CN100558635C - A kind of preparation method of V-Si molecular sieve - Google Patents
A kind of preparation method of V-Si molecular sieve Download PDFInfo
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- CN100558635C CN100558635C CNB2005100597668A CN200510059766A CN100558635C CN 100558635 C CN100558635 C CN 100558635C CN B2005100597668 A CNB2005100597668 A CN B2005100597668A CN 200510059766 A CN200510059766 A CN 200510059766A CN 100558635 C CN100558635 C CN 100558635C
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Abstract
The invention discloses a kind of preparation method of V-Si molecular sieve, this method is that silicon source, vanadium source, template, mineral alkali and water are mixed into the reaction mixture that glue obtains, in airtight still, obtain the V-Si molecular sieve of MFI structure under the crystallization condition, it is characterized in that said template is n-Butyl Amine 99 and/or triethylamine, template and SiO
2Mol ratio be 0.04～0.5: 1.
Description
Technical field
The invention relates to a kind of preparation method of V-Si molecular sieve, more specifically say so about a kind of preparation method of V-Si molecular sieve (VS-1) of the MFI of having structure.
Background technology
In molecular sieve, introduce and have coordination and the transition element vanadium of the feature of appraising at the current rate, molecular sieve performance and transition metal-catalyzed performance can be combined and produce the catalytic effect of uniqueness.Experiment shows, vanadium silicon class zeolite has good catalytic performance in many organic oxidizing reactions, the V-Si molecular sieve (VS-1) that for example has the MFI structure shows good catalytic performance in many organic oxidation reduction reactions such as toluene oxidation, phenol hydroxylation, xylidine oxidation, oxidation of alkanes, especially show good reaction preference, have a good application prospect.
Adopt pickling process or ion exchange method vanadium can be introduced in the supersiliceous zeolite, for example F.Cavani and F.Trifiro (Zeolites, 1988, Vol 8, January) reported and used NH
4VO
3Dipping HZSM-5 and HZSM-11 and obtain containing the ZSM-5 molecular sieve of vanadium; B.I.Whitington and J.R.Anderson (J.Phys.Chem, 1991,95,3306～3310) have reported the ZSM-5 molecular sieve that contains vanadium that adopts the preparation of post-modification method; Dan Shaochun etc. (Acta PhySico-Chimica Sinica, the 8th volume, the 3rd phase, the 339th page, 1992) have reported V
2O
5Obtain containing the molecular sieve of vanadium with the evenly back roasting in moisture atmosphere of ZSM-5 equimolecular sieve sample mix grinding.But, adopt aforesaid method to be difficult to vanadium is incorporated in the skeleton structure of molecular sieve, up to the present, real V-Si molecular sieve adopts the hydrothermal crystallizing method to obtain.
The bibliographical information that adopts the preparation of hydrothermal crystallizing method to have the V-Si molecular sieve (VS-1) of MFI structure is not a lot.Reported the method for the synthetic VS-1 of a kind of hydro-thermal in " Applied Catalysis, 18 (1985), 311～324 ", this method is to adopt VCl
3, Na
2SO
4, TPABr (4-propyl bromide), H
2SO
4, NaCl etc. is raw material, three kinds of solution that will contain different components mix the back centrifugations and go out throw out, the other three kinds solution that contain different components are mixed the back centrifugations go out solution, again this precipitation and this solution are mixed back hydrothermal crystallizing and obtain molecular sieve
Reported method is with VO (COO) in " Zeolite Chemisty and Catalysis, 191, P173～180 "
2With water glass be raw material, be template with TPABr, and added the ZSM-5 molecular sieve as crystal seed, be prepared into a kind of SiO of consisting of
2: 0.2VO
2: 39.2H
2The synthetic liquid of O: 0.3TPABr obtained VS-1 with this synthetic liquid in 10 days 160 ℃ of crystallization.
" Applied Catalysis, 68 (1991) L1-L7 " have also reported the method for synthetic VS-1, and the mole proportioning of used synthetic liquid is in this method: 100SiO
2: 11TPAOH (TPAOH): 11NH
3: (100x) VOSO
4: 1200H
2O, x=0.010 wherein, 0.020,0.040, used SiO
2Raw material is Ludox AS-40 (Dupont company, liquid Si O
2Solution), crystallization condition is at N
2Under the atmosphere in 180 ℃ of crystallization 3 days.
