CN106311219A - Preparation method and application of carbon doped silicon dioxide composite material - Google Patents
Preparation method and application of carbon doped silicon dioxide composite material Download PDFInfo
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- CN106311219A CN106311219A CN201610811164.1A CN201610811164A CN106311219A CN 106311219 A CN106311219 A CN 106311219A CN 201610811164 A CN201610811164 A CN 201610811164A CN 106311219 A CN106311219 A CN 106311219A
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- Prior art keywords
- silicon dioxide
- dioxide composite
- doped silicon
- carbon doped
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 46
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 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
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 11
- 230000023556 desulfurization Effects 0.000 claims abstract description 10
- 239000000295 fuel oil Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001400 block copolymer Polymers 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 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
- -1 polyoxyethylene Polymers 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000003921 oil Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 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
- 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
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000013335 mesoporous material Substances 0.000 description 8
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 6
- 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
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- SEBRPHZZSLCDRQ-UHFFFAOYSA-N 3-methyl-1-benzothiophene Chemical compound C1=CC=C2C(C)=CSC2=C1 SEBRPHZZSLCDRQ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction 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
- 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
- 238000013459 approach Methods 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
- 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
- BFFQFGGITJXTFP-UHFFFAOYSA-N 3-methyldioxetane Chemical compound CC1COO1 BFFQFGGITJXTFP-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 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
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 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
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material 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
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- B01J35/50—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
Landscapes
- 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 the field of multi-phase catalysts and relates to a preparation method of a carbon doped silicon dioxide composite material and application of the carbon doped silicon dioxide composite material to fuel oil desulfurization. The preparation method includes: sequentially mixing template agent, ethanol, hydrochloric acid, a metal source and a silicon source, continuously stirring the mixed reactant, drying the mixed reactant, grinding the obtained white solid, and calcining to obtain the mesoporous carbon-containing silicon dioxide material containing high-dispersity tungsten. The preparation method has the advantages that the method is simple in process; during synthesizing, polyoxyethylene polyoxypropylene ether block copolymer is used as the template agent and the carbon source and functional ion liquid is used as the metal source to synthesize the carbon doped silicon dioxide composite material; the carbon doped silicon dioxide composite material has high-durability catalytic activity on the removing of sulfide in fuel oil, fuel oil desulfurization rate can be increased effectively, the use amount of catalysts and oxidizing agent is reduced, the use of organic solvent is avoided, production cost can be lowered, oil quality can be increased, the material is recyclable, and environment pollution is reduced.
Description
Technical field
The invention belongs to heterogeneous catalyst field, refer in particular to a kind of carbon doped silicon dioxide composite preparation method and
Its application in fuel desulfuration.
Background technology
Since in recent years, auto industry is fast-developing, the most also brings people's great demand to fuel oil, and in fuel oil
Sulfide burning produced by waste gas but atmospheric environment can be damaged, the sulfur content therefore limiting fuel oil just seems outstanding
For necessity；Oxidative desulfurization techniques is because having relatively high desulfurization efficiency, and reaction condition is gentle, and running cost is low and technological process is simple
Get most of the attention etc. feature；At present the catalyst involved by oxidation sweetening includes organic acid, ionic liquid, polyoxometallate,
Metal-oxide and molecular sieve etc..
Mesoporous material enjoys pass because of characteristics such as its bigger specific surface area, adjustable pass and apertures in catalyst field
Note；By adding catalytic active center in the structure of mesoporous material, excellent multiphase load type mesoporous material can be developed and urge
Agent.The synthetic method of common support type catalyst of mesoporous material is broadly divided into following two: one is first synthesising mesoporous two
Silicon oxide, with infusion process supported active center；Another kind is that before mesoporous material synthesizes, inorganic metal salt is joined template
In the middle of agent, thus synthesize the mesoporous material obtained.Catalyst synthesized by both approaches would generally occur due to active center
The catalysis the best active problem that dispersion inequality is caused；It addition, the SiO 2 mesoporous materials synthesized by usual way exists
It is easily caused duct under high temperature to cave in, thus has influence on mesoporous order so that catalysis activity decreases；The present invention is with polyoxy
Ethylene polyoxypropylene ether block copolymers is template and carbon source, has the cation of surface active function and polyacid the moon of tungstenic
It is source metal that ion coupling forms Metal Substrate ionic liquid, successfully realizes the carbon doped silicon dioxide composite wood containing polymolecularity tungsten
The original position controlledly synthesis of material, and increase effectively the mesoporous material toleration to high temperature.
