CN104556116B - A kind of method of aerosol auxiliary synthesis TS-1 molecular sieve - Google Patents
A kind of method of aerosol auxiliary synthesis TS-1 molecular sieve Download PDFInfo
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Abstract
The method that the present invention relates to a kind of aerosol auxiliary synthesis TS 1 molecular sieve.TS 1 molecular sieve mainly passes through water heat transfer at present, but it is big to there is template consumption in the method, reactor utilization rate is low, production cost is high, the problems such as building-up process is complicated, for solving above-mentioned technical problem, the present invention provides a kind of and obtains molecular sieve precursor by aerosol householder method, uses the method that TPAOH makees template crystallization synthesis TS 1 molecular sieve.By the present invention, can prepare titanium atom and be evenly distributed, high-crystallinity and silicon titanium are than controlled little crystal grain TS 1 molecular sieve.The present invention is simple to operate, template consumption is low, pollute little, productivity and one-pot utilization rate is high, has good prospects for commercial application.
Description
Technical field
The invention belongs to the preparation method of molecular sieve, particularly to the side of a kind of aerosol auxiliary synthesis TS-1 molecular sieve
Method.
Background technology
Ti-Si zeolite molecular sieve (TS-1 molecular sieve), as a kind of novel effective catalyst, has been widely used in urging
Change reaction.Compared with other type of catalyst system and catalyzing, with TS-1 molecular sieve as catalyst, H2O2Low temperature for oxidant composition is urged
Changing oxidation system and have atom utilization height, principal product selectivity and yield height, environmentally safe, reaction condition is gentle, work
The advantages such as skill process is simple, safety.TS-1 molecular sieve is mainly by water heat transfer at present, but the method exists two mainly
Problem: 1. template consumption is big, and reactor utilization rate is low, production cost is high.Up to the present, TPAOH is still recognized
For being the optimal Template agent of synthesis TS-1 molecular sieve, in traditional Hydrothermal Synthesis, a large amount of use of TPAOH is led
The production cost causing TS-1 molecular sieve is higher, and reactor utilization rate is low, and as a example by the reactor of 1L, traditional Hydrothermal Synthesis about can
Synthesis 57.7g TS-1 zeolite product.How in the case of low TPAOH consumption, to produce TS-1 zeolite product
Become problem demanding prompt solution.2. building-up process is complicated.Owing to titanium source the most easily forms TiO2Precipitation, makes titanium former
Son hardly enters TS-1 framework of molecular sieve.Numerous researchers proposes corresponding solution, as being slowly added dropwise four at zero degree
Propyl group ammonium hydroxide, hydrolyzes titanium esters in the atmosphere without carbon dioxide, dissolves titanium esters etc. in isopropanol.But these methods make synthesis
Process is complicated, and the most still can not avoid TiO completely2The generation of precipitation.Therefore, seek more excellent synthetic route and become domestic and international
The study hotspot of researcher.
Aerosol processing is the most emerging Zeolite synthesis method, is widely used in Zeolite synthesis field.With
Conventional hydrothermal synthetic method is compared, because aerosol processing has some distinctive advantages, as high in yield, can the most quickly production etc. and
Paid close attention to by numerous researchers.But current aerosol method is mainly used in raw material and template are mixed to form aerosol
Synthesising mesoporous, large pore molecular sieve or the shaping aspect for molecular sieve.And the method is directly used in zeolite ts-1-1 molecular sieve
Building-up process is not reported so far.
Summary of the invention
For solving above-mentioned technical problem, the method that the invention provides a kind of aerosol auxiliary synthesis TS-1 molecular sieve.Tool
Body step is as follows:
A. by silicon source, titanium source, water, acidity regulator mixing, stir formation mixed liquor, is formed by aerosol device
Aerosol, drying obtains unformed amorphous ti silica.
B. above-mentioned amorphous ti silica is mixed with TPAOH solution, seals, at 90 ~ 190 DEG C, carry out crystallization,
Crystallization time is 3 hours ~ 10 days, is dried scrubbed for gained solid product or carry out roasting after convection drying, obtaining TS-1 and divide
Son sieve.
