CN114289032B - Preparation method and application of tungsten oxide loaded platinum-iron nano alloy catalyst - Google Patents
Preparation method and application of tungsten oxide loaded platinum-iron nano alloy catalyst Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 61
- 239000000956 alloy Substances 0.000 title claims abstract description 61
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 45
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 238000010438 heat treatment Methods 0.000 claims description 16
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- 239000005642 Oleic acid Substances 0.000 claims description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 11
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- 238000005406 washing Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
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- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
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- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 12
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- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
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- 238000005859 coupling reaction Methods 0.000 description 4
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- 239000000295 fuel oil Substances 0.000 description 4
- -1 polycyclic aromatic sulfides Chemical class 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 3
- NICUQYHIOMMFGV-UHFFFAOYSA-N 4-Methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C(C)=CC=C2 NICUQYHIOMMFGV-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 229930192474 thiophene Natural products 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to the field of preparation of catalytic materials, and discloses a preparation method and application of a tungsten oxide loaded platinum-iron nano alloy catalyst. The catalyst firstly adopts a co-reduction strategy to prepare the platinum-iron nano alloy, and then adopts an impregnation method to load the platinum-iron nano alloy on the surface-modified tungsten oxide, so that the successful preparation of the tungsten oxide-loaded platinum-iron nano alloy catalyst is realized. The catalyst prepared by the invention has the advantages of no toxicity, no harm, good dispersibility, high catalytic activity and higher desulfurization performance on various aromatic sulfur-containing organic matters.
Description
Technical Field
The invention belongs to the field of preparation of functional catalytic materials, and particularly relates to a preparation method of a tungsten oxide loaded platinum-iron nano alloy catalyst and application of the catalyst in catalytic oxidation of aromatic organic sulfur in diesel.
Background
Along with the high-speed development of economy, the problem of environmental pollution is more serious, and the production and the life of people are influenced. Among them, the problem of air pollution represented by haze, acid rain, etc. is increasing. The main cause of haze and acid rain is the combustion of sulfur-containing organics in fuel oils, and therefore, the production of clean sulfur-free fuel oils is important for environmental purification. The hydrodesulfurization method widely adopted in the industry at present has excellent removal effect on most of mercaptan and thioether, but the removal of aromatic thiophene sulfur with large steric hindrance requires harsh reaction conditions. Aiming at thiophene organic sulfur which is difficult to completely remove after hydrodesulfurization, the advantage of adopting an oxidation desulfurization technology is obvious. The operation condition of oxidative desulfurization is mild, the efficiency of removing thiophene sulfur is high, and the research is relatively extensive.
In recent years, noble metal nanocatalysts have been widely developed and exhibit excellent properties in many catalytic reactions. Recently, it has been discovered that noble metal platinum (Pt) can be used as a high activity catalytic site for activating molecular oxygen to catalyze and oxidize and remove aromatic thiophenic sulfur in fuel (chem. Eng. J.2020,380,122526; ind. Eng. Chem. Res.2021,60, 2828-2837). Although Pt nanocatalysts have been provided with the ability to catalyze oxidative desulfurization, their development is still limited by the disadvantages of high price and low reserves in order to further develop toward industrial applications. Therefore, it is practically significant to reduce the amount of Pt while ensuring that the catalytic performance is not lowered. The preparation of alloy catalysts is a very practical strategy.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a tungsten oxide loaded platinum-iron nano alloy catalyst and a preparation method thereof. The catalyst takes tungsten oxide modified by surface organic matters as a carrier, and platinum-iron nano alloy with good catalytic activity is loaded on the surface of the tungsten oxide to obtain a tungsten oxide loaded platinum-iron nano alloy catalyst;
in the catalyst, the mass percentage of the tungsten oxide and platinum-iron nano alloy modified by surface organic matters is as follows: 1:0.01 to 1:0.05.
