CN104445253A - Method for synthesizing nanocrystalline MEL zeolite cluster - Google Patents

Method for synthesizing nanocrystalline MEL zeolite cluster Download PDF

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CN104445253A
CN104445253A CN201310435405.3A CN201310435405A CN104445253A CN 104445253 A CN104445253 A CN 104445253A CN 201310435405 A CN201310435405 A CN 201310435405A CN 104445253 A CN104445253 A CN 104445253A
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mel zeolite
cluster
sio
mel
zeolite
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CN104445253B (en
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何欣
袁志庆
陶伟川
陈康成
滕加伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method for synthesizing a nanocrystalline MEL zeolite cluster, and the method is mainly used for solving the problem of complicated nanometer zeolite filtering process in the prior art. In order to better solve the problem, the technical scheme adopted by the invention is as follows: the method comprises the following steps: mixing a silicon source, an aluminum source, a template agent R1, a template agent R2, inorganic base M and water in proportion, wherein the mole ratio of Al2O3:R1:R2:M:H2O:SiO2 is (0-0.1):(0.01-1.5):(0.001-0.5):(0.01-1):(5-120):1; then crystallizing under a hydrothermal condition, filtering, washing and drying a crystallized product to obtain the nanocrystalline MEL zeolite cluster, wherein the nanocrystalline MEL zeolite cluster is gathered from MEL zeolite crystal grains of 10-200 nanometers into a cluster with the grain diameter of 0.2-10 micrometers. The method disclosed by the invention can be used for the industrial production of nanometer MEL zeolite.

