CN115583670A - Sea urchin-shaped or rod-shaped tungsten oxide and preparation method and application thereof - Google Patents
Sea urchin-shaped or rod-shaped tungsten oxide and preparation method and application thereof Download PDFInfo
- Publication number
- CN115583670A CN115583670A CN202211164210.5A CN202211164210A CN115583670A CN 115583670 A CN115583670 A CN 115583670A CN 202211164210 A CN202211164210 A CN 202211164210A CN 115583670 A CN115583670 A CN 115583670A
- Authority
- CN
- China
- Prior art keywords
- tungsten oxide
- rod
- shaped
- sea urchin
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 63
- 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 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 35
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 8
- 239000010935 stainless steel Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000004687 hexahydrates Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 238000007605 air drying Methods 0.000 abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 22
- 238000012360 testing method Methods 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 241000257465 Echinoidea Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- OGXRXFRHDCIXDS-UHFFFAOYSA-N methanol;propane-1,2,3-triol Chemical compound OC.OCC(O)CO OGXRXFRHDCIXDS-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a sea urchin-shaped or rod-shaped tungsten oxide, a preparation method and application thereof, wherein WCl is prepared 6 Dissolving black solid powder in ethanol or cyclohexanol, mixing, stirring, ultrasonic soaking until WCl is reached 6 Dissolving black solid powder in ethanol or cyclohexanol completely, ultrasonic soaking, transferring the solution to stainless steel reactor with polytetrafluoroethylene as inner container when the solution turns from yellow to dark blue, transferring the reactor into air drying oven, performing solvent heat treatment at 100-200 deg.C for 24 hr, cooling to room temperature, washing with anhydrous ethanol and deionized water for several times, vacuum drying, and grinding to obtain sea urchin-shaped tungsten oxide W 18 O 49 Or rod-shaped tungsten oxide WO 3 Sea urchin-like tungsten oxide W 18 O 49 Or rod-shaped tungsten oxide WO 3 The catalyst has larger specific surface area and excellent appearance, and the highest selectivity of 67 percent of n-propanol can be obtained by catalyzing the glycerol cracking by taking the catalyst as a carrier and loading a platinum-based catalyst, and the conversion rate of the glycerol is 100 percent.
Description
Technical Field
The invention relates to the technical field of nano materials and chemical engineering, in particular to echinoid or rodlike tungsten oxide and a preparation method and application thereof.
Background
With the increasing shortage of fossil fuels and the aggravation of environmental pollution, the utilization of renewable energy sources is crucial to the sustainable development of society. The biodiesel serving as a renewable energy source is partially used for replacing petroleum products and has a great application prospect, and the glycerol is a main byproduct in the production of the biodiesel from soybean oil or animal fatty oil and accounts for about 10wt% of the yield of the biodiesel, so that the conversion of the surplus glycerol into fine chemicals with high added values has important industrial value. The Pt-W supported catalyst reported at present has good catalytic performance in the preparation of propylene alcohol and propylene glycol from glycerol, and researches show that high oxygen defect, large specific surface area and the like are beneficial to improving the catalytic performance of the Pt-W catalyst, however, most of the reported tungsten oxides are calcined at high temperature, and the tungsten oxide obtained by high-temperature calcination generally easily destroys the internal structure texture, so that the obtained morphology is single and the crystal form is difficult to control.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide the echinoid or rodlike tungsten oxide and the preparation method and the application thereof.
In order to achieve the purpose, the invention is implemented according to the following technical scheme:
the first purpose of the invention is to provide a preparation method of sea urchin-shaped or rod-shaped tungsten oxide, in particular toThe method comprises the following steps: mixing WCl 6 Dissolving black solid powder in ethanol or cyclohexanol, wherein WCl 6 Adding black solid powder and ethanol or cyclohexanol in an amount of 0.01-0.05g/mL, mixing, stirring, ultrasonic soaking until WCl is reached 6 Completely dissolving black solid powder in ethanol or cyclohexanol, continuing ultrasonic impregnation, immediately transferring the solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container when the solution is changed from yellow to dark blue, then transferring the reaction kettle into an air-blast drying oven, carrying out solvent heat treatment at 100-200 ℃ for 24h, cooling to room temperature, respectively washing with absolute ethyl alcohol and deionized water for a plurality of times, then carrying out vacuum drying, and grinding to obtain the sea urchin-shaped tungsten oxide W 18 O 49 Or rod-shaped tungsten oxide WO 3 。
Further, the ultrasonic immersion time is 1-12min.
