CN107159188B - Preparation method and application of sea urchin-shaped tungsten-containing mesoporous silicon sphere material - Google Patents
Preparation method and application of sea urchin-shaped tungsten-containing mesoporous silicon sphere material Download PDFInfo
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- CN107159188B CN107159188B CN201710382332.4A CN201710382332A CN107159188B CN 107159188 B CN107159188 B CN 107159188B CN 201710382332 A CN201710382332 A CN 201710382332A CN 107159188 B CN107159188 B CN 107159188B
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 56
- 239000010937 tungsten Substances 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052710 silicon Inorganic materials 0.000 title abstract description 8
- 239000010703 silicon Substances 0.000 title abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000000295 fuel oil Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 125
- 239000000377 silicon dioxide Substances 0.000 claims description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000013335 mesoporous material Substances 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- -1 aromatic sulfides Chemical class 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000006477 desulfuration reaction Methods 0.000 abstract description 7
- 230000023556 desulfurization Effects 0.000 abstract description 7
- 239000003921 oil Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- 230000002045 lasting effect Effects 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
- 229910052681 coesite Inorganic materials 0.000 description 18
- 229910052906 cristobalite Inorganic materials 0.000 description 18
- 229910052682 stishovite Inorganic materials 0.000 description 18
- 229910052905 tridymite Inorganic materials 0.000 description 18
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 7
- 244000282866 Euchlaena mexicana Species 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- SEBRPHZZSLCDRQ-UHFFFAOYSA-N 3-methyl-1-benzothiophene Chemical compound C1=CC=C2C(C)=CSC2=C1 SEBRPHZZSLCDRQ-UHFFFAOYSA-N 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000126 substance Substances 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000001988 small-angle X-ray diffraction 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000002912 waste gas 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/635—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention belongs to the field of heterogeneous catalysts, and relates to a preparation method of a sea urchin-shaped tungsten-containing mesoporous silicon sphere material and application of the sea urchin-shaped tungsten-containing mesoporous silicon sphere material in fuel oil desulfurization. The preparation process comprises the steps of adopting a self-integration method of oil-water two-phase interface reaction, continuously stirring and mixing reactants at a low speed, then centrifuging the reactants, and sequentially washing the obtained white solid with alcohol, drying, grinding and calcining to obtain the tungsten-containing mesoporous silicon sphere material. The method has simple process, and in the synthesis process, the sea urchin-shaped mesoporous silicon sphere material containing tungsten is synthesized by taking hexadecyl trimethyl ammonium chloride (CTAC) as a template agent and sodium tungstate as a metal source, has quick and lasting catalytic activity on the removal of sulfides in the fuel, effectively improves the desulfurization rate of the oil product, greatly reduces the using amount of a catalyst and an oxidant, reduces the production cost, improves the quality of the oil product, and reduces the environmental pollution.
Description
Technical Field
The invention belongs to the field of heterogeneous catalysts, and particularly relates to a preparation method of a dispersive sea urchin-shaped tungsten-containing mesoporous silicon sphere material and application of the dispersive sea urchin-shaped tungsten-containing mesoporous silicon sphere material in fuel oil desulfurization.
Background
In recent years, due to the rapid development of the automobile industry, the demand of various countries in the world for fuel oil is increasing, and the waste gas generated by the combustion of sulfide in the fuel oil brings serious environmental problems, so that the limitation of the sulfur content of the fuel oil is particularly important; the oxidative desulfurization technology is concerned by the characteristics of high desulfurization efficiency, mild reaction conditions (under normal temperature and normal pressure), low operation cost, simple process flow and the like; the prior oxidative desulfurization usually adds a catalyst capable of accelerating the oxidation rate, and comprises the following components: heteropolyacids, light, ionic liquids, composites, and the like.
The mesoporous material has the pore size of 2-50nm, is characterized by having larger specific surface area and special pore channel structure, and is a good catalyst carrier if the mesoporous material can be divided into two types of silicon materials and non-silicon materials according to chemical components. The key point of synthesizing the mesoporous material is to select a proper precursor and a template substance to coordinately construct a composite structure, and then remove the template substance, thereby obtaining the mesoporous material. The metal catalytic active center is introduced into the structure of the material, so that a supported mesoporous material catalyst is developed, and the catalyst is an excellent heterogeneous reaction catalyst; the preparation method of the catalyst mainly comprises two steps: (1) firstly, synthesizing imidazole type ionic liquid containing tungsten as an active ingredient; (2) and loading the metal active center on a carrier by a self-integration method of oil-water two-phase interface reaction. The invention solves the problems that the traditional active center is not uniformly dispersed on the carrier, and the catalytic active center cannot effectively enter the pore canal, thus influencing the catalytic activity and the like; cations with surface active functions and polyacid anions containing tungsten are matched to form metal-based ionic liquid as a template and a metal source, so that the synthesis of the tungsten mesoporous silica material can be realized, the different pore diameters and the sizes of silica spheres of the supported mesoporous silica material can be adjusted by the concentrations of different CTAC and TEOS solutions, and the catalytic activity center of the supported mesoporous silica material can be adjusted by anions.
