample distribution is even, is of a size of 100nm left and right.
Embodiment 2
Synthetic method: the sodium hydroxide solution of 2g mass fraction 30%, 10g water, 0.1g Patent alum, 4g sodium fluoride, 5g 4-propyl bromide are added in reactor, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 1 DEG C/min temperature programming to 60 DEG C, and crystallization is after 1 day, 1 DEG C/min temperature programming to 100 DEG C, and crystallization is after 2 days, 1 DEG C/min temperature programming to 180 DEG C, crystallization 3 days. Be cooled to after room temperature, deionized water is washed centrifugal 3 times, dries 12h, obtains final products for 80 DEG C.
Sample XRD characterization result can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample is spherical pattern, and size is 120nm left and right.
Embodiment 3
Synthetic method: the sodium hydroxide solution of 2g mass fraction 30%, 0.1g Patent alum, 0.54g sodium fluoride, 8g 4-propyl bromide are added in 10g water, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 0.75 DEG C/min temperature programming to 80 DEG C, and crystallization is after 1 day, 0.75 DEG C/min temperature programming to 120 DEG C, and crystallization is after 2 days, 0.75 DEG C/min temperature programming to 180 DEG C, crystallization 3 days, obtains final products. XRD interpret sample has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample is granule nano molecular sieve, and size is 100nm left and right.
Embodiment 4
Synthetic method: the sodium hydroxide solution of 10g water, 2g mass fraction 30%, 0.1g Patent alum, 4g sodium fluoride, TPAOH (are ensured to its ratio is R1/SiO2=0.4) add in reactor, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 0.75 DEG C/min temperature programming to 80 DEG C, and crystallization is after 1 day, 0.75 DEG C/min temperature programming to 120 DEG C, and crystallization is after 2 days, 0.75 DEG C/min temperature programming to 180 DEG C, crystallization 3 days, obtains final products, obtains final products. Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample is evenly distributed, and size is 90nm left and right.
Embodiment 5
Synthetic method: the sodium hydroxide solution of 2g mass fraction 30%, 0.014g aluminium isopropoxide, 0.5g sodium fluoride, 17g 4-propyl bromide are added in 20g water, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 0.83 DEG C/min temperature programming to 60 DEG C, and crystallization is after 1 day, 0.83 DEG C/min temperature programming to 100 DEG C, and crystallization is after 2 days, 0.83 DEG C/min temperature programming to 180 DEG C, crystallization 3 days. Be cooled to after room temperature, deionized water is washed centrifugal 3 times, dries 12h, obtains final products for 80 DEG C. Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample is the granule nano molecular sieve of 100nm size.
Embodiment 6
Synthetic method: the sodium hydroxide solution of 15g water, 0.014g aluminium isopropoxide, 16g 4-propyl bromide, 2g mass fraction 30%, 1g sodium fluoride are added in reactor, after stirring, add 8g ethyl orthosilicate, stir 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, crystallization temperature is: 30 DEG C through 0.83 DEG C/min temperature programming to 80 DEG C, and crystallization is after 2 days, 0.83 DEG C/min temperature programming to 120 DEG C, and crystallization is after 2 days, 0.83 DEG C/min temperature programming to 180 DEG C, crystallization 5 days. Obtain final products. Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample is granule nano molecular sieve.
Embodiment 7
Synthetic method: the sodium hydroxide solution of 15g water, 1.6g mass fraction 40%, 0.051g Patent alum, 0.76g sodium fluoride, 2g 4-propyl bromide are added in reactor, after stirring, add 6.7g ethyl orthosilicate, stir 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, 30 DEG C through 0.83 DEG C/min temperature programming to 60 DEG C, and crystallization is after 1 day, 0.83 DEG C/min temperature programming to 100 DEG C, and crystallization is after 2 days, 0.83 DEG C/min temperature programming to 180 DEG C, crystallization 3 days. Be cooled to after room temperature, deionized water is washed centrifugal 3 times, dries 12h, obtains final products for 80 DEG C. Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample is granule nano molecular sieve.
Embodiment 8
Synthetic method: the sodium hydroxide solution of 2g mass fraction 40%, 0.014g aluminium isopropoxide, 0.98g sodium fluoride, 12g 4-propyl bromide are added in 13.4g water, after stirring, add 9g ethyl orthosilicate, stir 40min, the aging 24h of gel under room temperature. Afterwards, under 150rpm stirs, 30 DEG C through 0.83 DEG C/min temperature programming to 60 DEG C, and crystallization is after 1 day, 0.83 DEG C/min temperature programming to 100 DEG C, and crystallization is after 2 days, 0.83 DEG C/min temperature programming to 180 DEG C, crystallization 3 days. Be cooled to after room temperature, deionized water is washed centrifugal 3 times, dries 12h, obtains final products for 80 DEG C. Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample is granule nano molecular sieve.
