CN104477935A - Method for preparing hybrid porous molecular sieve by virtue of salt particle template method - Google Patents
Method for preparing hybrid porous molecular sieve by virtue of salt particle template method Download PDFInfo
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- CN104477935A CN104477935A CN201410675513.2A CN201410675513A CN104477935A CN 104477935 A CN104477935 A CN 104477935A CN 201410675513 A CN201410675513 A CN 201410675513A CN 104477935 A CN104477935 A CN 104477935A
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- molecular sieve
- salt
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Abstract
The invention relates to a method for preparing a hybrid porous molecular sieve by virtue of a salt particle template method, and in particular relates to synthesis of a hierarchical molecular sieve by taking sodium chloride as a template. The synthesis comprises the following steps: firstly, synthesizing salt particles, then uniformly precipitating various molecular sieves on the surfaces of the salt particles which are taken as hard templates, and finally synthesizing a hierarchical molecular sieve reserving salt particle cavities by virtue of a process of washing off the salt particles. The method disclosed by the invention has the following beneficial effects: (1) by virtue of the salt particle template, the molecular sieve material simultaneously integrating molecular sieve pores and salt particle-formed hierarchical pores is synthesized; by regulating the sizes of the salt particles, an effect of regulating the hierarchical porous molecular sieve is achieved; therefore, the method is direct in effect, simple and easy to implement; (2) the adopted salt particles are green and non-toxic, so that environmental pollution in the process of synthesizing the hierarchical porous molecular sieve is reduced; and (3) the salt particles protected by virtue of a protective agent can be further prevented from being dissolved in the synthesis process, so that influence on the formation of subsequent molecular sieves is avoided.
Description
Technical field
The present invention relates to the method for a kind of particulate templates legal system for hydridization duct molecular sieve, is particularly the synthesis that template is used for many-level molecule sieve with sodium-chlor.
Background technology
Molecular sieve has good thermostability, acidity and pore structure, is widely used in Industrial Catalysis and industrial production, such as cracking, toluene disproportionation, isopropyl benzene production and xylene isomerization etc.In catalyzed reaction, it has good shape selectivity at molecular layer mask and is easy to the feature of separation molecular sieve, but molecular sieve being diffusion or can be too long and narrow and occur the phenomenon of diffusion blocking due to molecular sieve pore passage when departing to activity at catalyzed reaction Middle molecule, affect the catalytic activity of catalyzer, selectivity also may cause catalyst deactivation and affect the life-span of catalyzer.This diffusional limitation hinders the development & application of molecular sieve in Industrial Catalysis, particularly in some chemical reaction needing rapid mass transfer and high conversion, seems particularly important.Relative to micro porous molecular sieve, macroporous structure clearly can the diffusion of material and transmission make reaction efficiency higher in accelerated reaction, and speed is faster.
In recent years, a focus in Zeolite synthesis is exactly the research and preparation of multi-stage porous molecular sieve, multi-stage porous molecular sieve overcomes the restriction of micro porous molecular sieve mass transfer by the method importing secondary pore (as: mesopore or macropore) in molecular sieve inside, thus can improve the catalytic activity of molecular sieve in catalyzed reaction and work-ing life.Many investigators have made large quantity research in this field, and successfully synthesize the molecular sieve with hierarchical porous structure.Shown by scientific research in early stage, the synthesis of multi-stage porous molecular sieve mainly comprises mesopore-micropore and macropore-micro porous molecular sieve two class, and makes this kind of molecular sieve become the important member of molecular sieves.Wherein, hierarchical porous structure molecular sieve has shorter the evolving path due to it and corresponding and next mass transfer promotes, it is made to obtain extensive concern at catalytic field, the very big raising of mass transfer makes catalyzer carbon accumulation resisting ability in catalyzed reaction improve, thus extends the life-span of catalyzer in industrial application.