the invention also aims at utilizing the tungsten oxide loaded platinum-iron nano alloy catalyst as a catalyst to catalyze and oxidize polycyclic aromatic sulfides in diesel oil, so that the sulfur content in the diesel oil reaches the national VI standard.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a tungsten oxide loaded platinum-iron nano alloy catalyst comprises the following steps:
(1) Under the conditions of no water, no oxygen and nitrogen protection, adding a certain amount of platinum source and iron source into the surfactant, heating and stirring until the platinum source and the iron source are completely dissolved to obtain a brown yellow solution; then heating to a reduction temperature at a certain heating rate, switching the air flow to be hydrogen-nitrogen mixed gas, co-reducing for a period of time, cooling to room temperature, precipitating the obtained platinum-iron nano alloy with ethanol, dispersing hexane, washing alternately for multiple times, and finally dispersing in hexane for storage;
(2) Adding tungsten chloride into absolute ethyl alcohol, stirring, dissolving, adding oleylamine and oleic acid as surface modifier, adding the obtained precursor solution into a reaction kettle, performing solvothermal reaction at a certain temperature, cooling to room temperature, and alternately washing the product with cyclohexane and ethanol to obtain tungsten oxide with the surface modified by oleylamine and oleic acid long carbon chain organic molecules, namely tungsten oxide modified by surface organic matters;
(3) And (3) weighing a certain amount of platinum-iron nano alloy in the step (1) and dispersing in a mixed solution of hexane and acetone, adding a certain amount of tungsten oxide modified by the surface organic matters in the step (2), performing ultrasonic dispersion, drying, introducing inert atmosphere, and treating for a period of time at a certain temperature to obtain the tungsten oxide-loaded platinum-iron nano alloy catalyst.
In the step (1), the platinum source and the iron source are platinum acetylacetonate and iron acetylacetonate respectively, and the molar ratio of platinum to iron is 3:1, a step of; the surfactant is oleylamine or octadecene; the temperature of the heating and stirring is 60 ℃.
In the step (1), the heating rate is 3-5 ℃/min; the reduction temperature is 200-240 ℃; the volume fraction of hydrogen in the hydrogen-nitrogen mixed gas is 5-10%; the reduction time is 1-1.5 hours.
In the step (2), the dosage ratio of the tungsten chloride, the absolute ethyl alcohol, the oleylamine and the oleic acid is 0.1-0.2 g:10mL:0.5mL:0.5mL; the solvothermal reaction temperature is 160-220 ℃ and the reaction time is 12-36 hours.
In the step (3), the mass ratio of the tungsten oxide modified by the surface organic matter to the platinum-iron nano alloy is 1:0.01 to 1:0.05; the inert atmosphere is argon and nitrogen; the treatment temperature is 150-250 ℃ and the treatment time is 1-4 hours.
The catalyst prepared by the invention presents brown yellow powdery solid in appearance, has no obvious smell, is insoluble in water, ethanol, acetonitrile, gasoline, diesel oil and other liquids, and belongs to an environment-friendly catalyst.
The catalyst is used for activating molecular oxygen to catalyze and oxidize and remove aromatic organic sulfur in diesel oil.
The beneficial effects of the invention are as follows:
according to the invention, tungsten oxide modified by surface organic matters is used as a carrier, platinum-iron nano alloy with good catalytic activity is loaded on the surface of tungsten oxide, so that the tungsten oxide loaded platinum-iron nano alloy catalyst is prepared, and the problems of high price and the like of a pure platinum nano catalyst are solved.
Drawings
FIG. 1 is a transmission electron microscope image of an oleylamine modified platinum iron nano alloy under 220℃synthesis conditions;
FIG. 2 is a transmission electron microscope image of an octadecene modified platinum-iron nano-alloy under 220℃synthesis conditions;
FIG. 3 is a transmission electron microscope image of an oleylamine modified platinum iron nano alloy under 240℃synthesis conditions;
FIG. 4 is a graph showing the catalytic oxidative desulfurization activity of the tungsten oxide-supported platinum-iron nano alloy catalyst obtained in example 3 on different sulfides;
FIG. 5 is a transmission electron microscope image of an octadecene modified platinum-iron nano-alloy under 240 ℃ synthesis conditions;
FIG. 6 is a transmission electron microscope image of an oleylamine modified platinum nano-alloy under 220℃synthesis conditions;
FIG. 7 is a graph of catalytic oxidative desulfurization activity of a comparative tungsten oxide supported platinum nanocatalyst versus dibenzothiophene.
Detailed Description
According to the technical gist of the present invention, the technical scheme, implementation process, principle and the like will be further explained below to better understand the present invention. However, it will be readily appreciated by those skilled in the art that the descriptions of the embodiments are provided for illustration only and should not limit the invention as described in the claims. The above technical features of the present invention and the technical features specifically described in the embodiments may be combined with each other to form a new or preferred technical solution.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1:
under the conditions of no water, no oxygen and nitrogen protection, 20mg of platinum acetylacetonate and 5mg of ferric acetylacetonate are weighed, 10mL of oleylamine is added into a flask, and the mixture is heated and stirred at 60 ℃ until the solution is completely dissolved, so that a brown yellow solution is obtained. Then the temperature is increased to 220 ℃ at a heating rate of 3 ℃/min, and thenSwitching the gas flow to 10% H 2 /N 2 The mixture was reduced at 220℃for 1.5 hours and then cooled to room temperature. And (3) precipitating the obtained platinum-iron (PtFe) nano alloy by adopting ethanol, dispersing by adopting hexane, alternately washing for multiple times, and finally dispersing and storing the PtFe nano alloy in hexane. The transmission electron microscope of the prepared PtFe nano alloy is shown in figure 1, the PtFe nano alloy takes the shape of nano particles, and the coupling exists between every 3 to 4 nano particles to form a triangle or chain shape.