Embodiment 9
Synthetic method: the sodium hydroxide solution of 14.4g water, 1.728g mass fraction 40%, 0.014g aluminium isopropoxide, 1.088g sodium fluoride, 17.3g TPAOH are added in reactor, after stirring, add 6.7g ethyl orthosilicate, stir 40min, the aging 18h of gel under room temperature. Afterwards, under 150rpm stirs, 30 DEG C through 0.75 DEG C/min temperature programming to 80 DEG C, and crystallization is after 1 day, 0.75 DEG C/min temperature programming to 120 DEG C, and crystallization is after 2 days, 0.75 DEG C/min temperature programming to 180 DEG C, crystallization 3 days. Be cooled to after room temperature, deionized water is washed centrifugal 3 times, dries 12h, obtains final products for 80 DEG C. Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample is nano molecular sieve.
Comparative example 1
Synthetic method method: the sodium hydroxide solution of 2g mass fraction 30%, 0.1g Patent alum, 4g sodium fluoride, 13g 4-propyl bromide are added in 10g water, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 0.83 DEG C/min temperature programming to 60 DEG C, and crystallization is after 1 day, 0.83 DEG C/min temperature programming to 100 DEG C, and crystallization is after 2 days, 0.83 DEG C/min temperature programming to 180 DEG C, crystallization 3 days. Be cooled to after room temperature, deionized water is washed centrifugal 3 times, dries 12h, obtains final products for 80 DEG C. Sample XRD characterization result can see that product has amorphous silica characteristic peak, but not ZSM-5 characteristic diffraction peak.
Comparative example 2
Synthetic method: the sodium hydroxide solution of 2g mass fraction 30%, 0.1g Patent alum, 4g sodium fluoride, 13g 4-propyl bromide are added in 10g water, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 3 DEG C/min temperature programming to 90 DEG C, after crystallization 12h, and 2.5 DEG C/min temperature programming to 160 DEG C, crystallization 24h. Obtain final products. Sample XRD characterization result can see that product has ZSM-5 characteristic diffraction peak, but degree of crystallinity decline, sample SEM photo can see that sample has amorphous spherical granule to disperse, distributing inhomogeneity.
Comparative example 3
Synthetic method: the sodium hydroxide solution of 2g mass fraction 30%, 0.1g Patent alum, 4g sodium fluoride, 13g 4-propyl bromide are added in 10g water, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 3 DEG C/min temperature programming to 100 DEG C, after crystallization 12h, and 3 DEG C/min temperature programming to 200 DEG C, crystallization 12h, obtains final products. Sample XRD characterization result can see that product has ZSM-5 characteristic diffraction peak, and sample SEM photo can be seen sample distribution heterogeneity, and has amorphous spherical granule to exist.
Comparative example 4
Synthetic method: the sodium hydroxide solution of 10g water, 2g mass fraction 30%, 0.1g Patent alum, 4g sodium fluoride, 13g 4-propyl bromide are added in reactor, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 5 DEG C/min temperature programming to 50 DEG C, and after crystallization 12h, 5 DEG C/min temperature programming to 100 DEG C, obtains final products. Sample XRD characterization result can see that product does not have ZSM-5 characteristic diffraction peak, and sample SEM photo can see that sample is that amorphous spherical granule disperses.
Comparative example 5
Synthetic method: the sodium hydroxide solution of 10g water, 2g mass fraction 30%, 0.1g Patent alum, 4g sodium fluoride, 13g 4-propyl bromide are added in reactor, after stirring, adding 6g mass fraction is 40% Ludox, stirs 30min, the aging 8h of gel under room temperature. Afterwards, under 150rpm stirs, room temperature is through 5 DEG C/min temperature programming to 50 DEG C, after crystallization 12h, and 5 DEG C/min temperature programming to 100 DEG C, 2.5 DEG C/min temperature programming to 160 DEG C, crystallization 24h, obtains final products. Sample XRD characterization result can see that product has ZSM-5 characteristic diffraction peak, but degree of crystallinity decline, sample SEM photo can see that product has amorphous spherical granule to disperse.
