CN109126841A - It is a kind of to prepare hud typed VPO@SiO2The method of catalyst - Google Patents
It is a kind of to prepare hud typed VPO@SiO2The method of catalyst Download PDFInfo
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- CN109126841A CN109126841A CN201810905675.9A CN201810905675A CN109126841A CN 109126841 A CN109126841 A CN 109126841A CN 201810905675 A CN201810905675 A CN 201810905675A CN 109126841 A CN109126841 A CN 109126841A
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- vpo
- catalyst
- sio
- hud typed
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 21
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- JCGCKSUCGVTMNB-UHFFFAOYSA-N acetic acid;formaldehyde Chemical compound O=C.CC(O)=O JCGCKSUCGVTMNB-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011258 core-shell material Substances 0.000 abstract description 7
- 238000005882 aldol condensation reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- LEABNKXSQUTCOW-UHFFFAOYSA-N [O].[P].[V] Chemical compound [O].[P].[V] LEABNKXSQUTCOW-UHFFFAOYSA-N 0.000 abstract description 2
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000540 VOPO4 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- B01J35/398—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
Abstract
The present invention relates to a kind of mesoporous silicon oxides to coat vanadium phosphorus oxide nano particle (VPO@SiO2) preparation method of catalyst belongs to organic catalysis technical field for formaldehyde acetic acid aldol condensation acrylic acid process.It is of the present invention to prepare hud typed VPO@SiO2The method of catalyst first prepares vanadium phosphorus oxygen nanoparticle, covers silicon dioxide layer in nanoparticle surface later, hud typed VPO@SiO is made2Catalyst.A kind of VPO@SiO of coreshell type structure will be prepared2Catalyst prevents the reunion and loss of active component in reaction process using the protective effect of shell, improves catalyst stability, lengthens catalyst service life.The present invention prepares acrylic acid reaction with its unique core-shell structure, the formaldehyde acetic acid aldol condensation steady in a long-term that is catalyzed.
Description
Technical field
The present invention relates to a kind of mesoporous silicon oxides to coat vanadium phosphorus oxide nano particle (VPO@SiO2) catalyst system
Preparation Method belongs to organic catalysis technical field for formaldehyde acetic acid aldol condensation acrylic acid process.
Background technique
Acrylic acid is raw material important in modern chemical industry, mainly for the production of acrylate and glacial acrylic acid.Acrylic acid
Ester such as methyl acrylate, ethyl acrylate etc. is mainly used in coating and adhesive industry；Glacial acrylic acid is then mainly used in life
Produce the industries such as super absorbent resin, papermaking chemical product and organic process.
Production acrylic acid is mostly used propylene two-step oxidizing process in world wide at present.Wherein raw material propylene is mainly derived from stone
Oil, this method will be with the reduction of petroleum resources and be affected.It is therefore desirable to develop a kind of novel, green production
Method.In recent years, it produces acrylic acid as raw material using the formaldehyde of excess capacity and acetic acid to have become a hot topic of research, this method not only may be used
To avoid the safety problem generated in oxidation of propylene due to the presence of oxygen, while also there is huge potential value, and
And meet the resource structures and Chemical Industry policy of China's richness coal, oil-poor, few gas.Therefore, pass through formaldehyde acetic acid aldol condensation
Method, which will prepare acrylic acid, to occupy huge advantage within the following certain time.
Current existing vpo catalyst is mostly using silica as carrier, if patent CN201710273203 is with five oxidations two
Vanadium is vanadium source, using phosphoric acid as phosphorus source, using ordered mesoporous silica dioxide SBA-15 as carrier, passes through filtering, dry and roasting after dipping
Burning prepares VPO/SBA-15 catalyst.But support type structure catalyst is the problem is that active component easily flows in reaction process
It loses.The present invention is intended to provide a kind of VPO@SiO of coreshell type structure2Catalyst prevents from reacting using the protective effect of shell
The reunion and loss of active component in the process improves catalyst stability, lengthens catalyst service life.
