CN111097407A - Load type nano Pt/Al2O3Process for preparing catalyst - Google Patents
Load type nano Pt/Al2O3Process for preparing catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 69
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 57
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 238000011068 loading method Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 238000006722 reduction reaction Methods 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 129
- 239000002105 nanoparticle Substances 0.000 abstract description 39
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 abstract description 21
- 239000006227 byproduct Substances 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 187
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000002904 solvent Substances 0.000 description 20
- 238000000635 electron micrograph Methods 0.000 description 18
- -1 polytetrafluoroethylene Polymers 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 238000002791 soaking Methods 0.000 description 18
- 239000010935 stainless steel Substances 0.000 description 18
- 229910001220 stainless steel Inorganic materials 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000012855 volatile organic compound Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B01J35/394—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
Abstract
The invention discloses a load type nanometer Pt/Al2O3The preparation method of the catalyst comprises the following steps: h is to be2PtCl6·6H2Dissolving O and triethylamine in propylene carbonate, and stirring and reducing for 0.5-6h under the hydrogen pressure of 1-4MPa and the reduction temperature of 10-40 ℃ to prepare Pt nano sol; mixing Al2O3Directly dipping the Pt nano sol into the obtained Pt nano sol to ensure that the theoretical loading of Pt is 0.1wt percentStirring, adsorbing, standing, drying, calcining at 350-400 ℃ for 4h to obtain Pt/Al2O3A catalyst. The invention provides Pt/Al2O3The preparation method of the catalyst can obtain the supported nano Pt/Al with high dispersity2O3The Pt nano particles in the catalyst have the particle size distribution of 2-3nm, no agglomeration occurs, the catalyst has narrower particle size distribution, and the smaller Pt nano particles have higher catalytic activity. The catalyst can completely convert toluene into H at 220 ℃ under the condition of low loading of noble metal (the loading is 0.1 percent)2O and CO2And no other by-products.
Description
(I) technical field
The invention belongs to the technical field of nano materials, and particularly relates to a supported nano Pt/Al2O3A method for preparing the catalyst.
(II) background of the invention
In recent years, China has placed increasing emphasis on controlling the emission of Volatile Organic Compounds (VOCs) due to the effects of organic aerosols, ozone and smoke on human health and the atmospheric environment. Some techniques for eliminating VOCs, such as thermal incineration, catalytic oxidation, condensation, absorption, biofiltration, adsorption and membrane techniques, have been used. Among these methods, catalytic oxidation is an effective, low-cost, extensive and environmentally friendly technology for eliminating VOCs at low temperatures. In the catalytic oxidation of VOC, the loaded noble metal Pt is considered to be the most effective component, has special effect on the catalytic conversion of toluene, has higher activity, and can effectively catalyze and convert various harmful gases such as toluene and the like at lower temperature.
The liquid phase method is the most common method for preparing Pt nano particles, but the development and application of the nano particles are limited by the problems of solvent pollution, complex process, complex post-treatment and the like in the existing method. Chen et Al supported Pt on Al by a precipitant2O3Then removing the precipitant to obtain Pt/Al2O3. The method has complicated steps and complex post-treatment, so a new preparation method is needed, Pt nano particles can be simply and conveniently synthesized, and small-sized Pt nano particles can be obtained, so that the catalytic activity is improved.
The article: 10.1021/acsami.8b07637, which invents a preparation method of alumina loaded with platinum nanoparticles, and the prepared Pt/Al is subjected to electrostatic spinning technology2O3Preparation of electro-spinning precursor into Pt/Al2O3And (3) nano materials. However, the invention has the following disadvantages: the operation is complex, aluminum powder needs to be heated and stirred overnight to be fully dissolved, then the aluminum powder is precipitated, then protective agents such as PVP and the like are added for protection, and then chloroplatinic acid is addedThen stirring is continued to obtain an electro-spinning precursor, and the Pt/Al is prepared by using an electrostatic spinning machine2O3And in addition, professional instruments and equipment such as an electrostatic spinning machine are required, so that the method has limitations. The Pt nano particles have low dispersity and wide particle size distribution of 2-4 nm.