0.2g of tungsten chloride is weighed and added into 10mL of absolute ethyl alcohol, and the mixture is stirred and dissolved. Then 0.5mL of oleylamine and 0.5mL of oleic acid were added as surface modifiers. The obtained precursor solution was added to the reaction vessel, and solvothermal reaction was performed at 200 ℃ for 12 hours. After cooling to room temperature, the product was alternately washed with cyclohexane and ethanol to obtain surface organic-modified tungsten oxide.
Then, 5mg of PtFe nano alloy was weighed and dispersed in a mixture of 6mL of hexane and 3mL of acetone, and 0.1g of tungsten oxide of which surface was modified with organic molecules was added thereto, followed by ultrasonic dispersion for 1 hour. And (3) drying at 80 ℃, and treating at 150 ℃ for 4 hours in a nitrogen atmosphere to obtain the tungsten oxide loaded platinum-iron nano alloy catalyst.
Example 2:
under the conditions of no water, no oxygen and nitrogen protection, 20mg of platinum acetylacetonate and 5mg of ferric acetylacetonate are weighed, 10mL of octadecene is added into a flask, and the mixture is heated and stirred at 60 ℃ until the octadecene is completely dissolved, so as to obtain a brown yellow solution. Then the temperature is increased to 220 ℃ at a heating rate of 3 ℃/min, and then the gas flow is switched to 10% H 2 /N 2 The mixture was reduced at 220℃for 1.5 hours and then cooled to room temperature. And (3) precipitating the obtained platinum-iron (PtFe) nano alloy by adopting ethanol, dispersing by adopting hexane, alternately washing for multiple times, and finally dispersing and storing the PtFe nano alloy in hexane. The transmission electron microscope of the prepared PtFe nano alloy is shown in figure 2. Compared with example 1, the PtFe nano alloy has improved dispersibility by adopting octadecene as a surfactant, and has a coupling phenomenon between every 2 to 3 nano particles.
0.1g of tungsten chloride is weighed and added into 10mL of absolute ethyl alcohol, and the mixture is stirred and dissolved. Then 0.5mL of oleylamine and 0.5mL of oleic acid were added as surface modifiers. The obtained precursor solution was added to the reaction vessel, and solvothermal reaction was performed at 160 ℃ for 36 hours. After cooling to room temperature, the product was alternately washed with cyclohexane and ethanol to obtain surface organic-modified tungsten oxide.
Then, 5mg of PtFe nano alloy was weighed and dispersed in a mixture of 6mL of hexane and 3mL of acetone, and 0.1g of tungsten oxide of which surface was modified with organic molecules was added thereto, followed by ultrasonic dispersion for 1 hour. And (3) drying at 80 ℃, and treating at 250 ℃ for 1 hour under an argon atmosphere to obtain the tungsten oxide loaded platinum-iron nano alloy catalyst.
Example 3:
under the conditions of no water, no oxygen and nitrogen protection, 20mg of platinum acetylacetonate and 5mg of ferric acetylacetonate are weighed, 10mL of oleylamine is added into a flask, and the mixture is heated and stirred at 60 ℃ until the solution is completely dissolved, so that a brown yellow solution is obtained. Then the temperature is raised to 240 ℃ at a heating rate of 4 ℃/min, and then the gas flow is switched to 10% H 2 /N 2 The mixture was reduced at 240℃for 1.5 hours and then cooled to room temperature. And (3) precipitating the obtained platinum-iron (PtFe) nano alloy by adopting ethanol, dispersing by adopting hexane, alternately washing for multiple times, and finally dispersing and storing the PtFe nano alloy in hexane. The transmission electron microscope of the prepared PtFe nano alloy is shown in FIG. 3. The PtFe nano alloy has better dispersity, and the coupling phenomenon exists between every 2 to 3 nano particles.
0.2g of tungsten chloride is weighed and added into 10mL of absolute ethyl alcohol, and the mixture is stirred and dissolved. Then 0.5mL of oleylamine and 0.5mL of oleic acid were added as surface modifiers. The obtained precursor solution was added to a reaction vessel, and solvothermal reaction was performed at 180 ℃ for 24 hours. After cooling to room temperature, the product was alternately washed with cyclohexane and ethanol to obtain surface organic-modified tungsten oxide.