Summary of the invention
The invention reside in the preparation method providing a kind of carbon doped silicon dioxide composite.
Further object is that the application providing above-mentioned material, and have the catalytic performance of excellence.
The preparation method of a kind of carbon doped silicon dioxide composite, comprises the steps:
(1) by template polyoxyethylene poly-oxygen propylene aether block copolymer EO106PO70EO106(being abbreviated as F127) uses ethanol
Dissolve, add a certain amount of hydrochloric acid, stir 90min, obtain mixed solution；
(2) tungstenic source metal is dissolved in acetonitrile, is subsequently adding in the mixed solution of step (1) gained, stirs, then
Add silicon source, copolycondensation 2h；
(3) step (2) products therefrom is at room temperature volatilized 6～10h, then is dried in an oven, be then ground to powder；
(4) step (3) gained powder is placed in temperature programming tube furnace it is warming up to 350 DEG C, keep 3h, then be warming up to
600～900 DEG C, keep 3h, obtain the carbon doped silicon dioxide composite of tungstenic.
In step (1), described template is rubbing of 1:500～1:2000, template and hydrochloric acid with the molar ratio of ethanol
That ratio is: 1:1～1:5.
In step (2), described tungstenic source metal is [Cnmim]3PW12O40, wherein n=4,8,12,16, described tungstenic metal
Source with the mol ratio of template is: 1:1～40；Described silicon source is tetraethyl orthosilicate, and silicon source with the mol ratio of template is:
40:1～180:1.
In step (3), the temperature being dried in described baking oven is 100 DEG C, and drying time is 24h.
In step (4), described programmed rate is: less than 600 DEG C 1 DEG C/min, more than 600 DEG C 5 DEG C/min.
The carbon doped silicon dioxide composite of a kind of tungstenic prepared by said method, has meso-hole structure.
The carbon doped silicon dioxide composite of the tungstenic described in claim 1～9 contains in catalytic oxidative desulfurization oil product
Aromatic series sulfide and aliphatic sulfides in application in terms of sulphur compound, predominantly catalytic oxidative desulfurization fuel oil, such as two
The oxidation reaction of benzothiophene (DBT), this course of reaction can be represented by the formula:
The carbon doped silicon dioxide composite of tungstenic all has higher removal efficiency to the different sulfur-bearing substrates in oil product, right
Aromatic series sulfide: benzothiophene (BT), 3-methyl benzothiophene (3-MBT), 4-MDBT (4-MDBT), 4,6-
Dimethyl Dibenzothiophene (4,6-DMDBT) desulfurization degree in 40 minutes respectively reaches 53.54%, and 99.19%, 96.22%
With 100%, dibenzothiophenes (DBT) desulfurization degree in 30 minutes i.e. be can reach 100%.
The carbon doped silicon dioxide composite of the tungstenic of the present invention demonstrates higher urging to sulfide in removing oil product
Changing activity, its excellent activity is mainly due to following factors:
(1) the carbon doped silicon dioxide composite of tungstenic has meso-hole structure, homogeneous pore-size distribution, bigger ratio table
Area, first these features ensure that the even height dispersion of active catalyst sites, and next ensure that sulfur-bearing substrate and activity
Being fully contacted of center.
(2) the tungsten species granule in the carbon doped silicon dioxide composite of tungstenic is less, thus has higher activity.