Summary of the invention
The present invention is intended to provide a kind of hud typed VPO@SiO2Catalyst is urged steadily in the long term with its unique core-shell structure
Change formaldehyde acetic acid aldol condensation and prepares acrylic acid reaction, it is specifically a kind of to prepare hud typed VPO@SiO2The method of catalyst.
The present invention is achieved by the following technical solutions: a kind of to prepare hud typed VPO@SiO2The method of catalyst, packet
Include following steps:
(1) VPO nano particle is prepared
By V2O5, benzyl alcohol, isobutanol mixing be placed in magnetic agitation in 140 DEG C of water-baths and be condensed back 6h, be added PEG continue
Flow back 1h, and 85% concentrated phosphoric acid is added dropwise into solution, continues the 6h that flows back, cooled to room temperature, filtering, and by gained sediment
It is washed 3 times, is placed in baking oven dry with isobutanol；Solid powder after drying is placed under 400 DEG C of environment and roasts 4h, is obtained
VPO nanoparticle；
(2) hud typed VPO@SiO is prepared2Catalyst
Dehydrated alcohol, deionized water, ammonium hydroxide, VPO nanoparticle and CTAB are mixed to form mixed liquor and ultrasound 5min, by institute
TEOS is added after obtaining mixed liquor stirring 30min, is placed in 60 DEG C of stirred in water bath 6h, filters, it is dry after ethanol washing 2 times, it is placed in
After roasting 2h under 200 DEG C of environment, it is placed under 550 DEG C of environment and roasts 6h, obtain hud typed VPO@SiO2Catalyst.
It as the further improvement of technical solution of the present invention, is calculated with g/ml, V2O5Mass volume ratio with PEG is 0.78.
As the further improvement of technical solution of the present invention, the V2O5Mass ratio with concentrated phosphoric acid is 1:2.79.
As the further improvement of technical solution of the present invention, the mass ratio of the V2O5, benzyl alcohol and isobutanol are 1:
3.14:2.39。
It is of the present invention to prepare hud typed VPO@SiO2The method of catalyst first prepares vanadium phosphorus oxygen nanoparticle, later
Silicon dioxide layer is covered in nanoparticle surface, hud typed VPO@SiO is made2Catalyst.A kind of coreshell type structure will be prepared
VPO@SiO2Catalyst prevents the reunion and loss of active component in reaction process using the protective effect of shell, improves catalysis
Agent stability lengthens catalyst service life.The present invention is steady in a long-term to be catalyzed formaldehyde acetic acid aldol with its unique core-shell structure
Condensation prepares acrylic acid reaction.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the electron microscope picture of the standby VPO nano particle obtained of embodiment of the present invention system 1.Institute as can be seen from Figure
The VPO nanoparticle size of preparation is smaller, distribution uniform, and average grain diameter is 75 nm.
Fig. 2 is the hud typed VPO@SiO that the embodiment of the present invention 1 prepares2Suction-desorption isotherm of catalyst and hole
Diameter scatter chart.The specific surface that BET multipoint method measures the catalyst is 825.56m2/ g, BJH method measure the average diameter in hole
For 4.1362nm.As can be seen from the figure Adsorption and desorption isotherms are in IV type hysteresis loop, and can be seen that by pore size distribution curve
Even mesoporous presence.On the one hand, core-shell structure provides micro- reaction environment for reaction, can effectively prevent the loss of active component；
On the other hand, the meso-hole structure on shell, is conducive to reactant and enters nucleocapsids to be in contact with active component, meanwhile, it is big to compare
The catalyst of surface area provides enough reactivity sites for reaction, and the catalytic performance of catalyst can be greatly improved.
Fig. 3 is the hud typed VPO@SiO that the embodiment of the present invention 1 prepares2The electron microscope of catalyst.By can in figure
To find out, VPO nanoparticle is wrapped up by silica perfection, and this unique nucleocapsid structure can be protected effectively during the reaction
Active component is protected, loss of active component and reunion are prevented, effectively lengthens the service life of catalyst.