" Stud.Surf.Sci.Catal., 125,149～156 " reported method is to adopt SiO
2And V
2O
5Xerogel floods with the TPAOH solution-wet, and crystallization prepares the VS-1 molecular sieve again.This method can make vanadium atom enter unformed SiO
2The position that segregation comes out enters the unitary maximum of MFI crystalline structure and is about 0.5 vanadium atom of every structural unit, but the part vanadium atom can move to octahedral site under hydration.Therefore having certain non-skeleton vanadium exists.
A kind of preparation method of VS-1 molecular sieve is disclosed among the CN1052453C, this method is that the vanadium source is dissolved in TPAOH (TPAOH) aqueous solution, and mix with 60～220 purpose solid silicone beads and to obtain reaction mixture, place 120～180 ℃ of crystallization to get V-Si molecular sieve in 2～8 days this reaction mixture, wherein the mole of said reaction mixture consists of: SiO
2/ VO
2=15～600, TPAOH/SiO
2=0.04～0.40, H
2O/SiO
2=1～30.
In sum, in the preparation method of the preparation V-Si molecular sieve that prior art provided, or preparation process is complicated, or owing to adopt expensive organic ammonium to do template, makes product cost very high; Or the preparation gained molecular sieve contain a certain amount of non-skeleton vanadium, thereby influenced the product activity.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method for preparing V-Si molecular sieve with low cost is provided.
The preparation method of V-Si molecular sieve provided by the invention, be that silicon source, vanadium source, template, mineral alkali and water are mixed into the reaction mixture that glue obtains, in airtight still, obtain the V-Si molecular sieve (VS-1) of MFI structure under the crystallization condition, it is characterized in that said template is n-Butyl Amine 99 and/or triethylamine, template and SiO
2Mol ratio be 0.04～0.5: 1.
In the method provided by the invention, said silicon source is selected from silica gel, silicon sol or water glass; Said vanadium source is selected from metavanadic acid, vanadic salts, oxyvanadium compound or organic vanadium complex compound, wherein more preferably vanadylic sulfate or Vanadium Pentoxide in FLAKES; Said template is n-Butyl Amine 99 and/or triethylamine.
More particularly, preparation method provided by the invention, the gelatigenous reaction mixture of wherein said mixing, the composition of each component is well known to those skilled in the art, and its preferred each component mole consists of:
SiO
2/VO
2＝5～1000
OH
-/SiO
2＝0.02～0.6
H
2O/SiO
2＝5～30
Preferred each component mole consists of:
Template/SiO
2=0.08～0.2
SiO
2/VO
2＝10～100
OH
-/SiO
2＝0.05～0.4
H
2O/SiO
2＝5～15
Among the preparation method provided by the invention, said crystallization condition is a crystallization 5 hours to 10 days under 120～200 ℃ of temperature, and preferred crystallization condition is earlier 60～120 ℃ of pre-crystallization 3～48 hours, again 120～200 ℃ of crystallization 5 hours to 10 days.
The preparation method of V-Si molecular sieve provided by the invention has following advantage:
(1) adopting cheap n-Butyl Amine 99 and/or triethylamine is template, has reduced preparation cost.
(2) prepared V-Si molecular sieve content of vanadium height is adjustable, IR and
51The sign of V MAS NMR shows that vanadium atom enters framework of molecular sieve, and the skeleton vanadium exists nothing but.
(3) prepared V-Si molecular sieve has good thermostability and good hydrothermal stability.For example, aged sample under the sample of roasting and 800 ℃/100% water vapor conditions under 550 ℃ of conditions, its spectrogram still keeps MFI crystal structure characteristic (embodiment 11).
(4) as the desulphurizing activated component of catalytic cracking agent, the V-Si molecular sieve of the inventive method preparation has higher desulfuration effect (embodiment 12) than the V-Si molecular sieve of prior art for preparing.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the V-Si molecular sieve of embodiment 1 preparation.
Fig. 2 is the X-ray diffraction spectrogram of the V-Si molecular sieve of embodiment 2 preparations.
Fig. 3 is the IR spectrogram of sample, A curve representation embodiment 1 sample among the figure, and B curve representation embodiment 2 samples, C curve are represented the pure silicon molecular sieve Silicate-1 of MFI structure.
