CN108525650A - A kind of X/Silicalite-1 core shells molecular sieve and preparation method thereof - Google Patents
A kind of X/Silicalite-1 core shells molecular sieve and preparation method thereof Download PDFInfo
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- 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
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Abstract
A kind of 1 core shell molecular sieves of X/Silicalite, including X molecular sieve kernel and 1 molecular sieve shells of Silicalite that are coated on outside kernel.The core shell molecular sieve is used for the adsorbing separation of arene isomer, has preferable adsorptive selectivity.
Description
Technical field
The present invention is a kind of core shell molecular sieve and preparation method, specifically, be a kind of Silicalite-1 being shell
Molecular sieve and preparation method thereof.
Background technology
Molecular sieve is a kind of crystalline material with special skeleton structure.Due to uniform micropore canals, adjustable
Acid and ion-exchange performance, molecular sieve are widely used in separation and catalytic field.Wherein, X molecular sieve is C8BTX aromatics adsorb
The active component of separating adsorbent, the X molecular sieve exchanged through specific ion can be from C8It is selectively adsorbing and separating in BTX aromatics pair
Dimethylbenzene (PX).Selectivity is a key index of adsorbent, and higher selectivity is conducive to improve product purity and device
Load.
The method for improving adsorbent selectivity includes mainly the type of modulation exchange ion and reduces the oxidation of X molecular sieve
Silicon/alumina ratio.USP3558730 discloses a kind of BaKX molecular sieves, and BaX and KX are apparently higher than to the selectivity of PX.
USP3997620 has found that compared with BaKX, X molecular sieve passes through Sr2+And Ba2+After exchange, although paraxylene/meta-xylene (PX/
MX it) decreases with paraxylene/ortho-xylene (PX/OX), but paraxylene/ethylbenzene (PX/EB) and paraxylene/to two
Ethylbenzene (PX/PDEB) significantly improves.
CN101254928A discloses a kind of preparation method of the low silicon/aluminium of little crystal grain than X molecular sieve, by synthetic system
Middle introducing sulfuric acid or water soluble sulfate can effectively reduce product silica/alumina molar ratio.
Document [Tung Cao Thanh Pham et al., Angew.Chem.Int.Ed., 2013,52,8693] report
A kind of Silicalite-1 molecular screen membranes, this molecular screen membrane can efficiently separate PX from PX and OX mixtures.However, should
Material is the Silicalite-1 molecular screen membranes generated on piece shape silica, and when molding need to be by silica gel piece surface titanium dioxide
The filling of silicon bead is smooth, is then forming one layer of Silicalite-1 molecular screen membrane above again.
USP4868146 discloses a kind of molecular sieve catalytic in mesoporous molecular sieve outer cladding silica inactive surfaces layer
Agent, the mesoporous molecular sieve are ZSM-5 or ZSM-23, and the preparation method of shell is：By molecular sieve core be added to including silicon source,
In optional directed agents, hydroxide ion and water, and hydro-thermal process under certain condition, add NH4F solution continues hydro-thermal
Processing a period of time obtains the internal active catalyst for having acid centre.
USP5888921 discloses a kind of method for the ZSM-5 molecular sieve preparing ALPO-5 film layers package.The method elder generation handle
ZSM-5 molecular sieve is added in ALPO-5 Zeolite synthesis systems；Hydro-thermal process under certain condition again obtains ZSM-5/
ALPO-5 composite molecular screen materials.The composite material can be used as fluid catalytic cracking additive and improve light olefins yields or propylene system
Isobutene catalyst.
CN101722034A discloses a kind of preparation method of modenite/ZSM-5 core-shell type molecular sieve materials.Specific step
Suddenly it is：First modenite is placed in modifier solution and is handled；Modenite modified ZSM-5 molecular sieve is placed in again to close
Hydro-thermal process in architectonical, the final modenite for obtaining ZSM-5 film layers package.The molecular screen material is anti-for toluene methylation
Answer catalyst.
CN103058215A discloses a kind of synthetic method of Beta/Y composite molecular screens.The specific steps are：First prepare Y points
Son sieve directed agents；Beta molecular sieve powders are added in Y molecular sieve directed agents again and are uniformly mixed；Finally, divide Beta is mixed with
The directed agents of son sieve are added in Y molecular sieve synthetic system, and Y molecular sieve is grown in Beta molecular sieve surfaces after hydrothermal treatment
Film.The composite molecular screen is used for catalyst carrier or acidic catalyst component, has hydrocarbon molecule cracking, isomerization performance.
