CN105833903B - A kind of tungsten-containing mesoporous titanium dioxide microballoon and its preparation method and application - Google Patents
A kind of tungsten-containing mesoporous titanium dioxide microballoon and its preparation method and application Download PDFInfo
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- CN105833903B CN105833903B CN201610208143.0A CN201610208143A CN105833903B CN 105833903 B CN105833903 B CN 105833903B CN 201610208143 A CN201610208143 A CN 201610208143A CN 105833903 B CN105833903 B CN 105833903B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 23
- 239000010937 tungsten Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 8
- 239000000295 fuel oil Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 230000009977 dual effect Effects 0.000 claims abstract description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000013335 mesoporous material Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 5
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 2
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 9
- 239000002608 ionic liquid Substances 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 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
- 238000004364 calculation method Methods 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000193 wide-angle powder X-ray diffraction 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/51—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
Application the present invention relates to a kind of tungsten-containing mesoporous titanium dioxide microballoon and preparation method thereof and in fuel oil oxidation sweetening belongs to material preparation and catalysis reaction technology field.Regulate and control the pattern and structure of mesoporous catalyst by adjusting carbon chain lengths in ionic liquid cation and different calcination temperatures in the present invention.Functionalized ion liquid, water, butyl titanate and ammonium hydroxide are mixed successively in preparation process, persistently stirring mixture makes it be fully hydrolyzed polycondensation, then it fills this blend into the reaction kettle that liner is polytetrafluoroethylene (PTFE) and carries out hydro-thermal process, product obtains tungsten-containing mesoporous titanium dioxide microspherical catalyst after being filtered, washed, drying, grind, calcine.Present invention process is easy to operate, functionalized ion liquid has dual function, and by one pot process presoma, the mesoporous TiO 2 microballoon of tungsten species high degree of dispersion can be obtained after temperature programming calcining, mild in oxidation sweetening reaction process conditional, catalyst desulfurizing is efficient and can recycle.
Description
Technical field
The present invention relates to a kind of tungsten-containing mesoporous titanium dioxide microballoon and preparation method thereof and answering in fuel oil oxidation sweetening
With belonging to material preparation and catalysis reaction technology field.
Technical background
Gasoline and diesel oil are the staple products of PETROLEUM PROCESSING industry, they are widely used in as the main fuel oil of engine
In auto industry.The use of fuel oil brings facility to social development and human lives, but also produces should not be underestimated simultaneously
Environmental problem.Wherein, the sulfur-containing compound in fuel oil not only will produce sulfur oxide (SO after fuel oil burningx) and pollute ring
Border, and excessive sulfate can be generated, lead to the catalyst poisoning of automobile exhaust gas processing apparatus, so as to cause the row of vehicle exhaust
High-volume increase.Solve the problems, such as that this is needed since source, therefore countries in the world are all in the research for carrying out clean fuel oil, wherein oxygen
Change desulfurization technology because desulfuration efficiency is high, reaction condition is relatively mild, it is easy to operate at low cost the features such as and obtained grinding extensively
Study carefully.In oxidative desulfurization techniques, develop efficient catalyst promote desulphurization reaction carry out be the key that influence desulfuration efficiency because
Element.
Mesoporous material usually has larger specific surface area, there is aperture pass and can be used as activity that size is adjustable
The features such as carrier of ingredient, has been successfully applied to desulfurization system.Wherein studying more has regular pore canal distribution
MCM series and SBA series mesoporous materials, but this kind of mesoporous material is selected to make building-up process complexity when carrier, it is loaded
Active constituent is easy to block mesopore orbit, and desulfuration efficiency is caused to reduce.In addition, about mesoporous TiO 2 in oxidation sweetening
Research is also less.And if one-step method introduces catalytic active center during synthesising mesoporous titanic oxide material, so not
The building-up process of catalyst can only be simplified, moreover it is possible to adjust the property of mesoporous material by changing the type of template.It is being situated between
In the building-up process of Porous materials, catalytic active center is first combined with ionic liquid template first, obtains functionalized ion liquid,
CTAB or CTAC as conventional mould agent are substituted with this functionalized ion liquid, in functionalized ion liquid self assembly
Activated centre can be made uniformly to arrange in the process, go after removing template that the mesoporous material of catalytic active center high degree of dispersion can be obtained
Catalyst.Easy to operate, of low cost, morphology controllable and efficient tungsten-contained mesic porous titanium dioxide can be developed by this design
Titanium catalyst, the mesoporous catalyst structural property are stablized, and are applied to desulfuration efficiency height when multiphase desulfurization system, recycle performance
It is good, there is good prospects for commercial application.
Invention content
It is an object of the present invention to provide a kind of preparation methods of one pot process tungsten-containing mesoporous titanium dioxide microballoon.The present invention's
Another has been designed to provide application of the above-mentioned mesoporous catalyst in catalytic oxidation desulfurization field.
The present invention is realized by following steps：
(1) functionalized ion liquid is prepared：
By quaternary ammonium type ionic liquid [(CnH2n+1)N(CH3)3] Cl (n=4,8,12,16,18) and H3PW12O40According to mole
Than being 3：1 ratio mixing is soluble in water, is filtered after being sufficiently stirred, and repeatedly washs solid until can't detect Cl in filtrate-For
Only, product [(C is obtainednH2n+1)N(CH3)3]3PW12O40(it is abbreviated as CnPW, n=4,8,12,16,18)
(2) one kettle way prepares tungsten-containing mesoporous titanium dioxide microballoon：
By CnPW is dissolved in acetonitrile, then sequentially adds deionized water, butyl titanate and ammonium hydroxide, and object to be mixed fills
Divide to be transferred to after being stirred in the reaction kettle that liner is polytetrafluoroethylene (PTFE) and carry out hydro-thermal process, obtained product is washed into
Property and drying, obtained mesoporous material presoma are expressed as CnPW-TiO2, then in temperature programming Muffle furnace under air atmosphere
Calcining, calcination temperature are indicated, to get to tungsten-containing mesoporous titanium dioxide microballoon, to be expressed as X-CnW-TiO with X2。
In the preparation method, functionalized ion liquid CnPW plays template and metal active centres dual function,
Middle cation carbon chain lengths n=4,8,12,16,18.
In the preparation method, butyl titanate and CnThe molar ratio of PW is 250:1–60:1.
In the preparation method, the molar ratio of butyl titanate and water is 1:100–1:200.
In the preparation method, the molar ratio of butyl titanate and ammonium hydroxide is 1:0.5–1:2.5.
The mixing time of mixture is 0.5-3.5h.
Hydro-thermal process temperature is 100-160 DEG C, and the time is 12-48h.
Product drying temperature is 100-140 DEG C, and the time is 1-6h.
Calcining refers in air atmosphere calcines in temperature programming Muffle furnace, X=350-850 DEG C of calcination temperature, heating speed
Rate is 1-10 DEG C/min, 1-5h of calcination time.
During conventional synthesising mesoporous material catalyst, it usually needs template is added to regulate and control meso-hole structure, and adds
Enter activated centre of the inorganic salts of the high metal of catalytic activity as synthesized material.Compared with conventional method, adopted in the present invention
With one kettle way one-step synthesis tungsten-containing mesoporous titanium dioxide microspherical catalyst, first complex functionality ionic liquid, ionic liquid at this time
It can play the role of template, while also function to the activated centre of catalyst, optimize the system of complex mesoporous material
Standby process.Hydrothermal treatment process is conducive to the formation of Long carbon chain ionic liquid induction titanium dioxide microballoon sphere, by adjusting presoma
Calcination temperature control the removal amount of template, thus to obtain the catalyst with different structure feature, be associated with catalyst knot
Structure-activity relationship between structure feature and catalytic activity.
Utilize wide-angle x-ray powder diffraction (XRD), surface analysis instrument (BET), scanning electron microscope (SEM), transmission
Electron microscope (TEM) etc. carries out pattern and structural analysis to product, is typical sulfur-containing compound allocation models oil with DBT, will
Above-mentioned synthesis load-type ion liquid is made catalyst and is reacted applied to oxidation sweetening.After gas-chromatography (GC) detection reaction
DBT surpluses assess the catalytic performance of catalyst.
Description of the drawings
Fig. 1 is to use C18PW is tungsten-contained mesic porous TiO prepared by template2The wide-angle XRD analysis of microspherical catalyst, can be with from figure
See the raising with calcination temperature, TiO2It is anatase phase from unformed crystal transition, and when calcination temperature reaches 750 DEG C
When there is apparent WO3Wide-angle XRD diffraction maximums.(a):350-C18W-TiO2,(b):450-C18W-TiO2,(c):550-
C18W-TiO2,(d):650-C18W-TiO2(e):750-C18W-TiO2。
Fig. 2 is to use C18PW is tungsten-contained mesic porous TiO prepared by template2The N of microspherical catalyst2Adsorption/desorption figure (A) and average
Graph of pore diameter distribution (B) has as can be seen from the figure obtained the N of I types when calcination temperature is less than 550 DEG C2Adsorption/desorption isotherms,
This is as caused by micropore and accumulation hole；And the N of IV types is obtained when calcination temperature is not less than 550 DEG C2Adsorption/desorption isothermal
Line shows that catalyst at this time has meso-hole structure.And calcination temperature be 550 DEG C and 650 DEG C when the more other temperature of pore-size distribution
Degree is more uniform, and average pore size is mainly distributed on 2-6nm, in macropore range；(a):350-C18W-TiO2,(b):450-C18W-
TiO2,(c):550-C18W-TiO2,(d):650-C18W-TiO2(e):750-C18W-TiO2。
Fig. 3 is to use C18PW is tungsten-contained mesic porous TiO prepared by template2Microspherical catalyst 550-C18W-TiO2SEM (A and B),
TEM photos (C) and X-ray energy spectrogram (EDS) (D), it can be seen that gained TiO2Carrier is the microballoon with meso-hole structure, activity
Ingredient WO3It is distributed in TiO2Microsphere surface can detect the various elements that mesoporous catalyst is included in EDS spectrograms, further
It illustrates ionic liquid loaded on carrier.
Fig. 4 is to use C18PW is tungsten-contained mesic porous TiO prepared by template2Microspherical catalyst 550-C18W-TiO2To different sulfur-bearing bottoms
The catalytic oxidative desulfurization Performance of object as can be seen from the figure has preferably removing effect to several substrates under the reaction conditions
Fruit is followed successively by the removing ability sequence of four kinds of substrates：DBT>4-MDBT>4,6-DMDBT>BT reacts corresponding desulfurization after 1h
Rate is respectively：100%, 96.1%, 85.2% and 82.6.
Specific implementation mode
1 tungsten-containing mesoporous titanium dioxide microballoon 550-C of embodiment18W-TiO2Preparation
Take 0.3179gC1828.85mL deionized waters are added in 5mL acetonitriles in PW ion liquid dissolvings under stirring condition, then
3.3692g butyl titanates and 0.58mL ammonium hydroxide is added, it is poly- four to be sufficiently stirred after reacting 3h mixing liquid being transferred to liner
In the reaction kettle of vinyl fluoride, it is put into air dry oven 100 DEG C of hydro-thermals for 24 hours.Products therefrom is fully washed to neutrality and is filtered,
The dry 3h at 120 DEG C, then by obtained solid grind into powder, by powder with 2 DEG C/min's in temperature programming Muffle furnace
Heating rate rises to 550 DEG C, and keeps 300min, is finally down to room temperature, you can obtains the catalysis of tungsten-containing mesoporous titanium dioxide microballoon
Agent 550-C18W-TiO2。
2 tungsten-containing mesoporous titanium dioxide microballoon 350-C of embodiment4W-TiO2Preparation
Take 0.2688gC428.85mL deionized waters are added in 5mL acetonitriles in PW ion liquid dissolvings under stirring condition, then
3.3692g butyl titanates and 0.58mL ammonium hydroxide is added, it is poly- four to be sufficiently stirred after reacting 2h mixing liquid being transferred to liner
In the reaction kettle of vinyl fluoride, it is put into 120 DEG C of hydro-thermal 36h in air dry oven.Products therefrom is fully washed to neutrality and is filtered,
The dry 2h at 140 DEG C, then by obtained solid grind into powder, by powder with 5 DEG C/min's in temperature programming Muffle furnace
Heating rate rises to 350 DEG C, and keeps 240min, is finally down to room temperature, you can obtains the catalysis of tungsten-containing mesoporous titanium dioxide microballoon
Agent 350-C4W-TiO2。
3 tungsten-containing mesoporous titanium dioxide microballoon 750-C of embodiment12W-TiO2Preparation
Take 0.2969gC1228.85mL deionized waters are added in 5mL acetonitriles in PW ion liquid dissolvings under stirring condition, then
3.3692g butyl titanates and 0.58mL ammonium hydroxide is added, it is poly- four to be sufficiently stirred after reacting 1h mixing liquid being transferred to liner
In the reaction kettle of vinyl fluoride, it is put into 160 DEG C of hydro-thermal 12h in air dry oven.Products therefrom is fully washed to suction filtration, at 100 DEG C
Lower dry 6h, then by obtained solid grind into powder, by powder with the heating of 10 DEG C/min speed in temperature programming Muffle furnace
Rate rises to 750 DEG C, and keeps 180min, is finally down to room temperature, you can obtains tungsten-containing mesoporous titanium dioxide microspherical catalyst 750-
C12W-TiO2。
4 tungsten-containing mesoporous titanium dioxide microballoon 550-C of embodiment18W-TiO2Oxidation sweetening Performance
By the mesoporous TiO 2 microspherical catalyst 550-C of 1 gained of embodiment18W-TiO2Applied to catalytic oxidative desulfurization mould
Sulfur-containing compound in type oil, specific dosage are：0.04g mesoporous catalysts, dioxygen water consumption n (O/S)=4 are added self-control and contain
DBT, 4-MDBT, 4,6-DMDBT and BT are the mould oil 5mL of 500ppm, are stirred to react under the conditions of 50 DEG C of waters bath with thermostatic control, are added
Start timing after hydrogen peroxide, stop after reacting 1h, tested with GC-MS at interval of 10min samplings primary, it follows that the catalysis
The removal effect of the different sulfur-bearing substrates of four kinds of agent pair, is as a result shown in attached drawing 4.
Desulfurization degree calculation formula is：S%=(C0-Ct)/C0×100.Wherein C0(ppm) indicate that the starting sulphur of mould oil contains
Amount, Ct(ppm) sulfur content of the mould oil when reacting t (min) is indicated.
Claims (7)
1. a kind of preparation method of tungsten-containing mesoporous titanium dioxide microballoon, TiO2Carrier is the microballoon with meso-hole structure, active constituent
WO3It is distributed in TiO2Microsphere surface, it is characterised in that：By [(CnH2n+1)N(CH3)3]3PW12O40It is dissolved in acetonitrile, then successively
Deionized water, butyl titanate and ammonium hydroxide is added, object to be mixed is transferred to liner after being thoroughly mixed be polytetrafluoroethylene (PTFE)
Reaction kettle in carry out hydro-thermal process, obtained product is washed to neutral and dry, obtained mesoporous material presoma indicates
For CnPW-TiO2, then calcined under air atmosphere in temperature programming Muffle furnace, calcination temperature indicates to be situated between to get to tungstenic with X
Porous titanium dioxide microballoon is expressed as X-CnW-TiO2；Functionalized ion liquid [(CnH2n+1)N(CH3)3]3PW12O40Play template
Agent and metal active centres dual function, wherein cationic carbon chain lengths n=4,8,12,16,18；Butyl titanate with
[(CnH2n+1)N(CH3)3]3PW12O40Molar ratio be 250:1–60:1；The molar ratio of butyl titanate and water is 1:100–1:
200；The molar ratio of butyl titanate and ammonium hydroxide is 1:0.5–1:2.5；The mixing time of mixture is 0.5-3.5h；Hydro-thermal process
Temperature is 100-160 DEG C, and the time is 12-48h；Product drying temperature is 100-140 DEG C, and the time is 1-6h；In air atmosphere
Calcining refers to and is calcined in temperature programming Muffle furnace, X=350-850 DEG C of calcination temperature, and heating rate is 1-10 DEG C/min, when calcining
Between 1-5h.
2. a kind of preparation method of tungsten-containing mesoporous titanium dioxide microballoon as described in claim 1, it is characterised in that：Cationic carbon
Chain length n=18.
3. a kind of preparation method of tungsten-containing mesoporous titanium dioxide microballoon as described in claim 1, it is characterised in that：Calcination temperature
X=550-850 DEG C.
4. a kind of preparation method of tungsten-containing mesoporous titanium dioxide microballoon as described in claim 1, it is characterised in that：Calcination temperature
X=550 or 650 DEG C.
5. a kind of preparation method of tungsten-containing mesoporous titanium dioxide microballoon as described in claim 1, it is characterised in that：Calcination temperature
X=550 DEG C.
6. a kind of tungsten-containing mesoporous titanium dioxide microballoon prepared by the preparation method as described in any in claim 1-5 is removing
Purposes in fuel oil in sulfur-bearing sulfide.
7. purposes as claimed in claim 6, it is characterised in that：The sulfur-bearing sulfide be DBT, 4-MDBT, 4,6-DMDBT or
BT is followed successively by the removing ability sequence of four kinds of substrates：DBT>4-MDBT>4,6-DMDBT>BT.
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| CN110302774A (en) * | 2019-06-20 | 2019-10-08 | 江苏大学 | A kind of preparation method and applications of the three-dimensional ordered macroporous titanic oxide material of witch culture |
| CN112028184B (en) * | 2020-09-15 | 2022-11-01 | 江苏恒湾环保科技有限公司 | Preparation method of mesoporous titanium oxide hollow microsphere electrode material |
| CN112371149A (en) * | 2020-10-23 | 2021-02-19 | 江苏大学 | Preparation method and application of tungsten oxide confinement-supported boron carbon nitrogen nanotube catalyst material |
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| CN103464141A (en) * | 2013-09-06 | 2013-12-25 | 江苏大学 | Mesoporous material containing high-dispersive tungsten as well as preparation method and application of mesoporous material containing high-dispersive tungsten |
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