Fig. 4 is the hud typed VPO@SiO that the embodiment of the present invention 1 prepares2The X-ray full-shape diffracted intensity of catalyst
Map.Diffraction maximum in figure is respectively carrier S iO2, active component VOPO4(VO)2PO7Diffraction maximum.Wherein VOPO4With
(VO)2PO7It is the main catalytic active component for being catalyzed formaldehyde acetic acid aldol reaction.
Fig. 5 is the hud typed VPO@SiO that the embodiment of the present invention 2 prepares2The electron microscope of catalyst.By can in figure
To find out, since its VPO nano particle diameter is in 100nm or more, cause most of VPO nanoparticle cannot be by silica packet
It wraps up in into silicon ball and be easy to cause the loss of catalyst activity component (as indicated by the arrows in the figure).
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Technical solution of the present invention is described in detail with reference to the accompanying drawing.
Embodiment 1
The chemical substance material that the present invention uses are as follows: cetyl trimethylammonium bromide CTAB, ammonium hydroxide (mass fraction 25%), nothing
Water-ethanol, vanadic anhydride, phosphoric acid (mass fraction 85%), deionized water, isobutanol, benzyl alcohol, gathers ethyl orthosilicate TEOS
Ethylene glycol PEG, preparing dosage with milligram, gram, milliliter is measurement unit:
CTAB:C16H33(CH3)3NBr 225.00mg±0. 01mg
Ammonium hydroxide: NH3·H2O 1.00mL±0.01mL
Dehydrated alcohol: C2H5OH 115.00 mL±0.01mL
TEOS:Si (OC2H5)4 1.00mL±0.01mL
Vanadic anhydride: V2O5 3.8837g ±0.0001g
Concentrated phosphoric acid: H3PO4 10.8237g±0.0001g
Deionized water: H2O 50.00mL±0.01mL
Isobutanol: C4H10O 60.0000g±0.0001g
Benzyl alcohol: C7H8O 12.1874g±0.0001g
PEG:HO (CH2CH2O)nH 5.00mL±0.01mL
1. preparing hud typed VPO@SiO2The method of catalyst is as follows:
(1) VPO nano particle is prepared
With V2O5For vanadium source, dense H3PO4For phosphorus source, VPO nano particle is prepared by Aqueous phase.
Measure 3.8837g ± 0.0001g V2O5, 12.1874g ± 0.0001g benzyl alcohol, 9.3000g ± 0.0001g it is different
Butanol is placed in three-necked flask, and after being placed in magnetic agitation in 140 DEG C of water-baths and being condensed back 6 h, 5.00 mL ± 0.01 are added
ML PEG continues 1 h that flows back, and 10.8237g ± 0.0001g concentrated phosphoric acid is slowly added dropwise into solution, cooling after continuing 6 h of reflux
It to room temperature, filters, and gained sediment is washed 3 times with isobutanol, be placed in 120 DEG C of baking ovens dry 10 h.By obtained solid
Powder is placed in Muffle kiln roasting and obtains VPO nanoparticle.
Roasting condition: sample is placed in Muffle furnace furnace chamber immediately below thermocouple, to ensure that temperature detection is correct.Adjust horse
Not furnace makes temperature be warming up to 400 DEG C by room temperature with the rate of 3 DEG C/min, 4 h of constant temperature.
(2) hud typed VPO@SiO is prepared2Catalyst
Using CTAB as surfactant, TEOS is silicon source, by hydrolysis-polymerization procedure, in VPO nanoparticle surface coated Si O2
Layer.
Successively measure 75.00 mL ± 0.01mL dehydrated alcohol, 50.00mL ± 0.01mL deionized water, 1.00mL ± 0.01
± 0. 01mg of mL ammonium hydroxide, 100.00mg VPO nanoparticle obtained by step (1) and ± 0. 01mg CTAB of 225.00mg are added
In beaker and ultrasound 5min, gained mixed liquor is transferred in three-neck flask, after being vigorously stirred 30min under room temperature, by mixed liquor
It is transferred in beaker and is added 1.00mL ± 0.01mL TEOS, is placed in 60 DEG C of water-baths and stirs 6 h, is filtered, ethanol washing 2 times
After dry, roasting removal CTAB template obtains hud typed VPO SiO2Catalyst.