The article: 10.1016/j.apcatb.2019.117943, invents a Pt/Al alloy2O3A method for preparing the catalyst. By precipitation, Pt NPs are supported on Al which is also prepared by precipitation2O3Thereby obtaining Pt/Al2O3A catalyst. However, the preparation process of the invention is complicated, and specific Al needs to be prepared by a precipitation method firstly2O3The carrier, and the preparation process of the carrier needs higher temperature and accurate control of the pH value to 5. In the preparation of the Pt nano sol, the pH value needs to be accurately regulated to 5, the Pt nano sol needs to be prepared at a higher reaction temperature (130 ℃), then stirring and adsorption are continued, and Pt is loaded on Al2O3The above. And the Pt nano particles have an agglomeration phenomenon, and the particle size distribution is wider and is between 2 and 5 nm.
Disclosure of the invention
In order to solve the problems, the invention provides a supported nano Pt/Al2O3Preparation method of catalyst, Pt/Al2O3Catalyst with H2PtCl6·6H2O is used as a precursor, triethylamine is used as a stabilizer, and Pt/Al with uniform granularity is prepared by a liquid-phase hydrogen reduction method2O3The catalyst is applied to catalytic oxidation of toluene, realizes complete oxidation of toluene at a lower temperature, and has better stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a Pt/Al alloy2O3A method for preparing a catalyst, the method comprising the steps of:
(1) h is to be2PtCl6·6H2Dissolving O and triethylamine in Propylene Carbonate (PC), stirring and reducing for 0.5-6h under the hydrogen pressure of 1-4MPa and the reduction temperature of 10-40 ℃,preparing Pt nano sol; said H2PtCl6·6H2The mass ratio of O to triethylamine was 1: 0 to 20;
(2) mixing Al2O3Directly dipping the Pt nano sol obtained in the step (1) to ensure that the theoretical loading capacity of Pt is 0.1 wt%, stirring, adsorbing, standing, drying, calcining for 4h at the temperature of 350-2O3A catalyst.
Further, in the step (1), the propylene carbonate is added in the amount of the H2PtCl6·6H2The mass of Pt in O is 1-10 mL/mg (preferably 3.3 mL/mg).
Further, in the step (1), the hydrogen pressure is preferably 4 MPa.
Further, in the step (1), the time for the reduction reaction is preferably 3 hours.
Further, in the step (1), the reduction temperature is preferably 10 ℃.
The invention uses a Transmission Electron Microscope (TEM) to observe the morphology of the catalyst, and uses a fixed bed to measure the catalytic activity of the catalyst on toluene oxidation. The results show that the Pt/Al synthesized by the method of the invention2O3The catalyst has the performance of efficiently catalyzing and oxidizing the toluene, can realize the complete oxidation of the toluene at a lower temperature, and has better stability.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides Pt/Al2O3The preparation method of the catalyst can obtain the supported nano Pt/Al with high dispersity2O3The Pt nano particles in the catalyst have the particle size distribution of 2-3nm, no agglomeration occurs, the catalyst has narrower particle size distribution, and the smaller Pt nano particles have higher catalytic activity. The catalyst can completely convert toluene into H at 220 ℃ under the condition of low loading of noble metal (the loading is 0.1 percent)2O and CO2No other by-products, therefore the Pt/Al prepared by the invention2O3Has high activity and stability, organic solvent can be repeatedly used, waste gas and waste water can not be generated, and the product is preparedThe preparation method is simple, the carrier is cheap and easy to obtain, the cost of the catalyst is greatly reduced, and the method is convenient for industrialization.
