CN108117089A - A kind of chabazite molecular sieve and its application - Google Patents
A kind of chabazite molecular sieve and its application Download PDFInfo
- Publication number
- CN108117089A CN108117089A CN201611070989.9A CN201611070989A CN108117089A CN 108117089 A CN108117089 A CN 108117089A CN 201611070989 A CN201611070989 A CN 201611070989A CN 108117089 A CN108117089 A CN 108117089A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- small
- chabazite
- hydroxide
- template
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/104—Oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of Chabazite-type molecular sieve and its applications, belong to molecular sieve inorganic microporous field of material preparation.The molecular sieve is by the inorganic porous material with CHA topological structures being self-assembly of by oxygen-octahedron and aluminum-oxygen tetrahedron, and for Si/Al molar ratios between 4~8, BET method specific surface area is 400 800m2/ g, crystal grain are 0.8 20 microns.The system with molecular sieve for preparing uses alkyl ammonium hydroxide and adamantyl ammonium hydroxide to reduce the dosage of expensive adamantyl ammonium hydroxide as double template, reduce manufacturing cost for middle.The molecular sieve has larger specific surface area and pore volume, and octatomic ring aperture window is conducive to improve CO2/N2Separating property, while the balance cation outside skeleton is conducive to improve N2/O2Separating property.
Description
Technical field
It is prepared the invention belongs to molecular sieve poromerics and its applied to CO2/N2And N2/O2Mixed gas isolation technics
Field, and in particular to a kind of Chabazite-type molecular sieve and its application.
Background technology
Chabasie has CHA topological structures, and skeleton is cross-linked to form elliposoidal cage construction by double hexatomic rings.Its eight yuan
The theoretical diameter of ring window is 0.38nm × 0.38nm, belongs to typical small pore molecular sieve.High silica alumina ratio (Si/Al>20) water chestnut
Zeolite has preferable hydrophobicity and hydrothermal stability, while has larger specific surface area and pore volume, therefore is having vapor
Remain to keep certain adsorption separation performance under the conditions of existing.In addition, its octatomic ring aperture window is conducive to play to mixing
The sieving actoion of gas.Such as CO2/N2Separation and N2/O2Separation etc..CO2/N2Efficiently separate to charcoal trapping be of great significance,
CO2Compare N2Kinetic diameter it is small, can preferentially diffuse into the duct of chabazite molecular sieve, while CO2With larger polarizability
And quadrupole moment, preferentially adsorbed.N2/O2Efficiently separate to pressure swing adsorption method air separation be of great significance, N2With larger
Quadrupole moment, preferentially adsorbed.
Naturally occurring chabasie with other zeolite coexistings, need could generally be obtained high-purity by pretreatment removing impurity
The chabasie of degree, which increase its production costs, are unfavorable for industrial applications.Artificial synthesized chabasie generally uses hydro-thermal method,
Silicon source, silicon source and alkali source are uniformly mixed and add in suitable organic formwork agent under certain hydrothermal condition and is obtained by the reaction.Specially
Sharp CN 104163434A disclose method of the crystal seed method synthesizing high-silicon aluminium than chabazite molecular sieve, by a certain amount of Ludox, hydrogen
Potassium oxide, sodium hydroxide, aluminum sulfate and hydroxide N, N, N- trimethyl adamantane ammonium pass through crystallization, roasting and ammonium after mixing
Exchange obtains product.It is silicon source and silicon source that patent CN 105236440A, which are disclosed using USY molecular sieve, uses tetraethyl hydrogen-oxygen
Change the method that ammonium synthesizes CHA molecular sieves for template.The patent uses USY molecular sieve as silicon source and silicon source, can not realize pair
The Effective Regulation of raw material silica alumina ratio and product silica alumina ratio.United States Patent (USP) US 4544538 discloses high silicon (Si/Al=15~30)
The synthetic method of chabasie, the template used be N, N, N- trimethyl -1- adamantane ammoniums.The chabasie of document report closes at present
Organic formwork agent has been used mostly into method, and common organic formwork agent is adamantane ammonium.Without using organic formwork agent synthesis
Chabasie crystallinity is relatively low, it is difficult to meet practical application request.
The content of the invention
It is an object of the invention to provide a kind of Chabazite-type molecular sieve and its preparation method and application, this method, which has, closes
Into the advantages that at low cost, product thermal stability and hydrothermal stability is good, available for CO2/N2And N2/O2Adsorbing separation.
