CN106311219B - A kind of preparation method and applications of carbon doped silicon dioxide composite material - Google Patents
A kind of preparation method and applications of carbon doped silicon dioxide composite material Download PDFInfo
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- CN106311219B CN106311219B CN201610811164.1A CN201610811164A CN106311219B CN 106311219 B CN106311219 B CN 106311219B CN 201610811164 A CN201610811164 A CN 201610811164A CN 106311219 B CN106311219 B CN 106311219B
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- silicon dioxide
- dioxide composite
- doped silicon
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 235000019441 ethanol Nutrition 0.000 claims abstract description 11
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000295 fuel oil Substances 0.000 claims abstract description 7
- -1 polyoxyethylene Polymers 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001400 block copolymer Polymers 0.000 claims abstract description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 23
- 238000010792 warming Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 239000010937 tungsten Substances 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 239000013335 mesoporous material Substances 0.000 description 8
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- SEBRPHZZSLCDRQ-UHFFFAOYSA-N 3-methyl-1-benzothiophene Chemical class C1=CC=C2C(C)=CSC2=C1 SEBRPHZZSLCDRQ-UHFFFAOYSA-N 0.000 description 1
- BFFQFGGITJXTFP-UHFFFAOYSA-N 3-methyldioxetane Chemical compound CC1COO1 BFFQFGGITJXTFP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
-
- 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
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to heterogeneous catalyst field, it is related to preparation method and its application in fuel desulfuration of a kind of carbon doped silicon dioxide composite material.Preparation process includes by template, ethyl alcohol, hydrochloric acid, source metal, silicon source mixes successively, and is persistently stirred reactant, then dries mixed reactant, gained white solid is ground, and after calcination processing, obtains the mesoporous carbon containing earth silicon material of the tungsten containing polymolecularity.Present invention process is simple, in the synthesis process using polyoxyethylene poly-oxygen propylene aether block copolymer as template and carbon source, functionalized ion liquid is that source metal synthesizes carbon doped silicon dioxide composite material, which has higher lasting catalytic activity to sulfide removing in fuel oil, can effectively improve desulfurizing oil rate, reduce the dosage of catalyst and oxidant, without using organic solvent, production cost is reduced, improves oil quality, and recyclable reuse, reduce environmental pollution.
Description
Technical field
The invention belongs to heterogeneous catalyst field, refer in particular to a kind of carbon doped silicon dioxide composite material preparation method and
Its application in fuel desulfuration.
Background technology
Since in recent years, auto industry is fast-developing, thus also brings great demand of the people to 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 with compared with high desulfurization efficiency, reaction condition is mild, and operating cost is low and technological process is simple
The features such as and attract attention；The catalyst involved by oxidation sweetening includes organic acid at present, ionic liquid, polyoxometallate,
Metal oxide and molecular sieve etc..
Mesoporous material in catalyst field receives pass because of characteristics such as its larger specific surface area, adjustable pass and apertures
Note；By the way that catalytic active center is added in the structure of mesoporous material, excellent multiphase load type mesoporous material can be developed and urged
Agent.The synthetic method of common support type catalyst of mesoporous material is broadly divided into following two：First, first synthesising mesoporous two
Silica, with infusion process supported active center；Another kind is that inorganic metal salt is added to template before mesoporous material synthesis
In agent, the mesoporous material that thus synthesizes.Catalyst synthesized by both methods usually will appear due to activated centre
The bad problem of catalytic activity caused by dispersion unevenness；In addition, the SiO 2 mesoporous materials synthesized by usual way exist
Duct is easily led under high temperature to cave in, to influence mesoporous order so that catalytic activity decreases；The present invention is with polyoxy
Ethylene polyoxypropylene ether block copolymers are template and carbon source, and the polyacid of cation and tungstenic with surface active function is cloudy
It is source metal that ion, which matches and to form Metal Substrate ionic liquid, successfully realizes the carbon doped silicon dioxide composite wood of the tungsten containing polymolecularity
The controlledly synthesis in situ of material, and increase effectively tolerance of the mesoporous material to high temperature.
Invention content
The invention reside in provide a kind of preparation method of carbon doped silicon dioxide composite material.
It is another object of the present invention to provide the applications of above-mentioned material, and have excellent catalytic performance.
