CN104445251B - The method of synthesizing nanocrystalline MFI zeolite cluster - Google Patents
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Abstract
A kind of method that the present invention relates to synthesizing nanocrystalline MFI zeolite cluster, mainly solves the problem that in prior art, nano zeolite cluster preparation process is complicated.The present invention by silicon source, aluminum source, template R1, template R2, inorganic base M, water are mixed in proportion, wherein Al2O3:R1:R2:M:H2O:SiO2Mol ratio be (0～0.1): (0.01～1.5): (0.01～0.5): (0.001～1): (10～120): 1, crystallization the most under hydrothermal conditions, crystallized product i.e. can get nanocrystalline M FI zeolite cluster through filtering, wash, drying, described nanocrystalline M FI zeolite cluster is collected as the technical scheme of the cluster that particle diameter is 0.2～20 micron by the MFI zeolite grain of 10～400 nanometers, preferably resolve this problem, can be used in the commercial production of nanometer MFI zeolite.
Description
Technical field
A kind of method that the present invention relates to synthesizing nanocrystalline MFI zeolite cluster.
Background technology
General particle size is referred to as nano material between the material of 1～100 nanometers, owing to it has big specific surface area, generally occurs within " nano effect ", has a wide range of applications field.The surface atom number of nano molecular sieve is increased dramatically with the minimizing of particle size with the ratio of body phase total atom number, so that nano molecular sieve becomes the new material with unique catalytic performance.Nano molecular sieve is compared bulky grain molecular sieve and is had bigger external surface area and higher micropore diffusion speed, all show superior performance at aspects such as improving the utilization rate of catalyst, enhancing macromole conversion capability, reduction deep reaction, raising selectivity and reduction coking and deactivation, therefore suffer from widely studied.But nano molecular sieve granule is the least, it is difficult to separate with mother solution, filters and reclaim difficulty in the preparation, thus hinder the commercial Application of nano molecular sieve.Simultaneously as nano molecular sieve has higher surface energy, serious agglomeration can be produced, cause using effect to be deteriorated.Therefore, the pattern and the granular size that the most effectively control nano molecular sieve reunion are nanoparticle zeolite field problem demanding prompt solutions.
Since 20 century 70 ZSM-5 zeolites come out, ZSM-5 zeolite is widely used in PETROLEUM PROCESSING and field of petrochemical industry as catalyst.Nano-sized ZSM-5 zeolite (< 100
And micron ZSM-5 zeolite (1 μm) has identical pore passage structure rnn), and mesh is as other nanoparticles, has identical pore passage structure, bulk effect, table and effect and quantum size effect.Mainly show as duct short, appearance and large percentage that acidic site accounts in total acid content, nano-ZSM-5
[(70～100)
Rnn] appearance and acid amount account for more than the 30% of total acid content, and micron ZSM-5
[(1～2) μm] appearance and acid amount be only total acid content about 3%.There is substantial amounts of intracrystalline pore (secondary pore) in nano-sized ZSM-5 zeolite, has strong anti-coking deactivation and sulfur poisoning resistance.Receive publicity as a kind of new catalytic material.Nano-ZSM-5 makes product separate difficulty with mother solution, accordingly, it would be desirable to study new synthetic route and the isolation technics with mother solution due to crystal grain less than 100nm.
Pointing out in " Microporous and Mesoporous Materials, 25 (1998): 59-74 ", nano-beta molecular sieve serosity is stable suspension, and sedimentation velocity is extremely slow, also will not be settled layering even if placing 1 year.The document proposes first to be diluted with water to by molecular sieve pulp low viscosity and low ph value, the method then using high speed centrifugation partition method to reclaim molecular sieve solid, operates 90 minutes under rotating speed 16000 revs/min.The method centrifugal rotational speed is high, and molecular sieve treating capacity is little, and disengaging time is long, and process is complicated, thus cannot be applied to large-scale commercial production.
Patent CN02100379.3 use sol-gel process by nano molecular sieve and SiO2Or Al2O3Or SiO2/Al2O3It is prepared as nano molecular sieve compound.The method makes nanometer molecular sieve slurry directly mix with the colloidal sol of carrier without filtration, it is to avoid the filter process being most difficult in nano molecular sieve preparation.But the method adds SiO2Or Al2O3Or SiO2/Al2O3, make the composition of obtained nano molecular sieve solid there occurs change, not only can not obtain pure nano molecular sieve, and process is complicated.