(IV) description of the drawings
FIG. 1: examples 1-4 preparation of Pt/Al2O3A catalytic performance map of (a);
FIG. 2: examples 5-7 preparation of Pt/Al2O3A catalytic performance map of (a);
FIG. 3: examples 8-10 preparation of Pt/Al2O3A catalytic performance map of (a);
FIG. 4: examples 11-14 preparation of Pt/Al2O3A catalytic performance map of (a);
FIG. 5: examples 15-18 preparation of Pt/Al2O3A catalytic performance map of (a);
FIG. 6: Pt/Al prepared in example 12O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 7: Pt/Al prepared in example 22O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 8: Pt/Al prepared in example 32O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 9: Pt/Al prepared in example 42O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 10: Pt/Al prepared in example 52O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 11: Pt/Al prepared in example 62O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 12: Pt/Al prepared in example 72O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 13: Pt/Al prepared in example 82O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 14: Pt/Al prepared in example 92O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 15: Pt/Al prepared in example 102O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 16: Pt/Al prepared in example 112O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 17: Pt/Al prepared in example 122O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 18: Pt/Al prepared in example 132O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 19: Pt/Al prepared in example 142O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 20: Pt/Al prepared in example 152O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 21: Pt/Al prepared in example 162O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 22: Pt/Al prepared in example 172O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
FIG. 23: Pt/Al prepared in example 182O3Catalyst electron micrograph (noble metal Pt loading 0.1%).
(V) detailed description of the preferred embodiments
The invention is further illustrated by the following specific examples, without restricting its scope.
The invention utilizes a fixed bed to measure the catalytic activity of the catalyst for toluene oxidation, and comprises the following main steps: 0.5g of the catalyst was placed in the middle of a fixed bed reaction tube, and saturated toluene vapor at 0 ℃ was introduced into the reaction tube by a bubbling method, and the concentration (volume fraction) of toluene in a mixed gas of toluene and air in the feed stream was 1000X 10-6The gas space velocity is 18000ml g-1·h-1Adopting Flame Ionization Detector (FID) and Thermal Conductivity Detector (TCD) to monitor the content of toluene and oxide in the tail gas on line, and measuring toluene conversion rate and CO at different temperatures2Selectivity, toluene reached temperatures (T) of 50% and 98%50And T98)。
Example 1
27mg (0.05mmol) of H2PtCl6·6H2O and 76mg (0.75mmol) of triethylamine were added together to 100mL of a solvent, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.1 mg/mL. Mixing 1g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.7nm, and the prepared Pt/Al2O3Catalyst for complete conversion of toluene to H at 250 deg.C2O and CO2No other by-products are formed.
Example 2
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.5nm, and the prepared Pt/Al2O3Catalyst completely converts toluene to H at 230 deg.C2O and CO2No other by-products are formed.
Example 3
135mg (0.25mmol) of H2PtCl6·6H2O and 380mg (3.75mmol) were added to 100mL of the solvent, dissolved with stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining 0.5mg/mL Pt nano-particlesAnd (3) sol. Adding 5g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. The average grain diameter of the Pt nano particles is 2.7nm, but the agglomeration phenomenon in a small range is generated. And the prepared Pt/Al2O3Catalyst completely converts toluene to H at 245 DEG C2O and CO2No other by-products are formed.
Example 4
270mg (0.5mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 760mg (7.5mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining 1mg/mL Pt nano sol. Mixing 10g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.7nm, and large-area agglomeration occurs. And the prepared Pt/Al2O3Catalyst completely converts toluene to H at 245 DEG C2O and CO2No other by-products are formed. TABLE 1 toluene conversion of 50% (T) over different catalysts50) And 98% (T)98) Reaction temperature of
As can be seen from Table 1 above, at H2When the concentration of the Pt nano sol is 0.3mg/mL under the conditions that the pressure is 4MPa, the reaction temperature is 10 ℃ and the reduction time is 3h, the Pt/Al2O3And wherein the Pt nanoparticles have an average particle size of 2.5nm and a complete conversion temperature of toluene of 230℃。
Example 5
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 1MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Since the preparation pressure is too low, Pt nanoparticles cannot be generated, and thus there is no catalytic activity for toluene oxidation.