Invention content
The object of the present invention is to provide a kind of X/Silicalite-1 core shells molecular sieve, which is used for aromatic hydrocarbons
The adsorbing separation of isomers has preferable adsorptive selectivity.
X/Silicalite-1 core shells molecular sieve provided by the invention includes X molecular sieve kernel and is coated on outside kernel
Silicalite-1 molecular sieve shells.
For core shell molecular sieve provided by the invention using X molecular sieve as kernel, Silicalite-1 molecular sieves are shell,
Silicalite-1 molecular sieves are completely coated on outside X molecular sieve.The core shell molecular sieve is for mixing C8Aromatics absorption detaches,
It is remarkably improved the adsorptive selectivity of paraxylene.
Description of the drawings
Fig. 1 is the XRD diagram for the X/Silicalite-1 core shell molecular sieves that present example 1 synthesizes.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) for the X/Silicalite-1 core shell molecular sieves that present example 1 synthesizes.
Fig. 3 is the XRD diagram for the X/Silicalite-1 core shell molecular sieves that present example 3 synthesizes.
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) for the X/Silicalite-1 core shell molecular sieves that present example 3 synthesizes.
Specific implementation mode
Using X molecular sieve as kernel, outer layer is X/Silicalite-1 core shells molecular sieve provided by the invention
Silicalite-1 shells, in adsorbing separation C8When paraxylene in aromatic hydrocarbons, selected since shell Silicalite-1 has
Shape selectivity, can be such that the paraxylene (PX) that X molecular sieve adsorbs more slowly passes through from Silicalite-1 molecular sieve layers, and between making
Dimethylbenzene (MX), ortho-xylene (OX) and ethylbenzene (EB) are easy to pass through from Silicalite-1 molecular sieve layers, to improve molecule
The adsorptive selectivity of sieve.
The SiO of X/Silicalite-1 core shells molecular sieve kernel X molecular sieve of the present invention2/Al2O3Molar ratio is preferred
2.0~3.0.
The kernel and shell molecular sieve of X/Silicalite-1 core shells molecular sieve of the present invention are simultaneously lived without catalysis
Property, cation is selected from Na+、K+、Li+、Cs+、Ca2+、Sr2+And Ba2+At least one of, for adsorbing separation C8Aromatic hydrocarbons is different
Structure body.
The size of microcrystal preferably 0.2~5.0 of X/Silicalite-1 core shells molecular sieve kernel X molecular sieve of the present invention
Micron, 0.2~3.0 micron more preferable, the thickness of Silicalite-1 molecular sieve shells can be 30 nanometers~1000 nanometers, preferably
35~200 nanometers, it is 40~100 nanometers more preferable.
The preparation method of X/Silicalite-1 core shells molecular sieve provided by the invention, includes the following steps：
(1) silicon source, template (R), water and optional inorganic base are uniformly mixed and obtain the Silicalite-1 conjunctions of alkalinity
Architectonical, the amount of silicon source is with SiO2Meter, the amount of inorganic base is with M2O is counted, and the molar ratio of each material is in the synthetic system：R/
SiO2=0.05~0.70, H2O/SiO2=10~150, M2O/SiO2=0~0.05, M are Na or K,
(2) NaX molecular sieves are added into the synthetic system obtained by (1) step to be uniformly mixed, NaX molecular sieves and the synthesis of addition
Contained SiO in system2Mass ratio be 0.2~20：1,
(3) mixture obtained by (2) step is subjected to hydrothermal crystallizing processing in 80~160 DEG C, obtained solid product is dry, roasting
It burns.
The above method (1) step is to prepare the synthetic system of Silicalite-1, and the silicon source is selected from ethyl orthosilicate, silicon
At least one of colloidal sol, waterglass, sodium metasilicate, silica gel and white carbon.The template (R) be selected from ethamine, n-butylamine, oneself
At least one of diamines, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, 4-propyl bromide and 4-propyl ammonium chloride.(1)
It is optional alkali compounds to walk the inorganic base, is selected from NaOH or KOH, the alkali for keeping Silicalite-1 synthetic systems
Property.If raw material compound alkalinity is too strong, can be added in appropriate amount of acid and part alkali.