Disclosure of Invention
The invention provides a sea urchin-shaped tungsten-containing mesoporous silica sphere material and a preparation method thereof.
Another object of the present invention is to provide the use of the above catalyst, and to provide excellent catalytic performance and cycle performance.
In order to achieve the experimental purpose, the invention provides a sea urchin-shaped tungsten-containing mesoporous silica sphere material, which specifically comprises the following steps:
(1) metal source precursor [ C16mim]4W10O32The preparation of (1):
adding sodium tungstate and water into a round-bottom flask in proportion, boiling for 5-20 min, adding a hydrochloric acid solution, stirring, and addingTemplate agent [ C16mim]Cl; standing to obtain white precipitate, washing, drying, and synthesizing metal source precursor [ C ]16mim]4W10O32And is ready for use;
(2) preparing 15-35 wt% of CTAC solutions with different mass fractions for later use; preparing TEOS aqueous solutions with different volume fractions of 5-20% for later use;
(3) adding the metal source precursor [ C ] prepared in the step (1) into a round-bottom flask16mim]4W10O32CTAC solution, triethanolamine, H prepared in step (2)2O, stirring and dissolving for the first time for 30-120 min, then dropwise adding into the TEOS aqueous solution prepared in the step (2), stirring for the second time, and continuously reacting for 8-24 h;
(4) and (3) centrifuging the product obtained in the step (3), washing with alcohol for 2 times, drying at 60-100 ℃ to obtain a white solid, grinding the solid into powder, putting the powder into a muffle furnace, carrying out temperature programming to 400-700 ℃, and keeping for 3-6 hours to obtain the dispersive echinoid tungsten-containing mesoporous silica sphere material.
In the step (1), the concentration of the hydrochloric acid solution is 3 mol/L; sodium tungstate, water, hydrochloric acid solution and template agent [ C ]16mim]The dosage proportion of Cl is as follows: 6.4 g: 40mL of: 13.4 mL: 2.67 g.
In the step (2), [ C ] mentioned16mim]4W10O3215-35 wt% CTAC solution, triethanolamine, H2O, 5-20% (v/v') TEOS aqueous solution is used in the following proportion: 0.0822 g: 25mL of: 0.18 mL: 36mL of: 20 mL.
In the step (3), the first stirring speed is 800-; the second stirring speed is 100-170 r/min.
In the step (4), the temperature programming rate is 2-5 ℃/min.
A sea urchin-shaped tungsten-containing mesoporous silica sphere material with a specific surface area of 550-1100 m2The mesoporous material has a mesoporous structure with a pore volume of 0.68-1.6 cm3The pore diameter is 4-7 nm.
The sea urchin-shaped tungsten-containing mesoporous silica sphere material prepared by the invention is applied to the aspect of removing sulfur-containing compounds in oil products by catalytic oxidation, is applied to the application of removing aromatic sulfides and aliphatic sulfides in fuel oil by catalytic oxidation, such as the oxidation reaction of Dibenzothiophene (DBT), and the reaction process can be represented by the following formula:
the sea urchin-shaped tungsten-containing mesoporous silica sphere material shows higher catalytic activity for removing sulfides in oil products, and the excellent activity of the sea urchin-shaped tungsten-containing mesoporous silica sphere material is mainly attributed to the following factors:
(1) the sea urchin-shaped tungsten-containing mesoporous silica sphere material has a mesoporous structure, uniform pore size distribution and a large specific surface area, and the characteristics firstly ensure the uniform and high dispersion of active sites of the catalyst and secondly ensure the full contact between a sulfur-containing substrate and an active center.
(2) The tungsten species particles in the sea urchin-shaped tungsten-containing mesoporous silica sphere material are smaller, so that the sea urchin-shaped tungsten-containing mesoporous silica sphere material has higher activity.
The sea urchin-shaped tungsten-containing mesoporous silica sphere material has higher removal rate on different sulfur-containing substrates in oil products, and has the advantages of: the desulfurization rates of Dibenzothiophene (DBT), 4, 6-dimethyldibenzothiophene (4,6-DMDBT), Benzothiophene (BT) and 3-methylbenzothiophene (3-MBT) can respectively reach 100%, 100%, 100% and 87.5% within 40min, wherein DBT can reach 100% within 30 min.
(3) The sea urchin-shaped tungsten-containing mesoporous silica sphere material prepared by the invention utilizes the functionalized ionic liquid as a template agent and a metal source in the synthesis step, simplifies the synthesis process, reduces the synthesis cost and provides a new idea for synthesizing the supported mesoporous silicon material; the catalyst has the advantages of mesoporous structure, large specific surface area, high dispersion of active sites, high catalytic activity and the like, and can overcome the defects in the prior art; can realize the catalytic activity site, make the sulfur-containing substrate fully contact with the active center, and finally realize the goal of deeply removing the sulfur-containing compounds in the fuel oil.
Drawings
FIG. 1 is a small-angle X-ray diffraction pattern of a sea urchin-like tungsten-containing mesoporous silica sphere material obtained in example 1;
FIG. 2 is an infrared spectrum of a sea urchin-shaped tungsten-containing mesoporous silica sphere material obtained in example 1;
FIG. 3 shows N of the sea urchin-shaped tungsten-containing mesoporous silica sphere material obtained in example 12Adsorption-desorption isotherm diagram;
FIG. 4 shows the sea urchin-shaped tungsten-containing mesoporous silica spheres 15-5-W/SiO obtained in example 12A transmission diagram of (a);
FIG. 5 is a graph showing the removal efficiency of the sea urchin-shaped tungsten-containing mesoporous silica sphere material obtained in example 1 for different sulfur-containing substrates.
Detailed Description
The invention is further described with reference to the following drawings and specific embodiments.
Example 1
Sea urchin-shaped tungsten-containing mesoporous silica sphere material 15-5-W/SiO2The preparation method comprises the following steps:
1) adding 6.4g of sodium tungstate and 40mL of water into a 150mL round-bottom flask, and boiling for 5 min; to the mixture was added diluted 13.4mL/3M hydrochloric acid, and after stirring, 2.67g of [ C ] was added16mim]Cl, standing for precipitation, washing and drying for later use
2) A150 ml round bottom flask was charged with 0.0822g of C containing a tungsten source16mim]4W10O32，25mL 15wt％CTAC,0.18mL TEA，36mL H2O, stirring and dissolving for 30 min; dropwise adding 20ml of 5% (v/v') TEOS into the solution, and continuously reacting for 8 hours; centrifuging the obtained product, washing with ethanol twice, drying at 80 deg.C for 8 hr, grinding into powder with mortar, heating to 400 deg.C at 2 deg.C/min in a temperature programmed tube furnace, and maintaining for 3 hr to obtain sea urchin-like tungsten-containing mesoporous silica ball material
Example 2
Sea urchin-shaped tungsten-containing mesoporous silica sphere material 15-10-W/SiO2The preparation method comprises the following steps:
1) adding 6.4g of sodium tungstate and 40mL of water into a 150mL round-bottom flask, and boiling for 10 min; to the mixture was added diluted 13.4mL/3M hydrochloric acid, and after stirring, 2.67g of [ C ] was added16mim]Cl, standing and precipitating,washing, drying, and reserving
2) 0.1644g of [ C ] containing a molybdenum source were placed in a 150ml round bottom flask16mim]4W10O32，25mL 15wt％CTAC,0.18mL TEA，36mL H2O, stirring and dissolving for 60 min; dropwise adding 20ml of 10% (v/v') TEOS into the solution, and continuously reacting for 12 h; centrifuging the obtained product, washing with ethanol twice, drying at 60 ℃ for 8h, grinding into powder with a mortar after drying, heating the powder to 500 ℃ at the speed of 2 ℃/min in a temperature programmed tube furnace, and keeping for 4h to obtain the sea urchin-shaped tungsten-containing mesoporous silica ball material.
Example 3
Sea urchin-shaped tungsten-containing mesoporous silica sphere material 15-20-W/SiO2The preparation method comprises the following steps:
1) adding 6.4g of sodium tungstate and 40mL of water into a 150mL round-bottom flask, and boiling for 15 min; to the mixture was added diluted 13.4mL/3M hydrochloric acid, and after stirring, 2.67g of [ C ] was added16mim]Cl, standing for precipitation, washing and drying for later use
2) A150 ml round bottom flask was charged with 0.3288g of [ C ] containing tungsten source16mim]4W10O32，25mL15wt％CTAC,0.18mL TEA，36mL H2O, stirring and dissolving for 30 min; dropwise adding 20ml of 20% (v/v') TEOS into the solution, continuously stirring, and continuously reacting for 16 h; centrifuging the obtained product, washing twice with ethanol, drying at 80 ℃ for 8h, grinding into powder with a mortar after drying, heating the powder to 550 ℃ at the speed of 2 ℃/min in a temperature programmed tube furnace, and keeping for 6h to obtain the sea urchin-shaped tungsten-containing mesoporous silica ball material.