Comparative example 6
Crystallization process stops stirring, and does not adopt programmed temperature method control synthetic. Synthetic method: the sodium hydroxide solution of 10g water, 2g mass fraction 30%, 0.1g Patent alum, 4g sodium fluoride, 13g 4-propyl bromide are added in reactor, after stirring, adding 6g mass fraction is 40% Ludox, stirs 40min, the aging 24h of gel under room temperature. Afterwards, put into teflon-lined steel bomb, 180 DEG C of crystallization 5 days, are cooled to after room temperature, and ionized water washs centrifugal 3 times, dry 12h, obtain final products for 80 DEG C. Sample XRD characterization result, can see that product has ZSM-5 characteristic diffraction peak, and SEM photo interpret sample presents 10 microns of spherical patterns, but not granule nano molecular sieve.
Claims (10)
1. prepare a method for little crystal grain molecular sieve of Nano zeolite, it is characterized in that concrete steps are:
By material proportion be:
SiO2：(5-200)H2O：(0.01-20)R1：(0.002-0.05)Al：(0-10)F-：(0-20)OH-，Take template R1, mineralizer, silicon source, aluminium source, hydroxide solution, add in reactor, stir, gelAging 5-36h, controls certain crystallization temperature, and 100-300rpm stirs lower crystallization 1-15 days; Be cooled to after room temperature, by productCentrifugal with deionized water washing, more than 80 DEG C of oven dry 12h, obtain end product;
Controlling crystallizing temperature is: room temperature is passed through 0.1-2 DEG C/min temperature programming to 50-90 DEG C, after crystallization 12-48h,0.1-2 DEG C/min temperature programming is to 100-150 DEG C, and after crystallization 36-60h, 0.1-2 DEG C/min temperature programming is to 160-200 DEG C,Crystallization 72-120h.
2. method according to claim 1, is characterized in that controlling crystallizing temperature is: room temperature is through 0.5-1.5 DEG C/minTemperature programming is to 60-80 DEG C, and after crystallization 24-48h, 0.5-1.5 DEG C/min temperature programming is to 100-130 DEG C, crystallization 36-48hAfter, 0.5-1.5 DEG C/min temperature programming is to 160-180 DEG C, crystallization 72-120h.
3. method according to claim 1, is characterized in that, crystallization process stirs with 100-300rpm.
4. method according to claim 1, is characterized in that, mineralizer used is sodium fluoride.
5. method according to claim 1, is characterized in that template R1 is hydroxylation tetramethyl-ammonium, hydroxylation tetraethylIn ammonium, hydroxylation tetrapropyl ammonium, bromination tetrapropyl ammonium, tetraethylammonium bromide at least one.
6. method according to claim 1, is characterized in that, described silicon source is Ludox, ethyl orthosilicate, nothingIn setting silicon oxide powder, silicate at least one, aluminium source is Patent alum, aluminium isopropoxide or meta-aluminate, aluminiumIn hydrochlorate at least one.
7. method according to claim 1, is characterized in that hydroxide used is NaOH.
8. method according to claim 1, is characterized in that H2O/SiO2＝5-100。
9. method according to claim 1, is characterized in that R1/SiO2＝0.2-10。
10. method according to claim 1, is characterized in that Si/Al=100-400.
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| CN106185979A (en) * | 2016-07-07 | 2016-12-07 | 昆明理工大学 | A kind of preparation method of multi-stage porous ZSM 5 molecular sieve |
| CN106865566A (en) * | 2017-03-15 | 2017-06-20 | 中国石油大学(北京) | Molecular sieves of a kind of ZSM 5 and its preparation method and application |
| CN111087002A (en) * | 2019-12-04 | 2020-05-01 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of mordenite molecular sieve |
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| CN101733143A (en) * | 2008-11-21 | 2010-06-16 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve with small crystal grains and application thereof |
| CN102464326A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing high-silicon mordenite |
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| CN106185979A (en) * | 2016-07-07 | 2016-12-07 | 昆明理工大学 | A kind of preparation method of multi-stage porous ZSM 5 molecular sieve |
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| CN106865566A (en) * | 2017-03-15 | 2017-06-20 | 中国石油大学(北京) | Molecular sieves of a kind of ZSM 5 and its preparation method and application |
| CN111087002A (en) * | 2019-12-04 | 2020-05-01 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of mordenite molecular sieve |
| CN111087002B (en) * | 2019-12-04 | 2021-10-22 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of mordenite molecular sieve |
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