Molecular sieve filtration method disclosed in patent CN97112269.5 be small crystal grain NaY molecular sieve serosity that average grain is less than 0.5 micron is mixed homogeneously with water, ammonium salt and a kind of acidic silicasol after, slurry pH value is adjusted to 2.8～3.5, then filters.Equally, the method makes the composition of obtained nano molecular sieve solid there occurs change, not only can not obtain pure nano molecular sieve, and process is complicated.
Molecular sieve filtration method disclosed in patent CN03122854.2 is to add alkaline medium, non-dielectric and water in molecular sieve pulp, alkaline medium addition to be controlled well makes mixture pH >=12, and the addition of alkaline medium, non-dielectric and water has certain restriction, process is complicated.
In the preparation method of the ultrafine granule five-element circular type zeolite disclosed in patent CN99102700.0, the ZSM-11 zeolite of 300 nanometers of synthesis, need high speed centrifugation to separate, process is complicated.
In the microwave synthesis method of the nanometer silicate basic hole material disclosed in patent CN20051001688.5, the product needed high speed centrifugation of synthesis separates, and process is complicated.
In the synthetic method of the nano mordenite molecular sieve disclosed in patent CN200610013526.9, the product needed high speed centrifugation of synthesis separates, and process is complicated.
Article [Wang little Li, Wu Lan, Li Yuping, Zhang Wei, the intercalation sub-spring, Dou Tao, petroleum journal (PETROLEUM PROCESSING), in October, 2006, supplementary issue: 228-230, the synthesis of suspension nano ZSM-11 zeolite and sign] report synthesis 10 nanometers within nanometer ZSM-11 zeolite, sintetics is off-white color suspension sample.Will be by ammonium salt: suspension, water quality adds people's ammonium salt than the proportioning for 1:10:100, and after heating, flocculating, washing centrifugation, process is complicated.
In sum, conventional art exists the shortcoming that nanocrystalline M FI zeolite cluster preparation process is complicated.
Summary of the invention
The technical problem to be solved is to there is the problem that nanocrystalline M FI zeolite cluster preparation process is complicated in conventional art, it is provided that a kind of method of synthesizing nanocrystalline MFI zeolite cluster, the method have easy, be beneficial to industrial feature.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of method of synthesizing nanocrystalline MFI zeolite cluster, is silicon source, aluminum source, template R1, template R2, inorganic base M, water to be mixed in proportion, wherein Al2O3:R1:R2:M:H2O:SiO2Mol ratio be (0～0.1): (0.01～1.5): (0.01～0.5): (
0.001～1): (10～120): 1, crystallization the most under hydrothermal conditions, crystallized product i.e. can get nanocrystalline M FI zeolite cluster through filtering, wash, drying, and described nanocrystalline M FI zeolite cluster is collected as, by the MFI zeolite grain of 10～400 nanometers, the cluster that particle diameter is 0.2～20 micron；Described template R1 is 1, in 6-hexamethylene diamine, n-butylamine at least one, template R2 is at least one in 4-propyl bromide, TPAOH, silicon source is at least one in Ludox, methyl silicate, tetraethyl orthosilicate, White Carbon black, waterglass, aluminum source is at least one in sodium aluminate, aluminum nitrate, aluminum sulfate, three aluminum ethylate .s, aluminum isopropylate., isobutanol aluminum, and inorganic base M is at least one in NaOH, KOH.
In such scheme, Al2O3:R1:R2:M: H2O: SiO2Preferred molar ratio be (0～0.05): (0.05～1): (0.02～0.4): (0.01～0.5): (20～80): 1, more preferably mol ratio are Al2O3:R1:R2:M: H2O: SiO2Mol ratio be(0.02～0.03):(
0.6～0.8): (0.05～0.2): (0.04～0.05): (
40～65): 1.Template R1 is 1,6-hexamethylene diamine and n-butylamine.Template R2 is 4-propyl bromide and TPAOH.Crystallization temperature is 100～250 DEG C, preferably 120～200 DEG C, and crystallization time is 24～240 hours, preferably 48～200 hours.Silicon source is Ludox；Aluminum source is sodium aluminate.Nanocrystalline M FI zeolite cluster is preferably collected as, by the MFI zeolite grain of 10～100 nanometers, the cluster that particle diameter is 0.2～2 micron, is more preferably collected as, by the MFI zeolite grain of 10～50 nanometers, the cluster that particle diameter is 0.2～0.4 micron.