Description

The method of synthesizing nanocrystalline MEL zeolite cluster
Technical field
The present invention relates to a kind of method of synthesizing nanocrystalline MEL zeolite cluster.
Background technology
General particle size is called nano material between the material of 1 ~ 100 nanometer, because it has large specific surface area, usually occurs " nano effect ", has a wide range of applications field.The surface atom number of nano molecular sieve sharply increases with the minimizing of particle size with the ratio of body phase total atom number, thus nano molecular sieve is become have the novel material of unique catalytic performance.Nano molecular sieve is compared macrobead molecular sieve and is had the higher micropore diffusion speed of larger Extra specific surface area sum, improve catalyzer utilization ratio, strengthen macromole conversion capability, reduce deep reaction, improve selectivity and reduce in coking and deactivation etc. and all show superior performance, be therefore subject to extensive research.But nano molecular sieve particle is too little, is difficult to be separated with mother liquor, filters in the preparation and reclaim difficulty, thus hinder the industrial application of nano molecular sieve.Meanwhile, because nano molecular sieve has higher surface energy, serious agglomeration can be produced, cause result of use to be deteriorated.Therefore, the pattern and the granular size that how effectively to 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 has been widely used in refining of petroleum and field of petrochemical industry as catalyzer.Nano-sized ZSM-5 zeolite (<100 rnn) and micron ZSM-5 zeolite (1 μm) have identical pore passage structure, and order is the same with other nanoparticles, there is identical pore passage structure, volume effect, table and effect and quantum size effect.Main manifestations is that duct is short, appearance and the large percentage that acidic site accounts in total acid content, nano-ZSM-5 [(70 ~ 100) rnn] appearance and acid amount account for more than 30% of total acid content, and micron ZSM-5 [(1 ~ 2) μm] appearance and acid amount be only about 3% of total acid content.There is a large amount of intracrystalline pores (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 and mother liquor separation difficulty because crystal grain is less than 100nm, therefore, needs the new synthetic route of research and the isolation technique with mother liquor.
Point out in " Microporous and Mesoporous Materials, 25 (1998): 59-74 ", nano-beta molecular sieve slurries are stable suspension, and settling velocity is extremely slow, 1 year also can not sedimentation layering even if placed.The document proposes first molecular sieve pulp to be diluted with water to low viscosity and low ph value, then adopts high speed centrifugation partition method to reclaim the method for molecular sieve solid, under rotating speed 16000 revs/min, operates 90 minutes.The method centrifugal rotational speed is high, and molecular sieve treatment capacity is little, and disengaging time is long, and process is complicated, thus cannot be applied to large-scale industrial production.
Adopt sol-gel method by nano molecular sieve and SiO in patent CN02100379.3 2or Al 2o 3or SiO 2/ Al 2o 3be prepared into nano molecular sieve compound.This method makes nanometer molecular sieve slurry directly mix with the colloidal sol of carrier without filtration, avoids filtration procedure the most difficult in nano molecular sieve preparation.But the method adds SiO 2or Al 2o 3or SiO 2/ Al 2o 3, 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.
The method of molecular sieve filtration disclosed in patent CN97112269.5 is, after the small crystal grain NaY molecular sieve slurries of less than 0.5 micron mix with water, ammonium salt and a kind of acidic silicasol, slurry pH value is adjusted to average grain 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.
The method of molecular sieve filtration disclosed in patent CN03122854.2 is in molecular sieve pulp, add alkaline medium, non-electrical medium and water, alkaline medium add-on of not only will controlling well makes mixture pH >=12, and the add-on of alkaline medium, non-electrical medium and water has certain restriction, process is complicated.
In the preparation method of ultrafine granule five-element circular type zeolite disclosed in patent CN99102700.0, the ZSM-11 zeolite of 300 nanometers of synthesis, needs high speed centrifugation to be separated, and process is complicated.
In the microwave synthesis method of nanometer silicate basic hole material disclosed in patent CN200510016885.5, the product needed high speed centrifugation of synthesis is separated, and process is complicated.
In the synthetic method of nano mordenite molecular sieve disclosed in patent CN200610013526.9, the product needed high speed centrifugation of synthesis is separated, and process is complicated.
Synthesis and characterization (the Wang little Li of suspension nano ZSM-11 zeolite, Wu Lan, Li Yuping, Zhang Wei, intercalation sub-spring, Dou Tao, petroleum journal (refining of petroleum), in October, 2006, supplementary issue: 228-230) report nanometer ZSM-11 zeolite within synthesis 10 nanometer, sintetics is creamy white suspension sample.Will by ammonium salt: suspension, quality adds people's ammonium salt than the proportioning for 1:10:100, and after heating, flocculation, washing centrifugation, process is complicated.
In sum, there is the shortcoming of nanocrystalline M EL zeolite cluster preparation process complexity in conventional art.
Summary of the invention
Technical problem to be solved by this invention is the problem that there is nanometer MEL zeolite filtration process complexity in conventional art, provides a kind of method of synthesizing nanocrystalline MEL zeolite cluster, the method have easy, be beneficial to industrial feature.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of synthesizing nanocrystalline MEL zeolite cluster, that silicon source, aluminium source, template R1, template R2, mineral alkali M, water are mixed by a certain percentage, crystallization under certain hydrothermal condition again, crystallized product after filtration, wash, dry, can obtain by the MEL zeolite grain of 10 ~ 200 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 10 micron.Under above-mentioned reaction conditions, the mol ratio of reactant is:
Al 2O 3/SiO 20～0.1
R1/SiO 20.01～1.5
R2/SiO 20.001～0.5
M/SiO 20.01～1
H 2O/SiO 25～120
Template R1 is Tetrabutyl amonium bromide or n-Butyl Amine 99; Template R2 is TBAH or TPAOH; Silicon source is at least one in silicon sol, methyl silicate, tetraethoxy, White Carbon black, water glass; Aluminium source is at least one in sodium aluminate, aluminum nitrate, Tai-Ace S 150, three aluminum ethylates, aluminum isopropylate, isobutanol aluminum; Mineral alkali 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:
Al 2O 3/SiO 20.08～0.011
R1/SiO 20.04～0.05
R2/SiO 20.02～0.03
M/SiO 20.08～0.1
H 2O/SiO 210～60
Preferred silicon source is at least one in silicon sol, methyl silicate, tetraethoxy; Preferred aluminium source is at least one in sodium aluminate, three aluminum ethylates, aluminum isopropylate, isobutanol aluminum; Preferred crystallization temperature scope is 100 ~ 200 DEG C, and crystallization time is 72 ~ 480 hours; Preferred silicon source is silicon sol; Preferred aluminium source is sodium aluminate; Preferred crystallization temperature scope is 120 ~ 180 DEG C, and crystallization time is 90 ~ 440 hours; Nanocrystalline M EL zeolite cluster preferably by the MEL zeolite grain of 10 ~ 60 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 0.8 micron, more preferably by the MEL zeolite grain of 10 ~ 20 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 0.4 micron.
The present invention is by the allotment to material molar ratio, optimize crystallization temperature and crystallization time, achieve unforeseeable technique effect, the nanocrystalline M EL zeolite cluster that the present invention prepares is by the MEL zeolite grain of 10 ~ 200 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 10 micron, works as Al 2o 3: R1:R2:M:H 2o:SiO 2mol 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 zeolite cluster that can prepare is by the MEL zeolite grain of 10 nanometers assemble that to be particle diameter the be cluster of 0.2 micron, is conducive to suitability for industrialized production.Adopt the inventive method, silicon source, aluminium source, template R1, template R2, mineral alkali M, water are mixed in proportion, wherein Al 2o 3: R1:R2:M:H 2o:SiO 2mol ratio be (0 ~ 0.1): (0.01 ~ 1.5): (0.001 ~ 0.5): (0.01 ~ 1): (5 ~ 120): 1, crystallization under hydrothermal conditions again, crystallized product after filtration, washing, dry can obtain nanocrystalline M EL zeolite cluster, described nanocrystalline M EL zeolite cluster, by the MEL zeolite grain of 10 ~ 200 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 10 micron, achieves good technique effect.
 
Accompanying drawing explanation
The XRD figure of the nano-cluster MEL zeolite that Fig. 1 synthesizes for [embodiment 1].
The SEM photo of the nano-cluster MEL zeolite that Fig. 2 synthesizes for [embodiment 1].
 
Below by embodiment, the present invention is further elaborated.
 
Embodiment
[embodiment 1]
By 1SiO 2: 0.011Al 2o 3: 0.04R1:0.02R2:0.08NaOH:10H 2o takes each material, 40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, and obtained nano-cluster MEL zeolite, XRD spectra is shown in Fig. 1, and Fig. 2 is shown in by SEM photo.Characterization result shows, by the MEL zeolite grain of 20 nanometers assemble that to be particle diameter the be cluster of 0.4 micron.
 
[embodiment 2]
By 1SiO 2: 0.05Al 2o 3: 0.08R1:0.02R2:0.1NaOH:100H 2o takes each material, 40% silicon sol, Tai-Ace S 150, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 150 DEG C of crystallization 360 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained nano-cluster MEL zeolite.Characterization result shows, by the MEL zeolite grain of 100 nanometers assemble that to be particle diameter the be cluster of 8 microns.
 
[embodiment 3]
By 1SiO 2: 0Al 2o 3: 0.8R1:0.05R2:0.15NaOH:150H 2o takes each material, tetraethoxy, Tai-Ace S 150, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 130 DEG C of crystallization 480 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained nano-cluster MEL zeolite.Characterization result shows, by the MEL zeolite grain of 200 nanometers assemble that to be particle diameter the be cluster of 10 microns.
 
[embodiment 4]
By 1SiO 2: 0.08Al 2o 3: 0.05R1:0.03R2:0.1KOH:60H 2o takes each material, water glass, isobutanol aluminum, Tetrabutyl amonium bromide, TBAH, potassium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 130 DEG C of crystallization 432 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained nano-cluster MEL zeolite.Characterization result shows, by the MEL zeolite grain of 10 nanometers assemble that to be particle diameter the be cluster of 0.2 micron.
 
[embodiment 5]
By 1SiO 2: 0.05Al 2o 3: 0.03R1:0.01R2:0.05KOH:20H 2o takes each material, White Carbon black, aluminum nitrate, Tetrabutyl amonium bromide, TBAH, potassium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 170 DEG C of crystallization 144 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained nano-cluster MEL zeolite.Characterization result shows, by the MEL zeolite grain of 30 nanometers assemble that to be particle diameter the be cluster of 0.8 micron.
 
[embodiment 6]
By 1SiO 2: 0.01Al 2o 3: 0.02R1:0.2R2:0.3KOH:40H 2o takes each material, 40% silicon sol, aluminum nitrate, Tetrabutyl amonium bromide, TBAH, potassium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 200 DEG C of crystallization 95 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained nano-cluster MEL zeolite.Characterization result shows, by the MEL zeolite grain of 50 nanometers assemble that to be particle diameter the be cluster of 4 microns.
 
[embodiment 7]
0.02:0.1:0.3:0.21:60:1 presses 1SiO 2: 0.02Al 2o 3: 0.1R1:0.3R2:0.21NaOH:60H 2o takes each material, White Carbon black, sodium aluminate, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 100 DEG C of crystallization 1000 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained nano-cluster MEL zeolite.Characterization result shows, by the MEL zeolite grain of 30 nanometers assemble that to be particle diameter the be cluster of 0.5 micron.
 
[embodiment 8]
By 1SiO 2: 0.03Al 2o 3: 0.5R1:0.25R2:0.34NaOH:80H 2o takes each material, 40% silicon sol, aluminum nitrate, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 150 DEG C of crystallization 900 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained nano-cluster MEL zeolite.Characterization result shows, by the MEL zeolite grain of 60 nanometers assemble that to be particle diameter the be cluster of 0.5 micron.
 
[comparative example 1]
By the condition of [embodiment 1], by 1SiO 2: 0.011Al 2o 3: 0.04R1:0.0005R2:0.08NaOH:10H 2o takes each material, 40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained MFI zeolite, but not MEL zeolite.Characterization result shows, MFI zeolite grain is 3 microns.
 
[comparative example 2]
By the condition of [embodiment 5], just do not add Tetrabutyl amonium bromide, by 1SiO 2: 0.05Al 2o 3: 0R1:0.01R2:0.05KOH:20H 2o takes each material, White Carbon black, aluminum nitrate, Tetrabutyl amonium bromide, TBAH, potassium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 170 DEG C of crystallization 144 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained MEL zeolite.Characterization result shows, MEL zeolite grain is 2.5 microns.
 
[comparative example 3]
By the condition of [embodiment 5], just do not add TBAH, by 1SiO 2: 0.05Al 2o 3: 0.03R1:0R2:0.05KOH:20H 2o takes each material, White Carbon black, aluminum nitrate, Tetrabutyl amonium bromide, potassium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 170 DEG C of crystallization 144 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained MFI zeolite, but not MEL zeolite.Characterization result shows, MFI zeolite grain is 2 microns.
 
[comparative example 4]
By the condition of [embodiment 1], by 1SiO 2: 0.011Al 2o 3: 0.006R1:0.02R2:0.08NaOH:10H 2o takes each material, 40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained MEL zeolite.Characterization result shows, MEL zeolite grain is 0.8 micron.
 
[comparative example 5]
By the condition of [embodiment 1], by 1SiO 2: 0.011Al 2o 3: 0.04R1:0.02R2:0.08NaOH:130H 2o takes each material, 40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained MEL zeolite.Characterization result shows, by the MEL zeolite grain of 1500 nanometers assemble that to be particle diameter the be cluster of 10 microns.
 
[comparative example 6]
By the condition of [embodiment 1], by 1SiO 2: 0.11Al 2o 3: 0.04R1:0.02R2:0.08NaOH:10H 2o takes each material, 40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C, obtained MFI zeolite, but not MEL zeolite.Characterization result shows, MFI zeolite grain is 5 microns.
 
[comparative example 7]
By the condition of [embodiment 1], by 1SiO 2: 0.011Al 2o 3: 0.04R1:0.02R2:1.1NaOH:10H 2o takes each material, 40% silicon sol, sodium metaaluminate, Tetrabutyl amonium bromide, TBAH, sodium hydroxide and water is mixed, stirs 20 minutes, in loading reactor, and 160 DEG C of crystallization 240 hours.Crystallization product filters, is washed to pH value is 8, dries 12 hours in 120 DEG C.Characterization result shows, the sample of synthesis is unformed product.
 
By the comparison of embodiment 1 and comparative example 1,4 ~ 7, the comparison of embodiment 5 and comparative example 2 ~ 3, can find out, Al in preparation process 2o 3: R1:R2:M:H 2o:SiO 2mol ratio very large to the Influence on test result of preparation, work as Al 2o 3: R1:R2:M:H 2o:SiO 2mol ratio be (0 ~ 0.1): (0.01 ~ 1.5): (0.001 ~ 0.5): (0.01 ~ 1): (5 ~ 120): when 1; nanocrystalline M EL zeolite cluster can be obtained by the MEL zeolite grain of 10 ~ 200 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 10 micron; and when the consumption of any one raw material exceedes this scope, then MEL zeolite grain can obviously become large or can not synthesize MEL zeolite.
 
Table 1

Claims (10)

1. the method for a synthesizing nanocrystalline MEL zeolite cluster, silicon source, aluminium source, template R1, template R2, mineral alkali M, water is it is characterized in that to mix by a certain percentage, crystallization under certain hydrothermal condition again, crystallized product after filtration, wash, dry, can obtain by the MEL zeolite grain of 10 ~ 200 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 10 micron, under above-mentioned reaction conditions, the mol ratio of reactant is:
Al 2O 3/SiO 20～0.1
R1/SiO 20.01～1.5
R2/SiO 20.001～0.5
M/SiO 20.01～1
H 2O/SiO 25～120
Template R1 is Tetrabutyl amonium bromide or n-Butyl Amine 99; Template R2 is TBAH or TPAOH; Silicon source is at least one in silicon sol, methyl silicate, tetraethoxy, White Carbon black, water glass; Aluminium source is at least one in sodium aluminate, aluminum nitrate, Tai-Ace S 150, three aluminum ethylates, aluminum isopropylate, isobutanol aluminum; Mineral alkali M is at least one in NaOH, KOH.
2. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 1, is characterized in that the mol ratio of reactant is:
Al 2O 3/SiO 20.08～0.011
R1/SiO 20.04～0.05
R2/SiO 20.02～0.03
M/SiO 20.08～0.1
H 2O/SiO 210～60
。
3. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 1, is characterized in that template R1 is Tetrabutyl amonium bromide.
4. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 1, is characterized in that template R2 is TBAH.
5. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 1, is characterized in that silicon source is silicon sol or White Carbon black.
6. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 1, is characterized in that aluminium source is at least one in sodium aluminate, aluminum nitrate, Tai-Ace S 150, isobutanol aluminum.
7. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 1, is characterized in that mineral alkali M is NaOH or KOH.
8. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 1, it is characterized in that crystallization temperature is 80 ~ 250 DEG C, crystallization time is 24 ~ 1200 hours.
9. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 1 or 2, is characterized in that obtaining by the MEL zeolite grain of 10 ~ 60 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 0.8 micron.
10. the method for synthesizing nanocrystalline MEL zeolite cluster according to claim 9, is characterized in that obtaining by the MEL zeolite grain of 10 ~ 20 nanometers assemble that to be particle diameter the be cluster of 0.2 ~ 0.4 micron.
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CN111097501B (en) * 2019-12-26 2022-10-18 中海油天津化工研究设计院有限公司 Bulk phase catalyst for inferior diesel oil hydrotreating and preparation method thereof

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