Example 6
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 2MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Due to the fact that the preparation pressure is too low, only a few Pt nano particles are generated, the average particle size of the Pt nano particles is 2.9nm, catalytic activity for toluene oxidation is poor, and complete conversion can be achieved at 280 ℃.
Example 7
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 3MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt (platinum) -based solvent with the load of 0.1%Al2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.8nm, and the prepared Pt/Al2O3Catalyst for complete conversion of toluene to H at 265 deg.C2O and CO2No other by-products are formed.
TABLE 2 toluene conversion of 50% (T) over different catalysts50) And 98% (T)98) Reaction temperature of
As can be seen from Table 2 above, H was added under the conditions of a Pt nanosol concentration of 0.3mg/mL, a reaction temperature of 10 ℃ and a reduction time of 3 hours2Pt/Al at a pressure of 4MPa2O3The catalytic effect of (3) is optimal. And wherein the average particle diameter of the Pt nano-particles is 2.5nm, and the complete conversion temperature of the toluene is 230 ℃.
Example 8
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 20 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.7nm, and the Pt nano particles are slightly agglomerated. And the prepared Pt/Al2O3Catalyst completely converts toluene to H at 245 DEG C2O and CO2No other by-products are formed.
Example 9
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3 hours at the temperature of 30 ℃ under the environment,thus obtaining the Pt nano sol of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.8nm, and the Pt nano particles are agglomerated in a small range. And the prepared Pt/Al2O3Catalyst for complete conversion of toluene to H at 250 deg.C2O and CO2No other by-products are formed.
Example 10
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h at the temperature of 40 ℃ under the environment to obtain the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.9nm, and the Pt nano particles are more agglomerated and connected into a grape string shape. And the prepared Pt/Al2O3Catalyst completely converts toluene to H at 260 deg.C2O and CO2No other by-products are formed.
TABLE 3 toluene conversion of 50% (T) over different catalysts50) And 98% (T)98) Reaction temperature of
| Examples of the invention | T50 | T98 |
| 8 | 215 | 245 |
| 9 | 215 | 250 |
| 10 | 225 | 260 |
As can be seen from Table 3 above, the concentration of Pt nanosol was 0.3mg/mL, H2Pt/Al at a reaction temperature of 10 ℃ under the conditions of a pressure of 4MPa and a reduction time of 3h2O3The catalytic effect of (3) is optimal. Wherein the average particle diameter of Pt nanoparticles is 2.5nm, and the complete conversion temperature of toluene is 230 DEG C
Example 11
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 0.5h under the condition of environment and 10 ℃ to obtain the Pt nano sol of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.7nm, and the prepared Pt/Al2O3Catalyst completely converts toluene to H at 255 deg.C2O and CO2No other by-products are formed.
Example 12
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a polytetrafluoroethylene linerIn a stainless steel autoclave at 4MPa H2Stirring and reacting for 1h under the condition of environment and 10 ℃ to obtain the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.6nm, and the prepared Pt/Al2O3Catalyst for complete conversion of toluene to H at 240 deg.C2O and CO2No other by-products are formed.
Example 13
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 2h under the condition of environment and 10 ℃ to obtain the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.6nm, and the prepared Pt/Al2O3Catalyst for complete conversion of toluene to H at 250 deg.C2O and CO2No other by-products are formed.
Example 14
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 228mg (2.25mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 6h under the condition of environment and 10 ℃ to obtain the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.7nm, and the prepared Pt/Al2O3Catalyst and process for preparing sameComplete conversion of toluene to H at 250 deg.C2O and CO2No other by-products are formed.
TABLE 4 toluene conversion of 50% (T) over different catalysts50) And 98% (T)98) Reaction temperature of
| Examples of the invention | T50 | T98 |
| 11 | 230 | 255 |
| 12 | 225 | 240 |
| 13 | 220 | 240 |
| 14 | 225 | 250 |
As can be seen from Table 4 above, the concentration of Pt nanosol was 0.3mg/mL, the reaction temperature was 10 ℃ and H2Pt/Al under the condition of 4MPa of pressure and 3h of reduction time2O3The catalytic effect of (3) is optimal. Wherein the average particle diameter of Pt nanoparticles is 2.5nm, and the complete conversion temperature of toluene is 230 DEG C
Example 15
81mg (0.15mmol) of H2PtCl6·6H2O is added to 100mL of solvent, dissolved with stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 26nm, and larger Pt nano particles appear. And the prepared Pt/Al2O3Catalyst completely converts toluene to H at 245 DEG C2O and CO2No other by-products are formed.
Example 16
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 76mg (0.75mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.3nm, and the prepared Pt/Al2O3Catalyst completely converts toluene to H at 220 deg.C2O and CO2No other by-products are formed.
Example 17
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 152mg (1.50mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying,then calcining for 4 hours at 400 ℃ to obtain Pt/Al with the load of 0.1 percent2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.4nm, and the prepared Pt/Al2O3Catalyst for complete conversion of toluene to H at 250 deg.C2O and CO2No other by-products are formed.
Example 18
81mg (0.15mmol) of H2PtCl6·6H2O was added to 100mL of a solvent together with 304mg (3.00mmol) of triethylamine, dissolved by stirring, and then transferred to a stainless steel autoclave lined with polytetrafluoroethylene at 4MPa H2Stirring and reacting for 3h under the condition of environment and 10 ℃, thus obtaining the Pt nano sol with the concentration of 0.3 mg/mL. 3g of Al2O3Adding the carrier into 10ml of the Pt nano sol, soaking and adsorbing, standing for 30min, drying, and calcining at 400 ℃ for 4h to obtain Pt/Al with 0.1% of load capacity2O3A catalyst. Wherein the average grain diameter of the Pt nano particles is 2.5nm, and the prepared Pt/Al2O3Catalyst completely converts toluene to H at 235 deg.C2O and CO2No other by-products are formed.
TABLE 5 toluene conversion of 50% (T) over different catalysts50) And 98% (T)98) Reaction temperature of
| Examples of the invention | T50 | T98 |
| 15 | 215 | 245 |
| 16 | 205 | 220 |
| 17 | 205 | 225 |
| 18 | 205 | 235 |
As can be seen from Table 5 above, in the case where the Pt nanosol concentration was 0.3mg/mL, the reaction temperature was 10 ℃ and the H content was high2The reduction time is 3h under the condition that the pressure is 4MPa, and the molar ratio of Pt to triethylamine is 1: 5, Pt/Al2O3The catalytic effect of (3) is optimal. And the average particle diameter of the Pt nano particles is 2.3nm, and the complete conversion temperature of the toluene is 220 ℃.
Claims (6)
1. Pt/Al2O3The preparation method of the catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) h is to be2PtCl6·6H2Dissolving O and triethylamine in propylene carbonate, and stirring and reducing for 0.5-6h under the hydrogen pressure of 1-4MPa and the reduction temperature of 10-40 ℃ to prepare Pt nano sol; said H2PtCl6·6H2The mass ratio of O to triethylamine was 1: 0 to 20;
(2) mixing Al2O3Directly dipping the Pt nano sol obtained in the step (1) to ensure that the theoretical loading capacity of Pt is 0.1 wt%, stirring, adsorbing, standing, drying, calcining for 4h at the temperature of 350-2O3A catalyst.
2. The method of claim 1, wherein: in the step (1), the addition amount of the propylene carbonate is the H2PtCl6·6H2The mass of Pt in O is 1-10 mL/mg.
3. The method of claim 1, wherein: in the step (1), the addition amount of the propylene carbonate is the H2PtCl6·6H2The mass of Pt in O was 3.3 mL/mg.
4. The method of claim 1, wherein: in the step (1), the hydrogen pressure is 4 MPa.
5. The method of claim 1, wherein: in the step (1), the time of the reduction reaction is 3 hours.
6. The method of claim 1, wherein: in the step (1), the reduction temperature is 10 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112871159A (en) * | 2021-01-18 | 2021-06-01 | 浙江工业大学 | Ru nano catalyst and preparation method and application thereof |
| CN113198465A (en) * | 2021-04-29 | 2021-08-03 | 浙江工业大学 | Ruthenium-platinum alloy catalyst and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886261A (en) * | 2012-09-10 | 2013-01-23 | 北京工业大学 | Alcohol-water solvent thermal synthetic method of flower-shaped Pd/CeO2 three-way catalyst |
| CN103551141A (en) * | 2013-09-29 | 2014-02-05 | 浙江工业大学 | Pt/MOx catalyst and application thereof in toluene catalytic combustion |
| CN103599774A (en) * | 2013-11-20 | 2014-02-26 | 浙江工业大学 | Pt/Al2O3 catalyst and application thereof in room-temperature catalytic oxidation of formaldehyde |
| CN106362736A (en) * | 2016-08-25 | 2017-02-01 | 浙江工业大学 | Low-load palladium-platinum core-shell structure catalyst and preparation method and application thereof |
| CN106423152A (en) * | 2016-09-26 | 2017-02-22 | 中国科学院福建物质结构研究所 | High-dispersion load type catalyst and preparation method and application thereof |
| CN107159202A (en) * | 2017-04-01 | 2017-09-15 | 浙江工业大学 | A kind of supported palladium catalyst of additive Mn and preparation method and application |
| CN108906039A (en) * | 2018-03-05 | 2018-11-30 | 浙江工业大学 | A kind of low-load amount Au catalyst and preparation method thereof and its application in catalysis oxidation toluene |
| CN110026246A (en) * | 2019-04-12 | 2019-07-19 | 天津大学 | It can be used for the preparation method of the porous organic framework atom level catalyst of the carried noble metal of constant temperature catalyzing degradation VOCs |
-
2019
- 2019-11-19 CN CN201911135277.4A patent/CN111097407A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102886261A (en) * | 2012-09-10 | 2013-01-23 | 北京工业大学 | Alcohol-water solvent thermal synthetic method of flower-shaped Pd/CeO2 three-way catalyst |
| CN103551141A (en) * | 2013-09-29 | 2014-02-05 | 浙江工业大学 | Pt/MOx catalyst and application thereof in toluene catalytic combustion |
| CN103599774A (en) * | 2013-11-20 | 2014-02-26 | 浙江工业大学 | Pt/Al2O3 catalyst and application thereof in room-temperature catalytic oxidation of formaldehyde |
| CN106362736A (en) * | 2016-08-25 | 2017-02-01 | 浙江工业大学 | Low-load palladium-platinum core-shell structure catalyst and preparation method and application thereof |
| CN106423152A (en) * | 2016-09-26 | 2017-02-22 | 中国科学院福建物质结构研究所 | High-dispersion load type catalyst and preparation method and application thereof |
| CN107159202A (en) * | 2017-04-01 | 2017-09-15 | 浙江工业大学 | A kind of supported palladium catalyst of additive Mn and preparation method and application |
| CN108906039A (en) * | 2018-03-05 | 2018-11-30 | 浙江工业大学 | A kind of low-load amount Au catalyst and preparation method thereof and its application in catalysis oxidation toluene |
| CN110026246A (en) * | 2019-04-12 | 2019-07-19 | 天津大学 | It can be used for the preparation method of the porous organic framework atom level catalyst of the carried noble metal of constant temperature catalyzing degradation VOCs |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112871159A (en) * | 2021-01-18 | 2021-06-01 | 浙江工业大学 | Ru nano catalyst and preparation method and application thereof |
| CN113198465A (en) * | 2021-04-29 | 2021-08-03 | 浙江工业大学 | Ruthenium-platinum alloy catalyst and application thereof |
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