The present invention is by the allotment to material molar ratio, optimize crystallization temperature and crystallization time, achieving unforeseeable technique effect, the nanocrystalline M FI zeolite cluster that the present invention prepares is to be collected as, by the MFI zeolite grain of 10～400 nanometers, the cluster that particle diameter is 0.2～20 micron, works as Al2O3:R1:R2:M:H2O:SiO2Mol ratio be(0.02～0.03): (
0.6～0.8): (0.05～0.2): (0.04～0.05): (
40～65): when 1, the nanocrystalline M FI zeolite cluster that can prepare is to be collected as, by the MFI zeolite grain of 10 nanometers, the cluster that particle diameter is 0.2 micron, the nanocrystalline M FI zeolite clustered particles prepared compared to existing technology is less, and the technique prepared is simpler, beneficially industrialized production.Use the inventive method, silicon source, aluminum source, template R1, template R2, inorganic base M, water are mixed in proportion, wherein Al2O3:R1:R2:M:H2O:SiO2Mol ratio be (0～0.1): (0.01～1.5): (0.01～0.5): (
0.001～1): (10～120): 1, crystallization the most under hydrothermal conditions, crystallized product i.e. can get nanocrystalline M FI zeolite cluster through filtering, wash, drying, described nanocrystalline M FI zeolite cluster is collected as, by the MFI zeolite grain of 10～400 nanometers, the cluster that particle diameter is 0.2～20 micron, achieves preferable technique effect.
Accompanying drawing explanation
The XRD figure of the nano-cluster MFI zeolite that Fig. 1 synthesizes for [embodiment 6].
The SEM photograph of the nano-cluster MFI zeolite that Fig. 2 synthesizes for [embodiment 6].
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
By 1SiO2:0.012Al2O3:0.4R1:0.02R2:0.01NaOH:42H2O weighs each material, by 40% Ludox, sodium metaaluminate, 4-propyl bromide, 1,6-hexamethylene diamine, sodium hydroxide and water mixing, stir 20 minutes, in loading reactor, 170 DEG C of crystallization 72 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite, and XRD spectra is shown in that Fig. 1, SEM photograph are shown in Fig. 2.Characterization result shows, the MFI zeolite grain of 400 nanometers be collected as the cluster that particle diameter is 20 microns.
[embodiment 2]
By 1SiO2:0Al2O3:0.2R1:0.02R2:0.01NaOH:60H2O weighs each material, by 40% Ludox, tetrapropyl hydrogen-oxygen ammonium, 1,6-hexamethylene diamine, sodium hydroxide and water mixing, stir 20 minutes, in loading reactor, 150 DEG C of crystallization 72 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the MFI zeolite grain of 350 nanometers be collected as the cluster that particle diameter is 4 microns.
[embodiment 3]
By 1SiO2:0.05Al2O3:0.6R1:0.01R2:0.02KOH:80H2O weighs each material, tetraethyl orthosilicate, aluminum sulfate, 4-propyl bromide, n-butylamine, potassium hydroxide and water is mixed, stir 20 minutes, in loading reactor, and 120 DEG C of crystallization 192 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the MFI zeolite grain of 200 nanometers be collected as the cluster that particle diameter is 5 microns.
[embodiment 4]
By 1SiO2:0.04Al2O3:0.1R1:0.2R2:0.02NaOH:100H2O weighs each material, by waterglass, isobutanol aluminum, 4-propyl bromide, 1,6-hexamethylene diamine, sodium hydroxide and water mixing, stir 20 minutes, in loading reactor, 100 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the MFI zeolite grain of 100 nanometers be collected as the cluster that particle diameter is 2 microns.
[embodiment 5]
By 1SiO2:0.02Al2O3:0.8R1:0.2R2:0.05KOH:30H2O weighs each material, White Carbon black, aluminum nitrate, TPAOH, n-butylamine, potassium hydroxide and water is mixed, stir 20 minutes, in loading reactor, and 170 DEG C of crystallization 72 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the MFI zeolite grain of 50 nanometers be collected as the cluster that particle diameter is 0.5 micron.