A kind of chabazite molecular sieve, the molecular sieve are the tool by being self-assembly of by oxygen-octahedron and aluminum-oxygen tetrahedron
There is the inorganic porous material of CHA topological structures, for Si/Al molar ratios between 4~8, BET method specific surface area is 400-800m2/
G, crystal grain are 0.8-20 microns, and carry out ion-exchanged using different metal cation, make binary compound in preparation process
Template, preparation method are as follows：
(1) suitable sodium hydroxide and silicon source are dissolved in a certain amount of water, are cooled to room temperature；
(2) it is added slowly with stirring the mixture of suitable template R1 and template R2 compositions and continues stirring 0.5
~1 is sufficiently mixed each component when small；
(3) be slowly added to suitable silicon source with vigorous stirring, and at room temperature continue stirring ageing 5-24 it is small when, then
Dynamic crystallization 2~5 days under the conditions of 120-200 DEG C；
(4) vacuum filtration isolates solid product after reaction, wash to pH be less than 8,100 DEG C of dry 6-12 it is small when,
When 500-600 DEG C of roasting 4~10 is small, calcination atmosphere is air；
(5) gained molecular screen primary powder is swapped with different metal ions, exchange temperature is 40-100 DEG C；
(6) molecular sieve powder after ion exchange is activated by vacuum activating or inert atmosphere, obtaining has excellent suction
The chabazite molecular sieve of attached performance.
Alkyl ammonium hydroxide (R1) and adamantyl ammonium hydroxide (R2) is as double template in step (2), and R1/R2
Molar ratio is 0.5:1~2:1.
Template R1 described in step (2) is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl hydroxide
One kind in ammonium and tetrabutylammonium hydroxide；R2 is selected from adamantane, amantadine, 1,3- adamantane diamines, 2- methyl adamantanes
And one kind in N, N, N- trimethyl -1- adamantyl ammonium hydroxide.
The one kind of silicon source used in the Ludox and sodium silicate nanahydrate that mass fraction is 30%；Silicon source is selected from hydrogen
One or more in aluminium oxide, sodium aluminate, Aluminum sol, Patent alum or ANN aluminium nitrate nonahydrate, one of which are hydrogen
Aluminium oxide, and the weight ratio of aluminium hydroxide is more than 10% in silicon source.
Raw material meets in preparation method：SiO2/Al2O3Molar ratio be 40:1~120:1, Na2O/Al2O3Molar ratio be
2:1~12:1, (R1+R2)/Al2O3Molar ratio be 2:1~20:1, H2O/Al2O3Molar ratio be 1000:1~5000:1.
Metal ion used in ion exchange is selected from Ag+、Li+、Ca2+In one kind or its combination.
The actual conditions swapped in step (5) with different metal ions is：Metal salt used is selected from corresponding gold
One kind in nitrate, acetate and chloride corresponding to category ion, preferably chloride；Concentration of metal ions used is
0.1~2mol/L, target cationic is 2~8 times excessive, and exchange temperature is 40~100 DEG C；When each swap time is 2~5 small,
It repeats 2~4 times.
The cation exchange degree is more than 95%.
A kind of application of chabazite molecular sieve, the molecular sieve can be used for CO2/N2/O2The separation of mixed gas, wherein
CO under room temperature normal pressure2Adsorbance is 2~8mmol/g, N2Adsorbance is 0.5~1.2mmol/g, O2Adsorbance for 0.2~
0.5mmol/g。
The purpose of the present invention is reached by following measure, prepares chabazite molecular sieve original powder by hydro-thermal method, then high temperature
Roasting removes template, then ion exchange is carried out using different metal cations, finally by vacuum activating or inertia
Atmosphere activates to obtain modified chabazite molecular sieve adsorbent.Metal ion used in ion-exchanged includes Ca2+、Li+With
Ag+.The template used is alkyl ammonium hydroxide (R1) and the mixture of adamantyl ammonium hydroxide (R2), uses cheap alkane
Base ammonium hydroxide can reduce the dosage of expensive adamantyl ammonium hydroxide, reduce production cost.