Roasting condition: sample is placed in Muffle furnace furnace chamber immediately below thermocouple, to ensure that temperature detection is correct.Adjust horse
Not furnace makes temperature be warming up to 200 DEG C, 2 h of constant temperature by room temperature with the rate of 2 DEG C/min, continues to heat up with the rate of 2 DEG C/min
Constant temperature 6h after to 550 DEG C.
2, test, analysis and characterization
With transmission electron microscope observation sample topography；
Crystal phase analysis is carried out with x-ray diffractometer；
The mesoporous measurement of silicon dioxide layer is carried out with specific surface and Porosimetry.
Embodiment 2
Except the additive amount of PEG in step (1) is 2.00mL ± 0.01mL, other are the same as preparing hud typed VPO@described in embodiment
SiO2The method of catalyst.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (4)
1. a kind of prepare hud typed VPO@SiO2The method of catalyst, which comprises the steps of:
(1) VPO nano particle is prepared
By V2O5, benzyl alcohol, isobutanol mixing be placed in magnetic agitation in 140 DEG C of water-baths and be condensed back 6h, be added PEG continue
Flow back 1h, and 85% concentrated phosphoric acid is added dropwise into solution, continues the 6h that flows back, cooled to room temperature, filtering, and by gained sediment
It is washed 3 times, is placed in baking oven dry with isobutanol；Solid powder after drying is placed under 400 DEG C of environment and roasts 4h, is obtained
VPO nanoparticle；
(2) hud typed VPO@SiO is prepared2Catalyst
Dehydrated alcohol, deionized water, ammonium hydroxide, VPO nanoparticle and CTAB are mixed to form mixed liquor and ultrasound 5min, by institute
TEOS is added after obtaining mixed liquor stirring 30min, is placed in 60 DEG C of stirred in water bath 6h, filters, it is dry after ethanol washing 2 times, it is placed in
After roasting 2h under 200 DEG C of environment, it is placed under 550 DEG C of environment and roasts 6h, obtain hud typed VPO@SiO2Catalyst.
2. a kind of hud typed VPO@SiO is prepared according to claim 12The method of catalyst, which is characterized in that with g/ml
It calculates, V2O5Mass volume ratio with PEG is 0.78.
3. a kind of hud typed VPO@SiO is prepared according to claim 12The method of catalyst, which is characterized in that described
V2O5Mass ratio with concentrated phosphoric acid is 1:2.79.
4. a kind of hud typed VPO@SiO is prepared according to claim 12The method of catalyst, which is characterized in that described
V2O5, benzyl alcohol and isobutanol mass ratio be 1:3.14:2.39.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810905675.9A CN109126841B (en) | 2018-08-10 | 2018-08-10 | Preparation of core-shell VPO @ SiO2Method for preparing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810905675.9A CN109126841B (en) | 2018-08-10 | 2018-08-10 | Preparation of core-shell VPO @ SiO2Method for preparing catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109126841A true CN109126841A (en) | 2019-01-04 |
| CN109126841B CN109126841B (en) | 2020-08-14 |
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| CN112691680A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Composite catalyst for acrolein synthesis and preparation method and application thereof |
| CN113877612A (en) * | 2021-11-10 | 2022-01-04 | 中国科学院山西煤炭化学研究所 | Multifunctional catalyst compounded by FeMo component and VPO component, and preparation method and application thereof |
| CN115178275A (en) * | 2022-06-09 | 2022-10-14 | 中国科学院青岛生物能源与过程研究所 | Core-shell structure M X O y @mSiO 2 -SO 3 H-type catalyst, preparation thereof and method for preparing furfural by catalyzing corncobs |
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