Example 4
Sea urchin-shaped tungsten-containing mesoporous silica sphere material 25-5-W/SiO2The preparation method comprises the following steps:
1) adding 6.4g of sodium tungstate and 40mL of water into a 150mL round-bottom flask, and boiling for 5 min; to the mixture was added diluted 13.4mL/3M hydrochloric acid, and after stirring, 2.67g of [ C ] was added16mim]Cl, standing for precipitation, washing and drying for later use
2) A150 ml round bottom flask was charged with 0.0822g of C containing a tungsten source16mim]4W10O32，25mL25wt％CTAC,0.18mL TEA，36mL H2O, stirring and dissolving for 30 min; dropwise adding 20ml of 5% (v/v') TEOS into the solution, continuously stirring, and continuously reacting for 24 hours; centrifuging the obtained product, washing twice with ethanol, drying at 70 ℃ for 8h, grinding into powder with a mortar after drying, heating the powder to 550 ℃ at the speed of 2 ℃/min in a temperature programmed tube furnace, and keeping for 5h to obtain the sea urchin-shaped tungsten-containing mesoporous silica ball material.
Example 5
Sea urchin-shaped tungsten-containing mesoporous silica sphere material 35-5-W/SiO2The preparation method comprises the following steps:
1) adding 6.4g of sodium tungstate and 40mL of water into a 150mL round-bottom flask, and boiling for 5 min; to the mixture was added diluted 13.4mL/3M hydrochloric acid, and after stirring, 2.67g of [ C ] was added16mim]Cl, standing for precipitation, washing and drying for later use
2) 0.0822g of [ C ] containing a molybdenum source were placed in a 150ml round bottom flask16mim]4W10O32，25mL35wt％CTAC,0.18mL TEA，36mL H2O, stirring and dissolving for 30 min; dropwise adding 20ml of 5% (v/v') TEOS into the solution, continuously stirring, and continuously reacting for 24 hours; centrifuging the obtained product, washing twice with ethanol, drying at 80 ℃ for 8h, grinding into powder with a mortar after drying, heating the powder to 550 ℃ at the speed of 2 ℃/min in a temperature programmed tube furnace, and keeping for 6h to obtain the sea urchin-shaped tungsten-containing mesoporous silica ball material.
Example 6
Sea urchin-shaped mesoporous silica sphere carrier 15-5-SiO2The preparation method comprises the following steps:
1) adding 6.4g of sodium tungstate and 40mL of water into a 150mL round-bottom flask, and boiling for 5 min; to the mixture was added diluted 13.4mL/3M hydrochloric acid, and after stirring, 2.67g of [ C ] was added16mim]Cl, standing for precipitation, washing and drying for later use
2) In a 150mL round bottom flask was added 25mL of 35 wt% CTAC,0.18mL of TEA, 36mL of H2O, stirring for 30 min; dropwise adding 20ml of 5% (v/v') TEOS into the solution, continuously stirring, and continuously reacting for 24 hours; the product obtained is centrifuged and washed twice with ethanolDrying at 80 ℃ for 8h, grinding into powder by using a mortar, heating the powder to 550 ℃ at the speed of 2 ℃/min in a temperature programmed tube furnace, and keeping for 6h to obtain the sea urchin-shaped mesoporous silica sphere carrier material.
The dispersive sea urchin-shaped mesoporous silica sphere material (W/SiO) obtained in example 1 was used2) The method is used for removing sulfur-containing compounds in oil products by catalytic oxidation, and comprises adding 0.005g W/SiO into a self-made double-neck jacketed bottle with a reflux condenser tube2，24μL H2O2(30%) 5mL of a mock oil having a sulfur content of 500ppm was heated in a water bath with stirring set at 60 ℃ using a heating temperature-controlled magnetic stirrer.
