CN105668579B - A kind of method with Ludox as the mesoporous molecular sieves of Silicalite 1 of silicon source Fast back-projection algorithm - Google Patents
A kind of method with Ludox as the mesoporous molecular sieves of Silicalite 1 of silicon source Fast back-projection algorithm Download PDFInfo
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- 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
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Abstract
The present invention relates to the preparation field of zeolite molecular sieve Silicalite 1, specifically a kind of method with Ludox as the mesoporous molecular sieves of Silicalite 1 of silicon source Fast back-projection algorithm.The present invention is that, with a small amount of 4-propyl bromide as micropore template agent, cheap KF is mesoporous template, adds micro crystal seed, using Ludox as silicon source, with deionized water as solvent, heated through in reactor, crystallization, it is made crystallization solution, through centrifugation, washing, dry, calcining, the molecular sieves of mesoporous Silicalite 1 are made, this preparation method selects raw material economy, reaction time is short, and informative data is accurate.
Description
Technical field
It is specifically a kind of fast by silicon source of Ludox the present invention relates to the preparation field of zeolite molecular sieve Silicalite-1
The method of the synthesising mesoporous Silicalite-1 molecular sieves of speed.
Background technology
In the zeolite molecular sieve material of numerous researchs, with mesoporous material because it improves mass transfer and increases active sites
The characteristics of point, enjoys the concern of various fields expert.Silicalite-1 is the pure silicon form of ZSM-5 molecular sieve, and it has high
Silica alumina ratio and 0.46-0.54nm micropore.Mesoporous Silicalite-1 molecular sieves have hydrophobicity and micropore, mesoporous two
Aperture is planted, and with the application potential of specific catalytic field.
Thank within 2008 and reported with Nano-meter CaCO3 in storehouse et al.3As mesoporous template, TPAOH (TPAOH)
For micropore template agent synthesizes mesoporous Silicalite-1, wherein TPAOH/SiO2=0.4, price TPAOH consumptions higher compared with
Greatly, and generated time be up to 7 days.Anil Kumar Sinha in 2014 et al. are using organosilan as mesoporous template, TPAOH
For micropore template agent has synthesized mesoporous Silicalite-1, wherein TPAOH/SiO2=0.5, micropore template agent large usage quantity is situated between
Hole template organosilan is expensive, and the reaction time is up to 5 days.The old victory group that connects of Shanghai Communications University utilizes Ke Ken within 2015
Da Er effects have synthesized mesoporous Silicalite-1.Specifically, the mixed solution of Ludox and TPAOH is continuous at 70 DEG C
Stirring evaporates moisture therein, until being gel, is then instilled in the polytetrafluoroethylcontainer container for fill gel minimal amount of
Water, in sealing to stainless steel cauldron, reacts at 130 DEG C.Although not using mesoporous template and generated time being shorter, close
Into being stirred continuously at 70 DEG C up to being gel, the degree of moisture evaporation is difficult to hold, and is reacted to sealing at 130 DEG C of later stage
It is required that strict, synthesis difficulty is larger, it is difficult to realize that high-volume synthesizes.
The content of the invention
The present invention is intended to provide a kind of obtain mesoporous Silicalite-1 points using economical raw material and quick method
Son sieve.
According to Zeolite synthesis classical theory, the synthesis of molecular sieve is divided into nucleation and grows two processes of crystalline substance, cold stage, instead
Answer thing that a large amount of mass transfers do not occur, carry out nucleation process, hot stage, reactant occurs violent mass transfer, on the basis of core, carries out
The growth of crystal.Ready crystal seed in advance is added in building-up process, as nucleus, makes building-up process skip nucleation stage, directly
Tap into crystal growing process, to shorten generated time.Obtained in the document acted on crystal seed by multiple, crystal seed has promotion anti-
The guide effect for answering thing to be generated toward target product, according to this point, it is possible to reduce or even go the use of template agent removing.Majority addition
Explained in the ZSM-5 synthesis documents of F ion, F ion has dissolving silicon, suppresses the ability that molecular sieve is formed.Although due to not having
There is a coordination of aluminium, the synthesis difficulty of Silicalite-1 is big, and the reaction time is more long, but crystal seed can be introduced and shorten synthesis
Time.The guide effect of crystal seed whether can be utilized, the use of template agent removing is gone, synthesis Silicalite-1 utilizes F ion
Dissolving silicon effect, produce it is mesoporous.A series of checking has been carried out for above idea inventor, crystal seed has been firstly added, fruit
The generated time of right Silicalite-1 greatly shortens, and then in the case where crystal seed is added, goes the use of template agent removing, sends out
The effect of the Silicalite-1 Template-free methods of the now coordination without aluminium, it is impossible to synthesize.Inventor adds on the basis of crystal seed is added
A small amount of template is added, has successfully grown Silicalite-1 molecular sieves, on this basis, inventor with the addition of few in the feed
Amount KF, successfully synthesizes mesoporous Silicalite-1 molecular sieves.
