CN105645425B - A kind of method using white carbon as the mesoporous molecular sieves of Silicalite 1 of silicon source Fast back-projection algorithm - Google Patents
A kind of method using white carbon as the mesoporous molecular sieves of Silicalite 1 of silicon source Fast back-projection algorithm Download PDFInfo
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- CN105645425B CN105645425B CN201610130032.2A CN201610130032A CN105645425B CN 105645425 B CN105645425 B CN 105645425B CN 201610130032 A CN201610130032 A CN 201610130032A CN 105645425 B CN105645425 B CN 105645425B
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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 zeolite molecular sieve Silicalite 1 preparation field, specifically a kind of method using white carbon as the mesoporous molecular sieves of Silicalite 1 of silicon source Fast back-projection algorithm.The present invention is using a small amount of 4-propyl bromide as micropore template agent, and cheap KF is mesoporous template, adds micro crystal seed, silicon source is used as using white carbon, using deionized water as solvent, through being heated in reactor, crystallization, crystallization solution is made, through centrifuging, washing, drying, calcining, the mesoporous molecular sieves of Silicalite 1 are made, this preparation method selects raw material economy, reaction time is short, and informative data is accurate.
Description
Technical field
The present invention relates to zeolite molecular sieve Silicalite-1 preparation field, is specifically a kind of fast by silicon source of white carbon
The method of the synthesising mesoporous Silicalite-1 molecular sieves of speed.
Background technology
In the zeolite molecular sieve material of numerous researchs, there is mesoporous material to improve mass transfer and increase active sites because of it
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
Kind aperture, and the application potential with specific catalytic field.
Thank within 2008 and reported in storehouse et al. with Nano-meter CaCO33As mesoporous template, TPAOH (TPAOH)
Synthesize mesoporous Silicalite-1, wherein TPAOH/SiO for micropore template agent2=0.4, the higher TPAOH dosages of price compared with
Greatly, and generated time is up to 7 days.Anil Kumar Sinha in 2014 et al. are used as mesoporous template, TPAOH using organosilan
Mesoporous Silicalite-1, wherein TPAOH/SiO have been synthesized for micropore template agent2=0.5, micropore template agent dosage is larger, 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 in 2015 utilizes Ke Ken
Da Er effects have synthesized mesoporous Silicalite-1.Specifically, by Ludox and TPAOH mixed solution at 70 DEG C constantly
Stirring evaporates moisture therein, until being gel, is then instilled in the polytetrafluoroethylcontainer container for fill gel minimal amount of
Water, seal to stainless steel cauldron, reacted 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 at 130 DEG C of later stage to sealing
It is required that strict, synthesis difficulty is larger, it is difficult to realizes 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 the raw material and quick method of economy
Son sieve.
According to Zeolite synthesis classical theory, the synthesis of molecular sieve is divided into nucleation and grows brilliant two processes, cold stage, instead
Answer thing that a large amount of mass transfers do not occur, carry out nucleation process, hot stage, violent mass transfer occurs for reactant, 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.By being obtained in multiple documents on crystal seed effect, 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 the coordination of aluminium, Silicalite-1 synthesis difficulty is big, and the reaction time is longer, but can introduce crystal seed, to shorten synthesis
Time.The guide effect of crystal seed whether can be utilized, goes the use of template agent removing, 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, has been firstly added crystal seed, fruit
Right Silicalite-1 generated time greatly shortens, and then in the case where adding crystal seed, goes the use of template agent removing, sends out
The effect of the Silicalite-1 Template-free methods of the now coordination without aluminium, can not be synthesized.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
KF is measured, 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 using white carbon
The method of Silicalite-1 molecular sieves, its step are：
(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 thermostatic crystallization reacts 72h at a temperature of 100 DEG C in sealing container, then natural
Room temperature is cooled to, forms SiO2/Al2O3For 2241 crystal seed S-1, any post-processing 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 white carbon, ethamine, 4-propyl bromide, potassium fluoride, oxidation
Sodium and deionized water mixing, then SiO in white carbon is incorporated as in mixed liquor2The crystal seed S-1 of quality 10%, stirring ageing 3h,
Then thermostatic crystallization reacts 24h at a temperature of 180 DEG C in sealing container, then naturally cools to room temperature, is centrifuged, is outwelled
Clear liquid, bottom reaction product is left, the then washing of addition deionized water, centrifugation is repeated three times, then in 85 DEG C of temperature
Lower dry 12h, 5h finally is calcined at 550 DEG C of air atmosphere again, that is, obtains mesoporous Silicalite-1 molecular sieves, this is mesoporous
Silica alumina ratio in Silicalite-1 molecular sieves is 4424.