Taking DBT as an example, the reaction formula is:
TABLE 1 catalytic Activity of different catalysts for DBT Oxidation
TABLE 2 pore structure Properties of different catalysts
FIG. 1 is a small-angle XRD analysis chart of sea urchin-shaped tungsten-containing mesoporous silica sphere material, (a)15-5-W/SiO2；(b)15-10-W/SiO2；(c)15-20-W/SiO2；
FIG. 2 shows an infrared spectrum of a sea urchin-shaped tungsten-containing mesoporous silica sphere material: (a) [ C ]16mim]4W10O32；(b)15-5-W/SiO2；(c)15-10-W/SiO2；(d)15-20-W/SiO2；(e)25-5-W/SiO2；(f)35-5-W/SiO2；
FIG. 3 shows N of sea urchin-like tungsten-containing mesoporous silica sphere material2Adsorption-desorption isotherm, (a)15-5-W/SiO2；(b)15-10-W/SiO2；(c)15-20-W/SiO2；
FIG. 4 shows the results of example 1, which shows the sea urchin-shaped tungsten-containing mesoporous silica spheres of 15-5-W/SiO2Transmission electron microscopy images of;
FIG. 5 shows the result of catalytic removal of different sulfur-containing substrates by sea urchin-like tungsten-containing mesoporous silica spheres, which shows that the sea urchin-like tungsten-containing mesoporous silica spheres have higher removal efficiency for different sulfur-containing substrates.
Claims (7)
1. A preparation method of a sea urchin-shaped tungsten-containing mesoporous silica sphere material is characterized by adopting an oil-water interface reaction method and specifically comprising the following steps:
(1) metal source precursor [ C16mim]4W10O32The preparation of (1):
adding sodium tungstate and water into a round-bottom flask in proportion, boiling for 5-20 min, adding a hydrochloric acid solution, stirring, and adding a template agent [ C ]16mim]Cl; standing to obtain white precipitate, washing, drying, and synthesizing metal source precursor [ C ]16mim]4W10O32And is ready for use;
(2) preparing 15-35 wt% of CTAC solutions with different mass fractions for later use; preparing TEOS aqueous solutions with different volume fractions of 5-20% for later use;
(3) adding the metal source precursor [ C ] prepared in the step (1) into a round-bottom flask16mim]4W10O32CTAC solution, triethanolamine, H prepared in step (2)2O, stirring and dissolving for the first time for 30-120 min, then dropwise adding into the TEOS aqueous solution prepared in the step (2), stirring for the second time, and continuously reacting for 8-24 h;
(4) and (3) centrifuging the product obtained in the step (3), washing with alcohol for 2 times, drying at 60-100 ℃ to obtain a white solid, grinding the solid into powder, putting the powder into a muffle furnace, carrying out temperature programming to 400-700 ℃, and keeping for 3-6 hours to obtain the dispersive echinoid tungsten-containing mesoporous silica sphere material.
2. The method for preparing sea urchin-shaped tungsten-containing mesoporous silica sphere material according to claim 1, wherein in step (1), the hydrochloric acid is usedThe concentration of the solution is 3 mol/L; sodium tungstate, water, hydrochloric acid solution and template agent [ C ]16mim]The dosage proportion of Cl is as follows: 6.4 g: 40mL of: 13.4 mL: 2.67 g.
3. The method for preparing sea urchin-shaped tungsten-containing mesoporous silica sphere material according to claim 1, wherein in step (2), [ C ] is16mim]4W10O3215-35 wt% CTAC solution, triethanolamine, H2O, 5-20% (v/v') TEOS aqueous solution is used in the following proportion: 0.0822 g: 25mL of: 0.18 mL: 36mL of: 20 mL.
4. The method for preparing sea urchin-shaped tungsten-containing mesoporous silica sphere material as claimed in claim 1, wherein in the step (3), the first stirring speed is 800-1000 r/min; the second stirring speed is 100-170 r/min.
5. The method for preparing the sea urchin-shaped tungsten-containing mesoporous silica sphere material according to claim 1, wherein in the step (4), the temperature programming rate is 2-5 ℃/min.
6. A sea urchin-shaped tungsten-containing mesoporous silica sphere material, which is obtained by the preparation method of any one of claims 1 to 5, and has a specific surface area of 550 to 1100m2The mesoporous material has a mesoporous structure with a pore volume of 0.68-1.6 cm3The pore diameter is 4-7 nm.
7. The application of the sea urchin-shaped tungsten-containing mesoporous silica sphere material of claim 6 in catalytic oxidation removal of aromatic sulfides and aliphatic sulfides in fuel oil.
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| CN103613101A (en) * | 2013-10-31 | 2014-03-05 | 华东师范大学 | Preparation method of mesoporous silica nanosphere having dendrimer-like open-framework structure |
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| Fabrication and characterization of tungsten-containing mesoporous silica for heterogeneous oxidative desulfurization;Ming Zhang et al.;《Chinese Journal of Catalysis》;20160605;第37卷(第6期);971-978 * |
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