CN104477935B

CN104477935B - The method that salt particulate templates method prepares hydridization duct molecular sieve

Info

Publication number: CN104477935B
Application number: CN201410675513.2A
Authority: CN
Inventors: 熊建民; 曾桂凤; 李工; 蒋振奇; 董春栋
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2014-11-21
Filing date: 2014-11-21
Publication date: 2016-08-24
Anticipated expiration: 2034-11-21
Also published as: CN104477935A

Abstract

The present invention relates to a kind of method that particulate templates method prepares hydridization duct molecular sieve, the synthesis particularly sieved for template for many-level molecule with sodium chloride.Synthesis step includes first synthesizing salt particulate, then with salt particulate for hard template at its various types of molecular sieve of surface homogeneous precipitation, is finally synthesizing out the multi-stage porous molecular sieve of reservation salt particle cavity finally by the method washing away salt particle.Beneficial effect: (1) is synthesized by the method for salt particle template, has molecular sieve pore passage simultaneously and has the molecular screen material of salt particle formation duct multistage pore canal；Reach the effect of multi-stage porous molecular sieve by regulation salt particle size, effect is direct, simple.(2) used by, salt particle is green non-poisonous, reduces the pollution to environment in multi-stage porous sieve synthesis procedure.(3) it is protected by with protective agent, is possible to prevent salt particle in further building-up process to be dissolved by the solution, affects the formation of follow-up molecular sieve.

Description

The method that salt particulate templates method prepares hydridization duct molecular sieve

Technical field

The present invention relates to a kind of method that particulate templates method prepares hydridization duct molecular sieve, the synthesis particularly sieved for template for many-level molecule with sodium chloride.

Background technology

Molecular sieve has good heat endurance, acidity and pore structure, is widely used in Industrial Catalysis and industrial production, such as cracking, toluene disproportionation, cumene production and xylene isomerization etc..In catalytic reaction, it has good shape selectivity and the feature being easily isolated at molecular level to molecular sieve, but molecular sieve is being diffusion or can be the longest and the narrowest and the phenomenon of diffusion blocking occur due to molecular sieve pore passage when departing from catalytic reaction Middle molecule to activity, affect the catalysis activity of catalyst, selective and catalysqt deactivation may be caused to affect the life-span of catalyst.This diffusion limits and hinders molecular sieve exploitation in Industrial Catalysis and application, is particularly particularly important in some chemical reaction need rapid mass transfer and high conversion.Relative to micro porous molecular sieve, macroporous structure clearly can accelerate the diffusion of material in reaction and make reaction efficiency higher with transmission, and speed is faster.

In recent years, a focus in Zeolite synthesis is exactly research and the 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 (such as: mesopore or macropore) inside molecular sieve, such that it is able to improve molecular sieve catalysis activity in catalytic reaction and service life.Many researchers have been made that numerous studies in this field, and successfully synthesize the molecular sieve with hierarchical porous structure.Be scientific investigations showed that by early stage, the synthesis of multi-stage porous molecular sieve mainly includes 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 diffusion path due to it and mass transfer that is corresponding and that come promotes, it is made to obtain extensive concern at catalytic field, being greatly improved so that catalyst carbon accumulation resisting ability in catalytic reaction improves of mass transfer, thus extend the catalyst life-span in commercial Application.

In the study on the synthesis of multi-stage porous molecular sieve, methods have been developed multiple different research methods, mainly include 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 for the dielectric material sacrificing template as synthesis multi-stage porous molecular sieve, such as: polystyrene, mesoporous silica gel, material with carbon element, fly ash micro-sphere, cotton thread, plant cell and inorganic template etc..But, these hard template method synthetic microporous-macropore multilevel hole material during, sometimes for the complicated follow-up removing process of hard template, process is loaded down with trivial details, and is attended by that hard template used removing is clean and changes original molecule in subtractive process sieves space structure and the defect of surface nature.Therefore, develop a kind of multi-stage porous Zeolite synthesis method simple, that easily acquisition and follow-up removing process are easily achieved 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.It is known that, salt is a kind of extensive application and industry and the material of daily life, nature has abundant and substantial amounts of deposit, it has easily acquisition and cheap feature, the exploitation multi-stage porous Zeolite synthesis technology with salt as hard template will reduce the synthesis cost of multi-stage porous molecular sieve greatly, promote the commercial Application of synthesized multi-stage porous molecular sieve.The salt particle of fine particle can the very convenient method by the water in alcohol removing saturated brine obtain, the particle obtained have particle uniformly, dimension adjustable, be prone to industrialized feature, it is as one of the most preferable hard template synthesizing multi-stage porous molecular sieve, is applied in synthesizing nano-silver particle.

Summary of the invention

It is an object of the invention to: a kind of method providing particulate templates method to prepare hydridization duct molecular sieve, be 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:

The method that salt particulate templates method prepares hydridization duct molecular sieve, said method comprising the steps of:

(1) synthesis salt particle template, the size of described salt particle is 10nm-20 μm；

(2) using salt particle template as the crystal seeds of synthesis of molecular sieve process, it is subsequently adding Zeolite synthesis liquid, then proceeds 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) removes salt particle template by solution washing, dries and removes solution；Obtain hydridization duct molecular sieve after drying.

Further, described method be additionally included in synthesis salt particle template during or salt particle template formed after be protected by with protective agent.

Further, the one in the described protective agent following protective agent of employing: LIPOPEG 39-S PEG-40, ARLACEL 165, ARLACEL P135 PEG-30, ARLATONE 2121, TWEEN 20, TWEEN 60, TWEEN 80。

Further, described synthesis salt particle uses the method synthesis of physical method or chemical dehydration.

Further, described salt particle is by anion and cation or the mixture of corresponding salt, and described anion is including, but not limited to Cl^-、NO₃ ^-、SO₄ ^2-、CH₃COO^-、HCOO^-、CH₃CH₂COO^-、 CO₃ ^-、HCO₃ ^-、 S^2-、 Br^-、 I^-、 PO₄ ^3-、SiO₃ ^2-；Cation is including, but not limited to Li⁺、 Na⁺、 K⁺、 Mg²⁺、 Ca²⁺、 NH₄ ⁺、 Ba²⁺、 Al³⁺、Fe³⁺、Fe²⁺、Zn²⁺、 Cu²⁺、 Ag⁺。

Further, at least one in following material of described solution, distilled water, methyl alcohol, ethanol, propyl alcohol, butanol, formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid washing.

Further, Zeolite synthesis liquid is silicon source, aluminium source, organic formwork agent and the mixture of salt particle crystal, adds alkali source, obtain alumino-silicate original solution after mixing, and silicon source, aluminium source are respectively with SiO₂、Al₂O₃Meter, feed intake Al₂O₃With SiO₂Mol ratio is 0-10 ；Template and SiO₂Mol ratio is 0-0.8；OH in alkali source^- With SiO₂Mol ratio is 0.01-0.5, and salt particle crystal shared weight ratio in mixed liquor is 1-70% 。

Further, being additionally included in muffle furnace and carry out baking operation in described step (3) after drying removing solution, described sintering 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.

Technical scheme is used to provide the benefit that:

(1) synthesized by the method for salt particle template；There is molecular sieve pore passage simultaneously and there is the molecular screen material of salt particle formation duct multistage pore canal；

(2) with salt particle as template, green non-poisonous, the effect of multi-stage porous molecular sieve is reached by regulation salt particle size, effect is direct, simple；

(3) for building-up process uses the solution of the possible dissolving salt particle arrived; synthesis salt particle template during or salt particle template formed after be protected by with protective agent; it is possible to prevent salt particle in further building-up process to be dissolved by the solution, affects the formation of follow-up molecular sieve；

(4) method of the synthesis multi-stage porous molecular sieve of the present invention, novel, is based primarily upon the method synthesis multi-stage porous molecular sieve of salt particulate templates.

Accompanying drawing explanation

The present invention will be further described below in conjunction with the accompanying drawings；

Fig. 1 is the 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 the sodalite crystallogram of the present invention；

Fig. 4 is the sodalite scanning electron microscope (SEM) photograph of the present invention；

Fig. 5 is the Y type molecular sieve crystallogram of the present invention；

Fig. 6 is the Y type molecular sieve scanning electron microscope (SEM) photograph of the present invention；

Fig. 7 is the Beta type molecular sieve crystal diffraction pattern of the present invention；

Fig. 8 is the Beta type molecular sieve scanning electron microscope (SEM) photograph of the present invention.

Detailed description of the invention

In conjunction with the accompanying drawings, the present invention is further detailed explanation.These accompanying drawings are the schematic diagram of simplification, and the basic structure of the present invention is described the most in a schematic way, and therefore it only shows the composition relevant with the present invention.

Embodiment 1

It is first embodiment synthesizing hydridization duct molecular sieve in the present invention as in Figure 2-4, the synthesis of multi-stage porous sodalite molecular sieve, its synthetic method comprises the following steps:

(1) ethylene glycol solution saturated for 5ml sodium chloride is mixed with 2.5ml ethylene glycol, stirs half an hour,

(2) it is then injected into 10ml butanol solution, and stirs half an hour simultaneously.Obtaining visible sodium chloride particulate in solution, the sodium chloride particulate that then use is obtained is as the crystal seeds of lower step Zeolite synthesis；

(3) when stirring, the solution obtained in step (2) adds 0.5g NaOH and 2g silica, stirs 2 hours；

(4) then solution obtained in step (3) is loaded in stainless steel cauldron crystallization 25 days at a temperature of 180 DEG C.After crystallization 25 days, by gained solution and powder filter, wash with distilled water, until not chloride ion-containing (testing with 0.1mol/L silver nitrate solution, not precipitation) in cleaning solution；

(5) then by gained powder roasting 2 days in the muffle furnace of 150 DEG C.I.e. obtain micropore-macropore multi-stage porous molecular sieve.

Shown in Fig. 2, for the micron order sodium chloride particle obtained in this solution, it can be seen that gained sodium chloride particle size is uniform, and particle integrity degree is good；

Shown in Fig. 3, by the XRD diffraction spectrogram of acquisition micropore-macropore multi-stage porous molecular sieve, from spectrogram it can be seen that 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 habit, and it can be seen that this molecular sieve has cavity structure from embedded figure, reach the feature of the molecular sieve of multistage pore canal.

Embodiment 2

It is second embodiment synthesizing hydridization duct molecular sieve in the present invention as seen in figs. 5-6, the synthesis of multi-stage porous Y type molecular sieve, its synthetic method comprises the following steps:

(1) the saturated water lithium chloride solution first by chloride containing lithium particulate configures the sodium hydroxide solution of 0.05mol/L；

(2) TWEEN 60 protective agent of 0.01mol/L is added the most in the solution；One during wherein TWEEN 60 can also change following protective agent 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:0.01Na₂O:0.3Al₂O₃:1SiO₂:110H₂The molar ratio of O adds a certain amount of tetramethyl-ammonium and aluminium isopropoxide, and completely, then dropping tetraethyl orthosilicate is in solution in stirring to reaction；

(4) placing 4 days the most under stirring at room temperature, gained solution loads in reactor crystallization 6 days at a temperature of 100 DEG C；

(5) being filtered by gained solution, and dry with at ethanol washing and 80 DEG C, finally roasting 8 hours at 550 DEG C, prepare the Y type molecular sieve of multistage pore canal.

Al in embodiment 2₂O₃ With SiO₂Mol ratio can also be 1:10;Organic formwork agent ((TMA)₂And SiO O)₂Mol ratio can also is that 1: 0.3 ;OH in alkali source^-With SiO₂Mol ratio is 1:0.5, salt particle crystal shared weight ratio in mixed liquor is 1%.

Embodiment 3

It is the 3rd embodiment synthesizing hydridization duct molecular sieve in the present invention as Figure 7-8, the synthesis of multi-stage porous Beta molecular sieve, its synthetic method comprises the following steps:

(1) saturated sodium-chloride water solution first by sodium chloride-containing particulate configures the sodium hydroxide solution of 0.05mol/L；

(2) according to 4.6 (TEA)₂O:2.2Na₂O:1Al₂O₃:30SiO₂:440H₂The saturated nacl aqueous solution of O(sodium chloride-containing particulate) molar ratio be sequentially added into following reagent.NaOH 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, then the silica gel solution prepared is instilled plastic；

(3) obtained solution is put in reactor 150 DEG C of crystallization 10 days, then use methyl alcohol washing and filtering, finally drying for one day at 75 DEG C, prepare the Beta type molecular sieve of multistage pore canal.

Al in embodiment 3₂O₃ With SiO₂Mol ratio can also be 1:4;Organic formwork agent ((TMA)₂And SiO O)₂Mol ratio can also is that 1: 0.2 ;OH in alkali source^-With SiO₂Mol ratio is 1:0.25, salt particle crystal shared weight ratio in mixed liquor is 70%.

Sodium chloride and lithium chloride in embodiment 1, embodiment 2 and embodiment 3 can change the salt that following any zwitterion combines into, and described anion is including, but not limited to Cl^-、NO₃ ^-、SO₄ ^2-、CH₃COO^-、HCOO^-、CH₃CH₂COO^-、 CO₃ ^-,HCO₃ ^-、 S^2-、 Br^-、 I^-、 PO₄ ^3-、SiO₃ ^2-；Cation is including, but not limited to Li⁺、 Na⁺、 K⁺、 Mg²⁺、 Ca²⁺、 NH₄ ⁺、 Ba²⁺、 Al³⁺、Fe³⁺、Fe²⁺、Zn²⁺、 Cu²⁺、 Ag⁺。

Distilled water in embodiment 1, the ethanol in embodiment 2 and the methyl alcohol in embodiment 3 can change at least one done in following solvent: distilled water, methyl alcohol, ethanol, propyl alcohol, butanol, 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; being only the detailed description of the invention of the present invention, protection scope of the present invention is not limited thereto, and any those familiar with the art is in the technical scope that the invention discloses; the change that can readily occur in or replacement, all should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claim is defined.

Claims

1. the method that salt particulate templates method prepares hydridization duct molecular sieve, it is characterised in that said method comprising the steps of:

(3) molecular sieve in step (2) removes salt particle template by solution washing, dries and removes solution；Obtain hydridization duct molecular sieve after drying；

Zeolite synthesis liquid is silicon source, aluminium source, organic formwork agent and the mixture of salt particle crystal, adds alkali source, obtain alumino-silicate original solution after mixing, and silicon source, aluminium source are respectively with SiO₂、Al₂O₃ Meter, feed intake Al₂O₃ With SiO₂Mol ratio is 0-10；Template and SiO₂Mol ratio is 0-0.8；OH in alkali source^-With SiO₂Mol ratio is 0.01-0.5, and salt particle crystal shared weight ratio in mixed liquor is 1-70%.

2. the method preparing hydridization duct molecular sieve according to the salt particulate templates method described in claim 1, it is characterised in that described method be additionally included in synthesis salt particle template during or salt particle template formed after be protected by with protective agent.

3. the method preparing hydridization duct molecular sieve according to the salt particulate templates method described in claim 2, it is characterised in that the one in the described protective agent following protective agent of employing: LIPOPEG 39-S PEG-40, ARLACEL 165, ARLACEL P135PEG-30, ARLATONE 2121, TWEEN 20, TWEEN 60, TWEEN 80。

4. the method preparing hydridization duct molecular sieve according to the salt particulate templates method described in claim 1, it is characterised in that: described synthesis salt particle uses the method synthesis of physical method or chemical dehydration.

5. the method preparing hydridization duct molecular sieve according to the salt particulate templates method described in claim 1, it is characterised in that: described salt particle is by anion and cation or the mixture of corresponding salt, and described anion is including, but not limited to Cl^-、NO₃ ^-、SO₄ ^2-、CH₃COO^-、HCOO^-、CH₃CH₂COO^-、 CO₃ ^2-、HCO₃ ^-、 S^2-、 Br^-、 I^-、 PO₄ ^3-、SiO₃ ^2-；Cation is including, but not limited to Li⁺、 Na⁺、 K⁺、 Mg²⁺、 Ca²⁺、 NH₄ ⁺、 Ba²⁺、 Al³⁺、Fe³⁺、Fe²⁺、Zn²⁺、 Cu²⁺、 Ag⁺。

6. the method preparing hydridization duct molecular sieve according to the salt particulate templates method described in claim 1, it is characterized in that: at least one in following material of described solution, distilled water, methyl alcohol, ethanol, propyl alcohol, butanol, formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid washing.

7. the method preparing hydridization duct molecular sieve according to the salt particulate templates method described in claim 1, it is characterised in that being additionally included in Muffle furnace after drying removing solution in described step (3) and carry out baking operation, described sintering temperature controls as 150-550 DEG C；Described roasting time is 8h-2d.

null8. the method preparing hydridization duct molecular sieve according to the salt particulate templates method described in claim 1，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.