The present invention is achieved by the following technical solutions：It is a kind of mesoporous as silicon source Fast back-projection algorithm with Ludox
The method of Silicalite-1 molecular sieves, its step is：
(1) preparation of crystal seed
It is 4.4 by mol ratio:0.1:25:756:100 TPAOH, sodium oxide molybdena, tetraethyl orthosilicate, deionization
Water and ethanol mix stirring 24h, and then the thermostatic crystallization reaction 72h at a temperature of 100 DEG C in the sealing container, then natural
Room temperature is cooled to, SiO is formed2/Al2O3It is 2241 crystal seed S-1, any later stage treatment is not done, it is stand-by；
(2) preparation of mesoporous Silicalite-1 molecular sieves
It is 1 by mol ratio:0.1:0.1:0.3:0.15:50 Ludox, ethamine, 4-propyl bromide, potassium fluoride, oxidation
Sodium and deionized water mix, then SiO in being incorporated as Ludox in mixed liquor2The crystal seed S-1 of quality 10%, stirring ageing 3h,
Then the thermostatic crystallization reaction 24h at a temperature of 180 DEG C in the sealing container, then naturally cools to room temperature, is centrifuged, and outwells
Clear liquid, leaves bottom product, is subsequently adding deionized water washing, centrifugation and is repeated three times, then in 85 DEG C of temperature
Under dry 12h, finally calcine 5h at 550 DEG C of air atmosphere again, that is, obtain mesoporous Silicalite-1 molecular sieves, this is mesoporous
Silica alumina ratio in Silicalite-1 molecular sieves is 1877.
Do not occur silicon source in the above step (1), but synthesize SiO2/Al2O3It is 2241 crystal seed S-1, reason is
The tetraethyl orthosilicate chemical raw material impure thing for being added, it contains micro Al2O3.The tetraethyl orthosilicate of in the market purchase
Learn raw material and contain micro Al2O3, this is the common knowledge of this area.During present invention specific implementation, the positive silicic acid second for being used
Ester chemical raw material is purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
The pattern of the mesoporous Silicalite-1 molecular sieves prepared to the present invention, color and luster, composition, Chemical Physics performance are carried out
Detection, analysis, sign, conclusion：The mesoporous Silicalite-1 molecular sieves are white powder, and crystal morphology glomeration is (referring to figure
4)。
Further, the present invention is calculated the surface area and pore volume of mesoporous Silicalite-1 molecular sieves, its
Detailed data is shown in Table 1.
Table 1
S in tableL:Lang Gemiaoer surface areas；SBET:Specific surface area；SEXT:External surface area；Vmicro:Micro pore volume；Vmeso:It is situated between
Pore volume.
In addition, inventor is studied whether crystal seed, ethamine play a role wherein, according to each parameter in table 2
Synthesized respectively, composite result is shown in Fig. 8.Wherein No. 1 product SiO2/Al2O3It is 1877, No. 2 product SiO2/Al2O3It is 673,3
Number product SiO2/Al2O3It is 1648, the crystal seed S-1 (SiO of high silica alumina ratio2/Al2O3For 2241) guiding reactant generates sial high
The product of ratio, without No. 2 samples that S-1 is added, its silica alumina ratio is greatly reduced.
Table 2
Further, inventor is studied the addition of TPABr, and according to table, 3 each parameters are synthesized respectively, is closed
See Fig. 9 into result.
Table 3
Further, inventor is also studied the addition of KF, is synthesized respectively according to each parameter of table 4, synthesis
Result is shown in Figure 10.
Table 4
The present invention compared with prior art, has the advantages that：It with a small amount of 4-propyl bromide is micropore mould to be
Plate agent, cheap KF is mesoporous template, micro crystal seed is added, using Ludox as silicon source, with deionized water as molten
Agent, heats through in reactor, and crystallization is made crystallization solution, through centrifugation, washing, dry, calcining, is made mesoporous
Silicalite-1 molecular sieves, this preparation method selects raw material economy, and the reaction time is short, and informative data is accurate.