A kind of preparation method of carbon doped silicon dioxide composite material, includes the following steps：
(1) by template polyoxyethylene poly-oxygen propylene aether block copolymer EO106PO70EO106(being abbreviated as F127) uses ethyl alcohol
A certain amount of hydrochloric acid is added in dissolving, stirs 90min, obtains mixed solution；
(2) tungstenic source metal is dissolved in acetonitrile, is then added in the mixed solution obtained by step (1), stirs evenly, then
Silicon source, copolycondensation 2h is added；
(3) step (2) products therefrom is volatilized 6~10h at room temperature, then dried in an oven, be then ground to powder；
(4) powder obtained by step (3) is placed in temperature programming tube furnace and is warming up to 350 DEG C, keep 3h, then be warming up to
600~900 DEG C, 3h is kept, the carbon doped silicon dioxide composite material of tungstenic is obtained.
In step (1), the molar ratio of the template and ethyl alcohol is 1:500~1:2000, template and hydrochloric acid rub
You are at ratio：1:1~1:5.
In step (2), the tungstenic source metal is [Cnmim]3PW12O40, wherein n=4,8,12,16, the tungstenic metal
The molar ratio of source and template is：1：1~40；The silicon source is tetraethyl orthosilicate, and the molar ratio of silicon source and template is：
40:1~180:1.
In step (3), dry temperature is 100 DEG C in the baking oven, and drying time is for 24 hours.
In step (4), described program heating rate is：600 DEG C or less 1 DEG C/min, 600 DEG C or more 5 DEG C/min.
A kind of carbon doped silicon dioxide composite material of tungstenic prepared by the above method has meso-hole structure.
The carbon doped silicon dioxide composite material of tungstenic described in claim 1~9 contains in catalytic oxidative desulfurization oil product
Application in terms of sulphur compound, fragrant family sulfide and aliphatic sulfides predominantly in catalytic oxidative desulfurization fuel oil, such as two
The oxidation reaction of benzothiophene (DBT), the reaction process can be represented by the formula：
The carbon doped silicon dioxide composite material of tungstenic has higher removal efficiency to the different sulfur-bearing substrates in oil product, right
Fragrant family sulfide：Benzothiophene (BT), 3- methyl benzothiophenes (3-MBT), 4-MDBT (4-MDBT), 4,6-
Dimethyl Dibenzothiophene (4,6-DMDBT) desulfurization degree in 40 minutes respectively reaches 53.54%, 99.19%, 96.22%
With 100%, to dibenzothiophenes (DBT), desulfurization degree can reach 100% in 30 minutes.
The carbon doped silicon dioxide composite material of the tungstenic of the present invention shows higher urge to sulfide in removing oil product
Change activity, excellent activity is mainly due to following factors：
(1) the carbon doped silicon dioxide composite material of tungstenic has meso-hole structure, uniform pore-size distribution, larger ratio table
Area, these features ensure that the even height dispersion of active catalyst sites first, next ensure that sulfur-bearing substrate and activity
Center comes into full contact with.
(2) the tungsten species particle in the carbon doped silicon dioxide composite material of tungstenic is smaller, thus has higher activity.
(3) the carbon doped silicon dioxide composite material of tungstenic prepared by the present invention is poly- using polyoxyethylene in synthesis step
Oxypropylene ether block copolymers simplify building-up process as source metal, reduce synthesis as template, functionalized ion liquid
Cost provides new approaches for the synthesis mesoporous carbon containing earth silicon material of support type；It is living compared with Large ratio surface with meso-hole structure
The advantages that property position high dispersive, catalytic activity is high, deficiency in the prior art can be overcome；It can realize the high score of active site
Property is dissipated, the high temperature resistance of catalyst is enhanced, makes coming into full contact with for sulfur-bearing substrate and activated centre, and can realize the letter of catalyst
Easily recycling and recycling, the final target for realizing sulfur-containing compound in deep removal fuel oil.And it is fired in catalytic oxidative desulfurization
In oil during sulfur-bearing substrate, without using organic solvent.
Description of the drawings
Fig. 1 is the X-ray diffractogram of each different catalysts；
Fig. 2 is the catalytic activity to different sulfur-bearing substrates of the carbon doped silicon dioxide composite material of 1 gained tungstenic of example
As a result；
Fig. 3 is the carbon doped silicon dioxide composite material of 1 gained tungstenic of example in different H2O2To in simulation oil under dosage
The removing result (30min) of DBT；
Fig. 4 be 1 gained tungstenic of example carbon doped silicon dioxide composite material at a temperature of differential responses in simulation oil
The removing result of DBT.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment further illustrates present disclosure.
Embodiment 1
A kind of preparation method of the carbon doped silicon dioxide composite material of tungstenic, includes the following steps：
1) 3.6000g F127 are weighed in round-bottomed flask, is dissolved with the ethyl alcohol of 9g at 40 DEG C, is added 2.2g's
The HCl solution of 0.2mol/L stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40It after being dissolved in 5mL acetonitriles, is added in 1), stirs 0.5h；
3) 3.7mL TEOS are slowly added into 2), after stirring copolycondensation 2h, are transferred to culture dish；
4) surface plate is placed to 6-10h at room temperature, drying in 100 DEG C of baking ovens is placed in after the solvent is volatilized and takes afterwards for 24 hours
Go out to be ground into powder；
5) powder is placed in heating tube furnace, is warming up to 350 DEG C under nitrogen atmosphere with the rate of 1 DEG C/min, kept
3h is further continued for being warming up to 600 DEG C with the rate of 1 DEG C/min, keeps 3h, obtain the carbon doped silicon dioxide composite material of tungstenic.
Embodiment 2
A kind of preparation method of the carbon doped silicon dioxide composite material of tungstenic, includes the following steps：
1) 3.6000g F127 are weighed in round-bottomed flask, is dissolved with the ethyl alcohol of 9g at 40 DEG C, is added 2.2g's
The HCl solution of 0.2mol/L stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40It after being dissolved in 5mL acetonitriles, is added in 1), stirs 0.5h；
3) 3.7mL TEOS are slowly added into 2), after stirring copolycondensation 2h, are transferred to culture dish；
4) surface plate is placed to 6-10h at room temperature, drying in 100 DEG C of baking ovens is placed in after the solvent is volatilized and takes afterwards for 24 hours
Go out to be ground into powder；
5) powder is placed in heating tube furnace, is warming up to 350 DEG C under nitrogen atmosphere with the rate of 1 DEG C/min, kept
3h is further continued for being warming up to 600 DEG C with the rate of 1 DEG C/min, then is warming up to 700 DEG C with the rate of 5 DEG C/min, is kept 3h, is obtained
The carbon doped silicon dioxide composite material of tungstenic.
Embodiment 3
A kind of preparation method of the carbon doped silicon dioxide composite material of tungstenic, includes the following steps：
1) 2.4000g F127 are weighed in round-bottomed flask, is dissolved with the ethyl alcohol of 9g at 40 DEG C, is added 2.2g's
The HCl solution of 0.2mol/L stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40It after being dissolved in 5mL acetonitriles, is added in 1), stirs 0.5h；
3) 3.7mL TEOS are slowly added into 2), after stirring copolycondensation 2h, are transferred to culture dish；
4) surface plate is placed to 6-10h at room temperature, drying in 100 DEG C of baking ovens is placed in after the solvent is volatilized and takes afterwards for 24 hours
Go out to be ground into powder；
5) powder is placed in heating tube furnace, is warming up to 350 DEG C under nitrogen atmosphere with the rate of 1 DEG C/min, kept
3h is further continued for being warming up to 600 DEG C with the rate of 1 DEG C/min, keeps 3h, obtain the carbon doped silicon dioxide composite material of tungstenic.
Embodiment 4
A kind of preparation method of the carbon doped silicon dioxide composite material of tungstenic, includes the following steps：
1) 3.6000g F127 are weighed in round-bottomed flask, is dissolved with the ethyl alcohol of 9g at 40 DEG C, is added 2.2g's
The HCl solution of 0.2mol/L stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40It after being dissolved in 5mL acetonitriles, is added in 1), stirs 0.5h；
3) 3.7mL TEOS are slowly added into 2), after stirring copolycondensation 2h, are transferred to culture dish；
4) surface plate is placed to 6-10h at room temperature, drying in 100 DEG C of baking ovens is placed in after the solvent is volatilized and takes afterwards for 24 hours
Go out to be ground into powder；
5) powder is placed in Muffle furnace, is warming up to 350 DEG C with the rate of 1 DEG C/min, keeps 3h, be further continued for 1 DEG C/
The rate of min is warming up to 600 DEG C, keeps 3h, obtains the carbon doped silicon dioxide composite material of tungstenic.
Embodiment 5
A kind of preparation method of the carbon doped silicon dioxide composite material of tungstenic, includes the following steps：
1) 1.2000g F127 are weighed in round-bottomed flask, is dissolved with the ethyl alcohol of 9g at 40 DEG C, is added 2.2g's
The HCl solution of 0.2mol/L stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40It after being dissolved in 5mL acetonitriles, is added in 1), stirs 0.5h；
3) 3.7mL TEOS are slowly added into 2), after stirring copolycondensation 2h, are transferred to culture dish；
4) surface plate is placed to 6-10h at room temperature, drying in 100 DEG C of baking ovens is placed in after the solvent is volatilized and takes afterwards for 24 hours
Go out to be ground into powder；
5) powder is placed in heating tube furnace, is warming up to 350 DEG C under nitrogen atmosphere with the rate of 1 DEG C/min, kept
3h is further continued for being warming up to 600 DEG C with the rate of 1 DEG C/min, keeps 3h, obtain the carbon doped silicon dioxide composite material of tungstenic.
Embodiment 6
A kind of preparation method of the carbon doped silicon dioxide composite material of tungstenic, includes the following steps：
1) 4.8000g F127 are weighed in round-bottomed flask, is dissolved with the ethyl alcohol of 9g at 40 DEG C, is added 2.2g's
The HCl solution of 0.2mol/L stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40It after being dissolved in 5mL acetonitriles, is added in 1), stirs 0.5h；
3) 3.7mL TEOS are slowly added into 2), after stirring copolycondensation 2h, are transferred to culture dish；
4) surface plate is placed to 6-10h at room temperature, drying in 100 DEG C of baking ovens is placed in after the solvent is volatilized and takes afterwards for 24 hours
Go out to be ground into powder；
5) powder is placed in Muffle furnace, is warming up to 350 DEG C with the rate of 1 DEG C/min, keeps 3h, be further continued for 5 DEG C/
The rate of min is warming up to 900 DEG C, keeps 3h, obtains the carbon doped silicon dioxide composite material of tungstenic.
Embodiment 7
By the carbon doped silicon dioxide composite material (W-SiO of 1 obtained tungstenic of embodiment2/ C) it is de- for catalysis oxidation
Except sulfur-containing compound in oil product, detailed process is as follows, and 5mg is added in the double neck set bottles of the self-control with reflux condensing tube at one
W-SiO2/ C, 24 μ L H2O2(30%), 5mL sulfur contents are the simulation oil of 500ppm, and it is anti-that heating water bath stirring is carried out at 60 DEG C
It answers.After reaction, it stands, upper layer oil sample is taken out in layering, carries out the analysis of sulfur content by GC after centrifugation.
By taking DBT as an example, reaction equation is：
Catalytic activity table of the catalyst synthesized under 1. different condition of table to oxidation DBT
Claims (6)
1. a kind of preparation method of carbon doped silicon dioxide composite material, which is characterized in that include the following steps：
(1) by template polyoxyethylene poly-oxygen propylene aether block copolymer EO106PO70EO106It is dissolved, is added a certain amount of with ethyl alcohol
Hydrochloric acid stirs 90min, obtains mixed solution；
(2) tungstenic source metal is dissolved in acetonitrile, is then added in the mixed solution obtained by step (1), stirs evenly, add
Silicon source, copolycondensation 2h；The tungstenic source metal is [Cnmim]3PW12O40, wherein n=4,8,12,16, the tungstenic source metal with
The molar ratio of template is：1：1~40；The silicon source is tetraethyl orthosilicate, and the molar ratio of silicon source and template is：40:1~
180:1；
(3) step (2) products therefrom is volatilized 6~10h at room temperature, then dried in an oven, be then ground to powder；
(4) powder obtained by step (3) is placed in temperature programming tube furnace and is warming up to 350 DEG C, keep 3h, then it is warming up to 600~
900 DEG C, 3h is kept, the carbon doped silicon dioxide composite material of tungstenic is obtained.
2. a kind of preparation method of carbon doped silicon dioxide composite material according to claim 1, which is characterized in that step
(1) in, the molar ratio of the template and ethyl alcohol is 1:500~1:2000, the molar ratio of template and hydrochloric acid is：1:1~
1:5。
3. a kind of preparation method of carbon doped silicon dioxide composite material according to claim 1, which is characterized in that step
(3) in, dry temperature is 100 DEG C in the baking oven, and drying time is for 24 hours.
4. a kind of preparation method of carbon doped silicon dioxide composite material according to claim 1, which is characterized in that step
(4) in, described program heating rate is：Temperature is less than or equal to use 1 DEG C/min at 600 DEG C, and temperature uses 5 when being more than 600 DEG C
℃/min。
5. a kind of carbon doped silicon dioxide composite material, which is characterized in that the carbon doped silicon dioxide composite material is to pass through
Made from any one of Claims 1 to 4 preparation method, there is meso-hole structure.
6. a kind of application of carbon doped silicon dioxide composite material as claimed in claim 5, which is characterized in that mix the carbon
Miscellaneous silicon dioxide composite material is used for fragrant family sulfide and aliphatic sulfides in catalytic oxidative desulfurization fuel oil.
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