(1) in synthetic system prepared by step, the molar ratio of each material is preferably：R/SiO2=0.1~0.6, H2O/SiO2=
10~100, M2O/SiO2=0~0.03, M are Na or K.
The method (2) step is addition NaX molecular sieves, the NaX molecular sieves into the synthetic system of Silicalite-1
SiO2/Al2O3Molar ratio preferably 2.0~3.0, the NaX molecular sieves of addition and contained SiO in synthetic system described in (1) step2's
Mass ratio is preferably 0.5~10：1, more preferable 1~8：1.NaX molecules are added in the synthetic system of the Silicalite-1
After sieve, it is uniformly mixing to obtain the synthetic mixture of core shell molecular sieve.
The above method (3) step is that hydrothermal crystallizing prepares shell molecular sieve, the temperature preferably 100 of the hydrothermal crystallizing processing~
160 DEG C, preferably 10~80 hours time of hydrothermal crystallizing processing.After crystallization, solid product is collected, through being filtered, washed, doing
Dry, roasting obtains the X molecular sieve of Silicalite-1 molecular sieves package, i.e. X/Silicalite-1 core shells molecular sieve.Described
Preferably 80~120 DEG C of drying temperature, preferably 4~12 hours time, preferably 520~560 DEG C of calcination temperature, the time preferably 2~6 is small
When.
X/Silicalite-1 core shells molecular sieve provided by the invention is suitable for adsorbing separation C8Isomers in aromatic hydrocarbons,
Such as paraxylene.The cation of its cation-bit can introduce required cation, such as K by ion exchange+、Li+、Cs+、Ca2+、
Sr2+And Ba2+。
To evaluate the adsorptive selectivity of sorbing material, dynamic pulse experimental provision can be used to measure the absorption choosing of sorbing material
The Adsorption and desorption rate of selecting property and paraxylene.The device is by groups such as feed system, adsorption column, heating furnace, pressure-control valves
At.Adsorption column is the stainless steel tube of 6 × 1800 millimeters of Ф, and sorbing material loading amount is 50 milliliters.Adsorption column lower inlet and charging
It is connected with nitrogen system, upper end outlet connects pressure-control valve, then is connect with effluent collector.Experiment strippant used is 30 bodies
The normal heptane of the p-Diethylbenzene (PDEB) and 70 volume % of product %.Pulsed feeds liquid group become respectively account for 5 volume % ethylbenzene (EB),
The p-Diethylbenzene of paraxylene (PX), meta-xylene (MX), ortho-xylene (OX), n -nonane (NC9) and 75 volume %.
The assay method of sorbing material adsorptive selectivity is：The tested sorbing material for being 300~850 μm by the grain size of weighing
Particle is packed into adsorption column ram-jolt, in 160~190 DEG C of dehydration activation in nitrogen atmosphere；It is passed through again in strippant removal system
Gas.System pressure is risen into 0.8MPa, temperature rises to 177 DEG C, and stopping is passed through strippant, when with 1.0-1Volume space velocity be passed through
8 milliliters of pulsed feeds liquid, are passed through strippant with same volume space velocity later, take 3 drop desorption liquid samples at intervals of two minutes, use gas
Analysis of hplc.Using desorption strippant volume as abscissa, a concentration of ordinate of NC9, EB, PX, MX and OX each component is drawn
Go out the desorption curve of above-mentioned each component.Wherein, NC9 is not adsorbed, and can be used as tracer to obtain the dead volume of adsorption system.It will
The midpoint of tracer half-peak breadth is as zero, the net retention volume at the measurement each component half-peak breadth midpoint EB, PX, MX, OX to zero
The net retention volume of R, arbitrary component are directly proportional to distribution coefficient when adsorption equilibrium, reflect between each component and sorbing material
Active force, the ratio between two component net retention volumes are selectivity β, as the net retention volume of PX and the ratio between the net retention volume of EB are
It is that sorbing material is denoted as β for the ratio between PX and EB absorption properties for adsorptive selectivities of the PX relative to EBP/E。
In order to indicate the adsorptive selectivity between the Adsorption and desorption rate of PX and PX and PDEB, the rate of adsorption of PX is introduced
[SA]10-90With desorption rate [SD]90-10.The rate of adsorption [SA]10-90Rise from 10% for PX concentration in the pulse desorption curve of PX
To the strippant volume needed for 90%, parsing rate [SD]90-10Drop to needed for 10% from 90% for PX concentration in desorption curve
Strippant volume, [SA]10-90/[SD]90-10Ratio is defined as the adsorptive selectivity β between PX and strippantPX/PDEB。
It is further illustrated the present invention below by example, but the present invention is not limited thereto.