In the study on the synthesis of multi-stage porous molecular sieve, methods have been developed multiple different research methods, wherein mainly comprise hard template method, soft template method, mesopore material precursor method and desiliconization method.Hard template method is the most effectual way of synthetic microporous-macropore multi-stage porous molecular screen material.Material of different nature is used to sacrifice the dielectric material of template as synthesis multi-stage porous molecular sieve, such as: polystyrene, mesoporous silica gel, carbon material, fly ash micro-sphere, cotton thread, vegetable cell and inorganic template etc.But, these hard template method synthetic microporous-process of macropore multilevel hole material in, sometimes need the complicated follow-up removing process of hard template, process is loaded down with trivial details, and is attended by hard template used and removes in clean and subtractive process and change the defect that original molecule sieves space structure and surface properties.Therefore, develop a kind of simple, that easily acquisition and follow-up removing process are easy to realize multi-stage porous Zeolite synthesis method and will overcome the technical bottleneck of this type of multi-stage porous Zeolite synthesis technique greatly, while simplifying synthesis technique, retain the physical and chemical performance of original molecular sieve.As everyone knows, salt is a kind of widespread use and material that is industrial and daily life, nature has abundant and a large amount of deposit, it has the feature with cheapness that very easily obtains, exploitation is that the multi-stage porous Zeolite synthesis technology of hard template will reduce the synthesis cost of multi-stage porous molecular sieve greatly with salt, promotes the industrial application of synthesized multi-stage porous molecular sieve.The salt particle of fine particle can the very convenient method removing the water in saturated brine by alcohol obtain, the particle obtained has uniform particles, dimension adjustable, is easy to industrialized feature, be as one of the most desirable hard template of synthesizing multi-stage porous molecular sieve, be applied in synthesis of nano Argent grain.
Summary of the invention
The object of the invention is: provide a kind of particulate templates legal system for the method for hydridization duct molecular sieve, is a kind of molecular sieve based on the synthesis of salt particulate hard template technology with hydridization multistage pore canal; Utilize the technology at salt microparticle surfaces orientated deposition molecular sieve, form certain thickness molecular sieve at salt microparticle surfaces.
For achieving the above object, the technical solution used in the present invention is as follows:
Salt particulate templates legal system, for the method for hydridization duct molecular sieve, said method comprising the steps of:
(1) synthesize salt particle template, the size of described salt particle is 10nm-20 μm;
(2) using the crystal seeds of salt particle template as synthesis of molecular sieve process, then add Zeolite synthesis liquid, then proceed to crystallization in reactor, form molecular sieve on salt particle surface; Controlling crystallizing temperature is 100-200 DEG C, and crystallization time is 4h-25d, forms molecular sieve at salt particle template surface;
(3) molecular sieve in step (2), by solution washing removing salt particle template, dries removing solution; Hydridization duct molecular sieve is obtained after drying.
Further, described method be also included in the process of synthesis salt particle template or salt particle template formed after protected with protective material.
Further, described protective material adopts the one in following protective material: LIPOPEG 39-S PEG-40, ARLACEL 165, ARLACEL P135 PEG-30, ARLATONE 2121, TWEEN 20, TWEEN 60, TWEEN 80.
Further, described synthesis salt particle adopts the method synthesis of physical method or chemical dehydration.
Further, described salt particle is by the mixture of negatively charged ion and positively charged ion or corresponding salt, and described negatively charged ion is including, but not limited to Cl
-, NO
3 -, SO
4 2-, CH
3cOO
-, HCOO
-, CH
3cH
2cOO
-, CO
3 -, HCO
3 -, S
2-, Br
-, I
-, PO
4 3-, SiO
3 2-; Positively charged ion is including, but not limited to Li
+, Na
+, K
+, Mg
2+, Ca
2+, NH
4 +, Ba
2+, Al
3+, Fe
3+, Fe
2+, Zn
2+, Cu
2+, Ag
+.
Further, described solution is selected from least one in following material, distilled water, methyl alcohol, ethanol, propyl alcohol, butanols, formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid washing.
Further, Zeolite synthesis liquid is the mixture of silicon source, aluminium source, organic formwork agent and salt particle crystal, and add alkali source after mixing, obtain silico-aluminate original solution, silicon source, aluminium source are respectively with SiO
2, Al
2o
3meter, feed intake Al
2o
3with SiO
2mol ratio is 0-10; Template and SiO
2mol ratio is 0-0.8; OH in alkali source
-with SiO
2mol ratio is 0.01-0.5, and salt particle crystal shared weight ratio in mixed solution is 1-70%.
Further, be also included in muffle furnace and carry out baking operation in described step (3) after drying removing solution, described maturing temperature controls as 150-550 DEG C; Described roasting time is 8h-2d.
Further, described method is applicable to the synthesis of following molecular sieve: ZSM-5, HZSM-5, ZSM-34, ZSM-35, ZSM-39, ZSM-11, Sodalite, Y, HY, USY, NTY, SSY, MCM-21, MCM-41, MCM-48, MCM-22, MCM-56, MCM-58, MCM-49, MCM-68, SBA-15, Beta, H-Beta, SAPO-11, SAPO-34, SAPO-5, ALPO4-12, ALPO4-5,10X, 13X, 13XAPG, A, NaA.
The beneficial effect of technical scheme of the present invention is adopted to be:
(1) synthesized by the method for salt particle template; There is molecular sieve pore passage simultaneously and there is the molecular screen material that salt particle forms duct multistage pore canal;
(2) take salt particle as template, green non-poisonous, by the effect regulating salt particle size to reach regulation and control multi-stage porous molecular sieve, effect is direct, simple;
(3) for the solution of the possible dissolved salt particle used in building-up process, in the process of synthesis salt particle template or salt particle template formed after protected with protective material, salt particle in further building-up process can be prevented to be dissolved by the solution, to affect the formation of follow-up molecular sieve;
(4) method of synthesis multi-stage porous molecular sieve of the present invention, novel, mainly based on the method synthesis multi-stage porous molecular sieve of salt particulate templates.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention will be further described;
Fig. 1 is salt particle template multi-stage porous composition principle schematic diagram of the present invention;
Fig. 2 is salt particle scanning electron microscope (SEM) photograph of the present invention;
Fig. 3 is sodalite crystallogram of the present invention;
Fig. 4 is sodalite scanning electron microscope (SEM) photograph of the present invention;
Fig. 5 is Y zeolite crystallogram of the present invention;
Fig. 6 is Y zeolite scanning electron microscope (SEM) photograph of the present invention;
Fig. 7 is Beta type molecular sieve crystal diffractogram of the present invention;
Fig. 8 is Beta type molecular sieve scanning electron microscope (SEM) photograph of the present invention.
Embodiment
In conjunction with the accompanying drawings, the present invention is further detailed explanation.These accompanying drawings are the schematic diagram of simplification, only basic structure of the present invention are described in a schematic way, and therefore it only shows the formation relevant with the present invention.
embodiment 1
As in Figure 2-4 for synthesizing first embodiment of hydridization duct molecular sieve in the present invention, the synthesis of multi-stage porous sodalite molecular sieve, its synthetic method comprises the following steps:
(1) ethylene glycol solution saturated for 5ml sodium-chlor is mixed with 2.5ml ethylene glycol, stirs half an hour,
(2) then inject 10ml butanol solution, and stir half an hour simultaneously.Visible sodium-chlor particulate is obtained, then with the crystal seeds of the sodium-chlor particulate obtained as lower step Zeolite synthesis in solution;
(3) under the state stirred, the solution obtained in step (2) adds 0.5g sodium hydroxide and 2g silicon-dioxide, stirs 2 hours;
(4) then institute in step (3) to be obtained in solution loading stainless steel cauldron at the temperature of 180 DEG C crystallization 25 days.Crystallization is after 25 days, by gained solution and powder filter, with distilled water wash, until not chloride ion-containing (by the test of 0.1mol/L silver nitrate solution, not precipitation) in washings;
(5) then by the roasting 2 days in the muffle furnace of 150 DEG C of gained powder.Namely micropore-macropore multi-stage porous molecular sieve is obtained.
Shown in Fig. 2, be the micron order sodium chloride particle obtained in this solution, can find out, gained sodium chloride particle size is even, and particle integrity degree is good;
Shown in Fig. 3, by the XRD diffraction spectrogram of acquisition micropore-macropore multi-stage porous molecular sieve, as can be seen from spectrogram, this molecular sieve is sodalite shaped molecular sieve;
Shown in Fig. 4, by the scanning electron microscope (SEM) photograph of acquisition multi-stage porous molecular sieve, as can be seen from Fig., synthesized by the multi-stage porous molecular sieve that goes out there is good sodalite crystal boundary, and as can be seen from embedded figure, this molecular sieve has cavity structure, reaches the feature of the molecular sieve of multistage pore canal.
embodiment 2
As seen in figs. 5-6 for synthesizing second embodiment of hydridization duct molecular sieve in the present invention, the synthesis of multi-stage porous Y zeolite, its synthetic method comprises the following steps:
(1) sodium hydroxide solution of the saturated water lithium chloride solution configuration 0.05mol/L of chloride containing lithium particulate is first used;
(2) TWEEN 60 protective material of 0.01mol/L is added again in the solution; Wherein TWEEN 60 can also change the one in following protective material into: LIPOPEG 39-S PEG-40, ARLACEL 165, ARLACEL P135 PEG-30, ARLATONE 2121, TWEEN 20, TWEEN 60, TWEEN 80;
(3) according to 0.8 (TMA)
2o:0.01Na
2o:0.3Al
2o
3: 1SiO
2: 110H
2the molar ratio of O adds a certain amount of tetramethyl-ammonium and aluminum isopropylate, is stirred to and reacts completely, and then drips tetraethoxy in solution;
(4) then place 4 days under stirring at room temperature, gained solution to load in reactor at the temperature of 100 DEG C crystallization 6 days;
(5) gained solution is filtered, and with oven dry at washing with alcohol and 80 DEG C, finally roasting 8 hours at 550 DEG C, prepares the Y zeolite of multistage pore canal.
Al in embodiment 2
2o
3with SiO
2mol ratio can also be 1:10; Organic formwork agent ((TMA)
2and SiO O)
2mol ratio can also be 1:0.3; OH in alkali source
-with SiO
2mol ratio is 1:0.5, and salt particle crystal shared weight ratio in mixed solution is 1%.
embodiment 3
As Figure 7-8 for synthesizing the 3rd embodiment of hydridization duct molecular sieve in the present invention, the synthesis of multi-stage porous Beta molecular sieve, its synthetic method comprises the following steps:
(1) sodium hydroxide solution of the saturated sodium-chloride water solution configuration 0.05mol/L of sodium chloride-containing particulate is first used;
(2) according to 4.6 (TEA)
2o:2.2Na
2o:1Al
2o
3: 30SiO
2: 440H
2the saturated nacl aqueous solution of O(sodium chloride-containing particulate) molar ratio add following reagent successively.Sodium hydroxide and sodium aluminate are added in the saturated nacl aqueous solution of sodium chloride-containing particulate and stir 1 hour, and be heated to 80 DEG C, add tetraethylamine hydroxide, the silica gel solution instillation plastic then will prepared;
(3) obtained solution is put into reactor 150 DEG C of crystallization 10 days, then filter by methanol wash, finally at 75 DEG C dry one day, prepare the Beta type molecular sieve of multistage pore canal.
Al in embodiment 3
2o
3with SiO
2mol ratio can also be 1:4; Organic formwork agent ((TMA)
2and SiO O)
2mol ratio can also be 1:0.2; OH in alkali source
-with SiO
2mol ratio is 1:0.25, and salt particle crystal shared weight ratio in mixed solution is 70%.
Sodium-chlor in embodiment 1, embodiment 2 and embodiment 3 and lithium chloride can change the salt that following any zwitterion combines into, and described negatively charged ion is including, but not limited to Cl
-, NO
3 -, SO
4 2-, CH
3cOO
-, HCOO
-, CH
3cH
2cOO
-, CO
3 -, HCO
3 -, S
2-, Br
-, I
-, PO
4 3-, SiO
3 2-; Positively charged ion is including, but not limited to Li
+, Na
+, K
+, Mg
2+, Ca
2+, NH
4 +, Ba
2+, Al
3+, Fe
3+, Fe
2+, Zn
2+, Cu
2+, Ag
+.
Distilled water in embodiment 1, the methyl alcohol in the ethanol in embodiment 2 and embodiment 3 can change at least one done in following solvent: distilled water, methyl alcohol, ethanol, propyl alcohol, butanols, formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid.
The inventive method is applicable to the synthesis of following molecular sieve: ZSM-5, HZSM-5, ZSM-34, ZSM-35, ZSM-39, ZSM-11, Sodalite, Y, HY, USY, NTY, SSY, MCM-21, MCM-41, MCM-48, MCM-22, MCM-56, MCM-58, MCM-49, MCM-68, SBA-15, Beta, H-Beta, SAPO-11, SAPO-34, SAPO-5, ALPO4-12, ALPO4-5,10X, 13X, 13XAPG, A, NaA.
The above; be only the specific embodiment of the present invention, protection scope of the present invention is not limited thereto, and is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should define with claim is as the criterion.
Claims (9)
1. salt particulate templates legal system is for the method for hydridization duct molecular sieve, it is characterized in that, said method comprising the steps of:
(1) synthesize salt particle template, the size of described salt particle is 10nm-20 μm;
(2) using the crystal seeds of salt particle template as synthesis of molecular sieve process, then add Zeolite synthesis liquid, then proceed to crystallization in reactor, form molecular sieve on salt particle surface; Controlling crystallizing temperature is 100-200 DEG C, and crystallization time is 4h-25d, forms molecular sieve at salt particle template surface;
(3) molecular sieve in step (2), by solution washing removing salt particle template, dries removing solution; Hydridization duct molecular sieve is obtained after drying.
2. salt particulate templates legal system according to claim 1 is for the method for hydridization duct molecular sieve, it is characterized in that, described method is also included in the process of synthesis salt particle template or salt particle template formed after protected with protective material.
3. salt particulate templates legal system according to claim 2 is for the method for hydridization duct molecular sieve; it is characterized in that; described protective material adopts the one in following protective material: LIPOPEG 39-S PEG-40; ARLACEL 165; ARLACEL P135 PEG-30, ARLATONE 2121, TWEEN 20; TWEEN 60, TWEEN 80.
4. salt particulate templates legal system according to claim 1 is for the method for hydridization duct molecular sieve, it is characterized in that: described synthesis salt particle adopts the method synthesis of physical method or chemical dehydration.
5. salt particulate templates legal system according to claim 1 for hydridization duct molecular sieve method, it is characterized in that: described salt particle is by the mixture of negatively charged ion and positively charged ion or corresponding salt, and described negatively charged ion is including, but not limited to Cl
-, NO
3 -, SO
4 2-, CH
3cOO
-, HCOO
-, CH
3cH
2cOO
-, CO
3 -, HCO
3 -, S
2-, Br
-, I
-, PO
4 3-, SiO
3 2-; Positively charged ion is including, but not limited to Li
+, Na
+, K
+, Mg
2+, Ca
2+, NH
4 +, Ba
2+, Al
3+, Fe
3+, Fe
2+, Zn
2+, Cu
2+, Ag
+.
6. salt particulate templates legal system according to claim 1 is for the method for hydridization duct molecular sieve, it is characterized in that: described solution is selected from least one in following material, distilled water, methyl alcohol, ethanol, propyl alcohol, butanols, formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid washing.
7. salt particulate templates legal system according to claim 1 is for the method for hydridization duct molecular sieve, it is characterized in that, Zeolite synthesis liquid is the mixture of silicon source, aluminium source, organic formwork agent and salt particle crystal, alkali source is added after mixing, obtain silico-aluminate original solution, silicon source, aluminium source are respectively with SiO
2, Al
2o
3meter, feed intake Al
2o
3with SiO
2mol ratio is 0-10; Template and SiO
2mol ratio is 0-0.8; OH in alkali source
-with SiO
2mol ratio is 0.01-0.5, and salt particle crystal shared weight ratio in mixed solution is 1-70%.
8. salt particulate templates legal system according to claim 1 is for the method for hydridization duct molecular sieve, it is characterized in that, is also included in muffle furnace and carries out baking operation in described step (3) after drying removing solution, and described maturing temperature controls as 150-550 DEG C; Described roasting time is 8h-2d.
9. salt particulate templates legal system according to claim 1 is for the method for hydridization duct molecular sieve, it is characterized in that, described method is applicable to the synthesis of following molecular sieve: ZSM-5, HZSM-5, ZSM-34, ZSM-35, ZSM-39, ZSM-11, Sodalite, Y, HY, USY, NTY, SSY, MCM-21, MCM-41, MCM-48, MCM-22, MCM-56, MCM-58, MCM-49, MCM-68, SBA-15, Beta, H-Beta, SAPO-11, SAPO-34, SAPO-5, ALPO4-12, ALPO4-5, 10X, 13X, 13XAPG, A, NaA.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1418814A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Porous material mordenite membrane |
| WO2003048044A1 (en) * | 2001-11-30 | 2003-06-12 | Exxonmobil Chemical Patents Inc. | Method of synthesizing molecular sieves |
| CN101214972A (en) * | 2008-01-07 | 2008-07-09 | 天津大学 | Dendritic titanium silicon molecular screen film and preparation method thereof |
| CN104291343A (en) * | 2014-09-25 | 2015-01-21 | 太原理工大学 | Synthesis method of mesoporous SBA-3 molecular sieve |
-
2014
- 2014-11-21 CN CN201410675513.2A patent/CN104477935B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418814A (en) * | 2001-11-14 | 2003-05-21 | 中国石油化工股份有限公司 | Porous material mordenite membrane |
| WO2003048044A1 (en) * | 2001-11-30 | 2003-06-12 | Exxonmobil Chemical Patents Inc. | Method of synthesizing molecular sieves |
| CN101214972A (en) * | 2008-01-07 | 2008-07-09 | 天津大学 | Dendritic titanium silicon molecular screen film and preparation method thereof |
| CN104291343A (en) * | 2014-09-25 | 2015-01-21 | 太原理工大学 | Synthesis method of mesoporous SBA-3 molecular sieve |
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