Preferably, said WCl 6 The adding ratio of the black solid powder to ethanol or cyclohexanol is 0.03g/mL.
Preferably, the vacuum drying condition is drying at 60 ℃ for 6-12h.
The second purpose of the invention is to provide the echinoid or rodlike tungsten oxide W prepared by the method 18 O 49 Or rod-shaped tungsten oxide WO 3 。
The third purpose of the invention is to provide the sea urchin-shaped tungsten oxide W 18 O 49 Or rod-shaped tungsten oxide WO 3 The application in preparing the reaction catalyst for preparing the n-propanol by the hydrogenation of the glycerol specifically comprises the following steps: mixing sea urchin-shaped tungsten oxide W 18 O 49 Or rod-shaped tungsten oxide WO 3 Immersing as a sample in an aqueous solution containing chloroplatinic acid hexahydrate, drying the immersed sample at 110 deg.C for 12h, then flowing at 300 deg.C 10% 2 Reduction under the conditions of/Ar (v/v) for 3h and at room temperature with 1% O 2 /N 2 (v/v) deactivation was carried out for 1h to obtain a catalyst having a Pt content of 2wt%.
Compared with the prior art, the sea urchin-shaped tungsten oxide W is prepared by adopting a solvothermal method 18 O 49 Or rod-shaped tungsten oxide WO 3 Sea urchin shaped tungsten oxide W 18 O 49 Or rod-shaped tungsten oxide WO 3 Are all provided withThe preparation method has the advantages that the specific surface area is large, the morphology is good, the highest selectivity of the n-propanol (67%) can be obtained by catalyzing the glycerol cracking with the platinum-based catalyst loaded as the carrier, the glycerol conversion rate is 100%, the preparation process is simple and feasible, the operation is simple, the method is green and pollution-free, and the large-scale production is easy.
Drawings
FIG. 1 shows the XRD test results of tungsten oxide powder prepared by reaction of ethanol as solvent at 120 deg.C, 160 deg.C, and 200 deg.C for 24 h.
FIG. 2 shows the XRD test result of the tungsten oxide powder prepared by the reaction of cyclohexanol at 160 deg.C and 200 deg.C for 24 h.
FIG. 3 is an electron microscope image of tungsten oxide powder prepared by reaction of ethanol as solvent at 120 ℃ for 24 h.
FIG. 4 is an electron microscope image of tungsten oxide powder prepared by using ethanol as a solvent and reacting at 160 ℃ for 24 hours.
FIG. 5 is an electron microscope image of tungsten oxide powder prepared by using ethanol as a solvent and reacting at 200 ℃ for 24 hours.
FIG. 6 is an electron microscope image of tungsten oxide powder prepared by using cyclohexanol as a solvent and reacting at 160 ℃ for 24 hours.
FIG. 7 is an electron micrograph of tungsten oxide powder obtained by reacting cyclohexanol as a solvent at 200 ℃ for 24 hours.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. The specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
3gWCl 6 Dissolving black solid powder in 100ml of 99% ethanol, mixing and stirring, carrying out ultrasonic impregnation for 12min, continuing ultrasonic impregnation after tungsten chloride is completely dissolved in the ethanol, immediately taking out the solution when the solution is changed from yellow to dark blue, transferring the solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, then transferring the reaction kettle into a forced air drying oven, carrying out solvent heat treatment at 120 ℃ for 24h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water for three times respectively, then drying in a vacuum drying oven at 60 ℃ for 12h, and grinding to obtain light blue tungsten oxide powder.
Example 2
3gWCl 6 Dissolving black solid powder in 100ml of 99% ethanol, mixing and stirring, performing ultrasonic impregnation for 12min, continuing ultrasonic impregnation after tungsten chloride is completely dissolved in the ethanol, immediately taking out the solution when the solution is changed from yellow to dark blue, transferring the solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, then transferring the reaction kettle into a forced air drying oven for solvent heat treatment at 160 ℃ for 24h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water for three times respectively, then drying in a vacuum drying oven at 60 ℃ for 12h, and grinding to obtain light blue tungsten oxide powder.