In example, using the adsorption capacity of toluene Gas Phase Adsorption measuring molecular sieve, concrete operation method is：At 35 DEG C
Under, so that the nitrogen (toluene partial pressure is 0.5MPa) of carrying toluene is contacted with the molecular sieve of certain mass, until toluene reaches absorption
Balance.The adsorption capacity of poor quality that tested molecular sieve is calculated by following formula of front and back molecular sieve is adsorbed according to toluene.
Wherein, C is adsorption capacity, and unit is milligrams per gram；m1To be tested the quality of molecular sieve before absorption toluene, unit is
Gram；m2To be tested the quality of molecular sieve after absorption toluene, unit is gram.
Example 1
(1) Silicalite-1 synthetic systems are prepared
Under constant stirring, by 6.67 grams of Ludox, tetrapropylammonium hydroxide (R) water of 9.47 grams of a concentration of 25 mass %
Solution, 9.25 grams of deionized waters are added in the stainless steel cauldron with polytetrafluoroethyllining lining, are vigorously stirred and are synthesized
The molar ratio of the system of Silicalite-1, each material is：R/SiO2=0.35, H2O/SiO2=35, Na2O/SiO2=0.
(2) X/Silicalite-1 core shells molecular sieve
Take 4 grams of SiO2/Al2O3The NaX molecular sieves that molar ratio is 2.45, size of microcrystal are 0.8~1.2 micron, are added
(1) Silicalite-1 synthetic systems prepared by step, stir evenly, in synthetic system described in the NaX molecular sieves and (1) step of addition
Contained SiO2Mass ratio be 2：1.In confined conditions, in 120 DEG C of static crystallizations 48 hours, crystallization product is cooled to 25
DEG C, through filtering, solids is fully washed with deionized water, 100 DEG C of drying 10 hours, 540 DEG C of roastings 4 hours obtain Na types X/
Silicalite-1 core shell molecular sieve-4 As, XRD diagram are shown in that Fig. 1, SEM figures are shown in Fig. 2.As shown in Figure 1, gained X/Silicalite-1
Core shell molecular sieve includes X molecular sieve and Silicalite-1 molecular sieve crystalline phases simultaneously；Fig. 2 shows that X molecular sieve surface forms
Silicalite-1 molecular sieve shells, shell thickness are 80 nanometers.
(3) ion exchange
Cationic exchange is carried out to X/Silicalite-1 core shell molecular sieve-4 As using the barium nitrate solution of 0.18mol/L,
Cation is exchanged and is carried out in tank vessel, and exchange temperature is 90 DEG C, and the time is 8 hours, when the liquid volume space velocity of exchange is 6-1,
80 DEG C of dryings 8 hours, obtain BaX/Silicalite-1 core shells molecular sieve-4 A ', toluene adsorption capacity and absorption property are shown in Table
1。
Example 2
X/Silicalite-1 core shell molecular sieves are prepared by the method for example 1, the difference is that 6.93 grams of positive silicon of (1) step
Acetoacetic ester replace Ludox, it is manufactured synthesis Silicalite-1 systems each molar ratio of material be：R/SiO2=0.35, H2O/
SiO2=35, Na2O/SiO2=0.(2) in step, by 2 grams of SiO2/Al2O3The NaX molecular sieves that molar ratio is 2.92 are added
It in Silicalite-1 synthetic systems, stirs evenly, the NaX molecular sieves of addition and contained SiO in synthetic system described in (1) step2
Mass ratio be 1：1.In confined condition in 100 DEG C of dynamic crystallizations 72 hours, crystallization product is cooled to 25 DEG C, it, will through filtering
Solids is fully washed with deionized water, 80 DEG C of dryings 12 hours, and 520 DEG C roast 6 hours, obtain Na types X/Silicalite-1
Core shell molecular sieve B, Silicalite-1 shell thickness is 96 nanometers.
Ba ion exchanges are carried out to core shell molecular sieve B by the method for example 1 (3) step, obtain BaX/Silicalite-1
Core shell molecular sieve B ', toluene adsorption capacity and absorption property are shown in Table 1.