Then, 5mg of PtFe nano alloy was weighed and dispersed in a mixture of 6mL of hexane and 3mL of acetone, and 0.1g of tungsten oxide of which surface was modified with organic molecules was added thereto, followed by ultrasonic dispersion for 1 hour. And (3) drying at 80 ℃, and treating at 200 ℃ for 2 hours in an argon atmosphere to obtain the tungsten oxide loaded platinum-iron nano alloy catalyst.
Dibenzothiophene (DBT) and 4-methyldibenzothiophene (4-MDBT), and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) are taken as model sulfides, and are dissolved in decalin to obtain model oil, wherein the initial concentration of sulfur content in the model oil is 500ppm. 20mL of model oil and 0.05g of tungsten oxide loaded platinum-iron nano alloy are taken in a reaction bottle, and are placed on a magnetic heating stirrer, and the reaction temperature is set to be 120 ℃. Air with a certain flow rate is introduced as an oxidant, and the stirring speed is 800rpm. In the reaction process, the sulfur content is detected by using a gas chromatograph Agilent GC-7890A, and the desulfurization rate is calculated. The desulfurization performance is shown in fig. 4, and the removal rates of 4,6-DMDBT, DBT and 4-MDBT of the tungsten oxide loaded platinum-iron nano alloy catalyst prepared in example 3 respectively reach 74.0%,29.2% and 6.6% after 2 hours of catalytic oxidation reaction. The time for complete catalytic oxidation to remove the above 3 sulfides is 3.5 hours, 4 hours and 5 hours, respectively.
Example 4:
under the conditions of no water, no oxygen and nitrogen protection, 20mg of platinum acetylacetonate and 5mg of ferric acetylacetonate are weighed, 10mL of octadecene is added into a flask, and the mixture is heated and stirred at 60 ℃ until the octadecene is completely dissolved, so as to obtain a brown yellow solution. Then the temperature is raised to 240 ℃ at a heating rate of 3 ℃/min, and then the gas flow is switched to 10% H 2 /N 2 The mixture was reduced at 240℃for 1.5 hours and then cooled to room temperature. And (3) precipitating the obtained platinum-iron (PtFe) nano alloy by adopting ethanol, dispersing by adopting hexane, alternately washing for multiple times, and finally dispersing and storing the PtFe nano alloy in hexane. The transmission electron microscope of the prepared PtFe nano alloy is shown in FIG. 5. PtFe nano alloy presents nano particle form and has good dispersibility.
0.2g of tungsten chloride is weighed and added into 10mL of absolute ethyl alcohol, and the mixture is stirred and dissolved. Then 0.5mL of oleylamine and 0.5mL of oleic acid were added as surface modifiers. The obtained precursor solution was added to a reaction vessel, and solvothermal reaction was performed at 180 ℃ for 24 hours. After cooling to room temperature, the product was alternately washed with cyclohexane and ethanol to obtain surface organic-modified tungsten oxide.
Then, 5mg of PtFe nano alloy was weighed and dispersed in a mixture of 6mL of hexane and 3mL of acetone, and 0.1g of tungsten oxide of which surface was modified with organic molecules was added thereto, followed by ultrasonic dispersion for 1 hour. And (3) drying at 80 ℃, and treating at 180 ℃ for 3 hours in a nitrogen atmosphere to obtain the tungsten oxide loaded platinum-iron nano alloy catalyst.
Comparative example:
under the conditions of no water, no oxygen and nitrogen protection, 20mg of platinum acetylacetonate is weighed, 10mL of oleylamine is added into a flask, and the mixture is heated and stirred at 60 ℃ until the solution is completely dissolved, so that a brown yellow solution is obtained. Then the temperature is raised to 240 ℃ at a heating rate of 3 ℃/min, and then the gas flow is switched to 10% H 2 /N 2 The mixture was reduced at 240℃for 1.5 hours and then cooled to room temperature. And (3) precipitating the obtained platinum nano particles by adopting ethanol, dispersing by adopting hexane, alternately washing for a plurality of times, and finally dispersing the platinum nano particles in hexane for storage. The transmission electron microscope of the prepared platinum nano-particles is shown in fig. 6, and the appearance of the nano-particles is shown, but the coupling phenomenon exists between every 2 to 3 nano-particles.