Brief description of the drawings
Fig. 1 is the XRD spectrum (as that X-ray diffraction instrument carries out crystal material phase analysis to the crystal seed S-1 prepared by the present invention
Synthesized) with XRD spectrum (simulated) contrast schematic diagram of silicalite molecular sieves in existing document material.Figure
The main peak position of middle both XRD diffraction maximums of display can be to upper, and the material that this explanation present invention is prepared is crystal seed
S-1。
Fig. 2 schemes for the SEM of crystal seed S-1.Show that S-1 is the spherical of diameter of up to 300nm in figure.
Fig. 3 carries out crystal thing phase point to the mesoporous Silicalite-1 molecular sieves prepared by the present invention for X-ray diffraction instrument
The XRD spectrum of silicalite molecular sieves in the XRD spectrum (as synthesized) and existing document material of analysis
(simulated) contrast schematic diagram.The peak position of both XRD diffraction maximums of display can be to upper, this explanation present invention in figure
The material for preparing is Silicalite-1 molecular sieves.
Fig. 4 is the SEM figures of mesoporous Silicalite-1 molecular sieves.Show that mesoporous Silicalite-1 molecular sieves are straight in figure
Footpath is spherical up to 500nm's.
Fig. 5 is the TGA schematic diagrames of the prepared mesoporous Silicalite-1 molecular sieves for obtaining of the present invention.
Fig. 6 is that the N2 adsorption of the prepared mesoporous Silicalite-1 molecular sieves for obtaining of the present invention characterizes schematic diagram.In figure
It has been shown that, there is obvious H2 types hysteresis loop, illustrates that the material has mesoporous pore size.
Fig. 7 is the pore-size distribution schematic diagram of the prepared mesoporous Silicalite-1 molecular sieves for obtaining of the present invention.Show in figure
Show, mesoporous Silicalite-1 molecular sieves have the micropore of 0.48~0.55nm, 3.5~4.3nm's is mesoporous.
Fig. 8 is the XRD spectrum comparison diagram for adding with not adding ethamine, the crystalline material of crystal seed synthesis.In figure 1 with table 2 in
The correspondence of sequence number 1, other are similarly.It shows：The crystallinity for not having the addition of ethamine, product is substantially reduced.
Fig. 9 is the XRD spectrum comparison diagram of the molecular sieve of different 4-propyl bromide addition synthesis.In figure 1 with table 3 in
The correspondence of sequence number 1, other are similarly.It shows：The 4-propyl bromide addition of 0.2mmol is very few, is not enough to assist crystal seed to produce
Silicalite-1 molecular sieves.
Figure 10 is the XRD spectrum comparison diagram of the molecular sieve of different potassium fluoride addition synthesis.In figure 1 with table 4 in sequence number 1
Correspondence, other are similarly.It shows：When potassium fluoride addition is more than 12mmol, potassium fluoride shows the suppression to molecular sieve growth
Make and use, do not grow molecular sieve.
Figure 11 to Figure 16 is that the N2 adsorption of the molecular sieve of different potassium fluoride addition synthesis characterizes schematic diagram.11 and table in figure
The correspondence of sequence number 1 in 4, other are sequentially corresponded to, but Figure 16 is corresponding with sequence number 7.Its display, it is not enough when KF additions are less than 6mmol
It is a large amount of mesoporous to produce；KF additions are more than 6mmol, during less than 12mmol, although generate molecular sieve, but KF to molecular sieve
Dissolving is too serious, mesoporous without producing；When KF additions are more than 12mmol, KF has been embodied and has been suppressed the work that molecular sieve is formed
With not forming molecular sieve and mesoporous；The addition of 6mmolKF is optimum addition, is generated optimal mesoporous.
Specific embodiment
In order to be explained in detail to the present invention, come to synthetic method of the present invention with reference to specific experiment process
Illustrate.
Chemical substance material：TPAOH (25% aqueous solution), deionized water, NaOH, positive silicic acid tetrem
Ester, 4-propyl bromide, potassium fluoride, ethamine (70% aqueous solution), Ludox (30% aqueous solution), its combination prepare consumption such as
Under：It is measurement unit with gram, milliliter
The preparation of crystal seed
The preparation of mesoporous Silicalite-1 molecular sieves
Embodiment
One kind is mesoporous using potassium fluoride, crystal seed and a small amount of template Fast back-projection algorithm with Ludox as silicon source
The method of Silicalite-1 molecular sieves, its step is：
(1) Hydrothermal Synthesiss crystal seed S-1
The synthesis of crystal seed S-1 is carried out in closed reactor, is completed in heating, standing crystallization process：
1. mixed reaction solution is prepared
TPAOH (25% aqueous solution) 17.89g, NaOH 0.04g are weighed, tetraethyl orthosilicate is instilled
28.85mL, deionized water 59.2mL；In 200mL beakers, 24h is stirred vigorously under normal temperature, into mixed reaction solution.
2. mixed reaction solution is transferred in polytetrafluoroethylcontainer container (200mL), is placed in stainless steel cauldron, and close
Close；Then reactor is placed in heating furnace, and it is closed.
3. heating furnace is opened, 100 DEG C of heating-up temperature, heat time 72h, mixed reaction solution carries out crystallization.
4. after crystallization, heating is stopped, crystallization solution is cooled to 25 DEG C with heating furnace.
5. obtaining crystal seed need not do any subsequent treatment, be stored in transparent glass container, closed preservation.
(2) the mesoporous Silicalite-1 molecular sieves of Hydrothermal Synthesiss
The synthesis of mesoporous Silicalite-1 molecular sieves is carried out in closed reactor, is in heating, is stood crystalline substance
Completed during change：
1. mixed reaction solution is prepared
Weigh NaOH 0.24g, 4-propyl bromide 0.53g, potassium fluoride 0.35g, Ludox 4g, crystal seed S-1
0.12g, instills ethamine (70% aqueous solution) 0.17mL, deionized water 15.11mL, is added in 50mL beakers, under normal temperature acutely
Stirring 3h, into mixed reaction solution.
2. mixed reaction solution is transferred in polytetrafluoroethylcontainer container (28mL), is placed in stainless steel cauldron, and close
Close；Then reactor is placed in heating furnace, and it is closed.
3. heating furnace is opened, 180 DEG C of heating-up temperature, heat time 24h, mixed reaction solution carries out crystallization.
4. after crystallization, heating is stopped, crystallization solution is cooled to 25 DEG C with heating furnace
(3) it is centrifuged
Crystallization solution after crystallization is placed in centrifuge tube, is put into centrifuge, rotating speed 9000r/min, when
Between 10min, product outwells upper strata waste liquid in centrifuge tube bottom sediment.
(4) wash, be centrifuged
Product is placed in beaker, deionized water 50mL, agitator treating 5min is added.
Cleaning solution is placed in centrifuge tube, is put into centrifuge, rotating speed 9000r/min, time 10min, product is in centrifugation
Pipe bottom sediment, outwells upper strata waste liquid.
Washing, suction filtration are carried out 3 times.
(5) it is vacuum dried
Product after washing is placed in quartz container, is subsequently placed in drying box and is dried, 85 DEG C of drying temperature is done
Dry time 12h.
(6) dried product is contained in crucible, and crucible is put into Muffle furnace, and 5h is calcined at 550 DEG C of air atmosphere, is risen
5 DEG C/min of warm speed, after calcining terminates, stops heating, and product is cooled to 25 DEG C, that is, obtains mesoporous with Muffle furnace
Silicalite-1 molecular sieves.
(7) product storage
Mesoporous Silicalite-1 molecular sieves to preparing are stored in transparent glass container, closed preservation.
Claims (1)
1. a kind of method with Ludox as the mesoporous Silicalite-1 molecular sieves of silicon source Fast back-projection algorithm, it is characterised in that its step
Suddenly it is：
（1）The preparation of crystal seed
It is 4.4 by mol ratio:0.1:25:756:100 TPAOH, sodium oxide molybdena, tetraethyl orthosilicate, deionized water with
And ethanol mixes stirring 24h, then thermostatic crystallization reaction 72h, subsequent natural cooling at a temperature of 100 DEG C in the sealing container
To room temperature, SiO is formed2/Al2O3It is 2241 crystal seed S-1, any later stage treatment is not done, it is stand-by；
（2）The preparation of mesoporous Silicalite-1 molecular sieves
It is 1 by mol ratio:0.1:0.1:0.3:0.15:50 Ludox, ethamine, 4-propyl bromide, potassium fluoride, sodium oxide molybdena and
Deionized water mixes, then SiO in being incorporated as Ludox in mixed liquor2The crystal seed S-1 of quality 10%, stirring ageing 3h, Ran Hou
Thermostatic crystallization reaction 24h at a temperature of 180 DEG C, then naturally cools to room temperature in sealing container, is centrifuged, and outwells supernatant,
Bottom product is left, deionized water washing, centrifugation is subsequently adding and is repeated three times, then dried at a temperature of 85 DEG C
12h, finally calcines 5h at 550 DEG C of air atmosphere again, that is, obtain mesoporous Silicalite-1 molecular sieves, and this is mesoporous
Silica alumina ratio in Silicalite-1 molecular sieves is 1877.
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