Fig. 4 is a sample
51V MAS NMR figure, A curve representation embodiment 1 sample among the figure, B curve representation embodiment 2 samples are indicated V simultaneously among the figure
2O
5Spectrogram.
Embodiment
Following embodiment will be described further content of the present invention, but content not thereby limiting the invention.
In each of the embodiments described below, remove special instruction, agents useful for same is commercially available chemically pure reagent.
The test condition of the X-ray diffraction spectrogram (XRD) of the molecular sieve of doing: collect by the Philips diffraction system, the super detector of this system equipment adopts copper K-α radiation, and diffraction data is that 0.017 degree progressively scans with 2 θ angles, the θ here is a Bragg angle, and clocking of per step is 35 seconds.
The infrared absorption of Bio-Rad FTS-135 infrared photometer test molecule sieve sample is adopted in the analysis of infrared spectra (IR) skeleton.Resolving power is 4cm
-1, scanning accumulative frequency 20 times.Solid sample is mixed according to quality with KBr at 1: 200, after the grinding, put into stainless steel mould and be pressed into circular ingot sheet, measure its skeletal vibration spectrum.
Nmr spectrum (MAS NMR) adopts VARIAN
UNITYINOVA-300 type nuclear magnetic resonance analyser is carried out nuclear magnetic resonance spectroscopy to molecular sieve.Test condition is:
51V MAS NMR resonant frequency is 78.854MHz, and rotor speed is 100Hz, and the duplicate delays time is 1s, sampling time 0.04s, and pulsewidth is 2 μ s, spectrum width is 197KHz, room temperature.
Adopt Rigaku 3271E type Xray fluorescence spectrometer to measure the constituent content of sieve sample.Test process: after the pressed powder pellet moulding, on Xray fluorescence spectrometer, measure the intensity of an elemental characteristic spectral line, obtain the content of element with external standard method.
Embodiment 1
With 10.6g silica gel (Lanzhou catalyst plant, igloss 3 heavy %, alumina content 1 weight %), 1.36g vanadylic sulfate, 1.33gNaOH and 36gH
2O mixes, and adds the 2.46g n-Butyl Amine 99 again, stirs, and the mole of gained reaction mixture thing consists of: SiO
2: 0.05VO
2: 0.2CH
3(CH
2)
3NH
2: 0.2NaOH: 12H
2O.With pack in the airtight crystallizing kettle under 120 ℃ of conditions crystallization 1 day of this reaction mixture, crystallization 1 day under 150 ℃ of conditions again, after filtration, washing, oven dry obtains sample Z1 under 120 ℃ of conditions.
The XRD spectra of Z1 is seen Fig. 1, shows that Z1 has typical MFI structure, and its relative crystallinity is 91.2% (with respect to well-crystallized's Silicate-1, down together, Silicate-1 is according to Stud.Surf.Sci.Catal., 18, and the described method synthetic of (1984) P159).
Z1 NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of: 0.024V
2O
5: SiO
2: 0.012Al
2O
3
IR skeleton analysis of spectra is seen the A curve of Fig. 3, has occurred the 970cm that Silicate-1 (seeing the C curve of Fig. 3) is not had on the IR spectrogram of Z1
-1Charateristic avsorption band, this has influenced the antisymmetric stretching vibration of Si-O key owing to the four-coordination vanadium has entered behind framework of molecular sieve and has caused, is considered to evidence (Qi Haihua etc., Chinese Journal of Inorganic Chemistry, 1989,5 (1): 1) that V enters framework of molecular sieve.
51V MAS NMR spectrogram is seen the A curve of Fig. 4, and the resonance peak of chemical shift-868.5ppm further specifies vanadium and entered framework of molecular sieve; Simultaneously, there is not the signal of chemical shift-612.4ppm in the A curve (at V
2O
5Curve in, the resonance peak of chemical shift-612.4ppm illustrates the existence of non-skeleton vanadium) can interpret sample not have non-skeleton vanadium.
Embodiment 2
With 15.9g silica gel, 6.12g vanadylic sulfate, 4gNaOH and 54gH
2O mixes, and adds the 4.94g n-Butyl Amine 99 again, stirs, and the mole of gained reaction mixture consists of: SiO
2: 0.15VO
2: 0.25CH
3(CH
2)
3NH
2: 0.4NaOH: 12H
2O.With this reaction mixture crystallization 4 days under 150 ℃ of conditions, after filtration, washing, under 120 ℃ of conditions dry two hours, obtain sample Z2.