(3) the carbon doped silicon dioxide composite of tungstenic prepared by the present invention utilizes polyoxyethylene to gather in synthesis step
Oxypropylene ether block copolymers is as template, and functionalized ion liquid, as source metal, simplifies building-up process, reduces synthesis
Cost, provides new approaches for synthesis support type mesoporous carbon containing earth silicon material；There is meso-hole structure, relatively Large ratio surface, live
Property position high dispersive, catalysis activity advantages of higher, deficiency of the prior art can be overcome；The high score of active site can be realized
Dissipate property, strengthen the resistance to elevated temperatures of catalyst, make being fully contacted of sulfur-bearing substrate and active center, the letter of catalyst can be realized again
Easily reclaim and recycle, finally realizing the target of sulfur-containing compound in deep removal fuel oil.And fire at catalytic oxidative desulfurization
In oil during sulfur-bearing substrate, all without using organic solvent.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of each different catalysts；
Fig. 2 is the catalysis activity to different sulfur-bearing substrates of the carbon doped silicon dioxide composite of example 1 gained tungstenic
Result；
Fig. 3 is that the carbon doped silicon dioxide composite of example 1 gained tungstenic is at different H2O2To in simulated oil under consumption
The removing result (30min) of DBT；
Fig. 4 be the carbon doped silicon dioxide composite of example 1 gained tungstenic at a temperature of differential responses in simulated oil
The removing result of DBT.
Detailed description of the invention
Below in conjunction with the accompanying drawings and present disclosure is further illustrated by specific embodiment.
Embodiment 1
The preparation method of the carbon doped silicon dioxide composite of a kind of tungstenic, comprises the following steps:
1) weigh 3.6000g F127 in round-bottomed flask, dissolve with the ethanol of 9g at 40 DEG C, add 2.2g's
The HCl solution of 0.2mol/L, stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40After being dissolved in 5mL acetonitrile, join 1) in the middle of, stir 0.5h；
3) 3.7mL TEOS is slowly added into 2) in the middle of, after stirring copolycondensation 2h, proceed to culture dish；
4) surface plate is placed at room temperature 6-10h, take after solvent volatilization is placed on and is dried 24h in the middle of 100 DEG C of baking ovens
Go out to grind to form powder body；
5) powder body is placed in intensification tube furnace, under nitrogen atmosphere with the ramp of 1 DEG C/min to 350 DEG C, keeps
3h, is further continued for the ramp with 1 DEG C/min to 600 DEG C, keeps 3h, obtains the carbon doped silicon dioxide composite of tungstenic.
Embodiment 2
The preparation method of the carbon doped silicon dioxide composite of a kind of tungstenic, comprises the following steps:
1) weigh 3.6000g F127 in round-bottomed flask, dissolve with the ethanol of 9g at 40 DEG C, add 2.2g's
The HCl solution of 0.2mol/L, stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40After being dissolved in 5mL acetonitrile, join 1) in the middle of, stir 0.5h；
3) 3.7mL TEOS is slowly added into 2) in the middle of, after stirring copolycondensation 2h, proceed to culture dish；
4) surface plate is placed at room temperature 6-10h, take after solvent volatilization is placed on and is dried 24h in the middle of 100 DEG C of baking ovens
Go out to grind to form powder body；
5) powder body is placed in intensification tube furnace, under nitrogen atmosphere with the ramp of 1 DEG C/min to 350 DEG C, keeps
3h, is further continued for the ramp with 1 DEG C/min to 600 DEG C, then with the ramp of 5 DEG C/min to 700 DEG C, keeps 3h, obtain
The carbon doped silicon dioxide composite of tungstenic.
Embodiment 3
The preparation method of the carbon doped silicon dioxide composite of a kind of tungstenic, comprises the following steps:
1) weigh 2.4000g F127 in round-bottomed flask, dissolve with the ethanol of 9g at 40 DEG C, add 2.2g's
The HCl solution of 0.2mol/L, stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40After being dissolved in 5mL acetonitrile, join 1) in the middle of, stir 0.5h；
3) 3.7mL TEOS is slowly added into 2) in the middle of, after stirring copolycondensation 2h, proceed to culture dish；
4) surface plate is placed at room temperature 6-10h, take after solvent volatilization is placed on and is dried 24h in the middle of 100 DEG C of baking ovens
Go out to grind to form powder body；
5) powder body is placed in intensification tube furnace, under nitrogen atmosphere with the ramp of 1 DEG C/min to 350 DEG C, keeps
3h, is further continued for the ramp with 1 DEG C/min to 600 DEG C, keeps 3h, obtains the carbon doped silicon dioxide composite of tungstenic.