Example 3
3gWCl 6 Dissolving black solid powder in 100ml of 99% ethanol, mixing and stirring, carrying out ultrasonic impregnation for 12min, continuing ultrasonic impregnation after tungsten chloride is completely dissolved in the ethanol, immediately taking out the solution when the solution is changed from yellow to dark blue, transferring the solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, then transferring the reaction kettle into a forced air drying oven for carrying out solvent heat treatment at 200 ℃ for 24h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water for three times respectively, then drying in a vacuum drying oven at 60 ℃ for 12h, and grinding to obtain light blue tungsten oxide powder.
Example 4
3g of WCl 6 Dissolving black solid powder in 100ml of 99% cyclohexanol, mixing and stirring, performing ultrasonic impregnation for 12min, continuing ultrasonic impregnation after tungsten chloride is completely dissolved in the cyclohexanol, immediately taking out when the solution is changed from yellow to dark blue, transferring the solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container, transferring the reaction kettle into a forced air drying oven, performing solvent heat treatment at 160 ℃ for 24h, cooling to room temperature, washing with absolute ethyl alcohol and deionized water for three times, drying in a vacuum drying oven at 60 ℃ for 12h, and grinding to obtain white tungsten oxide powder.
Example 5
3g of WCl 6 Dissolving black solid powder in 100ml of 99% cyclohexanol, mixing, stirring, ultrasonic soaking for 12min, continuing ultrasonic soaking after tungsten chloride is completely dissolved in cyclohexanol, taking out immediately when the solution changes from yellow to dark blue, transferring the solution toAnd (2) putting the reaction kettle into a stainless steel reaction kettle with a polytetrafluoroethylene inner container, carrying out solvent heat treatment on the reaction kettle for 24 hours at the temperature of 200 ℃ in an air-blast drying oven, cooling to room temperature, washing the reaction kettle for three times by using absolute ethyl alcohol and deionized water respectively, drying the reaction kettle for 12 hours at the temperature of 60 ℃ in a vacuum drying oven, and grinding the reaction kettle to obtain white tungsten oxide powder.
The XRD test results of the tungsten oxide powders obtained in examples 1, 2 and 3 are shown in fig. 1, and it is understood from the XRD test results in fig. 1 that the tungsten oxide powder obtained by using ethanol as a solvent is W 18 O 49 The electron micrographs of the tungsten oxide powders obtained in examples 1, 2 and 3 are shown in FIGS. 3, 4 and 5, respectively, and it is clear from FIGS. 3, 4 and 5 that the tungsten oxide powders W obtained using ethanol as a solvent 18 O 49 Is sea urchin shaped; XRD test results of the tungsten oxide powders obtained in examples 4 and 5 are shown in FIG. 2, and from the XRD test results in FIG. 2, it is understood that WO is the tungsten oxide powder obtained by using cyclohexanol as a solvent 3 As shown in FIGS. 6 and 7, the electron micrographs of the tungsten oxide powders obtained in examples 4 and 5 are respectively shown in FIGS. 6 and 7, and it is clear from FIGS. 6 and 7 that the tungsten oxide powder WO obtained using cyclohexanol as a solvent 3 Is rod-shaped; as is clear from FIGS. 3 to 7, the obtained sea urchin-like tungsten oxide W 18 O 49 And rod-shaped tungsten oxide WO 3 All have large specific surface area.
Application example 1
The sea urchin-shaped tungsten oxide W obtained in examples 1 to 3 was added 18 O 49 The preparation method of the catalyst for preparing the n-propanol by hydrogenation of glycerol comprises the following steps: w is to be 18 O 49 Sample immersion with chloroplatinic acid hexahydrate (H) 2 PtCl 6 •6H 2 O, aladdin, ≧ 37.5% 2 Reduction under the conditions of/Ar (v/v) for 3h and at room temperature with 1% O 2 /N 2 (v/v) passivation for 1h with a Pt content of 2wt%.