SiO in step A mixture system2: TiO2: H2O: H+Mol ratio be 1:0.001 ~ 0.1:4 ~ 60:0.01
~0.5；SiO in step B crystallization system2It is 1:0.015 ~ 0.3 with the mol ratio of TPAOH.
Preferably silicon source is one or more of tetraethyl orthosilicate, Ludox and amorphous silicon oxide powder；Titanium source is titanium
One or more of positive four butyl esters of acid, titanium sulfate, titanium tetrachloride and titanium trichloride；Acidity regulator is hydrochloric acid, sulfuric acid and nitric acid
One or more.
For making titanium atom preferably enter TS-1 framework of molecular sieve, described silicon source is tetraethyl orthosilicate and amorphous
In Si powder at least one.
For improving the degree of crystallinity of TS-1 molecular sieve and making titanium atom preferably enter TS-1 framework of molecular sieve, preferred steps B
SiO in crystallization system2It is 1:0.045-0.15 with the mol ratio of TPAOH.
In order to obtain, crystal grain is less, degree of crystallinity is higher, titanium atom runs off, and less TS-1 molecular sieve, preferably crystallization temperature are
110-150℃。
The invention has the beneficial effects as follows that the method assisted by aerosol can prepare high-crystallinity and silicon titanium less than controlled
Crystal grain TS-1 molecular sieve.The effect of this synthetic route mainly has: 1. titanium atom is uniformly dispersed and building-up process is simple.The method permits
Permitted to use acid to suppress TiO2Generation, obtain mixed liquor by simple stirring, finally make titanium atom be highly dispersed at molecule
In sieve skeleton frame.The most time-consuming steaming alcohol process can also be omitted, and effectively shortens synthesis cycle.2.SiO2With tetrapropyl hydrogen
The mol ratio of amine-oxides is 1:0.015 ~ 0.3, and template consumption is low.The application of aerosol householder method makes little crystal grain TS-1 divide
Son sieve can synthesize under conditions of extremely low TPAOH consumption.Up to the present, yet there are no relevant report such as
The TS-1 molecular sieve of little crystal grain is synthesized under this low template consumption.3. pollute little.Due to a large amount of reductions of template consumption,
Make quantity of wastewater effluent greatly reduce, work as TPAOH: SiO2Mol ratio≤0.05 time, even up to without crystallization waste liquid
Discharge.4. production process low pressure, low energy consumption.Traditional TS-1 Zeolite synthesis typically crystallization at 170 DEG C, aerosol auxiliary square
Method can synthesize under 110 DEG C of cryogenic conditions the TS-1 molecular sieve of high-quality.Water saturation vapour pressure is about at 170 DEG C
791.47KPa, 110 DEG C are about 143.24KPa, it can be seen that synthesis pressure reduces about 80%.Requirement to equipment under the conditions of this
It is substantially reduced and safer.Low temperature synthesis simultaneously also can reduce required energy consumption.The most higher reactor utilization rate.Aerosol assists
Due to the reduction of template consumption in method, required reaction volume is made to decline.The TS-1 molecular sieve of the reactor synthesis of 1L
About 560g, for 9.7 times of Hydrothermal Synthesis.The method is the production of a kind of little crystal grain TS-1 molecular sieve with prospects for commercial application
Method.
Accompanying drawing explanation
Fig. 1 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 1.
Fig. 2 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 1.
Fig. 3 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 2.
Fig. 4 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 2.
Fig. 5 is that the SEM by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 2 schemes.
Fig. 6 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 3.
Fig. 7 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 3.
Fig. 8 is that the SEM by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 3 schemes.
Fig. 9 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 4.
Figure 10 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 4.
Figure 11 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 5.
Figure 12 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 5.
Figure 13 is that the SEM by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 5 schemes.
Figure 14 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 6.
Figure 15 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 6.
Figure 16 is that the SEM by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 6 schemes.
Figure 17 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 7.
Figure 18 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 7.
Figure 19 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 8.
Figure 20 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 8.
Figure 21 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 9.
Figure 22 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 9.
Figure 23 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 10.
Figure 24 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 10.
Figure 25 is the XRD spectra by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 11.