Do not occur silicon source in the above step (1), but synthesize SiO2/Al2O3For 2241 crystal seed S-1, reason is
The impure thing of tetraethyl orthosilicate chemical raw material 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.The present invention is when it is implemented, used positive silicic acid second
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
Test, analysis and characterization, conclusion：The mesoporous Silicalite-1 molecular sieves are white powder, and crystal morphology glomeration is (referring to figure
4)。
Further, the present invention has carried out research meter to the surface area and pore volume of mesoporous Silicalite-1 molecular sieves
Calculate, 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.
Other inventor is studied KF addition, is synthesized respectively according to 2 each parameter of table, composite result is shown in
Fig. 8.
Table 2
The present invention compared with prior art, has the advantages that：It is using a small amount of 4-propyl bromide as micropore mould
Plate agent, cheap KF are mesoporous template, micro crystal seed are added, using white carbon as silicon source, using deionized water to be molten
Agent, through being heated in reactor, crystallization, crystallization solution is made, through centrifuging, washing, drying, calcining, is made mesoporous
Silicalite-1 molecular sieves, this preparation method select 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 existing literature material in silicalite molecular sieves XRD spectrum (simulated) contrast schematic diagram.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 prepares is crystal seed
S-1。
The SEM that Fig. 2 is crystal seed S-1 schemes.It is that diameter reaches the spherical of 300nm that S-1 is shown in figure.
Fig. 3 is that X-ray diffraction instrument carries out crystal thing phase point to the mesoporous Silicalite-1 molecular sieves prepared by the present invention
The XRD spectrum (as synthesized) of analysis and the XRD spectrum of silicalite molecular sieves in existing literature material
(simulated) contrast schematic diagram.The peak position of both XRD diffraction maximums of display can be to upper in figure, this explanation present invention
The material prepared is Silicalite-1 molecular sieves.
Fig. 4 is that the SEM of mesoporous Silicalite-1 molecular sieves schemes.Show that mesoporous Silicalite-1 molecular sieves are straight in figure
Footpath is cross up to 1um's.
Fig. 5 is the TGA schematic diagrames of the prepared mesoporous Silicalite-1 molecular sieves obtained of the present invention.
Fig. 6 is that the N2 adsorption of the prepared mesoporous Silicalite-1 molecular sieves obtained of the present invention characterizes schematic diagram.In figure
It has been shown that, has obvious hysteresis loop, illustrates that the material has mesoporous pore size, 0.2~0.5 section has H4 type hysteresis loops, and 05~1.0 section has H2 types
Hysteresis loop.
Fig. 7 is the pore-size distribution schematic diagram of the prepared mesoporous Silicalite-1 molecular sieves obtained of the present invention, is shown in figure
Show, mesoporous Silicalite-1 molecular sieves have 0.48~0.55nm micropore, and 3.0~4.3nm's is mesoporous.
Fig. 8 is the XRD spectrum comparison diagram of the molecular sieve of different potassium fluoride additions synthesis.Sequence number in figure in 1 corresponding table 2
1, other are similarly.Show in figure：When potassium fluoride addition is 12mmol, potassium fluoride shows the suppression to molecular sieve growth and made
With not growing molecular sieve.
Fig. 9 to Figure 13 is that the N2 adsorption of the molecular sieve of different potassium fluoride additions synthesis characterizes schematic diagram.Fig. 9 corresponding tables 2
In sequence number 1, other are sequentially corresponded to.It shows, when KF additions are less than 6mmol, it is a large amount of mesoporous to be not enough to generation；KF additions
More than 6mmol, although generating molecular sieve, dissolvings of the KF to molecular sieve is too serious, does not produce a large amount of mesoporous；6mmolKF
Addition be optimum addition, generate optimal mesoporous.