Embodiment 4
The preparation method of the carbon doped silicon dioxide composite of a kind of tungstenic, comprises the following steps:
1) weigh 3.6000g F127 in round-bottomed flask, dissolve with the ethanol of 9g at 40 DEG C, add 2.2g's
The HCl solution of 0.2mol/L, stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40After being dissolved in 5mL acetonitrile, join 1) in the middle of, stir 0.5h；
3) 3.7mL TEOS is slowly added into 2) in the middle of, after stirring copolycondensation 2h, proceed to culture dish；
4) surface plate is placed at room temperature 6-10h, take after solvent volatilization is placed on and is dried 24h in the middle of 100 DEG C of baking ovens
Go out to grind to form powder body；
5) powder body is placed in Muffle furnace, with the ramp of 1 DEG C/min to 350 DEG C, keeps 3h, be further continued for 1 DEG C/
The ramp of min, to 600 DEG C, keeps 3h, obtains the carbon doped silicon dioxide composite of tungstenic.
Embodiment 5
The preparation method of the carbon doped silicon dioxide composite of a kind of tungstenic, comprises the following steps:
1) weigh 1.2000g F127 in round-bottomed flask, dissolve with the ethanol of 9g at 40 DEG C, add 2.2g's
The HCl solution of 0.2mol/L, stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40After being dissolved in 5mL acetonitrile, join 1) in the middle of, stir 0.5h；
3) 3.7mL TEOS is slowly added into 2) in the middle of, after stirring copolycondensation 2h, proceed to culture dish；
4) surface plate is placed at room temperature 6-10h, take after solvent volatilization is placed on and is dried 24h in the middle of 100 DEG C of baking ovens
Go out to grind to form powder body；
5) powder body is placed in intensification tube furnace, under nitrogen atmosphere with the ramp of 1 DEG C/min to 350 DEG C, keeps
3h, is further continued for the ramp with 1 DEG C/min to 600 DEG C, keeps 3h, obtains the carbon doped silicon dioxide composite of tungstenic.
Embodiment 6
The preparation method of the carbon doped silicon dioxide composite of a kind of tungstenic, comprises the following steps:
1) weigh 4.8000g F127 in round-bottomed flask, dissolve with the ethanol of 9g at 40 DEG C, add 2.2g's
The HCl solution of 0.2mol/L, stirs 1.5h；
2) by 0.23g [C4mim]3PW12O40After being dissolved in 5mL acetonitrile, join 1) in the middle of, stir 0.5h；
3) 3.7mL TEOS is slowly added into 2) in the middle of, after stirring copolycondensation 2h, proceed to culture dish；
4) surface plate is placed at room temperature 6-10h, take after solvent volatilization is placed on and is dried 24h in the middle of 100 DEG C of baking ovens
Go out to grind to form powder body；
5) powder body is placed in Muffle furnace, with the ramp of 1 DEG C/min to 350 DEG C, keeps 3h, be further continued for 5 DEG C/
The ramp of min, to 900 DEG C, keeps 3h, obtains the carbon doped silicon dioxide composite of tungstenic.
Embodiment 7
By the carbon doped silicon dioxide composite (W-SiO of the tungstenic obtained by embodiment 12/ C) to be used for being catalyzed oxidation de-
Sulfur-containing compound in oil removing product, detailed process is as follows, adds 5mg in a self-control with reflux condensing tube double neck set bottle
W-SiO2/ C, 24 μ L H2O2(30%), 5mL sulfur content is the simulated oil of 500ppm, carries out heating in water bath stirring anti-at 60 DEG C
Should.After reaction terminates, stand, layering, take out upper strata oil sample, after centrifugation, carried out the analysis of sulfur content by GC.