The XRD spectra of Z2 is seen Fig. 2, shows that Z2 has typical MFI structure, and relative crystallinity is 83%.
Z2 NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of: 0.07V
2O
5: SiO
2: 0.008Al
2O
3
IR skeleton analysis of spectra is seen the B curve of Fig. 3, has occurred 970cm equally
-1Charateristic avsorption band, illustrate that V enters framework of molecular sieve.
51V MAS NMR spectrogram is seen the B curve of Fig. 4, and the resonance peak of its chemical shift-868.5ppm further specifies vanadium and entered framework of molecular sieve, and peak area obviously increases, and shows that its skeleton content of vanadium is more than Z1; Simultaneously, there is not the signal of chemical shift-612.4ppm interpret sample not have non-skeleton vanadium in the A curve.
Embodiment 3
With method and the step of embodiment 1, difference is V
2O
5With the consumption of NaOH, the mole of the reaction mixture of being prepared is formed: SiO
2: 0.02VO
2: 0.2CH
3(CH
2)
3NH
2: 0.1NaOH: 12H
2O.
With above-mentioned reaction mixture crystallization 5 days under 150 ℃ of conditions, crystallization product through filtration, washing, drying after, obtain sample Z3, its XRD spectra has the feature of Fig. 1, relative crystallinity is 94.7%.
Use NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of 0.009V
2O
5: SiO
2: 0.01Al
2O
3
The IR spectrogram of sample Z3 has the feature of Fig. 3 A curve,
51V MAS NMR spectrogram has the feature of Fig. 4 A curve.
Embodiment 4
With method and the step of embodiment 1, difference is V
2O
5With the consumption of NaOH, the mole of the reaction mixture of being prepared is formed: SiO
2: 0.1VO
2: 0.2CH
3(CH
2)
3NH
2: 0.15NaOH: 12H
2O
With above-mentioned reaction mixture crystallization 5 days under 150 ℃ of conditions, crystallization product through filtration, washing, drying after, obtain sample Z4, its XRD spectra has the feature of Fig. 1, relative crystallinity is 86.2%,
With sample NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of 0.05V
2O
5: SiO
2: 0.09Al
2O
3
The IR spectrogram of sample Z4 has the feature of Fig. 3 A curve,
51V MAS NMR spectrogram has the feature of Fig. 4 A curve.
With method and the step of embodiment 1, difference is V
2O
5With the consumption of NaOH, the mole of the reaction mixture of being prepared is formed: SiO
2: 0.2VO
2: 0.2CH
3(CH
2)
3NH
2: 0.4NaOH: 12H
2O
With above-mentioned reaction mixture crystallization 5 days under 150 ℃ of conditions, crystallization product through filtration, washing, drying after, obtain sample Z5, its XRD spectra has the feature of Fig. 1, relative crystallinity is 76.1%.
With sample NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of 0.089V
2O
5: SiO
2: 0.011Al
2O
3
The IR spectrogram of sample Z5 has the feature of Fig. 3 A curve,
51V MAS NMR spectrogram has the feature of Fig. 4 A curve.
Embodiment 6
With 1.26gVCl
3, the heavy % of 0.8gNaOH, 20g30 silicon sol mix, add triethylamine 1.01g and n-Butyl Amine 99 0.73g again, stir, the mole of gained mixture consists of SiO
2: 0.08VO
2: 0.2NaOH: 0.1 (C
2H
5)
3N: 0.1CH
3(CH
2)
3NH
2: 7.8H
2O with this mixture crystallization 1 day under 170 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample Z6.
The XRD crystalline phase figure of Z6 has the feature of Fig. 1, and relative crystallinity is 87.4%.
With sample NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of 0.038V
2O
5: SiO
2
The IR spectrogram of sample Z6 has the feature of Fig. 3 A curve,
51V MAS NMR spectrogram has the feature of Fig. 4 A curve.
Embodiment 7
With 0.632gNaVO
32H
2O, 0.8gNaOH and 30.3g40 are heavy, and % water glass mixes, and adds n-Butyl Amine 99 2.19g again, stirs, and the mole of gained mixture consists of SiO
2: 0.04VO
2: 0.2NaOH: 0.3CH
3(CH
2)
3NH
2: 10H
2O with this mixture crystallization 6 days under 150 ℃ of conditions, more after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample Z7.
The XRD crystalline phase figure of Z7 has the feature of Fig. 1, and relative crystallinity is 89.7%.
With sample NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of 0.018V
2O
5: SiO
2
The IR spectrogram of sample Z7 has the feature of Fig. 3 A curve,
51V MAS NMR spectrogram has the feature of Fig. 4 A curve.
Embodiment 8
With 1.76gV (C
2H
7O
2)
3, 1.2gNaOH, 6g silica gel and 36gH
2O mixes, and adds triethylamine 2.02g again, stirs, and the mole of gained mixture consists of SiO
2: 0.05VO
2: 0.3NaOH: 0.2 (C
2H
5)
3N: 20H
2O, with this mixture crystallization 2 days under 120 ℃ of conditions, crystallization 1 day under 150 ℃ of conditions more after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample Z8.
The XRD crystalline phase figure of Z8 has the feature of Fig. 1, and relative crystallinity is 89.2%.
With sample NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of 0.024V
2O
5: SiO
2: 0.07Al
2O
3
The IR spectrogram of sample Z8 has the feature of Fig. 3 A curve,
51V MAS NMR spectrogram has the feature of Fig. 4 A curve.
Embodiment 9
With 2gVOC
2O
4, 1.6gNaOH, 6g silica gel, 27gH
2O mixes, and adds n-Butyl Amine 99 1.46g again, stirs, and the mole of gained mixture consists of SiO
2: 0.13VO
2: 0.4NaOH: 0.2CH
3(CH
2)
3NH
2: 15H
2O, with this mixture crystallization 2 days under 120 ℃ of conditions, crystallization 3 days under 150 ℃ of conditions more after filtration, washing, under 120 ℃ of conditions dry two hours, obtains sample Z9.
The XRD crystalline phase figure of Z9 has the feature of Fig. 1, and relative crystallinity is 76.2%.
With sample NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of 0.06V
2O
5: SiO
2: 0.01Al
2O
3
The IR spectrogram of sample Z9 has the feature of Fig. 3 A curve,
51V MAS NMR spectrogram has the feature of Fig. 4 A curve.
The composition of reaction mixture is identical with embodiment 8, and with this reaction mixture crystallization 0.5 day under 120 ℃ of conditions, crystallization 2 days under 150 ℃ of conditions more after filtration, washing, under 120 ℃ of conditions dry two hours, promptly gets sample Z10.
The XRD spectra of Z10 has the feature of Fig. 1, and relative crystallinity is 79.3%.
With sample NH
4After Cl exchanged for several times repeatedly, the mole by its anhydrous oxide of fluorometric analysis consisted of 0.025V
2O
5: SiO
2: 0.012Al
2O
3
The IR spectrogram of sample Z10 has the feature of Fig. 3 A curve,
51V MAS NMR spectrogram has the feature of Fig. 4 A curve.
Embodiment 11
The present embodiment explanation adopts the V-Si molecular sieve of method preparation provided by the invention to have good thermostability and hydrothermal stability.
Molecular sieve Z1～the Z10 of the foregoing description preparation is distinguished roasting 6 hours under 550 ℃ of conditions, 20 hours and 48 hours, do XRD analysis then, their spectrogram still keeps the feature of Fig. 1.
The molecular sieve Z1 of embodiment 1 preparation was worn out 4 hours and 17 hours respectively under 800 ℃/100% water vapor conditions, do XRD analysis then, their spectrogram still keeps the feature of Fig. 1.
Embodiment 12
The catalytic performance of V-Si molecular sieve in cracking reaction of present embodiment explanation present method preparation.
With V-Si molecular sieve Z1, the Z6 of embodiment preparation and Z9 with according to the VS-1 silicon vanadium molecular sieve (numbering DB1) of the method preparation of CN1052453C embodiment 2 records, (lattice constant is to add the REUSY molecular sieve respectively
The heavy % of content of rare earth 68), silicon sol and kaolin makes catalyzer, wherein the content of V-Si molecular sieve is 10 heavy %, REUSY molecular sieve 47 heavy %, silicon sol 18 heavy % and kaolin 25 heavy %, the spray-dried catalyzer that is prepared into.