[embodiment 6]
By 1SiO2:0.01Al2O3:1R1:0.3R2:0.03KOH:50H2O weighs each material, 40% Ludox, sodium aluminate, TPAOH, n-butylamine, sodium hydroxide and water is mixed, stir 20 minutes, in loading reactor, and 200 DEG C of crystallization 48 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the MFI zeolite grain of 25 nanometers be collected as the cluster that particle diameter is 0.4 micron.
[embodiment 7]
By 1SiO2:0.02Al2O3:0.8R1:0.2R2:0.05NaOH:65H2O weighs each material, 40% Ludox, aluminum nitrate, 4-propyl bromide, n-butylamine, sodium hydroxide and water is mixed, stir 20 minutes, in loading reactor, and 175 DEG C of crystallization 90 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the MFI zeolite grain of 20 nanometers be collected as the cluster that particle diameter is 0.3 micron.
[embodiment 8]
By 1SiO2:0.03Al2O3:0.6R1:0.05R2:0.04KOH:40H2O weighs each material, by 40% Ludox, aluminum nitrate, TPAOH, 1,6-hexamethylene diamine, potassium hydroxide and water mixing, stir 20 minutes, in loading reactor, 1450 DEG C of crystallization 120 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the MFI zeolite grain of 10 nanometers be collected as the cluster that particle diameter is 0.2 micron.
[comparative example 1]
By 1SiO2:0.012Al2O3:0R1:0.02R2:0.01NaOH:42H2O weighs each material, by 40% Ludox, sodium metaaluminate, 4-propyl bromide, 1,6-hexamethylene diamine, sodium hydroxide and water mixing, stir 20 minutes, in loading reactor, 170 DEG C of crystallization 72 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nanometer MFI crystal grain.Characterization result shows, MFI zeolite grain is 2 microns.
[comparative example 2]
By 1SiO2:0.02Al2O3:0.8R1:0.2R2:0.05KOH:65H2O weighs each material, White Carbon black, aluminum nitrate, TPAOH, n-butylamine, potassium hydroxide and water is mixed, stir 20 minutes, in loading reactor, and 170 DEG C of crystallization 72 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, and characterization result shows, the product of synthesis is unformed material.
[comparative example 3]
By 1SiO2:0.03Al2O3:0.6R1:0.05R2:0.04KOH:150H2O weighs each material, by 40% Ludox, aluminum nitrate, TPAOH, 1,6-hexamethylene diamine, potassium hydroxide and water mixing, stir 20 minutes, in loading reactor, 145 DEG C of crystallization 120 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares MFI zeolite grain.Characterization result shows, MFI zeolite grain is 5.5 microns.
[comparative example 4]
By 1SiO2:0.12Al2O3:0.6R1:0.05R2:0.04KOH:40H2O weighs each material, by 40% Ludox, aluminum nitrate, TPAOH, 1,6-hexamethylene diamine, potassium hydroxide and water mixing, stir 20 minutes, in loading reactor, 145 DEG C of crystallization 120 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, MFI zeolite grain is 1.5 microns.
[comparative example 5]
By 1SiO2:0.03Al2O3:1.6R1:0.05R2:0.04KOH:40H2O weighs each material, by 40% Ludox, aluminum nitrate, TPAOH, 1,6-hexamethylene diamine, potassium hydroxide and water mixing, stir 20 minutes, in loading reactor, 145 DEG C of crystallization 120 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, MFI zeolite grain is 2.0 microns.
[comparative example 6]
By 1SiO2:0.03Al2O3:0.6R1:0.6R2:0.04KOH:40H2O weighs each material, by 40% Ludox, aluminum nitrate, TPAOH, 1,6-hexamethylene diamine, potassium hydroxide and water mixing, stir 20 minutes, in loading reactor, 145 DEG C of crystallization 120 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the MFI zeolite grain of 3.1 microns be collected as the cluster that particle diameter is 21 microns.
[comparative example 7]
By 1SiO2:0.03Al2O3:0.6R1:0.05R2:1.1KOH:40H2O weighs each material, by 40% Ludox, aluminum nitrate, TPAOH, 1,6-hexamethylene diamine, potassium hydroxide and water mixing, stir 20 minutes, in loading reactor, 145 DEG C of crystallization 120 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MFI zeolite.Characterization result shows, the product of synthesis is quartz.
By embodiment 8 and the comparison of comparative example 3～7, it can be seen that Al in preparation process2O3:R1:R2:M:H2O:SiO2Mol ratio very big on the result impact of preparation, work as Al2O3:R1:R2:M:H2O:SiO2Mol ratio be (0～0.1): (0.01～1.5): (0.01～0.5): (
0.001～1): (10～120): when 1; nanocrystalline M FI zeolite cluster can be prepared and be collected as, by the MFI zeolite grain of 20～400 nanometers, the cluster that particle diameter is 0.5～20 micron; and when the consumption of any raw material exceedes this scope, then MFI zeolite grain can substantially become big.
Table 1
Claims (10)
1. a method for synthesizing nanocrystalline MFI zeolite cluster, is characterized in that being mixed in proportion silicon source, aluminum source, template R1, template R2, inorganic base M, water, wherein Al2O3:R1:R2:M:H2O:SiO2Mol ratio be (0～0.1): (0.01～1.5): (0.01～0.5): (0.001～1): (10～120): 1, crystallization the most under hydrothermal conditions, crystallized product i.e. can get nanocrystalline M FI zeolite cluster through filtering, wash, drying, and described nanocrystalline M FI zeolite cluster is collected as, by the MFI zeolite grain of 10～400 nanometers, the cluster that particle diameter is 0.2～20 micron；Described template R1 is 1, in 6-hexamethylene diamine, n-butylamine at least one, template R2 is at least one in 4-propyl bromide, TPAOH, silicon source is at least one in Ludox, methyl silicate, tetraethyl orthosilicate, White Carbon black, waterglass, aluminum source is at least one in sodium aluminate, aluminum nitrate, aluminum sulfate, three aluminum ethylate .s, aluminum isopropylate., isobutanol aluminum, and inorganic base M is at least one in NaOH, KOH.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that Al2O3:R1:R2:M:
H2O: SiO2Mol ratio be (0～0.05): (0.05～1): (0.02～0.4): (0.01～0.5): (20～80): 1.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that Al2O3:R1:R2:M:
H2O: SiO2Mol ratio be(0.02～0.03):(0.6～0.8): (0.05～0.2): (0.04～0.05): (40～65): 1.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that template R1 is 1,6-hexamethylene diamine and n-butylamine.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that template R2 is 4-propyl bromide and TPAOH.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that crystallization temperature is 100～250 DEG C, and crystallization time is 24～240 hours.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that crystallization temperature is 120～200 DEG C, and crystallization time is 24～200 hours.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that silicon source is Ludox；Aluminum source is sodium aluminate.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that nanocrystalline M FI zeolite cluster is collected as, by the MFI zeolite grain of 10～100 nanometers, the cluster that particle diameter is 0.2～2 micron.
The method of synthesizing nanocrystalline MFI zeolite cluster the most according to claim 1, it is characterised in that nanocrystalline M FI zeolite cluster is collected as, by the MFI zeolite grain of 10～50 nanometers, the cluster that particle diameter is 0.2～0.4 micron.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102000601A (en) * | 2010-09-30 | 2011-04-06 | 上海师范大学 | Multistage pore structure nano molecular sieve catalyst and preparation method thereof |
| CN102190317A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | ZSM-5 sieve material used for aromatic hydrocarbons alkylation reaction and preparation method thereof |
| CN102380412A (en) * | 2011-09-06 | 2012-03-21 | 太原理工大学 | Method for preparing MFI catalyst carrying transition elements and MFI catalyst application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102190317A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | ZSM-5 sieve material used for aromatic hydrocarbons alkylation reaction and preparation method thereof |
| CN102000601A (en) * | 2010-09-30 | 2011-04-06 | 上海师范大学 | Multistage pore structure nano molecular sieve catalyst and preparation method thereof |
| CN102380412A (en) * | 2011-09-06 | 2012-03-21 | 太原理工大学 | Method for preparing MFI catalyst carrying transition elements and MFI catalyst application |
Non-Patent Citations (1)
| Title |
|---|
| 不同晶粒大小ZSM-5分子筛的合成研究;殷基明等;《精细石油化工进展》;20050930;第6卷(第9期);第8-11页 * |
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