Embodiment
In order to which the present invention is explained in detail, come with reference to specific experiment process to synthetic method of the present invention
Illustrate.
Chemical substance material：TPAOH (25% aqueous solution), deionized water, sodium hydroxide, positive silicic acid tetrem
Ester, 4-propyl bromide, potassium fluoride, ethamine (70% aqueous solution), white carbon, it is as follows that it combines preparation dosage：It is with gram, milliliter
Measurement unit.
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 using white carbon as silicon source
The method of Silicalite-1 molecular sieves, its step are：
(1) Hydrothermal Synthesiss crystal seed S-1
Crystal seed S-1 synthesis is carried out in closed reactor, is completed in heating, standing crystallization process
1. prepare mixed reaction solution
TPAOH (25% aqueous solution) 17.89g, sodium hydroxide 0.04g are weighed, instills tetraethyl orthosilicate
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), it is placed in stainless steel cauldron, and it is close
Close；Then reactor is placed in heating furnace, and it is closed；
3. opening heating furnace, 100 DEG C, heat time 72h of heating-up temperature, mixed reaction solution carries out crystallization.It is 4. brilliant
After changing reaction, stop heating, crystallization solution is cooled to 25 DEG C with heating furnace
5. any subsequent treatment need not be done by obtaining crystal seed, it is 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. prepare mixed reaction solution
Weigh sodium hydroxide 0.24g, 4-propyl bromide 0.53g, potassium fluoride 0.35g, white carbon 1.2g, crystal seed S-1
0.12g, ethamine (70% aqueous solution) 0.17mL, deionized water 17.91mL are instilled, is added in 50mL beakers, under normal temperature acutely
3h is stirred, into mixed reaction solution；
2. mixed reaction solution is transferred in polytetrafluoroethylcontainer container (28mL), it is placed in stainless steel cauldron, and it is close
Close；Then reactor is placed in heating furnace, and it is closed；
3. opening heating furnace, 180 DEG C, heat time 24h of heating-up temperature, mixed reaction solution carries out crystallization.It is 4. brilliant
After changing reaction, stop heating, crystallization solution is cooled to 25 DEG C with heating furnace
(3) centrifuge
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, centrifuge
Product is placed in beaker, adds deionized water 50mL, agitator treating 5min；
Cleaning solution is placed in centrifuge tube, is put into centrifuge, rotating speed 9000r/min, time 10min, product are centrifuging
Pipe bottom sediment, outwell upper strata waste liquid.
Washing, filter progress 3 times.
(5) it is dried in vacuo
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
Warm 5 DEG C/min of speed, after calcining terminates, stop heating, product is cooled to 25 DEG C with Muffle furnace, that is, obtained mesoporous
Silicalite-1 molecular sieves.
(7) product storage
The mesoporous Silicalite-1 molecular sieves of preparation are stored in transparent glass container, closed preservation.
Claims (1)
- A kind of 1. method using white carbon as the mesoporous Silicalite-1 molecular sieves of silicon source Fast back-projection algorithm, it is characterised in that it is walked Suddenly it is：（1）The preparation of crystal seedIt 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 reacts 72h, subsequent natural cooling at a temperature of 100 DEG C in sealing container To room temperature, SiO is formed2/Al2O3For 2241 crystal seed S-1, any post-processing is not done, it is stand-by；（2）The preparation of mesoporous Silicalite-1 molecular sievesIt is 1 by mol ratio:0.1:0.1:0.3:0.15:50 white carbon, ethamine, 4-propyl bromide, potassium fluoride, sodium oxide molybdena and Deionized water is mixed, then SiO in white carbon is incorporated as in mixed liquor2The crystal seed S-1 of quality 10%, stirring ageing 3h, Ran Hou Thermostatic crystallization reacts 24h at a temperature of 180 DEG C in sealing container, then naturally cools to room temperature, is centrifuged, outwells supernatant, Bottom reaction product is left, the then washing of addition deionized water, centrifugation is repeated three times, is then dried at a temperature of 85 DEG C 12h, 5h finally is calcined at 550 DEG C of air atmosphere again, that is, obtains mesoporous Silicalite-1 molecular sieves, this is mesoporous Silica alumina ratio in Silicalite-1 molecular sieves is 4424.
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