The synthetic method of zeolite molecular sieve includes hydro-thermal method, solid-phase synthesis, Microwave-assisted synthesis method, ultrasonic wave added synthesis
Method and hydroxyl radical free radical accelerate crystallization method etc..Hydro-thermal method is the most common method of synthesis of molecular sieve, is often referred in water or other are molten
In the presence of agent, high-temperature high-voltage reaction synthesis of molecular sieve crystal is utilized.Based on this, solvent-thermal method and ion have been derived at present
Hot method.Influencing the factor of Zeolite synthesis includes alkali concn, the Si/Al that feeds intake, temperature and Template Types etc..
In raw material reaction system, the molar ratio that the ratio of double template is R1/R2 is 0.5:1~2:1, R1 addition is effective
The dosage of R2 is reduced, while large effect will not be caused to product crystallinity, therefore reduces production cost.
Silicon source used in the present invention is one kind in the Ludox and sodium silicate nanahydrate that mass fraction is 30%；Silicon source
For the one or more in aluminium hydroxide, sodium aluminate, Aluminum sol, Patent alum, ANN aluminium nitrate nonahydrate, one of which is
Aluminium hydroxide.The specific structure with comparison generation chabasie of each component is most important in raw material mixed liquor, raw material in the present invention
Mixed liquor the ratio of each component is：SiO2/Al2O3Molar ratio be 40:1~120:1, Na2O/Al2O3Molar ratio be 2:1~
12:1, (R1+R2)/Al2O3Molar ratio be 2:1~20:1, H2O/Al2O3Molar ratio be 1000:1~5000:1.
It is to make molecular sieve for excellent adsorption separation performance to carry out ion-exchanged to the molecular screen primary powder of synthesis
Main means.Metal ion used in the present invention includes Ca2+、Li+And Ag+, metal salt used be selected from corresponding metal from
One kind in nitrate, acetate and chloride corresponding to son.Ca is first carried out headed by ion exchange order2+It exchanges, Ran Houfen
Li is not carried out+And Ag+It exchanges, obtains the chabazite molecular sieve that different metal ions exchange.Since the molecular sieve after ion exchange contains
There is a certain amount of moisture, this can influence the absorption property of molecular sieve, therefore modified molecular sieve need be activated to remove
Remove moisture therein.Activation method of the present invention has heating in vacuum activation method and inert atmosphere heat-activated method, activation
Temperature is 300~600 DEG C.
The preparation method of chabasie provided by the invention has low production cost, product thermal stability and hydrothermal stability
The advantages that good.Modified chabasie BET specific surface area is between 400~800m2Between/g, pore size distribution is between 0.3~0.8nm
Between, Si/Al molar ratios are between 4~8.Homogeneous micropore distribution and highly polar surface are conducive to improve its CO2/N2And N2/
O2Separating property.
Description of the drawings
Fig. 1 is the XRD spectra of Si/Al crystallized products when being respectively 25.3 and 51.5 of feeding intake.
Fig. 2 be feed intake Si/Al when being 51.5 crystallized product be respectively 1000 times and 5000 times of scanning electricity in amplification factor
Mirror photo.
Fig. 3 is Na prepared in embodiment 1+The chabasie of exchange is under 298K to CO2、N2And O2Adsorption isotherm
(P0For standard atmospheric pressure).
Specific embodiment
It further illustrates the present invention in the following with reference to the drawings and specific embodiments, but does not form limitation of the invention.
All numbers occurred in description and claims of this specification, are not construed as absolute exact value, these numbers
In the technical staff of value in the art the is understood and permitted error range of known technology.
Embodiment 1
(1) by 0.4167g NaOH and 0.164g NaAlO2It is dissolved in 26.2g deionized waters, adds under stiring
10.55g N, N, N- trimethyl -1- adamantyl ammonium hydroxide.Continue stirring to be completely dissolved and be cooled to room temperature to solid,
Be vigorously stirred down be slowly added dropwise 30% Ludox of 10.1g and continue stirring 6 it is small when.Mixed liquor is transferred to equipped with polytetrafluoroethyl-ne
In the autoclave of alkene liner, dynamic crystallization 4 days under the conditions of 160 DEG C.Room temperature is naturally cooling to after reaction, and vacuum is taken out
Solid product is filtered out, is washed with a large amount of deionized waters to filter liquor pH and is less than 8.By product when drying 12 is small under the conditions of 100 DEG C
White powder is obtained, then removes template when roasting 12 is small under the conditions of 550 DEG C, calcination atmosphere is air.