Evaluation of catalyst Activity: the reaction for preparing the n-propanol by the hydrogenation of the glycerol is carried out in a 50ml high-pressure reaction kettle, a thermocouple is arranged in the high-pressure reaction kettle and a magnetic stirrer is externally connected with the high-pressure reaction kettle. First, 0.05g of catalyst and 10ml of glycerol methanol solution (3 wt%) were put into the above reactor. The reactor was purged six times with hydrogen to remove air and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240 ℃ with a stirring speed of 600 rpm. After two hours of reaction, the reactor was quickly transferred to cold water for quick cooling. After cooling, collecting the gas product by an air bag and analyzing, centrifugally separating the reaction liquid product from the catalyst and the reaction liquid, and taking the supernatant for gas phase analysis.
The detection result of the glycerol catalysis test is as follows: reacting for 24 hours at 120 ℃ by using ethanol as a solvent to obtain W 18 O 49 The selectivity of the n-propanol obtained by catalyzing glycerol by using platinum as a carrier is 58%, and the conversion rate of the glycerol is 100%; w obtained by taking ethanol as solvent and reacting for 24 hours at 160 DEG C 18 O 49 The selectivity of the n-propanol obtained by catalyzing glycerol by using platinum as a carrier is 50%, and the conversion rate of the glycerol is 100%; w obtained by taking ethanol as solvent and reacting for 24 hours at 200 DEG C 18 O 49 The selectivity of the n-propanol obtained by catalyzing glycerol by using platinum as a carrier is 67%, and the conversion rate of the glycerol is 100%.
Application example 2
The rod-shaped tungsten oxide WO obtained in the above examples 4 to 5 3 The preparation method of the catalyst for preparing the n-propanol by hydrogenation of glycerol comprises the following steps: w is to be 18 O 49 Sample immersion with chloroplatinic acid hexahydrate (H) 2 PtCl 6 •6H 2 O, aladdin, ≧ 37.5% 2 Reduction under the conditions of/Ar (v/v) for 3h and at room temperature with 1% O 2 /N 2 (v/v) passivation for 1h with a Pt content of 2wt%.
Evaluation of catalyst Activity: the reaction for preparing the n-propanol by the hydrogenation of the glycerol is carried out in a 50ml high-pressure reaction kettle, a thermocouple is arranged in the high-pressure reaction kettle and a magnetic stirrer is externally connected with the high-pressure reaction kettle. First, 0.05g of catalyst and 10ml of glycerol methanol solution (3% by weight) were placed in the above reactor. The reactor was purged six times with hydrogen to remove air and the initial pressure was set to 6MPa. The reactor was rapidly heated to 240 ℃ with a stirring speed of 600 rpm. After two hours of reaction, the reactor was quickly transferred to cold water for quick cooling. After cooling, collecting the gas product by an air bag and analyzing, centrifugally separating the reaction liquid product from the catalyst and the reaction liquid, and taking the supernatant for gas phase analysis.
The detection result of the glycerin catalysis test is as follows: WO obtained by taking cyclohexanol as solvent and reacting at 160 ℃ for 24 hours 3 The selectivity of the n-propanol obtained by catalyzing glycerol by using platinum as a carrier is 58%, and the conversion rate of the glycerol is 100%; WO obtained by taking cyclohexanol as solvent and reacting for 24 hours at 200 DEG C 3 The selectivity of the n-propanol obtained by catalyzing glycerol by using platinum as a carrier is 60%, and the conversion rate of the glycerol is 100%.
The technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.
Claims (7)
1. A preparation method of urchin-shaped or rod-shaped tungsten oxide is characterized by comprising the following specific steps: mixing WCl 6 Dissolving black solid powder in ethanol or cyclohexanol, wherein WCl 6 Adding black solid powder and ethanol or cyclohexanol at a ratio of 0.01-0.05g/mL, mixing, stirring, ultrasonic soaking until WCl 6 Completely dissolving black solid powder in ethanol or cyclohexanol, continuing ultrasonic impregnation, immediately transferring the solution to a stainless steel reaction kettle with a polytetrafluoroethylene inner container when the solution is changed from yellow to dark blue, then transferring the reaction kettle into an air-blast drying oven, carrying out solvent heat treatment at 100-200 ℃ for 24h, cooling to room temperature, respectively washing with absolute ethyl alcohol and deionized water for a plurality of times, then carrying out vacuum drying, and grinding to obtain the sea urchin-shaped tungsten oxide W 18 O 49 Or rod-shaped tungsten oxide WO 3 。
2. The method for producing sea urchin-like or rod-like tungsten oxide according to claim 1, characterized in that: the ultrasonic dipping time is 1-12min.