Figure 26 is the ultraviolet-visible absorption spectroscopy by aerosol auxiliary synthesis TS-1 molecular sieve catalyst of embodiment 11.
Detailed description of the invention
The detailed description of the invention of the present invention is described below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
By positive for 0.85g metatitanic acid four butyl esters, 2g hydrochloric acid, 53.6g water and 31.26g tetraethyl orthosilicate mix and blend 0.5 hour
Forming uniform solution, the mol ratio of each composition is SiO2: TiO2: H2O: H+For 1:0.0167:20:0.13.Then pass through
Aerosol generator forms aerosol, and drying obtains amorphous ti silica, and 1g amorphous ti silica puts into 1.67ml band polytetrafluoroethyl-ne
In the stainless steel synthesis reactor of alkene liner, adding the 0.20g TPAOH aqueous solution (mass fraction 25%), titanium silicon aoxidizes
SiO in thing2It is 1:0.015 with the mol ratio of TPAOH, carries out crystallization 24 under the conditions of being sealed in 170 DEG C little
Time, gained solid product is dried through 100 DEG C, roasting 6h removed template method at 540 DEG C, obtain final products TS-1 molecular sieve
0.95g, is equivalent to 1L crystallizing kettle and can produce 569g TS-1 molecular sieve.Exist without liquid phase after crystallization, i.e. useless without discharging crystallization
Liquid.XRD spectra and the ultraviolet-visible absorption spectroscopy spectrogram of this product are shown in Fig. 1 and Fig. 2, it can be seen that on XRD spectra
2theta is 7.9 °, 8.8 °, 23 °, 23.9 °, have 5 diffraction maximums respectively, for the characteristic diffraction peak of TS-1 molecular sieve at 24.4 °.
Illustrate that aerosol auxiliary law can be at SiO2It is to synthesize TS-under conditions of 1:0.015 with the mol ratio of TPAOH
1 molecular sieve.On Fig. 2, it can be seen that the characteristic peak of framework titania at 220nm, do not find at 270nm at unformed titanium and 330nm
The absworption peak of anatase, illustrates that titanium atom is uniformly dispersed.
Embodiment 2
The amorphous ti silica 1g being dried to obtain by aerosol in example 1 puts into the synthesis of band teflon-lined stainless steel
In still, add the 0.61g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With tetrapropyl hydrogen
The mol ratio of amine-oxides is 1:0.045, carries out crystallization 24 hours under the conditions of being sealed in 110 DEG C, by gained solid product warp
100 DEG C of dried roasting 6h removed template methods at 540 DEG C, obtain final products TS-1 molecular sieve.Exist without liquid phase after crystallization, i.e.
Without discharging crystallization waste liquid.The XRD spectra of this product, ultraviolet-visible absorption spectroscopy spectrogram and SEM Electronic Speculum figure be shown in Fig. 3,
Fig. 4 and Fig. 5.It will be seen that on XRD spectra 2theta be 7.9 °, 8.8 °, 23 °, 23.9 °, have 5 diffraction respectively at 24.4 °
Peak, for the characteristic diffraction peak of TS-1 molecular sieve.On Fig. 4, it can be seen that the characteristic peak of framework titania at 220nm, do not find 270nm
Locate the absworption peak of anatase at unformed titanium and 330nm, illustrate that titanium atom is uniformly dispersed.On SEM Electronic Speculum figure, it can be seen that produce
Product are the monodispersed TS-1 zeolite crystal of 150-300nm.
Embodiment 3
The amorphous ti silica 1g being dried to obtain by aerosol in example 1 puts into the synthesis of band teflon-lined stainless steel
In still, add the 4.04g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With tetrapropyl hydrogen
The mol ratio of amine-oxides is 1:0.3, carries out crystallization 24 hours under the conditions of being sealed in 170 DEG C, by gained solid product warp
It is dried at 100 DEG C after washing, roasting 6h removed template method at 540 DEG C, obtains final products TS-1 molecular sieve.This product
XRD spectra, ultraviolet-visible absorption spectroscopy spectrogram and SEM Electronic Speculum figure are shown in Fig. 6, Fig. 7 and Fig. 8.It will be seen that XRD spectra
On 2theta be 7.9 °, 8.8 °, 23 °, 23.9 °, have 5 diffraction maximums respectively, for the feature diffraction of TS-1 molecular sieve at 24.4 °
Peak.On Fig. 7, it can be seen that the characteristic peak of framework titania and the absworption peak of anatase at 330nm at 220nm, declaratives titanium is former
Son defines Detitanium-ore-type TiO2.On SEM Electronic Speculum figure, it can be seen that product is the TS-1 molecular sieve of 2um-10um.
Embodiment 4
The amorphous ti silica 1g being dried to obtain by aerosol in example 1 puts into the synthesis of band teflon-lined stainless steel
In still, add the 1.35g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With tetrapropyl hydrogen
The mol ratio of amine-oxides is 1:0.1, carries out crystallization 3 hours under the conditions of being sealed in 190 DEG C, by gained solid product warp
It is dried at 100 DEG C after washing, roasting 6h removed template method at 540 DEG C, obtains final products TS-1 molecular sieve.This product
XRD spectra and ultraviolet-visible absorption spectroscopy spectrogram are shown in Fig. 9 and Figure 10.It will be seen that on XRD spectra at 2theta be
7.9 °, 8.8 °, 23 °, 23.9 °, have 5 diffraction maximums respectively, for the characteristic diffraction peak of TS-1 molecular sieve at 24.4 °.On Figure 10,
It can be seen that the characteristic peak of framework titania at 220nm, do not find at 270nm the absworption peak of anatase at unformed titanium and 330nm, say
Bright titanium atom is uniformly dispersed.
Embodiment 5
The amorphous ti silica 1g being dried to obtain by aerosol in example 1 puts into the synthesis of band teflon-lined stainless steel
In still, add the 0.61g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With tetrapropyl hydrogen
The mol ratio of amine-oxides is 1:0.045, carries out crystallization 24 hours, by gained solid product under the conditions of being sealed in 170 DEG C
It is dried at 100 DEG C after scrubbed, roasting 6h removed template method at 540 DEG C, obtains final products TS-1 molecular sieve.Nothing after crystallization
Liquid phase exists, i.e. without discharging crystallization waste liquid.The XRD spectra of this product, ultraviolet-visible absorption spectroscopy spectrogram and SEM Electronic Speculum figure divide
It is not shown in Figure 11, Figure 12 and Figure 13.It will be seen that on XRD spectra 2theta be 7.9 °, 8.8 °, 23 °, 23.9 °, at 24.4 °
There are 5 diffraction maximums respectively, for the characteristic diffraction peak of TS-1 molecular sieve.On Figure 12, it can be seen that the feature of framework titania at 220nm
Peak, does not finds at 270nm the absworption peak of anatase at unformed titanium and 330nm, illustrates that titanium atom is uniformly dispersed.In SEM Electronic Speculum
On figure, it can be seen that product is the block TS-1 molecular sieve being sticked together, and is formed without scattered crystal grain.
Embodiment 6
The amorphous ti silica 1g being dried to obtain by aerosol in example 1 puts into the synthesis of band teflon-lined stainless steel
In still, add the 0.61g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With tetrapropyl hydrogen
The mol ratio of amine-oxides is 1:0.045, carries out crystallization 24 hours under the conditions of being sealed in 150 DEG C, by gained solid product warp
It is dried at 100 DEG C after washing, roasting 6h removed template method at 540 DEG C, obtains final products TS-1 molecular sieve.Aneroid after crystallization
Exist mutually, i.e. without discharging crystallization waste liquid.The XRD spectra of this product, ultraviolet-visible absorption spectroscopy spectrogram and SEM Electronic Speculum figure are respectively
It is shown in Figure 14, Figure 15 and Figure 16.It will be seen that be 7.9 °, 8.8 °, 23 °, 23.9 °, 24.4 ° of punishment at 2theta on XRD spectra
There are not 5 diffraction maximums, for the characteristic diffraction peak of TS-1 molecular sieve.On Figure 15, it can be seen that the feature of framework titania at 220nm
Peak, does not finds at 270nm the absworption peak of anatase at unformed titanium and 330nm, illustrates that titanium atom is uniformly dispersed.In SEM Electronic Speculum
On figure, it can be seen that product is the monodispersed TS-1 zeolite crystal of 300-600nm.
Embodiment 7
The amorphous ti silica 1g being dried to obtain by aerosol in example 1 puts into the synthesis of band teflon-lined stainless steel
In still, add the 2.0g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With tetrapropyl hydrogen-oxygen
The mol ratio changing ammonium is 1:0.15, carries out crystallization 24 hours, by gained solid product through washing under the conditions of being sealed in 170 DEG C
It is dried at 100 DEG C after washing, roasting 6h removed template method at 540 DEG C, obtains final products TS-1 molecular sieve.The XRD of this product
Spectrogram and ultraviolet-visible absorption spectroscopy spectrogram are shown in Figure 17 and Figure 18.It will be seen that on XRD spectra at 2theta be
7.9 °, 8.8 °, 23 °, 23.9 °, have 5 diffraction maximums respectively, for the characteristic diffraction peak of TS-1 molecular sieve at 24.4 °.On Figure 18,
It can be seen that the characteristic peak of framework titania at 220nm, do not find at 270nm the absworption peak of anatase at unformed titanium and 330nm, say
Bright titanium atom is uniformly dispersed.
Embodiment 8
By 0.474g titanium tetrachloride, 2g hydrochloric acid, 32.6g water and 30g Ludox mix and blend 1 hour, each composition mole
Proportioning is SiO2: TiO2: H2O: H+For 1:0.0167:20:0.13.Then gas is formed by aerosol generator molten
Glue, drying obtains amorphous ti silica, and 1g amorphous ti silica is put in band teflon-lined stainless steel synthesis reactor, then adds
Enter the 0.61g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With rubbing of TPAOH
You join is 1:0.045, carries out crystallization 24 hours under the conditions of being sealed in 170 DEG C, is dried through 100 DEG C by gained solid product
After at 540 DEG C roasting 6h removed template method, obtain final products TS-1 molecular sieve.Exist without liquid phase after crystallization, i.e. without discharge
Crystallization waste liquid.XRD spectra and the ultraviolet-visible absorption spectroscopy spectrogram of this product are shown in Figure 19 and Figure 20, it can be seen that XRD
On spectrogram 2theta be 7.9 °, 8.8 °, 23 °, 23.9 °, have 5 diffraction maximums respectively, for the feature of TS-1 molecular sieve at 24.4 °
Diffraction maximum.On Figure 20, it can be seen that the characteristic peak of unformed titanium at framework titania and 270nm at 220nm, do not find at 330nm
The absworption peak of anatase.
Embodiment 9
By positive for 0.28g metatitanic acid four butyl esters, 2g hydrochloric acid, 53.6g water and 3g amorphous silicon oxide powder mix and blend 1 hour,
The mol ratio of each composition is SiO2: TiO2: H2O: H+For 1:0.0167:60:0.4.Then aerosol generator is passed through
Forming aerosol, drying obtains amorphous ti silica, and 1g amorphous ti silica puts into the synthesis of band teflon-lined stainless steel
In still, add the 2.7g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With tetrapropyl hydrogen-oxygen
The mol ratio changing ammonium is 1:0.2, carries out crystallization 24 hours, by gained solid product through washing under the conditions of being sealed in 170 DEG C
Wash, dried roasting 6h removed template method at 540 DEG C, obtain final products TS-1 molecular sieve.The XRD spectra of this product and ultraviolet
Visible absorption spectra spectrogram is shown in Figure 21 and Figure 22, it can be seen that on XRD spectra 2theta be 7.9 °, 8.8 °, 23 °,
23.9 °, have 5 diffraction maximums respectively, for the characteristic diffraction peak of TS-1 molecular sieve at 24.4 °.On Figure 22, it can be seen that 220nm
The characteristic peak of place's framework titania, does not finds at 270nm the absworption peak of anatase at unformed titanium and 330nm, illustrates that titanium atom disperses
Uniformly.
Embodiment 10
By little to 2.31g titanium trichloride, 6.83g red fuming nitric acid (RFNA), 159.6g water and 31.26g tetraethyl orthosilicate mix and blend 0.5
Time formed uniform solution, the mol ratio of each composition is SiO2: TiO2: H2O: H+For 1:0.1:60:0.5.Then pass through
Aerosol generator forms aerosol, and drying obtains amorphous ti silica, and 1g amorphous ti silica puts into band polytetrafluoroethyllining lining
Stainless steel synthesis reactor in, add the 1.35g TPAOH aqueous solution (mass fraction 25%), in amorphous ti silica
SiO2It is 1:0.1 with the mol ratio of TPAOH, carries out crystallization under the conditions of being sealed in 130 DEG C 24 hours, by institute
Solid product through 100 DEG C of dried roasting 6h removed template methods at 540 DEG C, obtain final products TS-1 molecular sieve.This product
XRD spectra and ultraviolet-visible absorption spectroscopy spectrogram be shown in Figure 23 and Figure 24, it can be seen that at 2theta on XRD spectra
Be 7.9 °, 8.8 °, 23 °, 23.9 °, have 5 diffraction maximums respectively, for the characteristic diffraction peak of TS-1 molecular sieve at 24.4 °.At Figure 24
On, it can be seen that the characteristic peak of framework titania at 220nm, do not find the absorption of anatase at unformed titanium and 330nm at 270nm
Peak, illustrates that titanium atom is uniformly dispersed.
Embodiment 11
0.06g titanium sulfate, 0.12g sulfuric acid, 10.8g water and 31.26g tetraethyl orthosilicate mix and blend are formed for 1 hour
Uniform solution, the mol ratio of each composition is SiO2: TiO2: H2O: H+For 1:0.001:4:0.01.Then molten by gas
Glue generator forms aerosol, and drying obtains amorphous ti silica, and 1g amorphous ti silica puts into band teflon-lined not
In rust steel synthesis reactor, add the 1.35g TPAOH aqueous solution (mass fraction 25%), SiO in amorphous ti silica2With
The mol ratio of TPAOH is 1:0.1, carries out crystallization 240 hours, by gained solid under the conditions of being sealed in 90 DEG C
Product, through 100 DEG C of dried roasting 6h removed template methods at 540 DEG C, obtains final products TS-1 molecular sieve.The XRD spectrum of this product
Figure and ultraviolet-visible absorption spectroscopy spectrogram are shown in Figure 25 and Figure 26, it can be seen that on XRD spectra 2theta be 7.9 °,
8.8 °, 23 °, 23.9 °, have 5 diffraction maximums respectively, for the characteristic diffraction peak of TS-1 molecular sieve at 24.4 °.On Figure 26, permissible
See the characteristic peak of framework titania at 220nm, do not find at 270nm the absworption peak of anatase at unformed titanium and 330nm, titanium is described
Atom is uniformly dispersed.
Comparative example
50g tetraethyl orthosilicate adds 70g TPAOH (mass fraction 20%), by positive for 2.3g metatitanic acid four fourths
Ester and 15g isopropanol join in above-mentioned solution after mixing, and add 60g deionized water, add after mixing uniformly after mixing
Putting in band teflon-lined stainless steel synthesis reactor, the mol ratio of each composition is: SiO2: TiO2: H2O:TPAOH
For 1:0.028:27:0.287.160 DEG C of crystallization 12h, are dried through 100 DEG C after centrifuge washing, and at 540 DEG C, roasting 6h removes mould
Plate agent, obtains final products TS-1 molecular sieve.
Colluded the present invention, high-crystallinity and silicon titanium can be prepared than controlled little crystal grain TS-1 molecular sieve.This synthetic route
Have the advantage that 1. titanium atoms are uniformly dispersed and building-up process is simple.2. template consumption is low, pollutes little.3. production process
Pressure is low, low energy consumption.4. reactor rate of using by oneself is high.
The above, be only several case study on implementation of the present invention, and the present invention not does any pro forma restriction,
Although the present invention discloses as above with preferable case study on implementation, but is not limited to the present invention, any skill being familiar with this specialty
Art personnel, in the range of without departing from technical solution of the present invention, when structure and the technology contents of available the disclosure above are made a little
Change or be modified to the equivalent case study on implementation of equivalent variations.But every content without departing from technical solution of the present invention, foundation
Any simple modification, equivalent variations and the modification that above case study on implementation is done by the technical spirit of the present invention, the most still belongs to the present invention
In technical scheme.
Claims (5)
1., by a method for aerosol auxiliary synthesis TS-1 molecular sieve, comprise the following steps:
A. by silicon source, titanium source, water, acidity regulator mixing, stir formation mixed liquor, forms gas by aerosol device molten
Glue, drying obtains unformed amorphous ti silica；
B. above-mentioned amorphous ti silica is mixed with TPAOH solution, seal, at 90 ~ 190 DEG C, carry out crystallization, crystallization
Time is 3 hours ~ 10 days, is dried scrubbed for gained solid product or carry out roasting after convection drying, obtaining TS-1 molecular sieve；
SiO in step A mixture system2: TiO2: H2O: H+Mol ratio be 1:0.001 ~ 0.1:4 ~ 60:0.01 ~ 0.5；
SiO in step B crystallization body2It is 1:0.015 ~ 0.3 with the mol ratio of TPAOH.
Method the most according to claim 1, it is characterised in that described silicon source is tetraethyl orthosilicate, Ludox and nothing
One or more of setting silicon oxide powder；Described titanium source is positive four butyl esters of metatitanic acid, titanium sulfate, titanium tetrachloride and titanium trichloride
One or more；Described acidity regulator is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Method the most according to claim 2, it is characterised in that described silicon source is tetraethyl orthosilicate and amorphous silicon oxide
In powder at least one.
Method the most according to claim 1, it is characterised in that SiO in step B crystallization system2With TPAOH
Mol ratio is 1:0.045-0.15.
Method the most according to claim 1, it is characterised in that described crystallization temperature is 110-150 DEG C.
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| CN105776244B (en) * | 2016-03-23 | 2018-08-21 | 大连理工大学 | A method of TS-1 molecular sieves are synthesized by aerosol processing/spray drying process assisted Solid-state |
| CN106000375B (en) * | 2016-06-22 | 2018-05-11 | 徐州恒鼎生物科技有限公司 | A kind of method that Ti-Si composite oxide and its catalysis prepare 3- picolines |
| CN115845917A (en) * | 2022-12-23 | 2023-03-28 | 大连理工大学 | Preparation method and application of micron Au/TS-1 catalyst for propylene gas-phase epoxidation reaction in oxyhydrogen system |
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|---|---|---|---|---|
| CN1167010A (en) * | 1997-04-16 | 1997-12-10 | 天津理工学院 | Process of synthesizing titanium-silicon molecular sieve TS-1 using silica gel as raw material |
| CN103214000A (en) * | 2013-04-22 | 2013-07-24 | 江苏怡达化学股份有限公司 | Synthesis method of titanium-silicon molecular sieve TS-1 |
| CN103418432A (en) * | 2013-08-03 | 2013-12-04 | 大连理工大学 | Hierarchical-pore titanium silicon molecular sieve catalyst synthesized with assistance of aerosol and preparation method of hierarchical-pore titanium silicon molecular sieve catalyst |
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| FR2920757B1 (en) * | 2007-09-07 | 2009-11-13 | Inst Francais Du Petrole | CRYSTALLIZED MATERIAL COMPRISING SILICON HIERARCHISED AND ORGANIZED POROSITY |
| FR2969513B1 (en) * | 2010-12-22 | 2013-04-12 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF A SPHERICAL MATERIAL HIERARCHISED POROSITY COMPRISING METALLIC PARTICLES PIEGEES IN A MESOSTRUCTURED MATRIX |
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| CN1167010A (en) * | 1997-04-16 | 1997-12-10 | 天津理工学院 | Process of synthesizing titanium-silicon molecular sieve TS-1 using silica gel as raw material |
| CN103214000A (en) * | 2013-04-22 | 2013-07-24 | 江苏怡达化学股份有限公司 | Synthesis method of titanium-silicon molecular sieve TS-1 |
| CN103418432A (en) * | 2013-08-03 | 2013-12-04 | 大连理工大学 | Hierarchical-pore titanium silicon molecular sieve catalyst synthesized with assistance of aerosol and preparation method of hierarchical-pore titanium silicon molecular sieve catalyst |
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