CN110330055A - A kind of preparation method and applications of three-dimensional ordered macroporous tungsten trioxide material - Google Patents
A kind of preparation method and applications of three-dimensional ordered macroporous tungsten trioxide material Download PDFInfo
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- CN110330055A CN110330055A CN201910536713.2A CN201910536713A CN110330055A CN 110330055 A CN110330055 A CN 110330055A CN 201910536713 A CN201910536713 A CN 201910536713A CN 110330055 A CN110330055 A CN 110330055A
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- tungsten trioxide
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- ordered macroporous
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003921 oil Substances 0.000 claims abstract description 72
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 41
- 230000023556 desulfurization Effects 0.000 claims abstract description 40
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 25
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000013019 agitation Methods 0.000 claims abstract description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000000295 fuel oil Substances 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000006837 decompression Effects 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 235000019441 ethanol Nutrition 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 25
- 239000011593 sulfur Substances 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- -1 aliphatic sulfides Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000001590 oxidative effect Effects 0.000 abstract description 14
- 239000007800 oxidant agent Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005287 template synthesis 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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/76—Dibenzothiophenes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to heterogeneous catalyst fields, are related to the preparation method and its application of a kind of three-dimensional ordered macroporous tungsten trioxide material；Step are as follows: ethyl alcohol and distilled water are mixed, ammonium metatungstate is added, obtains mixed solution；PMMA is added；Decompression suction filtration is carried out after standing, the PMMA after being impregnated is placed in Muffle furnace after drying at room temperature, three-dimensional ordered macroporous tungsten trioxide material is obtained after calcination processing；Material and model oil product mixing prepared by the present invention, is placed in magnetic agitation in oil bath, and is passed through air and carries out desulfurization；Present invention process is simple, resulting materials have preferable catalytic activity to sulfide removing in fuel oil, desulfurizing oil rate can be effectively improved, the dosage for reducing catalyst, the air for using environmental protection to be easy to get is as oxidant, without using organic solvent, reduce production cost, oil quality, and recyclable reuse are improved, environmental pollution is reduced.
Description
Technical field
The invention belongs to heterogeneous catalyst fields, and in particular to a kind of preparation side of three-dimensional ordered macroporous tungsten trioxide material
Method and its application in fuel desulfuration.
Background technique
Since in recent years, auto industry is fast-developing, thus also brings people to the great demand of fuel oil, and in fuel oil
Sulfide burning caused by exhaust gas atmospheric environment can but be damaged, therefore limit fuel oil sulfur content just seem outstanding
For necessity；Oxidative desulfurization techniques are because having compared with high desulfurization efficiency, and reaction condition is mild, and operating cost is low and process flow is simple
The features such as and attract attention；Catalyst involved in oxidation sweetening includes organic acid at present, ionic liquid, polyoxometallate,
Metal oxide and molecular sieve etc..
Large pore material is because the characteristics such as its biggish aperture and specific surface area, adjustable pass and aperture are in catalyst field
It is concerned；Precursor solution is immersed using template in the gap of template, removes, can open using solidification, template
Issue excellent large pore material catalyst.The colloid crystal being commonly used is polystyrene (PS) and poly-methyl methacrylate
High molecular materials and the silica such as ester (PMMA).These colloidal crystal templates are reversely replicated, presentation counter opal can be obtained
The material of structure.Key is filling of the raw material of target product in colloid crystal gap.The mode of being generally filled with includes colloidal sol-
Gel method, chemical reaction method, electrodeposition process and chemical vapour deposition technique etc..Sol-gel processing is most widely used, the method
It is easy to operate, it is at low cost, and each component distribution is uniform.Electrochemical deposition method is colloid crystal as electrode, is dipped into containing target
In the electroplate liquid of material ions, after setting voltage or electric current, target material can be in the gap of colloidal crystal by bottom to top
It gradually grows, the advantages of the method is that target material is filled in hole completely, the disadvantage is that must first be in colloidal crystal surface
One layer of conductive layer is covered, the difficulty of motor preparation is increased.Currently, there is document report soft using P123, F127 and CTAB etc.
A series of templated synthesis catalyst of small-bores, however since its lesser aperture leads to that it is easy to block and soft template method closes
At the process is more complicated, be not suitable for industrial application；In addition macropore is synthesized by macromolecular self-assembly method there are also document report to urge
Agent, although possessing macroporous structure, pore-size distribution is inhomogenous and thermostabilization is poor, cannot bear high temperature.It therefore is to overcome this
A little problems, the present invention are not easy to block up using PMMA as the large pore material of macropore template synthesis three-dimensional order in catalysis reaction
It fills in and has excellent stability.
Summary of the invention
In view of the deficienciess of the prior art, the invention reside in provide a kind of three-dimensional ordered macroporous tungsten trioxide material
Preparation method and applications；Three-dimensional ordered macroporous tungsten trioxide material prepared by the present invention has three-dimensional ordered macroporous structure, compared with
Big aperture, pore volume and specific surface area, duct interconnected have excellent activity during oxidation sweetening, can
Sulfide in efficient removal oil product, and compared to oxidants such as traditional hydrogen peroxide, there are at high cost, risk is big etc.
Problem, the required oxidant oxygen of the present invention largely exists in air, cheap and easy to get, and production cost can be greatly reduced.
In order to achieve the goal above, the present invention includes the following steps:
(1) ethyl alcohol and distilled water are mixed first, ammonium metatungstate is then added, at room temperature stirring and dissolving, obtains mixed solution；
Then macropore template polymethyl methacrylate (i.e. PMMA) is added in mixed solution；After standing a period of time, subtracted
Pressure filters, and removes surplus liquid；It is standby to obtain desciccate after drying a period of time at room temperature by PMMA after being impregnated
With；
(2) product of step (1) after dry is placed in Muffle furnace, the temperature programming under certain heating rate is added
Thermal response obtains three-dimensional ordered macroporous tungsten trioxide material after reaction.
Using the three-dimensional ordered macroporous tungsten trioxide material of preparation as catalyst, applied in oil product sulfur-containing compound it is de-
It removes, the specific steps are as follows:
(3) three-dimensional ordered macroporous tungsten trioxide material obtained by step (2) and model oil product are mixed, is placed in magnetic force in oil bath
Stirring, and be passed through air and carry out desulfurization；
(4) after desulfurization, three-dimensional ordered macroporous tungsten trioxide material and model oil product are centrifuged, point
After drying from obtained solid, i.e., recycling obtains three-dimensional ordered macroporous tungsten trioxide material, is used for this catalytic desulfurization, circulation
It uses.
The present invention carries out sulphur content determination using gas chromatograph, and the amount for carrying out sulphur content determination every time is 1 μ L.
Preferably, the amount ratio of ethyl alcohol described in step (1), distilled water, ammonium metatungstate and polymethyl methacrylate is
1-3mL:1-5mL:0.7391-7.3906g:0.5-5g.
Preferably, stirring rate described in step (1) is 100-1000rpm, mixing time 1-24h.
Preferably, standing a period of time described in step (1) is 1-24h.
Preferably, the time dry described in step (1) is 8-72h.
Preferably, programmed rate described in step (2) are as follows: 0.5-3 DEG C/min；Described program heating temperature be
200-800 DEG C, reaction time 2-5h.
Preferably, the amount ratio of three-dimensional ordered macroporous tungsten trioxide material described in step (3) and model oil product is 0.01-
0.1g:20-200mL
Preferably, model oil product described in step (3) is the oil product of the 200ppm containing sulfur content, configuration method are as follows: will
The internal standard hexadecane of 0.7653g and the sulfide 4 of 1.0239g, 6-DMDBT is added in beaker, using dodecane as solvent, mixes molten
The volumetric flask of 1000mL is transferred to after solution, constant volume shakes up, and obtains internal standard 1000ppm, and sulfur content is the 4,6-DMDBT of 200ppm
Mould oil.
Preferably, oil bath temperature described in step (3) is 110-130 DEG C, and air mass flow 50-100mL/min, magnetic force stirs
Mixing revolving speed is 800-1000rpm.
Preferably, the revolving speed of centrifuge separation described in step (4) is 4000rpm, time 3-5min.
Preferably, drying temperature described in step (4) is 80 DEG C, time 6-12h.
A kind of three-dimensional ordered macroporous tungsten trioxide material of above method preparation, has good three-dimensional ordered macroporous knot
Structure.
Three-dimensional ordered macroporous tungsten trioxide material prepared by the present invention sulfur-containing compound side in catalytic oxidative desulfurization oil product
The application in face, fragrant family sulfide or aliphatic sulfides predominantly in catalytic oxidative desulfurization fuel oil, such as 4,6- dimethyl two
The oxidation reaction of benzothiophene (4,6-DMDBT), the reaction process can be represented by the formula:
Three-dimensional ordered macroporous tungsten trioxide material has higher removal efficiency to the different sulfur-bearing substrates in oil product, to fragrance
Family sulfide 4,6-DMDBT reacts 4h, and desulfurization degree can reach 99%, for sulfide DBT, reacts 8h, desulfurization degree can reach
98%, for sulfide 4-MDBT, react 7h, desulfurization degree 99%.
The invention has the benefit that
(1) three-dimensional ordered macroporous tungsten trioxide material prepared by the present invention has three-dimensional ordered macroporous structure, biggish hole
Diameter, pore volume and specific surface area, duct interconnected, these features ensure that the abundant of sulfur-bearing substrate and activated centre first
Contact, next solves the problems, such as duct blocking.
(2) in three-dimensional ordered macroporous tungsten trioxide material prepared by the present invention there are oxygen defect, thus work with higher
Property.
(3) three-dimensional ordered macroporous tungsten trioxide material prepared by the present invention utilizes poly-methyl methacrylate in synthesis step
Ester simplifies synthesis process as source metal, reduces synthesis cost as template, ammonium metatungstate, big for synthesis three-dimensional order
Mesoporous metal oxide provides new approaches；With macroporous structure, compared with Large ratio surface, aperture, pore volume, catalytic activity height etc. is excellent
Point can overcome deficiency in the prior art；Both it had been able to achieve the abundant exposure of active site, has made sulfur-bearing substrate and activated centre
Contact it is good, and be able to achieve the simple recycling and recycling of catalyst, sulfur-bearing chemical combination in fuel oil is removed in depth in final realize
The target of object.And in catalytic oxidative desulfurization fuel oil during sulfur-bearing substrate, without using organic solvent.
(4) three-dimensional ordered macroporous tungsten trioxide material prepared by the present invention has excellent work during oxidation sweetening
Property, can sulfide in efficient removal oil product, and there are at high cost, dangerous compared to oxidants such as traditional hydrogen peroxide
Property it is big the problems such as, the required oxidant oxygen of the present invention largely exists in air, cheap and easy to get, can be greatly reduced and be produced into
This.
Detailed description of the invention
Fig. 1 is the scanning figure of three-dimensional ordered macroporous tungsten trioxide material prepared by example 1.
Fig. 2 is the XPS figure of three-dimensional ordered macroporous tungsten trioxide material prepared by example 1.
Fig. 3 is catalytic activity result of the three-dimensional ordered macroporous tungsten trioxide material to different sulfur-bearing substrates of the preparation of example 1
Figure.
Fig. 4 is circulation of the three-dimensional ordered macroporous tungsten trioxide material to 4,6-DMDBT in removing simulation oil of the preparation of example 1
Results of property figure.
Specific embodiment
With reference to the accompanying drawing and specific embodiment further illustrates the contents of the present invention.
Desulfurization degree test:
By three-dimensional ordered macroporous tungsten trioxide material (3DOM WO3) it is used for sulfur-containing compound in catalytic oxidative desulfurization oil product,
Detailed process is as follows, and 10mg 3DOM WO is added in a three-neck flask with reflux condensing tube3, 20mL sulfur content is
The simulation oil of 200ppm carries out heating stirring reaction at 120 DEG C；After reaction, it stands, layering, takes out upper layer oil sample, warp
It crosses after being centrifugated and carries out the analysis of sulfur content by GC.
By taking 4,6-DMDBT as an example, reaction equation are as follows:
Embodiment 1:
(1) 3mL distilled water and 3mL dehydrated alcohol are mixed first, the ammonium metatungstate of 3.6953g is then added, at room temperature
The revolving speed of 600rpm stirs 1h, and mixed solution is obtained after dissolution；Then the macropore template polymethyl methacrylate of 1.0g is added
Enter in mixed solution；After standing 4h, decompression suction filtration is carried out, removes surplus liquid；PMMA after being impregnated, does at room temperature
It is dry for 24 hours, it is spare to obtain desciccate；
(2) product of step (1) after dry is placed in Muffle furnace, is warming up to 400 DEG C with the rate of 1 DEG C/min, keeps
3h obtains three-dimensional ordered macroporous tungsten trioxide material；
(3) three-dimensional ordered macroporous tungsten trioxide material obtained by step (2) is directly mixed with model oil product, three-dimensional order is big
The amount ratio of hole tungsten trioxide material and model oil product is 0.1g:100mL, and model oil product is 4,6- that sulfur content is 200ppm
DMDBT mould oil is placed in magnetic agitation in oil bath, and is passed through air and carries out desulfurization；Wherein oil bath temperature is 120 DEG C, empty
Throughput is 80mL/min, magnetic agitation rotating speed 1000rpm.
It (4) with revolving speed is 4000rpm by three-dimensional ordered macroporous tungsten trioxide material and model oil product after desulfurization
5min is centrifuged, isolated solid is after 80 DEG C, drying 8h, as three-dimensional ordered macroporous tungsten trioxide material,
It can be re-used for desulfurization, be recycled.
Three-dimensional ordered macroporous tungsten trioxide material is made in embodiment 1, for removing 4 in fuel oil using oxygen as oxidant,
6-DMDBT, the desulfurization degree that above-mentioned steps (3) are measured after 8 hours is 99%.
Embodiment 2:
(1) 1mL distilled water and 5mL dehydrated alcohol are mixed first, the ammonium metatungstate of 0.7391g is then added, at room temperature
The revolving speed of 300rpm stirs 12h, and mixed solution is obtained after dissolution；Then the macropore template polymethyl methacrylate of 0.5g is added
Enter in mixed solution；After standing 1h, decompression suction filtration is carried out, removes surplus liquid；PMMA after being impregnated, does at room temperature
Dry 8h, it is spare to obtain desciccate；
(2) product of step (1) after dry is placed in Muffle furnace, is warming up to 400 DEG C with the rate of 1 DEG C/min, keeps
2h obtains three-dimensional ordered macroporous tungsten trioxide material；
(3) three-dimensional ordered macroporous tungsten trioxide material obtained by step (2) is directly mixed with model oil product, three-dimensional order is big
The amount ratio of hole tungsten trioxide material and model oil product is 0.1g:200mL, and model oil product is 4,6- that sulfur content is 200ppm
DMDBT mould oil is placed in magnetic agitation in oil bath, and is passed through air and carries out desulfurization；Wherein oil bath temperature is 130 DEG C, empty
Throughput is 100mL/min, magnetic agitation rotating speed 900rpm.
It (4) with revolving speed is 4000rpm by three-dimensional ordered macroporous tungsten trioxide material and model oil product after desulfurization
4min is centrifuged, isolated solid is after 80 DEG C, drying 12h, as three-dimensional ordered macroporous tungsten trioxide material,
It can be re-used for desulfurization, be recycled.
Three-dimensional ordered macroporous tungsten trioxide material is made in embodiment 2, for removing 4 in fuel oil using oxygen as oxidant,
6-DMDBT, the desulfurization degree that above-mentioned steps (3) are measured after 8 hours is 89%.
Embodiment 3:
(1) 5mL distilled water and 1mL dehydrated alcohol are mixed first, the ammonium metatungstate of 7.3906g is then added, at room temperature
The revolving speed of 1000rpm stirs 8h, and mixed solution is obtained after dissolution；Then the macropore template polymethyl methacrylate of 5g is added
In mixed solution；After standing for 24 hours, decompression suction filtration is carried out, removes surplus liquid；PMMA after being impregnated, does at room temperature
Dry 72h, it is spare to obtain desciccate；
(2) product of step (1) after dry is placed in Muffle furnace, is warming up to 400 DEG C with the rate of 1 DEG C/min, keeps
5h obtains three-dimensional ordered macroporous tungsten trioxide material；
(3) three-dimensional ordered macroporous tungsten trioxide material obtained by step (2) is directly mixed with model oil product, three-dimensional order is big
The amount ratio of hole tungsten trioxide material and model oil product is 0.05g:100mL, and model oil product is 4,6- that sulfur content is 200ppm
DMDBT mould oil is placed in magnetic agitation in oil bath, and is passed through air and carries out desulfurization；Wherein oil bath temperature is 130 DEG C, empty
Throughput is 80mL/min, magnetic agitation rotating speed 800rpm.
It (4) with revolving speed is 4000rpm by three-dimensional ordered macroporous tungsten trioxide material and model oil product after desulfurization
3min is centrifuged, isolated solid is after 80 DEG C, drying 6h, as three-dimensional ordered macroporous tungsten trioxide material,
It can be re-used for desulfurization, be recycled.
Three-dimensional ordered macroporous tungsten trioxide material is made in embodiment 3, for removing 4 in fuel oil using oxygen as oxidant,
6-DMDBT, the desulfurization degree that above-mentioned steps (3) are measured after 8 hours is 91%.
Embodiment 4:
A kind of preparation method of three-dimensional ordered macroporous tungsten trioxide material, including the following steps:
(1) 3mL distilled water and 3mL dehydrated alcohol are mixed first, the ammonium metatungstate of 3.6953g is then added, at room temperature
The revolving speed of 800rpm stirs 12h, and mixed solution is obtained after dissolution；Then the macropore template polymethyl methacrylate of 1g is added
In mixed solution；After standing 10h, decompression suction filtration is carried out, removes surplus liquid；PMMA after being impregnated, does at room temperature
Dry 36h, it is spare to obtain desciccate；
(2) product of step (1) after dry is placed in Muffle furnace, is warming up to 300 DEG C with the rate of 0.5 DEG C/min, protects
3h is held, three-dimensional ordered macroporous tungsten trioxide material is obtained；
(3) three-dimensional ordered macroporous tungsten trioxide material obtained by step (2) is directly mixed with model oil product, three-dimensional order is big
The amount ratio of hole tungsten trioxide material and model oil product is 0.01g:20mL, and model oil product is 4,6- that sulfur content is 200ppm
DMDBT mould oil is placed in magnetic agitation in oil bath, and is passed through air and carries out desulfurization；Wherein oil bath temperature is 110 DEG C, empty
Throughput is 50mL/min, magnetic agitation rotating speed 800rpm.
It (4) with revolving speed is 4000rpm by three-dimensional ordered macroporous tungsten trioxide material and model oil product after desulfurization
3min is centrifuged, isolated solid is after 80 DEG C, drying 6h, as three-dimensional ordered macroporous tungsten trioxide material,
It can be re-used for desulfurization, be recycled.
Three-dimensional ordered macroporous tungsten trioxide material is made in embodiment 4, for removing 4 in fuel oil using oxygen as oxidant,
6-DMDBT, the desulfurization degree that above-mentioned steps (3) are measured after 8 hours is 85%.
Embodiment 5:
(1) 4mL distilled water and 2mL dehydrated alcohol are mixed first, the ammonium metatungstate of 3.6953g is then added, at room temperature
The revolving speed of 600rpm stirs 4h, and mixed solution is obtained after dissolution；Then the macropore template polymethyl methacrylate of 1g is added
In mixed solution；After standing 8h, decompression suction filtration is carried out, removes surplus liquid；PMMA after being impregnated, is dried at room temperature
It is spare to obtain desciccate by 10h；
(2) product of step (1) after dry is placed in Muffle furnace, is warming up to 500 DEG C with the rate of 2 DEG C/min, keeps
3h obtains three-dimensional ordered macroporous tungsten trioxide material；
(3) three-dimensional ordered macroporous tungsten trioxide material obtained by step (2) is directly mixed with model oil product, three-dimensional order is big
The amount ratio of hole tungsten trioxide material and model oil product is 0.05g:80mL, and model oil product is 4,6- that sulfur content is 200ppm
DMDBT mould oil is placed in magnetic agitation in oil bath, and is passed through air and carries out desulfurization；Wherein oil bath temperature is 110 DEG C, empty
Throughput is 80mL/min, magnetic agitation rotating speed 800rpm.
It (4) with revolving speed is 4000rpm by three-dimensional ordered macroporous tungsten trioxide material and model oil product after desulfurization
3min is centrifuged, isolated solid is after 80 DEG C, drying 8h, as three-dimensional ordered macroporous tungsten trioxide material,
It can be re-used for desulfurization, be recycled.
Three-dimensional ordered macroporous tungsten trioxide material is made in embodiment 5, for removing 4 in fuel oil using oxygen as oxidant,
6-DMDBT, the desulfurization degree that above-mentioned steps (3) are measured after 8 hours is 93%.
Embodiment 6:
A kind of preparation method of three-dimensional ordered macroporous tungsten trioxide material, including the following steps:
(1) 2mL distilled water and 4mL dehydrated alcohol are mixed first, the ammonium metatungstate of 3.6953g is then added, at room temperature
The revolving speed of 600rpm stirs 12h, and mixed solution is obtained after dissolution；Then the macropore template polymethyl methacrylate of 3g is added
In mixed solution；After standing 12h, decompression suction filtration is carried out, removes surplus liquid；PMMA after being impregnated, does at room temperature
Dry 48h, it is spare to obtain desciccate；
(2) product of step (1) after dry is placed in Muffle furnace, is warming up to 800 DEG C with the rate of 3 DEG C/min, keeps
3h obtains three-dimensional ordered macroporous tungsten trioxide material；
(3) three-dimensional ordered macroporous tungsten trioxide material obtained by step (2) is directly mixed with model oil product, three-dimensional order is big
The amount ratio of hole tungsten trioxide material and model oil product is 0.05g:80mL, and model oil product is 4,6- that sulfur content is 200ppm
DMDBT mould oil is placed in magnetic agitation in oil bath, and is passed through air and carries out desulfurization；Wherein oil bath temperature is 110 DEG C, empty
Throughput is 80mL/min, magnetic agitation rotating speed 800rpm.
It (4) with revolving speed is 4000rpm by three-dimensional ordered macroporous tungsten trioxide material and model oil product after desulfurization
3min is centrifuged, isolated solid is after 80 DEG C, drying 8h, as three-dimensional ordered macroporous tungsten trioxide material,
It can be re-used for desulfurization, be recycled.
Three-dimensional ordered macroporous tungsten trioxide material is made in embodiment 6, for removing 4 in fuel oil using oxygen as oxidant,
6-DMDBT, the desulfurization degree that above-mentioned steps (3) are measured after 8 hours is 81%.
Fig. 1 is the scanning figure of three-dimensional ordered macroporous tungsten trioxide material prepared by example 1, as can be seen from the figure synthesized
Catalyst have preferable three-dimensional ordered macroporous structure；
Fig. 2 is the XPS figure of the three-dimensional ordered macroporous tungsten trioxide material of the gained of example 1, Cong Tuzhong it is observed that catalyst not
There is only W6+W4f5/2And W4f7/2Characteristic peak, and occur two at 37.48eV and 35.33eV and belong to W5+'s
W4f5/2And W4f7/2Characteristic peak shows to exist simultaneously W in catalyst6+And W5+, it was demonstrated that the presence of oxygen defect in catalyst.
Fig. 3 is catalytic activity result of the 1 three-dimensional ordered macroporous tungsten trioxide material of gained of example to different sulfur-bearing substrates；This
The three-dimensional ordered macroporous tungsten trioxide material of invention preparation can not only remove 4,6-DMDBT, can be also used for DBT and 4-MDBT
Removing；
As can be seen from Figure 3, catalyst all has preferable oxidation sweetening activity to three kinds of sulfide, and 4h is interior to sulfide 4,6-
The removal efficiency of DMDBT can reach to reach in 98%, 7h the removal efficiency of DBT in 99%, 8h and reach to the removal efficiency of 4-MDBT
99%, the removal effect to different sulfide is 4,6-DMDBT > 4-MDBT > DBT；
Fig. 4 is cyclicity of the 1 three-dimensional ordered macroporous tungsten trioxide material of gained of example to 4,6-DMDBT in removing simulation oil
Energy result, the results showed that catalyst has good cycle performance, and after recycling 6 times, catalytic activity is not decreased obviously, and can be reached
To 93% or more, illustrates that the catalyst has preferable stability, be conducive to industrial application.Wherein the stability of catalyst is main
Derived from its three-dimensional ordered macroporous structure, effectively slow down duct blocking.
Illustrate: above embodiments are only to illustrate the present invention and not limit the technical scheme described by the invention；Therefore,
Although this specification is referring to above-mentioned each embodiment, the present invention has been described in detail, the common skill of this field
Art personnel should be appreciated that and still can modify to the present invention or equivalent replacement；And all do not depart from spirit of the invention and
The technical solution and its improvement of range, should all cover in scope of the presently claimed invention.
Claims (10)
1. a kind of preparation method of three-dimensional ordered macroporous tungsten trioxide material, which is characterized in that including according to lower step:
(1) ethyl alcohol and distilled water are mixed first, ammonium metatungstate is then added, at room temperature stirring and dissolving, obtains mixed solution；Then
Macropore template polymethyl methacrylate is added in mixed solution；After standing a period of time, decompression suction filtration is carried out, is soaked
It is spare to obtain desciccate after drying a period of time at room temperature for polymethyl methacrylate after stain；
(2) product of step (1) after dry is placed in Muffle furnace, the temperature programming under certain heating rate heat anti-
It answers, three-dimensional ordered macroporous tungsten trioxide material is obtained after reaction.
2. a kind of preparation method of three-dimensional ordered macroporous tungsten trioxide material according to claim 1, which is characterized in that
Ethyl alcohol described in step (1), distilled water, ammonium metatungstate and polymethyl methacrylate amount ratio be 1-3mL:1-5mL:
0.7391-7.3906g:0.5-5g.
3. a kind of preparation method of three-dimensional ordered macroporous tungsten trioxide material according to claim 1, which is characterized in that
Stirring rate described in step (1) is 100-1000rpm, mixing time 1-24h.
4. a kind of preparation method of three-dimensional ordered macroporous tungsten trioxide material according to claim 1, which is characterized in that
Standing a period of time described in step (1) is 1-24h；The time of the drying is 8-72h.
5. a kind of preparation method of three-dimensional ordered macroporous tungsten trioxide material according to claim 1, which is characterized in that
Programmed rate described in step (2) are as follows: 0.5-3 DEG C/min；The temperature of described program heating is 200-800 DEG C, when reaction
Between be 2-5h.
6. the three-dimensional ordered macroporous tungsten trioxide material of method preparation according to any one of claims 1 to 5 is for urging
Change the purposes of fragrant family sulfide or aliphatic sulfides in oxidation removal fuel oil, which is characterized in that steps are as follows: will be prepared
Three-dimensional ordered macroporous tungsten trioxide material directly and model oil product mix, be placed in magnetic agitation in oil bath, and be passed through air into
Row desulfurization；After desulfurization, three-dimensional ordered macroporous tungsten trioxide material and model oil product are centrifuged, point
After drying from obtained solid, i.e., recycling obtains three-dimensional ordered macroporous tungsten trioxide material, is recycled.
7. purposes according to claim 6, which is characterized in that the three-dimensional ordered macroporous tungsten trioxide material and mould oil
The amount ratio of product is 0.01-0.1g:20-200mL.
8. purposes according to claim 6, which is characterized in that the model oil product is the oil product of the 200ppm containing sulfur content；
Configuration method are as follows: by the sulfide 4 of the internal standard hexadecane of 0.7653g and 1.0239g, 6-DMDBT mixing is molten with dodecane
Agent is transferred to the volumetric flask of 1000mL after mixed dissolution, and constant volume shakes up, and obtains internal standard 1000ppm, and sulfur content is 200ppm's
4,6-DMDBT model oil product.
9. purposes according to claim 6, which is characterized in that the temperature of the oil bath is 110-130 DEG C, and air mass flow is
50-100mL/min, the revolving speed of magnetic agitation are 800-1000rpm.
10. purposes according to claim 6, which is characterized in that the revolving speed of the centrifuge separation is 4000rpm, and the time is
3-5min；The drying temperature is 80 DEG C, time 6-12h.
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| CZ308897B6 (en) * | 2020-11-03 | 2021-08-11 | Univerzita Pardubice | Process for preparing submicron and / or micron crystalline tungsten oxide tubes, and submicron and / or micron crystalline tungsten oxide tubes prepared in this way |
| CN114029048A (en) * | 2021-12-10 | 2022-02-11 | 福州大学 | Preparation method and application of tungsten oxide catalyst coated by porous carbon |
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| CZ308897B6 (en) * | 2020-11-03 | 2021-08-11 | Univerzita Pardubice | Process for preparing submicron and / or micron crystalline tungsten oxide tubes, and submicron and / or micron crystalline tungsten oxide tubes prepared in this way |
| CN114029048A (en) * | 2021-12-10 | 2022-02-11 | 福州大学 | Preparation method and application of tungsten oxide catalyst coated by porous carbon |
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