(2) 1g molecular screen primary powders are weighed and add in round-bottomed flask, add in the CaCl of 60ml 1mol/L2Solution, in 80 DEG C of water-baths
Heat and magnetic agitation under conditions of carry out ion exchange, continue 5 it is small when.After filter and isolate solid, and wash to filtering
Go out liquid and can't detect chlorion.Above step is repeated twice, by product when drying 12 is small under the conditions of 100 DEG C.It will be dried
Product be heated under vacuum 300 DEG C activation 6 it is small when.
The XRD diagram of prepared chabazite molecular sieve original powder is former as shown in the corresponding diffraction patterns of Si/Al=25.3 in Fig. 1
Powder pattern is as shown in Figure 2.
Embodiment 2
(1) by 0.4167g NaOH and 0.156g Al (OH)3It is dissolved in 21.36g deionized waters, adds under stiring
10.55g N, N, N- trimethyl -1- adamantyl ammonium hydroxide.Continue stirring to be completely dissolved and be cooled to room temperature to solid,
Be vigorously stirred down be slowly added dropwise 30% Ludox of 10.1g and continue stirring 6 it is small when.Mixed liquor is transferred to equipped with polytetrafluoroethyl-ne
In the autoclave of alkene liner, dynamic crystallization 4 days under the conditions of 160 DEG C.Room temperature is naturally cooling to after reaction, and vacuum is taken out
Solid product is filtered out, is washed with a large amount of deionized waters to filter liquor pH and is less than 8.By product when drying 12 is small under the conditions of 100 DEG C
White powder is obtained, then removes template when roasting 12 is small under the conditions of 550 DEG C, calcination atmosphere is air.
(2) 1g molecular screen primary powders are weighed and add in round-bottomed flask, the NaCl solution of 60ml 1mol/L are added in, in 80 DEG C of water-baths
Heat and magnetic agitation under conditions of carry out ion exchange, continue 5 it is small when.After filter and isolate solid, and wash to filtering
Go out liquid and can't detect chlorion.Above step is repeated twice, by product when drying 12 is small under the conditions of 100 DEG C.It will be dried
Product be heated under vacuum 300 DEG C activation 6 it is small when.
Prepared Na+The CO of the chabazite molecular sieve of exchange2、N2And O2Absorption property it is as shown in Figure 3.
Embodiment 3
(1) by 0.4167g NaOH and 0.078g Al (OH)3It is dissolved in 21.22g deionized waters, adds under stiring
10.55g N, N, N- trimethyl -1- adamantyl ammonium hydroxide.Continue stirring to be completely dissolved and be cooled to room temperature to solid,
Be vigorously stirred down be slowly added dropwise 30% Ludox of 10.3g and continue stirring 6 it is small when.Mixed liquor is transferred to equipped with polytetrafluoroethyl-ne
In the autoclave of alkene liner, dynamic crystallization 4 days under the conditions of 160 DEG C.Room temperature is naturally cooling to after reaction, and vacuum is taken out
Solid product is filtered out, is washed with a large amount of deionized waters to filter liquor pH and is less than 8.By product when drying 12 is small under the conditions of 100 DEG C
White powder is obtained, then removes template when roasting 12 is small under the conditions of 550 DEG C, calcination atmosphere is air.
(2) 1g molecular screen primary powders are weighed and add in round-bottomed flask, the LiCl solution of 60ml 2mol/L are added in, in 80 DEG C of water-baths
Heat and magnetic agitation under conditions of carry out ion exchange, continue 5 it is small when.After filter and isolate solid, and wash to filtering
Go out liquid and can't detect chlorion.Above step is repeated twice, by product when drying 12 is small under the conditions of 100 DEG C.It will be dried
Product be heated under vacuum 300 DEG C activation 6 it is small when.
The XRD diagram of prepared chabazite molecular sieve original powder is as shown in the corresponding diffraction patterns of Si/Al=51.5 in Fig. 1.