3. The method for producing sea urchin-like or rod-like tungsten oxide according to claim 1, characterized in that: the WCl 6 Addition of black solid powder with ethanol or cyclohexanolThe addition ratio was 0.03g/mL.
4. The method for producing sea urchin-like or rod-like tungsten oxide according to claim 1, characterized in that: the vacuum drying condition is drying for 6-12h at 60 ℃.
5. The echinoid or rodlike tungsten oxide W prepared by the method for preparing echinoid or rodlike tungsten oxide according to claim 1 18 O 49 Or rod-shaped tungsten oxide WO 3 。
6. The sea urchin-shaped tungsten oxide W as claimed in claim 5 18 O 49 Or rod-shaped tungsten oxide WO 3 The application in preparing the catalyst for preparing the n-propanol by hydrogenating the glycerol.
7. The echinoid tungsten oxide W of claim 6 18 O 49 Or rod-shaped tungsten oxide WO 3 Characterized in that sea urchin-shaped tungsten oxide W is added 18 O 49 Or rod-shaped tungsten oxide WO 3 Immersing as a sample in an aqueous solution containing chloroplatinic acid hexahydrate, drying the immersed sample at 110 deg.C for 12h, then flowing at 300 deg.C 10% 2 Reduction under Ar (v/v) conditions for 3h and at room temperature with 1% O 2 /N 2 (v/v) deactivation was carried out for 1h to obtain a catalyst with a Pt content of 2wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211164210.5A CN115583670A (en) | 2022-09-23 | 2022-09-23 | Sea urchin-shaped or rod-shaped tungsten oxide and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211164210.5A CN115583670A (en) | 2022-09-23 | 2022-09-23 | Sea urchin-shaped or rod-shaped tungsten oxide and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115583670A true CN115583670A (en) | 2023-01-10 |
Family
ID=84778296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211164210.5A Pending CN115583670A (en) | 2022-09-23 | 2022-09-23 | Sea urchin-shaped or rod-shaped tungsten oxide and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115583670A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116081691A (en) * | 2023-03-27 | 2023-05-09 | 陕西科技大学 | Preparation of W by utilizing oxygen defect 18 O 49 /WO 3 Method for heterogeneous electrocatalyst, electrocatalyst and application |
| CN116818745A (en) * | 2023-08-31 | 2023-09-29 | 中国计量科学研究院 | Rapid detection method of rhodamine 6G |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618045A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in glycerol hydrogenolysis for preparation of 1,3-propylene glycol |
| CN107915212A (en) * | 2016-10-08 | 2018-04-17 | 中国科学院大连化学物理研究所 | Caterpillar shape WN nano materials that lamella stacks and preparation method thereof |
| CN107966479A (en) * | 2017-11-16 | 2018-04-27 | 厦门大学 | A kind of Pd/W for improving hydrogen gas sensor performance18O49The preparation method of composite material |
| CN110057875A (en) * | 2018-01-19 | 2019-07-26 | 天津大学 | Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick and its preparation method and application of Argent grain modification |
| CN112892521A (en) * | 2021-01-11 | 2021-06-04 | 湖南大学 | Oxygen-enriched vacancy echinoid tungsten oxide and preparation method and application thereof |
-
2022
- 2022-09-23 CN CN202211164210.5A patent/CN115583670A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618045A (en) * | 2014-10-29 | 2016-06-01 | 中国科学院大连化学物理研究所 | Application of bimetallic catalyst in glycerol hydrogenolysis for preparation of 1,3-propylene glycol |
| CN107915212A (en) * | 2016-10-08 | 2018-04-17 | 中国科学院大连化学物理研究所 | Caterpillar shape WN nano materials that lamella stacks and preparation method thereof |
| CN107966479A (en) * | 2017-11-16 | 2018-04-27 | 厦门大学 | A kind of Pd/W for improving hydrogen gas sensor performance18O49The preparation method of composite material |
| CN110057875A (en) * | 2018-01-19 | 2019-07-26 | 天津大学 | Polypyrrole-tungsten oxide nucleocapsid heterogeneous structural nano stick and its preparation method and application of Argent grain modification |