Example 3
X/Silicalite-1 core shell molecular sieves are prepared by the method for example 1, the difference is that in (2) step, by 10 grams
SiO2/Al2O3The NaX molecular sieves that molar ratio is 2.46 are added in Silicalite-1 synthetic systems, stir evenly, the NaX points
The size of microcrystal of son sieve is 0.4~0.8 micron, the NaX molecular sieves of addition and contained SiO in synthetic system described in (1) step2Matter
Amount is than being 5：1.In confined conditions in 120 DEG C of dynamic crystallizations 48 hours, crystallization product is cooled to 25 DEG C, through filtering, will be consolidated
Body object is fully washed with deionized water, 120 DEG C of dryings 6 hours, and 560 DEG C roast 2 hours, obtain Na type X/Silicalite-1 cores/
Shell molecular sieve C, XRD spectra and SEM photograph are shown in that Fig. 3 and Fig. 4, Silicalite-1 shell thicknesses are 58 nanometers respectively.
Ba ion exchanges are carried out to core shell molecular sieve C by the method for example 1 (3) step, obtain BaX/Silicalite-1
Core shell molecular sieve C ', toluene adsorption capacity and absorption property are shown in Table 1.
Example 4
X/Silicalite-1 core shell molecular sieves are prepared by the method for example 1, the difference is that in (2) step, by 5 grams of SiO2/
Al2O3The NaX molecular sieves that molar ratio is 2.78 are added in Silicalite-1 synthetic systems, stir evenly, the NaX molecular sieves
Size of microcrystal be 0.6~1.0 micron, the NaX molecular sieves of addition and contained SiO in synthetic system described in (1) step2Mass ratio
It is 2.5：1.In confined conditions in 160 DEG C of dynamic crystallizations 16 hours, crystallization product is cooled to 25 DEG C, through filtering, by solid
Object is fully washed with deionized water, 100 DEG C of dryings 10 hours, and 540 DEG C roast 4 hours, obtain Na type X/Silicalite-1 core shells
Molecular sieve D, Silicalite-1 shell thickness is 72 nanometers.
Ba ion exchanges are carried out to core shell molecular sieve D by the method for example 1 (3) step, obtain BaX/Silicalite-1
Core shell molecular sieve D ', toluene adsorption capacity and absorption property are shown in Table 1.
Example 5
Prepare X/Silicalite-1 core shell molecular sieves by the method for example 1, unlike (1) step by 10.07 grams of water glass
Glass (Na2O content is 6.16 mass %, SiO2Content be 19.86 mass %), 5.32 grams of 4-propyl bromides (R), 47.55 grams go
The sulfuric acid solution of ionized water and 2.72 grams of a concentration of 2mol/L are added in the stainless steel cauldron with polytetrafluoroethyllining lining, acutely
Silicalite-1 synthetic systems are stirred to get, each molar ratio of material is：R/SiO2=0.60, H2O/SiO2=100, Na2O/
SiO2=0.30.(2) in step, by 8 grams of SiO2/Al2O3Silicalite-1 synthesis is added in the NaX molecular sieves that molar ratio is 2.63
System stirs evenly, and the size of microcrystal of the NaX molecular sieves is 1.2~1.6 microns, NaX molecular sieves and (1) step institute of addition
State contained SiO in synthetic system2Mass ratio be 4：1.In confined conditions, in 140 DEG C of dynamic crystallizations 24 hours, crystallization is produced
Object is cooled to 25 DEG C, and through filtering, solids is fully washed with deionized water, 100 DEG C of drying 10 hours, and 540 DEG C to roast 4 small
When, it is 64 nanometers to obtain Na type X/Silicalite-1 core shell molecular sieve E, Silicalite-1 shell thicknesses.
Ba ion exchanges are carried out to core shell molecular sieve E by the method for example 1 (3) step, obtain BaX/Silicalite-1
Core shell molecular sieve E ', toluene adsorption capacity and absorption property are shown in Table 1.
Example 6
By example 1 method prepare X/Silicalite-1 core shell molecular sieves, unlike (1) step by 2 grams of white carbons,
Tetrapropylammonium hydroxide (R) aqueous solution and 0.03g sodium hydroxides addition band polytetrafluoroethylene (PTFE) of 8.12 grams of a concentration of 25 mass %
In the stainless steel cauldron of liner, it is vigorously stirred to obtain Silicalite-1 synthetic systems, each molar ratio of material is：R/SiO2=
0.30, H2O/SiO2=11, Na2O/SiO2=0.01.(2) in step, by 16 grams of SiO2/Al2O3The NaX molecules that molar ratio is 2.51
Silicalite-1 synthetic systems are added in sieve, stir evenly, and the size of microcrystal of the NaX molecular sieves is 1.8~2.2 microns, is added
The NaX molecular sieves entered and contained SiO in synthetic system described in (1) step2Mass ratio be 8：1.In confined conditions, in 150 DEG C
Crystallization product is cooled to 25 DEG C by dynamic crystallization 36 hours, and through filtering, solids is fully washed with deionized water, and 100 DEG C dry
Dry 10 hours, 540 DEG C roasted 4 hours, and it is thick to obtain Na type X/Silicalite-1 core shell molecular sieve F, Silicalite-1 shell
Degree is 42 nanometers.
Ba ion exchanges are carried out to core shell molecular sieve F by the method for example 1 (3) step, obtain BaX/Silicalite-1
Core shell molecular sieve F ', toluene adsorption capacity and absorption property are shown in Table 1.
Example 7
By example 1 method prepare X/Silicalite-1 core shell molecular sieves, unlike (1) step by 2 grams of silica gel,
1.11 grams of 4-propyl ammonium chlorides (R), 0.09g sodium hydroxides and 16.34 grams of deionized waters are added with polytetrafluoroethyllining lining not
It becomes rusty in steel reaction kettle, is vigorously stirred to obtain Silicalite-1 synthetic systems, each molar ratio of material is：R/SiO2=0.15, H2O/
SiO2=27, Na2O/SiO2=0.03.(2) in step, by 4 grams of SiO2/Al2O3The NaX molecular sieves that molar ratio is 2.34 are added
Silicalite-1 synthetic systems, stir evenly, and the size of microcrystal of the NaX molecular sieves is 2.2~2.6 microns, the NaX of addition
Molecular sieve and contained SiO in synthetic system described in (1) step2Mass ratio be 2：1.In confined conditions, in 150 DEG C of dynamic crystallizations
48 hours, crystallization product is cooled to 25 DEG C, through filtering, solids is fully washed with deionized water, 120 DEG C of dryings 6 hours,
550 DEG C roast 4 hours, obtain Na type X/Silicalite-1 core shell molecular sieve G, Silicalite-1 shell thicknesses and are received for 82
Rice.
Ba ion exchanges are carried out to core shell molecular sieve G by the method for example 1 (3) step, obtain BaX/Silicalite-1
Core shell molecular sieve G ', toluene adsorption capacity and absorption property are shown in Table 1.
Example 8
X/Silicalite-1 core shell molecular sieves are prepared by the method for example 1, the difference is that (1) step is molten by 6.67 grams of silicon
Band polytetrafluoros are added in glue, tetrapropylammonium hydroxide (R) aqueous solution of 9.47 grams of a concentration of 25 mass %, 19.26 grams of deionized waters
In the stainless steel cauldron of ethylene liner, it is vigorously stirred to obtain Silicalite-1 synthetic systems, each molar ratio of material is：R/
SiO2=0.35, H2O/SiO2=52, Na2O/SiO2=0.(2) in step, by 2 grams of SiO2/Al2O3NaX points that molar ratio is 2.18
Silicalite-1 synthetic systems are added in son sieve, stir evenly, and the size of microcrystal of the NaX molecular sieves is 2.4~3.0 microns,
The NaX molecular sieves of addition and contained SiO in synthetic system described in (1) step2Mass ratio be 1：1.In confined conditions, in 130
DEG C dynamic crystallization 36 hours, 25 DEG C are cooled to by crystallization product, through filtering, solids are fully washed with deionized water, 100 DEG C
10 hours dry, 540 DEG C roast 4 hours, obtain Na type X/Silicalite-1 core shell molecular sieve H, Silicalite-1 shells
Thickness is 96 nanometers.
Ba ion exchanges are carried out to core shell molecular sieve H by the method for example 1 (3) step, obtain BaX/Silicalite-1
Core shell molecular sieve H ', toluene adsorption capacity and absorption property are shown in Table 1.
Comparative example 1
Take SiO2/Al2O3The NaX molecular sieves that molar ratio is 2.45, carry out it using the barium nitrate solution of 0.18mol/L
Cation exchanges, and cation is exchanged and carried out in tank vessel, and exchange temperature is 90 DEG C, and the time is 8 hours, the liquid bulk of exchange
When product air speed is 6-1, BaX molecular sieves are obtained, toluene adsorption capacity and adsorption performance data are shown in Table 1.
Comparative example 2
Under constant stirring, by 6.67 grams of Ludox, tetrapropylammonium hydroxide (R) water of 9.47 grams of a concentration of 25 mass %
Solution, 9.25 grams of deionized waters are added in the stainless steel cauldron with polytetrafluoroethyllining lining, are vigorously stirred to obtain
Silicalite-1 synthetic systems, each molar ratio of material are：R/SiO2=0.35, H2O/SiO2=35, Na2O/SiO2=0.Close
Under the conditions of closing, in 120 DEG C of static crystallizations 48 hours, crystallization product is cooled to 25 DEG C, through filtering, by solids deionized water
Fully washing, 100 DEG C of drying 10 hours, 540 DEG C of roastings 4 hours obtain Silicalite-1 molecular sieve S, toluene adsorption capacity
It is shown in Table 1 with adsorption performance data.
Table 1
Claims (13)
1. a kind of X/Silicalite-1 core shells molecular sieve, including X molecular sieve kernel and it is coated on outside kernel
Silicalite-1 molecular sieve shells.
2. X/Silicalite-1 core shells molecular sieve described in accordance with the claim 1, it is characterised in that kernel X molecular sieve
SiO2/Al2O3Molar ratio is 2.0~3.0.
3. X/Silicalite-1 core shells molecular sieve described in accordance with the claim 1, it is characterised in that the crystalline substance of kernel X molecular sieve
Grain grain size is 0.2~5.0 micron.
4. X/Silicalite-1 core shells molecular sieve described in accordance with the claim 1, it is characterised in that the sun of kernel X molecular sieve
Ion is selected from Na+、K+、Li+、Cs+、Ca2+、Sr2+And Ba2+At least one of.
5. X/Silicalite-1 core shells molecular sieve described in accordance with the claim 1, it is characterised in that Silicalite-1 molecules
The thickness of screen shell layer is 30~1000 nanometers.
6. the preparation method of X/Silicalite-1 core shells molecular sieve, includes the following steps described in a kind of claim 1：
(1) silicon source, template (R), water and optional inorganic base are uniformly mixed and obtain the Silicalite-1 compound bodies of alkalinity
System, the amount of silicon source is with SiO2Meter, the amount of inorganic base is with M2O is counted, and the molar ratio of each material is R/SiO in the synthetic system2=
0.05~0.70, H2O/SiO2=10~150, M2O/SiO2=0~0.05, M are Na or K,
(2) NaX molecular sieves are added into the synthetic system obtained by (1) step to be uniformly mixed, the NaX molecular sieves and synthetic system of addition
In contained SiO2Mass ratio be 0.2~20：1,
(3) mixture obtained by (2) step is subjected to hydrothermal crystallizing processing in 80~160 DEG C, obtained solid product is dry, roasting.
7. according to the method for claim 6, it is characterised in that (1) silicon source described in step is selected from ethyl orthosilicate, Ludox, water
At least one of glass, sodium metasilicate, silica gel and white carbon.
8. according to the method for claim 6, it is characterised in that (1) template described in step (R) be selected from ethamine, n-butylamine, oneself
At least one of diamines, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, 4-propyl bromide and 4-propyl ammonium chloride.
9. according to the method for claim 6, it is characterised in that (1) inorganic base described in step is selected from NaOH or KOH.
10. according to the method for claim 6, it is characterised in that (1) molar ratio of each material is in synthetic system described in step：
R/SiO2=0.1~0.6, H2O/SiO2=10~100, M2O/SiO2=0~0.03, M are Na or K.
11. according to the method for claim 6, it is characterised in that (2) in mixture described in step the addition of NaX molecular sieves with
Contained SiO in synthetic system2Mass ratio be 0.5~10：1.
12. according to the method for claim 6, it is characterised in that (3) step carry out hydrothermal crystallizing processing temperature be 100~
160℃。
13. according to the method for claim 6, it is characterised in that (3) time that step carries out hydrothermal crystallizing is 8~140 hours.
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