As a example by DBT, reaction equation is:
The catalyst of the synthesis catalysis activity table to oxidation DBT under table 1. different condition
Claims (7)
1. the preparation method of a carbon doped silicon dioxide composite, it is characterised in that comprise the steps:
(1) by template polyoxyethylene poly-oxygen propylene aether block copolymer EO106PO70EO106Dissolve with ethanol, add a certain amount of
Hydrochloric acid, stirs 90min, obtains mixed solution；
(2) tungstenic source metal is dissolved in acetonitrile, is subsequently adding in the mixed solution of step (1) gained, stirs, add
Silicon source, copolycondensation 2h；
(3) step (2) products therefrom is at room temperature volatilized 6～10h, then is dried in an oven, be then ground to powder；
(4) step (3) gained powder be placed in temperature programming tube furnace be warming up to 350 DEG C, keep 3h, then be warming up to 600～
900 DEG C, keep 3h, obtain the carbon doped silicon dioxide composite of tungstenic.
The preparation method of a kind of carbon doped silicon dioxide composite the most according to claim 1, it is characterised in that step
(1), in, the mol ratio that molar ratio is 1:500～1:2000, template and hydrochloric acid of described template and ethanol is: 1:1～
1:5。
The preparation method of a kind of carbon doped silicon dioxide composite the most according to claim 1, it is characterised in that step
(2), in, described tungstenic source metal is [Cnmim]3PW12O40, wherein n=4,8,12,16, described tungstenic source metal and template
Mol ratio is: 1:1～40；Described silicon source is tetraethyl orthosilicate, and silicon source with the mol ratio of template is: 40:1～180:1.
The preparation method of a kind of carbon doped silicon dioxide composite the most according to claim 1, it is characterised in that step
(3), in, the temperature being dried in described baking oven is 100 DEG C, and drying time is 24h.
The preparation method of a kind of carbon doped silicon dioxide composite the most according to claim 1, it is characterised in that step
(4) in, described programmed rate is: less than 600 DEG C 1 DEG C/min, more than 600 DEG C 5 DEG C/min.
6. a carbon doped silicon dioxide composite, it is characterised in that described carbon doped silicon dioxide composite is to pass through
Claims 1 to 5 prepares, and has meso-hole structure.
7. the application of a carbon doped silicon dioxide composite as claimed in claim 6, it is characterised in that described carbon is mixed
Miscellaneous silicon dioxide composite material is aromatic series sulfide and aliphatic sulfides in catalytic oxidative desulfurization fuel oil.
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| CN108940260A (en) * | 2018-06-15 | 2018-12-07 | 江苏大学 | A kind of preparation method and applications aoxidizing tungsten load macroporous silica composite material |
| CN110127654A (en) * | 2019-05-31 | 2019-08-16 | 天津大学 | A kind of preparation method of uniform micron pore size three-dimensional carbon network |
| CN110170327A (en) * | 2019-05-21 | 2019-08-27 | 南京工业大学 | Mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof |
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| WO2014050615A1 (en) * | 2012-09-27 | 2014-04-03 | 旭化成ケミカルズ株式会社 | Composite oxide catalyst, method for producing same, and method for producing unsaturated nitrile |
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| WO2014050615A1 (en) * | 2012-09-27 | 2014-04-03 | 旭化成ケミカルズ株式会社 | Composite oxide catalyst, method for producing same, and method for producing unsaturated nitrile |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940260A (en) * | 2018-06-15 | 2018-12-07 | 江苏大学 | A kind of preparation method and applications aoxidizing tungsten load macroporous silica composite material |
| CN110170327A (en) * | 2019-05-21 | 2019-08-27 | 南京工业大学 | Mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof |
| CN110170327B (en) * | 2019-05-21 | 2022-04-19 | 南京工业大学 | Mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof |
| CN110127654A (en) * | 2019-05-31 | 2019-08-16 | 天津大学 | A kind of preparation method of uniform micron pore size three-dimensional carbon network |
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