| CN112892521A (en) * | 2021-01-11 | 2021-06-04 | 湖南大学 | Oxygen-enriched vacancy echinoid tungsten oxide and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 包智颖: "氧化钨纳米线的制备、表征与气敏性能研究", 中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑, no. 8, pages 027 - 698 * |
| 王桂茹主编: "《催化剂与催化作用》", vol. 1, 31 August 2000, 大连理工大学出版社, pages: 323 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116081691A (en) * | 2023-03-27 | 2023-05-09 | 陕西科技大学 | Preparation of W by utilizing oxygen defect 18 O 49 /WO 3 Method for heterogeneous electrocatalyst, electrocatalyst and application |
| CN116818745A (en) * | 2023-08-31 | 2023-09-29 | 中国计量科学研究院 | Rapid detection method of rhodamine 6G |
| CN116818745B (en) * | 2023-08-31 | 2024-01-26 | 中国计量科学研究院 | Rapid detection method of rhodamine 6G |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112121863B (en) | Catalyst for catalytic transfer hydrogenation and preparation method and application thereof | |
| CN109594101B (en) | Preparation method of porous carbon supported ruthenium catalyst | |
| CN111672530B (en) | Preparation method of CuCo-N/C nano catalyst and application of CuCo-N/C nano catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propylene glycol | |
| CN115583670A (en) | Sea urchin-shaped or rod-shaped tungsten oxide and preparation method and application thereof | |
| CN109603843A (en) | A kind of core-shell catalyst and preparation method thereof and the application in reformation hydrogen production | |
| CN110935480A (en) | Vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction | |
| CN111701596B (en) | Preparation method of atomic-scale active site catalyst for synthesizing ammonia under mild condition | |
| CN112778243A (en) | Method for preparing 2,5-dimethylfuran by catalytic hydrogenation of 5-hydroxymethylfurfural | |
| CN112657521A (en) | Preparation method of chromium-doped cobalt phosphide nanorod array grown on carbon cloth in situ | |
| CN115090292B (en) | Preparation method of cobalt-zinc bimetallic alloy catalyst and application of cobalt-zinc bimetallic alloy catalyst in catalyzing hydrodeoxygenation reaction of fatty acid methyl ester and fatty acid | |
| CN113649017B (en) | Preparation method and application of vegetable oil hydrodeoxygenation water-resistant core-shell type catalyst | |
| CN111001429A (en) | Preparation method of nitrogen-doped modified zinc oxide visible-light-driven photocatalyst | |
| CN115212911A (en) | Nickel-loaded nitrogen-doped hierarchical pore biochar material and preparation method and application thereof | |
| CN113101946B (en) | NiMoO4Base Z-type heterojunction photocatalyst and preparation and application thereof | |
| CN109999863A (en) | A kind of preparation method of nano nickel phosphide carbon composite catalytic agent | |
| CN113089014B (en) | Super-hydrophilic super-gas-dredging efficient hydrogen evolution catalyst with core-shell structure and preparation method thereof | |
| CN112569945B (en) | Metal-loaded dolomite catalyst for preparing ethanol by glycerol dehydration and preparation thereof | |
| CN113299933B (en) | Preparation method of non-noble metal direct methanol fuel cell anode catalyst | |
| CN109289925B (en) | Preparation and application of graphite-like phase carbon nitride/cadmium organic coordination polymer nanocomposite | |
| CN111420654B (en) | Carbon-based nano material and preparation method and application thereof | |
| CN113292519A (en) | Magnetic gold-cobalt composite catalyst and preparation method and application thereof | |
| CN111085228A (en) | Phosphorus doped Mn0.3Cd0.7S nanorod photocatalyst and preparation method and application thereof | |
| CN110010914A (en) | A kind of one-dimensional PtCuCo alloy nano chain catalyst and synthetic method suitable for methanol fuel cell under high temperature | |
| CN108409551A (en) | The method that Ru-MACHO catalyzing glycerols restore carbon dioxide | |
| CN116747868B (en) | Microporous carbon cage sphere domain-limited cobalt nanoparticle material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |