CN104445253B - The method of synthesizing nanocrystalline MEL zeolite cluster - Google Patents
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Abstract
A kind of method that the present invention relates to synthesizing nanocrystalline MEL zeolite cluster, mainly solves the problem that in prior art, nano zeolite filter 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): (0.001～0.5): (0.01～1): (5～120): 1, crystallization the most under hydrothermal conditions, crystallized product i.e. can get nanocrystalline M EL zeolite cluster through filtering, wash, drying, described nanocrystalline M EL zeolite cluster is collected as the technical scheme of the cluster that particle diameter is 0.2～10 micron by the MEL zeolite grain of 10～200 nanometers, preferably resolve this problem, can be used in the commercial production of nanometer MEL zeolite.
Description
Technical field
A kind of method that the present invention relates to synthesizing nanocrystalline MEL 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 occur within " nano effect ", have a wide range of applications field.The surface atom number of nano molecular sieve and body phase total atom number it
Ratio is increased dramatically with the minimizing of particle size, so that nano molecular sieve becomes the new material with unique catalytic performance.Receive
Rice molecular sieve is compared bulky grain molecular sieve and is had bigger external surface area and higher micropore diffusion speed, is improving catalyst
Utilization rate, strengthen macromole conversion capability, reduce deep reaction, improve selectivity and reduce the equal table of aspect such as coking and deactivation
Reveal superior performance, therefore suffer from widely studied.But nano molecular sieve granule is the least, it is difficult to separate with mother solution, in the preparation
Filter and reclaim difficulty, thus hindering the commercial Application of nano molecular sieve.Simultaneously as nano molecular sieve has higher table
Face energy, can produce serious agglomeration, cause using effect to be deteriorated.Therefore, the most effectively control what nano molecular sieve was reunited
Pattern and granular size are nanoparticle zeolite field problem demanding prompt solutions.
Since 20 century 70 ZSM-5 zeolites come out, ZSM-5 zeolite is widely used in oil as catalyst and adds
Work and field of petrochemical industry.Nano-sized ZSM-5 zeolite (< 100 rnn) and micron ZSM-5 zeolite (1 μm) have identical
Pore passage structure, and mesh is as other nanoparticles, has identical pore passage structure, bulk effect, table and effect and amount
Sub-dimensional 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
It is only about the 3% of total acid content.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 due to crystal grain less than 100nm make product with
Mother solution separates difficulty, accordingly, it would be desirable to study new synthetic route and the isolation technics with mother solution.
Pointing out in " Microporous and Mesoporous Materials, 25 (1998): 59-74 ", nanometer β is divided
Sub-screening the pulp liquid is stable suspension, and sedimentation velocity is extremely slow, also will not be settled layering even if placing 1 year.The document proposes
First molecular sieve pulp is diluted with water to low viscosity and low ph value, then uses high speed centrifugation partition method to reclaim molecular sieve solid
Method, operates 90 minutes under rotating speed 16000 revs/min.The method centrifugal rotational speed is high, and molecular sieve treating capacity is little, disengaging time
Long, 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/Al2O3
It is prepared as nano molecular sieve compound.The method makes nanometer molecular sieve slurry directly mix with the colloidal sol of carrier without filtration,
Avoid the filter process being most difficult in nano molecular sieve preparation.But the method adds SiO2Or Al2O3Or SiO2/Al2O3, make institute
The composition of the nano molecular sieve solid obtained 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 is by little crystalline substance that average grain is less than 0.5 micron
After grain NaY molecular sieve serosity is mixed homogeneously with water, ammonium salt and a kind of acidic silicasol, slurry pH value is adjusted to 2.8～3.5,
Then filter.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-in molecular sieve pulp
Electrolyte and water, alkaline medium addition to be controlled well makes mixture pH >=12, and alkaline medium, non-dielectric and water
Addition have certain restriction, process is complicated.
In the preparation method of the ultrafine granule five-element circular type zeolite disclosed in patent CN99102700.0, the 300 of synthesis are received
The ZSM-11 zeolite of rice, needs high speed centrifugation to separate, and process is complicated.
In the microwave synthesis method of the nanometer silicate basic hole material disclosed in patent CN200510016885.5, close
The product needed high speed centrifugation become separates, and process is complicated.
In the synthetic method of the nano mordenite molecular sieve disclosed in patent CN200610013526.9, the product of synthesis
Needing high speed centrifugation to separate, process is complicated.
The synthesis of suspension nano ZSM-11 zeolite and characterize (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) report the nanometer ZSM-11 boiling within synthesis 10 nanometers
Stone, sintetics is off-white color suspension sample.Will be by ammonium salt: suspension, water quality adds people's ammonium than the proportioning for 1:10:100
Salt, after heating, flocculating, washing centrifugation, process is complicated.
In sum, conventional art exists the shortcoming that nanocrystalline M EL zeolite cluster preparation process is complicated.
Summary of the invention
The technical problem to be solved is to there is complicated the asking of nanometer MEL zeolite filtration process in conventional art
Topic, it is provided that a kind of method of synthesizing nanocrystalline MEL 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 synthesizing nanocrystalline MEL zeolite group
Bunch method, be that silicon source, aluminum source, template R1, template R2, inorganic base M, water are mixed by a certain percentage, then at certain water
Crystallization under heat condition, crystallized product, through filtering, wash, drying, can obtain and be gathered by the MEL zeolite grain of 10～200 nanometers
Integrate as the cluster that particle diameter is 0.2～10 micron.Under above-mentioned reaction condition, the mol ratio of reactant is:
Al2O3/SiO20～0.1
R1/SiO20.01～1.5
R2/SiO20.001～0.5
M/SiO20.01～1
H2O/SiO25～120
Template R1 is tetrabutyl ammonium bromide or n-butylamine；Template R2 is TBAH or tetrapropyl hydroxide
Ammonium；Silicon source is at least one in Ludox, methyl silicate, tetraethyl orthosilicate, White Carbon black, waterglass；Aluminum source is sodium aluminate, nitre
Acid aluminum, aluminum sulfate, three aluminum ethylate .s, aluminum isopropylate., isobutanol aluminum at least one；Inorganic base M is at least one in NaOH, KOH；
Crystallization temperature is 80～250 DEG C；Crystallization time is 24～1200 hours.
The mol ratio of the reaction system of optimization of the present invention is:
Al2O3/SiO20.08～0.011
R1/SiO20.04～0.05
R2/SiO20.02～0.03
M/SiO20.08～0.1
H2O/SiO210～60
Preferably silicon source is at least one in Ludox, methyl silicate, tetraethyl orthosilicate；Preferably aluminum source is aluminic acid
In sodium, three aluminum ethylate .s, aluminum isopropylate., isobutanol aluminum at least one；Preferably crystallization temperature scope is 100～200 DEG C, during crystallization
Between be 72～480 hours；Preferred silicon source is Ludox；Preferred aluminum source is sodium aluminate；Preferred crystallization temperature model
Enclosing is 120～180 DEG C, and crystallization time is 90～440 hours；Nanocrystalline M EL zeolite cluster is preferably boiled by the MEL of 10～60 nanometers
Stone crystal grain is collected as the cluster that particle diameter is 0.2～0.8 micron, is more preferably assembled by the MEL zeolite grain of 10～20 nanometers
For the cluster that particle diameter is 0.2～0.4 micron.
The present invention, by the allotment to material molar ratio, optimizes crystallization temperature and crystallization time, achieves unforeseeable
Technique effect, the nanocrystalline M EL zeolite cluster that the present invention prepares is to be collected as by the MEL zeolite grain of 10～200 nanometers
Particle diameter is the cluster of 0.2～10 micron, works as Al2O3:R1:R2:M: H2O: SiO2Mol ratio be (0.08～0.011):
(0.04～0.05): (0.02～0.03): (0.08～0.1): (10～60): when 1, the nanocrystalline M EL that can prepare
Zeolite cluster is to be collected as, by the MEL zeolite grain of 10 nanometers, the cluster that particle diameter is 0.2 micron, is conducive to industry metaplasia
Produce.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): (0.001～0.5): (0.01～
1): (5～120): 1, then crystallization under hydrothermal conditions, crystallized product i.e. can get nanocrystalline M EL boiling through filtering, wash, drying
Stone cluster, it is 0.2～10 that described nanocrystalline M EL zeolite cluster is collected as particle diameter by the MEL zeolite grain of 10～200 nanometers
The cluster of micron, achieves preferable technique effect.
Accompanying drawing explanation
The XRD figure of the nano-cluster MEL zeolite that Fig. 1 synthesizes for [embodiment 1].
The SEM photograph of the nano-cluster MEL zeolite that Fig. 2 synthesizes for [embodiment 1].
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
By 1SiO2:0.011Al2O3:0.04R1:0.02R2:0.08NaOH:10H2O weighs each material, by molten for 40% silicon
Glue, sodium metaaluminate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water mixing, stir 20 minutes, load reaction
In still, 160 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
MEL zeolite, XRD spectra is shown in that Fig. 1, SEM photograph are shown in Fig. 2.Characterization result shows, the MEL zeolite grain of 20 nanometers be collected as
The cluster of a diameter of 0.4 micron of grain.
[embodiment 2]
By 1SiO2:0.05Al2O3:0.08R1:0.02R2:0.1NaOH:100H2O weighs each material, by 40% Ludox,
Aluminum sulfate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water mixing, stir 20 minutes, loads in reactor,
150 DEG C of crystallization 360 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MEL boiling
Stone.Characterization result shows, the MEL zeolite grain of 100 nanometers be collected as the cluster that particle diameter is 8 microns.
[embodiment 3]
By 1SiO2:0Al2O3:0.8R1:0.05R2:0.15NaOH:150H2O weighs each material, by tetraethyl orthosilicate, sulfur
Acid aluminum, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water mixing, stir 20 minutes, loads in reactor, and 130
DEG C crystallization 480 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MEL zeolite.
Characterization result shows, the MEL zeolite grain of 200 nanometers be collected as the cluster that particle diameter is 10 microns.
[embodiment 4]
By 1SiO2:0.08Al2O3:0.05R1:0.03R2:0.1KOH:60H2O weighs each material, by waterglass, isobutanol
Aluminum, tetrabutyl ammonium bromide, TBAH, potassium hydroxide and water mixing, stir 20 minutes, loads in reactor, 130 DEG C
Crystallization 432 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MEL zeolite.Table
Levy result to show, the MEL zeolite grain of 10 nanometers be collected as the cluster that particle diameter is 0.2 micron.
[embodiment 5]
By 1SiO2:0.05Al2O3:0.03R1:0.01R2:0.05KOH:20H2O weighs each material, by White Carbon black, nitric acid
Aluminum, tetrabutyl ammonium bromide, TBAH, potassium hydroxide and water mixing, stir 20 minutes, loads in reactor, 170 DEG C
Crystallization 144 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MEL zeolite.Table
Levy result to show, the MEL zeolite grain of 30 nanometers be collected as the cluster that particle diameter is 0.8 micron.
[embodiment 6]
By 1SiO2:0.01Al2O3:0.02R1:0.2R2:0.3KOH:40H2O weighs each material, by 40% Ludox, nitre
Acid aluminum, tetrabutyl ammonium bromide, TBAH, potassium hydroxide and water mixing, stir 20 minutes, loads in reactor, and 200
DEG C crystallization 95 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MEL zeolite.
Characterization result shows, the MEL zeolite grain of 50 nanometers be collected as the cluster that particle diameter is 4 microns.
[embodiment 7]
0.02:0.1:0.3:0.21:60:1 presses 1SiO2:0.02Al2O3:0.1R1:0.3R2:0.21NaOH:60H2O weighs
Each material, mixes White Carbon black, sodium aluminate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water, stirs 20 points
Clock, loads in reactor, 100 DEG C of crystallization 1000 hours.Crystallization product filters, is washed to pH value is 8, dries 12 in 120 DEG C little
Time, prepare nano-cluster MEL zeolite.Characterization result shows, the MEL zeolite grain of 30 nanometers it is 0.5 micro-for being collected as particle diameter
The cluster of rice.
[embodiment 8]
By 1SiO2:0.03Al2O3:0.5R1:0.25R2:0.34NaOH:80H2O weighs each material, by 40% Ludox,
Aluminum nitrate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water mixing, stir 20 minutes, loads in reactor,
150 DEG C of crystallization 900 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, prepares nano-cluster MEL boiling
Stone.Characterization result shows, the MEL zeolite grain of 60 nanometers be collected as the cluster that particle diameter is 0.5 micron.
[comparative example 1]
By the condition of [embodiment 1], by 1SiO2:0.011Al2O3:0.04R1:0.0005R2:0.08NaOH:10H2O claims
Take each material, 40% Ludox, sodium metaaluminate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water mixed,
Stir 20 minutes, load in reactor, 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, in 120 DEG C of bakings
Dry 12 hours, prepared MFI zeolite, rather than MEL zeolite.Characterization result shows, MFI zeolite grain is 3 microns.
[comparative example 2]
By the condition of [embodiment 5], simply do not add tetrabutyl ammonium bromide, by 1SiO2: 0.05Al2O3: 0R1:0.01R2:
0.05KOH:20H2O weighs each material, by White Carbon black, aluminum nitrate, tetrabutyl ammonium bromide, TBAH, potassium hydroxide
Mix with water, stir 20 minutes, in loading reactor, 170 DEG C of crystallization 144 hours.Crystallization product filters, is washed to pH value is 8,
Dry 12 hours in 120 DEG C, prepare MEL zeolite.Characterization result shows, MEL zeolite grain is 2.5 microns.
[comparative example 3]
By the condition of [embodiment 5], simply do not add TBAH, by 1SiO2: 0.05Al2O3: 0.03R1:0R2:
0.05KOH:20H2O weighs each material, White Carbon black, aluminum nitrate, tetrabutyl ammonium bromide, potassium hydroxide and water is mixed, and stirs 20
Minute, load in reactor, 170 DEG C of crystallization 144 hours.Crystallization product filters, is washed to pH value is 8, dries 12 in 120 DEG C little
Time, prepared MFI zeolite, rather than MEL zeolite.Characterization result shows, MFI zeolite grain is 2 microns.
[comparative example 4]
By the condition of [embodiment 1], by 1SiO2:0.011Al2O3:0.006R1:0.02R2:0.08NaOH:10H2O weighs
Each material, mixes 40% Ludox, sodium metaaluminate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water, stirs
Mix 20 minutes, load in reactor, 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, in 120 DEG C of drying
12 hours, prepare MEL zeolite.Characterization result shows, MEL zeolite grain is 0.8 micron.
[comparative example 5]
By the condition of [embodiment 1], by 1SiO2:0.011Al2O3:0.04R1:0.02R2:0.08NaOH:130H2O weighs
Each material, mixes 40% Ludox, sodium metaaluminate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water, stirs
Mix 20 minutes, load in reactor, 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, in 120 DEG C of drying
12 hours, prepare MEL zeolite.Characterization result shows, the MEL zeolite grain of 1500 nanometers being collected as particle diameter is 10 microns
Cluster.
[comparative example 6]
By the condition of [embodiment 1], by 1SiO2:0.11Al2O3:0.04R1:0.02R2:0.08NaOH:10H2O weighs respectively
Material, mixes 40% Ludox, sodium metaaluminate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water, stirring
20 minutes, load in reactor, 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 in 120 DEG C
Hour, prepared MFI zeolite, rather than MEL zeolite.Characterization result shows, MFI zeolite grain is 5 microns.
[comparative example 7]
By the condition of [embodiment 1], by 1SiO2:0.011Al2O3:0.04R1:0.02R2:1.1NaOH:10H2O weighs respectively
Material, mixes 40% Ludox, sodium metaaluminate, tetrabutyl ammonium bromide, TBAH, sodium hydroxide and water, stirring
20 minutes, load in reactor, 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 in 120 DEG C
Hour.Characterization result shows, the sample of synthesis is unformed product.
By embodiment 1 and the comparison of comparative example 1,4～7, embodiment 5 and the comparison of comparative example 2～3, 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): (0.001～0.5): (0.01～1): (5～120): when 1, can
Preparing nanocrystalline M EL zeolite cluster and being collected as particle diameter by the MEL zeolite grain of 10～200 nanometers is 0.2～10 micron
Cluster, and when the consumption of any raw material exceedes this scope, then MEL zeolite grain can substantially become big or can not synthesize
Go out MEL zeolite.
Table 1
Claims (10)
1. a method for synthesizing nanocrystalline MEL zeolite cluster, it is characterized in that by silicon source, aluminum source, template R1, template R2,
Inorganic base M, water mix by a certain percentage, then crystallization under certain hydrothermal condition, crystallized product through filtering, wash, drying,
Can obtain and be collected as the cluster that particle diameter is 0.2～10 micron, above-mentioned reaction bar by the MEL zeolite grain of 10～200 nanometers
Under part, the mol ratio of reactant is:
Al2O3/SiO20～0.1
R1/SiO20.01～1.5
R2/SiO20.001～0.5
M/SiO20.01～1
H2O/SiO25～120
Template R1 is tetrabutyl ammonium bromide or n-butylamine；Template R2 is TBAH or TPAOH；
Silicon source is at least one in Ludox, methyl silicate, tetraethyl orthosilicate, White Carbon black, waterglass；Aluminum source is sodium aluminate, nitric acid
In aluminum, aluminum sulfate, three aluminum ethylate .s, aluminum isopropylate., isobutanol aluminum at least one；Inorganic base M is at least one in NaOH, KOH.
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 1, it is characterised in that the mol ratio of reactant
It is:
Al2O3/SiO20.08～0.011
R1/SiO20.04～0.05
R2/SiO20.02～0.03
M/SiO20.08～0.1
H2O/SiO210～60.
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 1, it is characterised in that template R1 is the tetrabutyl
Ammonium bromide.
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 1, it is characterised in that template R2 is the tetrabutyl
Ammonium hydroxide.
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 1, it is characterised in that silicon source is Ludox or white
Carbon black.
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 1, it is characterised in that aluminum source is sodium aluminate, nitre
Acid aluminum, aluminum sulfate, isobutanol aluminum at least one.
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 1, it is characterised in that inorganic base M be NaOH or
KOH。
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 1, it is characterised in that crystallization temperature be 80～
250 DEG C, crystallization time is 24～1200 hours.
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 1 or claim 2, it is characterised in that can obtain by 10
～60 the MEL zeolite grain of nanometer be collected as the cluster that particle diameter is 0.2～0.8 micron.
The method of synthesizing nanocrystalline MEL zeolite cluster the most according to claim 9, it is characterised in that can obtain by 10～
The MEL zeolite grain of 20 nanometers is collected as the cluster that particle diameter is 0.2～0.4 micron.
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| CN1240193A (en) * | 1999-04-21 | 2000-01-05 | 中国石油化工集团公司 | Ultrafine granule five-element circular type zeolite |
| US7585490B2 (en) * | 2005-04-15 | 2009-09-08 | University Of Iowa Research Foundation | Synthesis and use of nanocrystalline zeolites |
| CN102530968A (en) * | 2012-01-10 | 2012-07-04 | 苏州苏凯路化学科技有限公司 | Production method of spiral bi-thienyl silicon oxide nanometer material |
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| CN1240193A (en) * | 1999-04-21 | 2000-01-05 | 中国石油化工集团公司 | Ultrafine granule five-element circular type zeolite |
| US7585490B2 (en) * | 2005-04-15 | 2009-09-08 | University Of Iowa Research Foundation | Synthesis and use of nanocrystalline zeolites |
| CN102530968A (en) * | 2012-01-10 | 2012-07-04 | 苏州苏凯路化学科技有限公司 | Production method of spiral bi-thienyl silicon oxide nanometer material |
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| ZSM-11的合成及表征;刘师前等;《精细石油化工进展》;20110331;第12卷(第3期);第24-28页 * |
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