0.2g of tungsten chloride is weighed and added into 10mL of absolute ethyl alcohol, and the mixture is stirred and dissolved. Then 0.5mL of oleylamine and 0.5mL of oleic acid were added as surface modifiers. The obtained precursor solution was added to a reaction vessel, and solvothermal reaction was performed at 180 ℃ for 24 hours. After cooling to room temperature, the product was alternately washed with cyclohexane and ethanol to obtain surface organic-modified tungsten oxide.
Then, 5mg of platinum nanoparticles were weighed and dispersed in a mixture of 6mL of hexane and 3mL of acetone, and 0.1g of tungsten oxide of which the surface was modified with organic molecules was added thereto, followed by ultrasonic dispersion for 1 hour. And (3) drying at 80 ℃, and treating at 200 ℃ for 2 hours in Ar atmosphere to obtain the tungsten oxide supported platinum nano catalyst. The catalyst is used for activating molecular oxygen oxidation desulfurization, and the performance is shown in figure 7. The tungsten oxide supported platinum nano catalyst has poor removal rate of dibenzothiophene in fuel oil and basically has no catalytic oxidation desulfurization performance 3 hours before the reaction. The dibenzothiophene in the fuel oil can be completely converted after the reaction is carried out step by step for 7 hours.
Claims (7)
1. The preparation method of the tungsten oxide loaded platinum-iron nano alloy catalyst is characterized by comprising the following steps of:
(1) Under the conditions of no water, no oxygen and nitrogen protection, adding a certain amount of platinum source and iron source into the surfactant, heating and stirring until the platinum source and the iron source are completely dissolved to obtain a brown yellow solution; then heating to a reduction temperature at a certain heating rate, switching the air flow to be hydrogen-nitrogen mixed gas, co-reducing for a period of time, cooling to room temperature, precipitating the obtained platinum-iron nano alloy with ethanol, dispersing hexane, washing alternately for multiple times, and finally dispersing in hexane for storage;
(2) Adding tungsten chloride into absolute ethyl alcohol, stirring, dissolving, adding oleylamine and oleic acid as surface modifier, adding the obtained precursor solution into a reaction kettle, performing solvothermal reaction at a certain temperature, cooling to room temperature, and alternately washing the product with cyclohexane and ethanol to obtain tungsten oxide with the surface modified by oleylamine and oleic acid long carbon chain organic molecules, namely tungsten oxide modified by surface organic matters;
(3) And (3) weighing a certain amount of platinum-iron nano alloy in the step (1) and dispersing in a mixed solution of hexane and acetone, adding a certain amount of tungsten oxide modified by the surface organic matters in the step (2), performing ultrasonic dispersion, drying, introducing inert atmosphere, and treating for a period of time at a certain temperature to obtain the tungsten oxide-loaded platinum-iron nano alloy catalyst.
2. The method of manufacturing according to claim 1, wherein: in the step (1), the platinum source and the iron source are platinum acetylacetonate and iron acetylacetonate respectively, and the molar ratio of platinum to iron is 3:1, a step of; the surfactant is oleylamine or octadecene; the temperature of the heating and stirring is 60 ℃.
3. The method of manufacturing according to claim 1, wherein: in the step (1), the heating rate is 3-5 ℃/min; the reduction temperature is 200-240 ℃; the volume fraction of hydrogen in the hydrogen-nitrogen mixed gas is 5-10%; the reduction time is 1-1.5 hours.
4. The method of manufacturing according to claim 1, wherein: in the step (2), the dosage ratio of the tungsten chloride, the absolute ethyl alcohol, the oleylamine and the oleic acid is 0.1-0.2 g:10mL:0.5mL:0.5mL; the solvothermal reaction temperature is 160-220 ℃ and the reaction time is 12-36 hours.
5. The method of manufacturing according to claim 1, wherein: in the step (3), the mass ratio of the tungsten oxide modified by the surface organic matter to the platinum-iron nano alloy is 1:0.01 to 1:0.05; the inert atmosphere is argon and nitrogen; the treatment temperature is 150-250 ℃ and the treatment time is 1-4 hours.
6. A tungsten oxide loaded platinum-iron nano alloy catalyst is characterized in that: the catalyst is prepared by the preparation method of any one of claims 1 to 5, wherein tungsten oxide modified by surface organic matters is used as a carrier, and platinum-iron nano alloy with good catalytic activity is loaded on the surface of the tungsten oxide; wherein, the mass ratio of the tungsten oxide modified by the surface organic matter to the platinum-iron nano alloy is as follows: 1:0.01 to 1:0.05.
7. use of the tungsten oxide loaded platinum-iron nano alloy catalyst according to claim 6 for activating molecular oxygen to catalyze and oxidize to remove aromatic organic sulfur in diesel oil.
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