Consisting of of benchmark catalyzer: REUSY molecular sieve 57 heavy %, silicon sol 18 heavy %, kaolin 25 heavy %.
Catalyzer carries out miniature light-oil cracking evaluation after 800 ℃/100% water vapour wore out in 4 hours.
Adopting the sulphur content of raw material is 403mg/L.Miniature light-oil cracking evaluation the results are shown in following table.
Table
| Catalyzer | The benchmark catalyzer | ||||
| The molecular sieve numbering | / | Z1 | Z6 | Z9 | DB1 |
| MA(800℃/8h) | 64 | 64 | 64 | 64 | 64 |
| C/O | 1.29 | 1.21 | 1.21 | 1.21 | 1.21 |
| Temperature of reaction/ |
500 | 500 | 500 | 500 | 500 |
| Dry gas | 1.83 | 1.72 | 1.65 | 1.57 | 1.45 |
| Liquefied gas | 10.65 | 10.54 | 10.35 | 9.98 | 9.01 |
| Gasoline | 47.80 | 46.05 | 45.97 | 44.76 | 41.00 |
| Diesel oil | 21.16 | 21.02 | 20.67 | 20.05 | 18.45 |
| Heavy oil | 16.37 | 18.26 | 18.89 | 21.19 | 24.59 |
| Coke | 2.20 | 2.42 | 2.48 | 2.54 | 2.65 |
| Amount to | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
| Transformation efficiency/m% | 62.47 | 60.73 | 60.16 | 58.85 | 49.80 |
| Yield of light oil/m% | 68.95 | 67.07 | 66.64 | 64.81 | 63.55 |
| Light receipts+liquefied gas/m% | 79.60 | 77.61 | 77.35 | 74.79 | 69.00 |
| Heavy oil/coke | 7.45 | 7.55 | 7.62 | 8.34 | 9.60 |
| Coke/transformation efficiency | 0.04 | 0.04 | 0.04 | 0.04 | 0.08 |
| Content of sulfur in gasoline, mg/L | 318.7 | 197 | 182 | 167 | 210.0 |
As can be seen from the above table, the V-Si molecular sieve of the inventive method preparation has the V-Si molecular sieve higher desulfuration effect than the ordinary method preparation, and the transformation efficiency height, and the amount of coke of generation is few.
Claims (8)
1. the preparation method of a V-Si molecular sieve, be that silicon source, vanadium source, template, mineral alkali and water are mixed into the reaction mixture that glue obtains, in airtight still, obtain the V-Si molecular sieve of MFI structure under the crystallization condition, it is characterized in that said template is n-Butyl Amine 99 and/or triethylamine, template and SiO
2Mol ratio be 0.04～0.5: 1.
2. according to the process of claim 1 wherein that said silicon source is selected from silica gel bead, water glass or silicon sol.
3. according to the process of claim 1 wherein that said vanadium source is selected from metavanadic acid, vanadic salts, oxyvanadium compound or organic vanadium complex compound.
4. according to the process of claim 1 wherein that said vanadium source is selected from vanadylic sulfate or Vanadium Pentoxide in FLAKES.
5. according to the method for claim 1, the mole of said reaction mixture consists of:
SiO
2/VO
2＝5～1000
OH
-/SiO
2＝0.02～0.6
H
2O/SiO
2＝5～30。
6. according to the method for claim 5, wherein the mole of reaction mixture consists of:
Template/SiO
2=0.08～0.2
SiO
2/VO
2＝10～100
OH/SiO
2＝0.05～0.4
H
2O/SiO
2＝5～15。
7. according to the method for claim 1, said crystallization condition is 120～200 ℃ of following crystallization 5 hours～10 days.
8. according to the method for claim 1, said crystallization condition is 60～120 ℃ of pre-crystallization 3～48 hours down, again 120～200 ℃ of crystallization 5 hours to 10 days.
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| CN109721515B (en) * | 2017-10-31 | 2020-12-04 | 中国石油化工股份有限公司 | Preparation method of sulfone |
| CN108906114B (en) * | 2018-07-19 | 2021-02-09 | 北京石油化工学院 | Vanadium-containing mesoporous silica ball catalyst and preparation method and application thereof |
| CN111392742B (en) * | 2020-04-16 | 2021-09-07 | 中南大学 | Molecular sieve material AM-6, and preparation method and application thereof |
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