Embodiment 4
(1) by 0.4167g NaOH and 0.164g NaAlO2It is dissolved in 24g deionized waters, adds in 5.28g under stiring
The mixed liquor of N, N, N- trimethyl -1- adamantyls ammonium hydroxide and 2.1g tetraethyl ammonium hydroxides.It is complete to solid to continue stirring
Fully dissolved is simultaneously cooled to room temperature, be slowly added dropwise with vigorous stirring 10.1g30% Ludox and continue stirring 6 it is small when.It will mixing
Liquid is transferred in the autoclave equipped with polytetrafluoroethyllining lining, dynamic crystallization 4 days under the conditions of 160 DEG C.After reaction
Room temperature is naturally cooling to, solid product is filtered by vacuum out, is washed with a large amount of deionized waters to filter liquor pH and is less than 8.Product is existed
White powder is obtained when drying 12 is small under the conditions of 100 DEG C, then removes template when roasting 12 is small under the conditions of 550 DEG C, is roasted
Atmosphere is air.
(2) 1g molecular screen primary powders are weighed and add in round-bottomed flask, the LiCl solution of 60ml 2mol/L are added in, in 80 DEG C of water-baths
Heat and magnetic agitation under conditions of carry out ion exchange, continue 5 it is small when.After filter and isolate solid, and wash to filtering
Go out liquid and can't detect chlorion.Above step is repeated twice, by product when drying 12 is small under the conditions of 100 DEG C.It will be dried
Product be heated under vacuum 300 DEG C activation 6 it is small when.
Embodiment 5
(1) by 0.4167g NaOH and 0.164g NaAlO2It is dissolved in 24g deionized waters, adds in 5.28g under stiring
The mixed liquor of N, N, N- trimethyl -1- adamantyls ammonium hydroxide and 2.1g tetraethyl ammonium hydroxides.It is complete to solid to continue stirring
Fully dissolved is simultaneously cooled to room temperature, be slowly added dropwise with vigorous stirring 30% Ludox of 10.1g and continue stirring 6 it is small when.It will mixing
Liquid is transferred in the autoclave equipped with polytetrafluoroethyllining lining, dynamic crystallization 4 days under the conditions of 160 DEG C.After reaction
Room temperature is naturally cooling to, solid product is filtered by vacuum out, is washed with a large amount of deionized waters to filter liquor pH and is less than 8.Product is existed
White powder is obtained when drying 12 is small under the conditions of 100 DEG C, then removes template when roasting 12 is small under the conditions of 550 DEG C, is roasted
Atmosphere is air.
(2) 1g Na are weighed+The molecular sieve of exchange adds in round-bottomed flask, adds in the AgNO of 60ml 0.1mol/L3Solution,
Carry out ion exchange under conditions of 80 DEG C of heating water baths and magnetic agitation, continue 5 it is small when.After filter isolate solid, and
Washing to filter liquor can't detect chlorion.Above step is repeated twice, by product when drying 12 is small under the conditions of 100 DEG C.It will
Dried product be heated under vacuum 300 DEG C activation 6 it is small when.
Embodiment 6
(1) by 0.4167g NaOH and 0.164g Al (OH)3It is dissolved in 24g deionized waters, adds under stiring
The mixed liquor of 5.28g N, N, N- trimethyl -1- adamantyls ammonium hydroxide and 2.1g tetraethyl ammonium hydroxides.Continue stirring extremely
Solid is completely dissolved and is cooled to room temperature, be slowly added dropwise with vigorous stirring 10.1g30% Ludox and continue stirring 6 it is small when.
Mixed liquor is transferred in the autoclave equipped with polytetrafluoroethyllining lining, dynamic crystallization 4 days under the conditions of 160 DEG C.Reaction
After be naturally cooling to room temperature, solid product is filtered by vacuum out, with a large amount of deionized waters wash to filter liquor pH be less than 8.It will
Product obtains white powder when drying 12 is small under the conditions of 100 DEG C, then removes template when roasting 12 is small under the conditions of 550 DEG C
Agent, calcination atmosphere are air.
(2) 1g Na are weighed+The molecular sieve of exchange adds in round-bottomed flask, adds in the AgNO of 60ml 0.1mol/L3Solution,
Carry out ion exchange under conditions of 80 DEG C of heating water baths and magnetic agitation, continue 5 it is small when.After filter isolate solid, and
Washing to filter liquor can't detect chlorion.Above step is repeated twice, by product when drying 12 is small under the conditions of 100 DEG C.It will
Dried product be heated under vacuum 300 DEG C activation 6 it is small when.
Claims (9)
1. a kind of chabazite molecular sieve, it is characterised in that：The molecular sieve is by from group by oxygen-octahedron and aluminum-oxygen tetrahedron
The inorganic porous material with CHA topological structures formed is filled, between 4~8, BET method specific surface area is Si/Al molar ratios
400-800m2/ g, crystal grain are 0.8-20 microns, and use different metal cation progress ion-exchanged, in preparation process
Make binary composite mould plate agent, its preparation method is as follows：
(1) suitable sodium hydroxide and silicon source are dissolved in a certain amount of water, are cooled to room temperature；
(2) mixture of suitable template R1 and template R2 compositions is added slowly with stirring as double template, and after
Continuous stirring 0.5~1 is sufficiently mixed each component when small；
(3) be slowly added to suitable silicon source with vigorous stirring, and at room temperature continue stirring ageing 5-24 it is small when, Ran Hou
Dynamic crystallization 2~5 days under the conditions of 120-200 DEG C；
(4) vacuum filtration isolates solid product after reaction, wash to pH be less than 8,100 DEG C of dry 6-12 it is small when, 500-
When 600 DEG C of roastings 4~10 are small, calcination atmosphere is air；
(5) gained molecular screen primary powder is swapped with different metal ions, exchange temperature is 40-100 DEG C；
(6) molecular sieve powder after ion exchange is activated by vacuum activating or inert atmosphere, obtaining has good adsorbent
The chabazite molecular sieve of energy.
A kind of 2. chabazite molecular sieve according to claim 1, it is characterised in that the template R1 choosings described in step (2)
One kind from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide；R2 is selected from
Adamantane, amantadine, 1,3- adamantane diamines, 2- methyl adamantanes and N, N, N- trimethyl -1- adamantyl ammonium hydroxide
In one kind.
3. a kind of chabazite molecular sieve according to claim 1, it is characterised in that template R1/R2's rubs in step (2)
You are than being 0.5:1~2:1.
4. a kind of chabazite molecular sieve according to claim 1, it is characterised in that silicon source used is selected from mass fraction
One kind in 30% Ludox and sodium silicate nanahydrate；Silicon source is aluminium hydroxide or aluminium hydroxide and sodium aluminate, Aluminum sol, ten
One or more mixtures in eight hydrazine aluminum sulfates or ANN aluminium nitrate nonahydrate, and the weight ratio of aluminium hydroxide is more than in silicon source
10%.
5. a kind of chabazite molecular sieve according to claim 1, it is characterised in that each raw material meets in preparation method：SiO2/
Al2O3Molar ratio be 40:1~120:1, Na2O/Al2O3Molar ratio be 2:1~12:1, (R1+R2)/Al2O3Molar ratio
For 2:1~20:1, H2O/Al2O3Molar ratio be 1000:1~5000:1.
A kind of 6. chabazite molecular sieve according to claim 1, it is characterised in that metal ion used in ion exchange
Selected from Ag+、Li+、Ca2+In one kind or its combination.
7. a kind of chabazite molecular sieve according to claim 1, it is characterised in that step (5) middle different metal ions into
Row exchange actual conditions be：Metal salt used is selected from nitrate, acetate and chlorination corresponding to corresponding metal ion
One kind in object, concentration of metal ions used are 0.1~2mol/L, and target cationic is 2~8 times excessive, exchange temperature 40
~100 DEG C；When each swap time is 2~5 small, repeat 2~4 times.
8. a kind of chabazite molecular sieve according to claim 1, it is characterised in that the cation exchange degree is more than
95%.
9. the application of a kind of chabazite molecular sieve according to claim 1, it is characterised in that the molecular sieve can be used for
CO2/N2/O2CO under the separation of mixed gas, wherein room temperature normal pressure2Adsorbance is 2~8mmol/g, N2Adsorbance for 0.5~
1.2mmol/g, O2Adsorbance is 0.2~0.5mmol/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611070989.9A CN108117089B (en) | 2016-11-29 | 2016-11-29 | Chabazite molecular sieve and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611070989.9A CN108117089B (en) | 2016-11-29 | 2016-11-29 | Chabazite molecular sieve and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108117089A true CN108117089A (en) | 2018-06-05 |
| CN108117089B CN108117089B (en) | 2021-08-27 |
Family
ID=62224680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611070989.9A Active CN108117089B (en) | 2016-11-29 | 2016-11-29 | Chabazite molecular sieve and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108117089B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114130423A (en) * | 2021-11-26 | 2022-03-04 | 中触媒新材料股份有限公司 | CHA molecular sieve with characteristic framework structure and synthesis method and application thereof |
| CN114275795A (en) * | 2021-11-26 | 2022-04-05 | 中触媒新材料股份有限公司 | CHA chabazite molecular sieve synthesis method and denitration catalysis application |
| CN115515900A (en) * | 2020-04-29 | 2022-12-23 | 香港理工大学 | Process for preparing zeolites |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380564A (en) * | 2008-09-08 | 2009-03-11 | 大连理工大学 | Adsorption agent for removing aldehydes gas in carbon dioxide and preparation method thereof |
| CN102350303A (en) * | 2011-07-18 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Zeolite molecular sieve material which has high-efficiency CO2 capturing function and preparation method thereof |
| CN102665902A (en) * | 2009-11-24 | 2012-09-12 | 巴斯夫欧洲公司 | Process for the preparation of zeolites having CHA structure |
-
2016
- 2016-11-29 CN CN201611070989.9A patent/CN108117089B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380564A (en) * | 2008-09-08 | 2009-03-11 | 大连理工大学 | Adsorption agent for removing aldehydes gas in carbon dioxide and preparation method thereof |
| CN102665902A (en) * | 2009-11-24 | 2012-09-12 | 巴斯夫欧洲公司 | Process for the preparation of zeolites having CHA structure |
| CN102350303A (en) * | 2011-07-18 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Zeolite molecular sieve material which has high-efficiency CO2 capturing function and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115515900A (en) * | 2020-04-29 | 2022-12-23 | 香港理工大学 | Process for preparing zeolites |
| CN114130423A (en) * | 2021-11-26 | 2022-03-04 | 中触媒新材料股份有限公司 | CHA molecular sieve with characteristic framework structure and synthesis method and application thereof |
| CN114275795A (en) * | 2021-11-26 | 2022-04-05 | 中触媒新材料股份有限公司 | CHA chabazite molecular sieve synthesis method and denitration catalysis application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108117089B (en) | 2021-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105967205B (en) | The manufacturing method of zeolite | |
| CN107758691B (en) | The preparation method of high silicon CHA types SSZ-13 molecular sieves | |
| JP6034224B2 (en) | Beta-type zeolite and method for producing the same | |
| JP2019518702A (en) | Process for producing high silica content zeolite from fly ash | |
| CN111039303B (en) | Application of modified M-SAPO-RHO type zeolite molecular sieve as ethylene selective adsorbent | |
| CN107512728B (en) | Preparation method of FAU type zeolite molecular sieve with card-inserted structure and hierarchical pores | |
| CN106145138B (en) | A kind of method for synthesizing the zeolite molecular sieve with chabazite structure | |
| CN104891523B (en) | A kind of preparation method of mesoporous Y type molecular sieve | |
| CN105000573B (en) | Large block porous zeolite composed of nano-crystal grains and preparation method thereof | |
| CN108264057A (en) | A kind of method of the controllable ZSM-5 zeolite of synthesis in solid state wellability | |
| CN103214006B (en) | Preparation method of composite zeolite with core/shell structure | |
| CN108117089A (en) | A kind of chabazite molecular sieve and its application | |
| CN110357121A (en) | A kind of preparation method of little crystal grain nanometer hierarchical pore SSZ-13 molecular sieve | |
| CN107640776A (en) | A kind of preparation method with micro- meso-hole structure MFI molecular sieves | |
| JP2017532279A (en) | Molecular sieve SSZ-101 | |
| CN106608636A (en) | Preparation method for EUO-structured or NES-structured molecular sieve | |
| CN109928406B (en) | Analcime and its synthesis method | |
| CN104828837B (en) | A kind of method of synthesizing submicron NaA molecular sieve | |
| CN106115733A (en) | A kind of preparation method of multi-stage porous mordenite molecular sieve | |
| JP6100361B2 (en) | Molecular sieve SSZ-87 and its synthesis | |
| CN102463135B (en) | EU-1/MOR composite molecular sieve and preparation method thereof | |
| TW202012311A (en) | Rho zeolites and method of making the same | |
| CN110548481A (en) | Hollow-structure CO adsorbent with nano copper salt coated by Y-type molecular sieve and preparation method and application thereof | |
| JP2010155759A (en) | Method for synthesizing mesoporous aluminosilicate | |
| CN110963503B (en) | K-SAPO-34 zeolite molecular sieve and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |