CN107185525B - Octahedral Pt nanoparticle loaded gamma-Al2O3Process for preparing form catalyst - Google Patents
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- 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
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- 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
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
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- B01D—SEPARATION
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- 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
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- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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Abstract
The invention provides octahedral Pt nano particle loaded gamma-Al2O3The preparation method of the catalyst comprises the steps of loading a Pt precursor on MIL-53(Al) by a double-solvent method, and then reducing and calcining to obtain the catalyst Pt/gamma-Al2O3(ii) a By means of the two characteristics that MOFs materials can be used as precursors of metal oxides and carriers of heterogeneous catalysts, MIL-53A (Al) can be used as gamma-Al in the preparation process2O3The precursor can induce Pt nano particles to regrow into an octahedral structure. Pt/gamma-Al prepared by the invention2O3The loading amount of Pt in the type catalyst is 1.7-10.1%, Pt particles are represented by regular octahedral morphology, the average size is about 13nm, and the Pt particles can be uniformly dispersed in a carrier gamma-Al2O3The surface area of the catalyst is higher and can reach 208.5m2(ii) in terms of/g. The catalyst can completely catalyze and oxidize propylene into nontoxic and harmless CO at the temperature of 270 DEG C2And H2O, reaction for preparing aniline by reducing p-nitrobenzene at 100 DEG CThe catalytic selectivity of the catalyst can reach more than 60 percent.
Description
Technical Field
The invention relates to the field of inorganic nano catalytic materials, in particular to octahedral Pt nano particle loaded gamma-Al for preparing aniline by catalytic oxidation elimination of Hydrocarbon (HC) and catalytic reduction of nitrobenzene2O3A method for preparing the catalyst.
Background
Pt nanoparticle loaded gamma-Al2O3Type catalyst (Pt/gamma-Al)2O3) The method has important application in a plurality of fields of automobile tail gas treatment, diesel tail gas treatment, hydrocarbon selective hydrogenation and the like. For example, in the treatment of tail gas from gasoline and diesel vehicles, Pt/gamma-Al2O3Can play a role in catalytic oxidation elimination of HC; in the industries of fuel, medicine, agriculture and the like, Pt/gamma-Al can be adopted2O3The nitrobenzene is catalyzed to reduce and hydrogenate to prepare the aniline.
Morphology and size of Pt nano-particles and gamma-Al on carrier2O3The dispersion of (b) is an important factor affecting catalytic activity and selectivity, and octahedral Pt nanoparticles are considered to have higher activity in alkane hydrogenation reactions and VOC complete oxidation reactions. Therefore, in the catalyst synthesis process, how to control the morphology and size of the Pt nano particles and how to improve the Pt on the carrier gamma-Al2O3The degree of dispersion of (a) is still a current key issue. At present, a microemulsion method, an electrochemical deposition method and the like are mainly adopted to synthesize a supported noble metal nano catalyst, a surfactant and the like are taken as a template agent to control the morphology, the size and the dispersion degree of nano particles on a carrier, but the Pt/gamma-Al prepared by the methods2O3The dispersion degree of Pt in the catalyst is not high, the performance of the catalyst is general, and the subsequent treatment of a surfactant is involved, so that the cost is high.
Metal Organic Frameworks (MOFs) materials have received much attention due to their structural specificity; the MOFs material consists of organic ligand and metal' nodeA long-range ordered porous material can be used as a carrier to prepare a catalyst, but the catalyst taking the MOFs material as the carrier has poor thermal stability and water stability, and is more limited in use. However, MOFs can be used as a precursor to prepare metal oxides with specific structures and also as a "template" for the synthesis of monodisperse nanoparticles, which is given to Pt/gamma-Al2O3The preparation of the catalyst provides a new idea.
Therefore, the invention designs Pt/gamma-Al2O3The preparation method of the catalyst utilizes Metal Organic Frameworks (MOFs) materials to prepare Pt/gamma-Al with high Pt dispersity2O3A catalyst.
Disclosure of Invention
In view of the above, the present invention provides an octahedral Pt nanoparticle loaded gamma-Al2O3The preparation method of the catalyst comprises the steps of selecting an Al-based MOFs material MIL-53(Al) with a 'flexible' one-dimensional pore structure as a medium, introducing Pt nano particles into the MIL-53(Al) by a 'double-solvent' method, and calcining to obtain Pt/gamma-Al2O3The Pt in the prepared catalyst has high dispersity and excellent performance, and can convert hydrocarbons into nontoxic and harmless CO through catalysis2And H2And O, when the product is used for preparing aniline by nitrobenzene reduction, the selectivity of the prepared aniline can reach more than 60 percent.
The octahedral Pt nano particle loaded gamma-Al provided by the invention2O3The preparation method of the type catalyst is characterized by comprising the following steps: the Pt precursor is loaded on MIL-53(Al) by a double-solvent method, and then the catalyst Pt/gamma-Al can be prepared by reduction and calcination2O3；
Further, the method specifically comprises the following steps:
a. pt precursor loading was performed using a two-solvent method: mixing n-hexane and MIL-53(Al), performing ultrasonic stirring to obtain MIL-53(Al) suspension, slowly dripping Pt precursor aqueous solution into the MIL-53(Al) suspension under a stirring state to obtain mixed solution, continuously stirring the obtained mixed solution for a certain time, performing solid-liquid separation treatment, and performing vacuum drying on the obtained solid at room temperature for a certain time to obtain MIL-53(Al) powder loaded with a Pt precursor;
b. Pt/MIL-53(Al) preparation: subjecting the powder obtained in step a to high temperature treatment with H2Reducing the/Ar mixed gas to obtain a Pt/MIL-53(Al) mixture;
c、Pt/γ-Al2O3preparing a catalyst: b, calcining the Pt/MIL-53(Al) mixture obtained in the step b in air at high temperature to obtain the target catalyst Pt/gamma-Al2O3；
Further, in the step c, the calcining temperature is 600-700 ℃, and the calcining time is 3-6 hours;
further, in the step a, the concentration of the Pt precursor water solution is 0.004-0.104 mol/L, and the Pt precursor water solution is dropwise added into the MIL-53(Al) suspension according to the mass ratio of 0.5-2.0%;
further, in the step a, normal hexane and MIL-53(Al) are taken according to the mass ratio of 66: 1-176: 1;
further, in the step a, the precursor of Pt comprises K2PtCl4、K2PtCl6、H2PtCl6One of (1);
further, in the step b, the reduction temperature is 200-500 ℃, the reduction time is 4-8H, and H is generated during reduction2The flow rate of the/Ar mixed gas is 50-300 mL/min;
further, in said step b, according to H2Preparing H with Ar at a volume ratio of 1/9-1/12A mixed gas of/Ar;
further, the MIL-53(Al) preparation step comprises the following steps: taking terephthalic acid and Al (NO)3)3·9H2Mixing and stirring O and deionized water, placing at 215-225 ℃ for constant-temperature reaction for 72-96 h, cooling the mixed solution obtained by the reaction, performing solid-liquid separation treatment, washing the obtained solid, and then placing at 280-300 ℃ for calcining for 42-50 h to obtain MIL-53(Al) powder;
further, terephthalic acid and Al (NO) are taken according to the weight ratio of 0.96-1.15: 4.6-5.2: 203)3·9H2O and deionized water。
The invention has the beneficial effects that: the invention selects Al-based MOFs material MIL-53(Al) with 'flexible' one-dimensional pore structure as a medium by virtue of the two characteristics that the MOFs material can be used as a precursor of a metal oxide and can be used as a carrier of a heterogeneous catalyst, and Pt/gamma-Al is prepared by introducing Pt nano particles into the MIL-53(Al) in a 'double-solvent' normal method and calcining the Pt/gamma-Al2O3The catalyst MIL-53A (Al) can be used as gamma-Al in the preparation process2O3The precursor can induce Pt nano particles to regrow into an octahedral structure.
Pt/gamma-Al prepared by the invention2O3The loading amount of Pt in the type catalyst is 1.7-10.1%, Pt particles are represented by regular octahedral morphology, the average size is about 13nm, and the Pt particles can be uniformly dispersed in a carrier gamma-Al2O3The surface area of the catalyst is higher and can reach 208.5m2(ii) in terms of/g. The catalyst can completely catalyze and oxidize propylene into nontoxic and harmless CO at the temperature of 270 DEG C2And H2O, the catalytic selectivity of the reaction for preparing aniline by reducing p-nitrobenzene at 100 ℃ can reach more than 60 percent. Therefore, the catalyst has good application prospect in the processes of catalyzing and eliminating Hydrocarbon (HC), catalyzing and reducing nitrobenzene to prepare aniline and the like.
Drawings
The invention is further described below with reference to the following figures and examples:
FIG. 1 shows the prepared catalyst Pt/gamma-Al2O3X-ray diffraction (XRD) patterns of (1), wherein curve A, B, C, D corresponds to the samples of comparative example, example 1, example 2, example 3, respectively;
FIG. 2 shows the prepared catalyst Pt/gamma-Al2O3Activity curves for the complete oxidation of propylene, wherein curve A, B, C, D corresponds to the samples of example 1, example 2, example 3, comparative example, respectively;
FIG. 3 shows the prepared catalyst Pt/gamma-Al2O3The activity curve of catalytic nitrobenzene reduction for aniline production, wherein curve A, B, C, D corresponds to the samples of example 1, example 2, example 3 and comparative example, respectively;
FIG. 4 is a transmission electron micrograph of a comparative example;
FIG. 5 is a TEM photograph of a sample of example 1.
Detailed Description
The octahedral Pt nanoparticles of this example were loaded with gamma-Al2O3The preparation method of the type catalyst is characterized by comprising the following steps: the Pt precursor is loaded on MIL-53(Al) by a double-solvent method, and then the catalyst Pt/gamma-Al can be prepared by reduction and calcination2O3(ii) a By means of two characteristics that MOFs materials can be used as precursors of metal oxides and carriers of heterogeneous catalysts, Al-based MOFs materials MIL-53(Al) with 'flexible' one-dimensional pore structures are selected as media, Pt nanoparticles are introduced into the MIL-53(Al) through a 'double-solvent' normal method, and then the Pt/gamma-Al nanoparticles are calcined to obtain the Pt/gamma-Al nanoparticles2O3A catalyst; MIL-53(Al) can be used as Gamma-Al in the preparation process of the catalyst2O3The precursor can induce Pt nano particles to regrow into an octahedral structure, and the prepared Pt/gamma-Al2O3The loading amount of Pt in the type catalyst is 1.7-10.1%, Pt particles are represented by regular octahedral morphology, the average size is about 13nm, and the Pt particles can be uniformly dispersed in a carrier gamma-Al2O3The surface area of the catalyst is higher and can reach 208.5m2(ii) in terms of/g. The catalyst can completely catalyze and oxidize propylene into nontoxic and harmless CO at the temperature of 270 DEG C2And H2O, the catalytic selectivity of the reaction for preparing aniline by reducing p-nitrobenzene at 100 ℃ can reach more than 60 percent. Therefore, the catalyst has good application prospect in the processes of catalyzing and eliminating Hydrocarbon (HC), catalyzing and reducing nitrobenzene to prepare aniline and the like.
In this embodiment, the method specifically includes the following steps:
a. pt precursor loading was performed using a two-solvent method: mixing n-hexane and MIL-53(Al), performing ultrasonic stirring to obtain MIL-53(Al) suspension, stirring for 2-4 hours, slowly dripping Pt precursor aqueous solution into the MIL-53(Al) suspension under a stirring state to obtain a mixed solution, continuously stirring the obtained mixed solution for a certain time, preferably continuously stirring for 2-4 hours, performing solid-liquid separation treatment, and performing vacuum drying on the obtained solid at room temperature for a certain time, preferably for 12-24 hours to obtain MIL-53(Al) powder loaded with a Pt precursor;
b. Pt/MIL-53(Al) preparation: subjecting the powder obtained in step a to high temperature treatment with H2Reducing the/Ar mixed gas to obtain a Pt/MIL-53(Al) mixture;
c、Pt/γ-Al2O3preparing a catalyst: b, calcining the Pt/MIL-53(Al) mixture obtained in the step b in air at high temperature to obtain the target catalyst Pt/gamma-Al2O3(ii) a The method has the advantages of easily controlled conditions and good reproducibility of catalyst preparation.
In the embodiment, in the step c, the calcining temperature is 600-700 ℃, preferably 650 ℃; the calcination time is 3-6 h, preferably 4 h; the calcination condition is selected to be beneficial to obtaining the catalyst Pt/gamma-Al with excellent performance and uniformly dispersed Pt2O3Too high a temperature or too long a time may affect the performance of the catalyst, while too low a temperature or too short a time may result in incomplete calcination, which may affect the yield and performance of the catalyst.
In the embodiment, in the step a, the concentration of the Pt precursor aqueous solution is 0.004-0.104 mol/L, preferably 0.008-0.052 mol/L, and the Pt precursor aqueous solution is dropwise added into the MIL-53(Al) suspension according to the mass ratio of 0.5-2.0%, preferably 1.0%; the preparation method of the Pt precursor water solution comprises the steps of taking a Pt precursor according to a set concentration, dissolving the Pt precursor in deionized water, and uniformly stirring to obtain the Pt precursor water solution; the Pt precursor aqueous solution with the concentration can realize the uniform dispersion of Pt nanoparticles, the dispersion is easy to cause uneven when the Pt nanoparticles are too high, and the activity of the catalyst is influenced when the Pt nanoparticles are too low, so that the product performance is finally influenced.
In the embodiment, in the step a, normal hexane and MIL-53(Al) are taken according to the mass ratio of 66: 1-176: 1; the mixture ratio can prepare the Al-based MOFs material MIL-53(Al) with excellent performance and a flexible one-dimensional pore structure.
In this embodiment, in the step a, the precursor of Pt includes K2PtCl4、K2PtCl6、H2PtCl6These Pt precursors are readily loaded into MIL-53(Al) materials and subsequently readily reduced to Pt/MIL-53(Al) mixtures.
In the embodiment, in the step b, the reduction temperature is 200-500 ℃, preferably 250-300 ℃, and the reduction time is 4-8 hours, preferably 5-6 hours; in the reduction, H2The flow rate of the/Ar mixed gas is 50-300 mL/min; so that the reduction reaction can be more fully carried out.
In this example, in the step b, according to H2Preparing H with Ar at a volume ratio of 1/9-1/12A mixed gas of/Ar; ensuring that there is sufficient hydrogen for the reduction reaction to occur.
In this embodiment, the MIL-53(Al) is prepared by the steps of: taking terephthalic acid and Al (NO)3)3·9H2Mixing and stirring O and deionized water, placing the mixture at 215-225 ℃ for constant temperature reaction for 72-96 h, preferably 220 ℃ for constant temperature reaction for 72h, cooling the mixed solution obtained by the reaction, performing solid-liquid separation treatment, washing the obtained solid with deionized water, and then placing the washed solid at 280-300 ℃ for calcination for 42-50 h, preferably at 300 ℃ for calcination for 48h to obtain MIL-53(Al) powder; the preparation method is simple, and the prepared MIL-53(Al) material has excellent structural performance and can be used for preparing Pt/gamma-Al with the same excellent performance2O3A catalyst.
In this embodiment, terephthalic acid and Al (NO) are taken in a weight ratio of 0.96-1.15: 4.6-5.2: 203)3·9H2O and deionized water; the preferable weight ratio is 1.15:5.2:20, and the MIL-53(Al) material prepared under the proportioning condition has excellent structural performance.
In this example, a tube furnace was selected for reduction to prepare Pt/MIL-53(Al), and a muffle furnace was selected for calcination of Pt/MIL-53(Al) to prepare Pt/γ -Al2O3The temperature rise rate of the catalyst and the muffle furnace is 2-10 ℃/min.
In the embodiment, the loading amount (mass fraction) of Pt in the Pt/MIL-53 mixture is controlled to be 0.3-2%, and preferably 0.5-1.5%; the target catalyst Pt/gamma-Al2O3Wherein the loading amount (mass fraction) of Pt is1.7 to 10.1 percent; the dispersion degree of Pt is improved, so that the Pt is dispersed more uniformly.
In this embodiment, all the devices used are common laboratory devices.
Pt/gamma-Al prepared in this example2O3The catalyst is mainly used for the complete catalytic oxidation of hydrocarbon and the catalytic reduction of nitrobenzene to prepare aniline;
(1) the application in the complete catalytic oxidation reaction of propylene: when the propylene concentration is 1 percent, the space velocity is 30000h-1When the propylene can be completely converted into CO at 270 DEG C2And H2O。
(2) The application in the reaction of preparing aniline by reducing nitrobenzene is as follows: the nitrobenzene/He mixed gas with the concentration of 0.3 percent is reduced for 10min at the temperature of 100 ℃ by 3 percent hydrogen, and the selectivity of the aniline can reach more than 60 percent.
The following are specific examples:
example 1
(1) MIL-53(Al) preparation: terephthalic acid (1.15g,6.94mmol) and Al (NO) are taken3)3·9H2Mixing O (5.2g,13.86mmol) and deionized water (20mL,1.11mol) into a 100mL self-pressing kettle cup, ultrasonically vibrating for 10 minutes, placing into a stainless steel self-pressing kettle, screwing, and reacting in an electric heating box at 220 ℃ for 72 hours to obtain a white powder which is a wet MIL-53(Al) sample; the wet sample is washed by deionized water and then calcined in a muffle furnace at 300 ℃ for 48 hours to obtain dry MIL-53(Al) powder;
(2) pt precursor loading was performed using a two-solvent method: adding 0.3g of dry MIL-53(Al) into 60mL of n-hexane, carrying out ultrasonic treatment for several minutes, and rapidly stirring for 2 hours to obtain an MIL-53(Al) suspension; will K2PtCl4Dissolving the Pt precursor solution in deionized water to prepare a Pt precursor solution with the concentration of 0.013 mol/L; slowly dripping 0.6mLPt precursor solution into the MIL-53(Al) suspension under the stirring state, continuously stirring for 2 hours, carrying out solid-liquid separation treatment, and vacuum drying the obtained solid at room temperature for 24 hours to obtain the Pt precursor loaded MIL-53(Al) powder;
(3) Pt/MIL-53(Al) preparation: loading the Pt precursor-loaded MIL-53(Al) powder prepared in the step (2)Finally, in a tube furnace H at 200 ℃2Reducing for 5 hours in an atmosphere of/Ar (the volume ratio is 1/9, and the flow rate is 200mL/min) to obtain a Pt/MIL-53(Al) mixture;
(4)Pt/γ-Al2O3preparing a catalyst: calcining the Pt/MIL-53(Al) prepared in the step (3) in a muffle furnace at 600 ℃ for 3 hours to obtain the target Pt/gamma-Al2O3A catalyst; the muffle furnace heating rate is 2 ℃/min.
Example 2
(1) MIL-53(Al) preparation: terephthalic acid (1.15g,6.94mmol) and Al (NO) are taken3)3·9H2Mixing O (5.2g,13.86mmol) and deionized water (20mL,1.11mol) into a 100mL self-pressing kettle cup, ultrasonically vibrating for 10 minutes, placing into a stainless steel self-pressing kettle, screwing, and reacting in an electric heating box at 220 ℃ for 72 hours to obtain an MIL-53(Al) sample with wet white powder; the wet sample is washed by deionized water and then calcined in a muffle furnace at 300 ℃ for 48 hours to obtain dry MIL-53(Al) powder;
(2) pt precursor loading was performed using a two-solvent method: adding 0.3g of dry MIL-53(Al) into 60mL of n-hexane, carrying out ultrasonic treatment for several minutes, and rapidly stirring for 2 hours to obtain an MIL-53(Al) suspension; will K2PtCl4Dissolving the Pt precursor solution in deionized water to prepare a Pt precursor solution with the concentration of 0.026 mol/L; slowly dripping 0.6ml of the precursor solution into the MIL-53(Al) suspension under the stirring state, continuously stirring for 2 hours, carrying out solid-liquid separation treatment, and drying the obtained solid in vacuum for 12 hours at room temperature to obtain the Pt precursor loaded MIL-53(Al) powder;
(3) Pt/MIL-53(Al) preparation: putting the MIL-53(Al) powder loaded with the Pt precursor prepared in the step (2) into a tube furnace H at 200 DEG C2Reducing for 6 hours in an atmosphere of/Ar (the volume ratio is 1/9, and the flow rate is 300mL/min) to obtain a Pt/MIL-53(Al) mixture;
(4)Pt/γ-Al2O3preparing a catalyst: calcining the Pt/MIL-53(Al) prepared in the step (3) in a muffle furnace at 650 ℃ for 4 hours to obtain target Pt/gamma-Al2O3A catalyst; the muffle furnace heating rate is 5 ℃/min.
Example 3
(1) MIL-53(Al) preparation: terephthalic acid (1.15g,6.94mmol) and Al (NO) are taken3)3·9H2Mixing O (5.2g,13.86mmol) and deionized water (20mL,1.11mol) into a 100mL self-pressing kettle cup, ultrasonically vibrating for 10 minutes, placing into a stainless steel self-pressing kettle, screwing, and reacting in an electric heating box at 220 ℃ for 72 hours to obtain an MIL-53(Al) sample with wet white powder; the wet sample is washed by deionized water and then calcined in a muffle furnace at 300 ℃ for 48 hours to obtain dry MIL-53(Al) powder;
(2) pt precursor loading was performed using a two-solvent method: adding 0.3g of dry MIL-53(Al) into 80mL of n-hexane, carrying out ultrasonic treatment for several minutes, and rapidly stirring for 2 hours to obtain an MIL-53(Al) suspension; h is to be2PtCl6Dissolving the Pt precursor solution in deionized water to prepare a Pt precursor solution with the concentration of 0.026 mol/L; slowly dripping 1.2ml of the precursor solution into the MIL-53(Al) suspension under the stirring state, continuously stirring for 2 hours, carrying out solid-liquid separation treatment, and vacuum drying the obtained solid at room temperature for 24 hours to obtain the Pt precursor loaded MIL-53(Al) powder;
(3) Pt/MIL-53(Al) preparation: putting the MIL-53(Al) powder loaded with the Pt precursor prepared in the step (2) into a tube furnace H at 300 DEG C2Reducing for 4 hours in an atmosphere of/Ar (the volume ratio is 1/9, and the flow rate is 50mL/min) to obtain a Pt/MIL-53(Al) mixture;
(4)Pt/γ-Al2O3preparing a catalyst: calcining the Pt/MIL-53(Al) prepared in the step (3) in a muffle furnace at 600 ℃ for 4 hours to obtain the target Pt/gamma-Al2O3A catalyst; the muffle furnace heating rate is 5 ℃/min.
Example 4
(1) MIL-53(Al) preparation: taking 0.96g of terephthalic acid and Al (NO)3)3·9H2Mixing 4.6g of O and 20mL of deionized water into a 100mL self-pressure kettle cup, placing the mixture into a stainless steel self-pressure kettle after ultrasonic oscillation for 10 minutes, screwing the mixture, and reacting the mixture in an electric heating box at 215 ℃ for 96 hours to obtain a wet MIL-53(Al) sample as white powder; the wet sample is washed by deionized water and then calcined in a muffle furnace at 280 ℃ for 50 hours to obtain dry MIL-53(Al) powder;
(2) pt precursor loading was performed using a two-solvent method: adding 0.45g of dried MIL-53(Al) into 80mL of n-hexane, carrying out ultrasonic treatment for several minutes, and rapidly stirring for 4 hours to obtain an MIL-53(Al) suspension; will K2PtCl6Dissolving the Pt precursor solution in deionized water to prepare a Pt precursor solution with the concentration of 0.104 mol/L; slowly dripping 0.4ml of precursor solution into the MIL-53(Al) suspension under the stirring state, continuously stirring for 4 hours, carrying out solid-liquid separation treatment, and vacuum drying the obtained solid at room temperature for 24 hours to obtain the Pt precursor loaded MIL-53(Al) powder;
(3) Pt/MIL-53(Al) preparation: putting the MIL-53(Al) powder loaded with the Pt precursor prepared in the step (2) into a tube furnace H at 500 DEG C2Reducing for 8 hours in an atmosphere of/Ar (the volume ratio is 1/1, and the flow rate is 100mL/min) to obtain a Pt/MIL-53(Al) mixture;
(4)Pt/γ-Al2O3preparing a catalyst: calcining the Pt/MIL-53(Al) prepared in the step (3) in a muffle furnace at 700 ℃ for 6 hours to obtain the target Pt/gamma-Al2O3A catalyst; the muffle furnace heating rate is 5 ℃/min.
Example 5
(1) MIL-53(Al) preparation: taking 0.96g of terephthalic acid and Al (NO)3)3·9H2Mixing 4.6g of O and 20mL of deionized water into a 100mL self-pressure kettle cup, placing the mixture into a stainless steel self-pressure kettle after ultrasonic oscillation for 10 minutes, screwing the mixture, and reacting the mixture in an electric heating box at 225 ℃ for 84 hours to obtain a wet MIL-53(Al) sample as white powder; the wet sample is washed by deionized water and then calcined in a muffle furnace at 300 ℃ for 42 hours to obtain dry MIL-53(Al) powder;
(2) pt precursor loading was performed using a two-solvent method: adding 0.55g of dried MIL-53(Al) into 60mL of n-hexane, carrying out ultrasonic treatment for several minutes, and rapidly stirring for 4 hours to obtain an MIL-53(Al) suspension; h is to be2PtCl6Dissolving the Pt precursor solution in deionized water to prepare a Pt precursor solution with the concentration of 0.004 mol/L; slowly dripping 1.2ml of LPt precursor solution into the MIL-53(Al) suspension under the stirring state, continuously stirring for 4 hours, carrying out solid-liquid separation treatment, and vacuum drying the obtained solid at room temperature for 24 hours to obtain the final productMIL-53(Al) powder loaded with Pt precursor;
(3) Pt/MIL-53(Al) preparation: putting the MIL-53(Al) powder loaded with the Pt precursor prepared in the step (2) into a tube furnace H at 200 DEG C2Reducing for 8 hours in an atmosphere of/Ar (the volume ratio is 1/5, and the flow rate is 50mL/min) to obtain a Pt/MIL-53(Al) mixture;
(4)Pt/γ-Al2O3preparing a catalyst: calcining the Pt/MIL-53(Al) prepared in the step (3) in a muffle furnace at 600 ℃ for 4 hours to obtain the target Pt/gamma-Al2O3A catalyst; the muffle furnace heating rate is 5 ℃/min.
Comparative example:
(1) MIL-53(Al) preparation: terephthalic acid (1.15g,6.94mmol) and Al (NO) are taken3)3·9H2Mixing O (5.2g,13.86mmol) and deionized water (20mL,1.11mol) into a 100mL self-pressing kettle cup, ultrasonically vibrating for 10 minutes, placing into a stainless steel self-pressing kettle, screwing, and reacting in an electric heating box at 220 ℃ for 72 hours to obtain an MIL-53(Al) sample with wet white powder; the wet sample is washed by deionized water and then calcined in a muffle furnace at 300 ℃ for 48 hours to obtain dry MIL-53(Al) powder;
(2) preparation of comparative sample: 0.3g of dried MIL-53(Al) was calcined in a 600 ℃ muffle furnace for 4 hours to obtain gamma-Al without loading Pt nanoparticles2O3As a comparative sample.
The prepared samples were tested as follows:
1. the X-ray diffraction experiments were performed on the sample of example 1, the sample of example 2, the sample of example 3, and the comparative sample, respectively, and the results are shown in fig. 1.
As can be seen from the figure, the comparative example sample showed γ -Al2O3A phase diffraction peak; the sample of example 1, the sample of example 2, and the sample of example 3 all exhibited diffraction peaks for Pt.
2. The activity evaluation of the catalytic oxidation of propylene was performed on the samples of example 1, example 2, example 3, and comparative example, respectively.
The dosage of the catalyst is 30mg, and the catalyst is tableted, sieved (40-60 meshes) and mixed with 270mg of quartz sandAnd then the mixture is put into a phi 6 quartz reaction tube. The feed gas consists of propylene (1 percent), O2(10 percent), N2(3 percent) and He balance, and the reaction space velocity is 30000h-1. The reactor was heated from room temperature to 400 ℃ at a rate of 20 ℃/h, and CO generated after the mixed gas passed through the catalyst bed was detected on line by gas chromatography (Shimadzu GC 2014)2And (4) concentration.
The results of the tests are shown in FIG. 2, where curve A, B, C corresponds to the catalytic activity of the sample of example 1, the sample of example 2, and the sample of example 3, respectively. The results show that the obtained catalyst can completely convert propylene into CO within 270 DEG C2And H2O。
3. The activity evaluation for producing aniline by catalytic nitrobenzene reduction was performed on the sample of example 1, the sample of example 2, the sample of example 3, and the sample of comparative example in a gas-phase fixed-bed reactor.
The amount of the catalyst was 5mg, and the powdered catalyst was mixed with 1g of quartz sand and charged into an adaptive reaction tube having an inner diameter of 1 cm. The gas phase nitrobenzene is provided by the liquid nitrobenzene process using He at 70 c. The composition of the raw material gas is nitrobenzene (0.3%), H2 (3%), He (96.7%), and the total flow of the raw material gas is 100 mL/min. The reactor was raised from room temperature to 200 ℃ at a rate of 20 ℃/h, and the aniline concentration produced after the mixed gas passed through the catalyst bed was measured on-line by gas chromatography (Shimadzu GC 2014).
The results of the tests are shown in FIG. 3, where curve A, B, C, D corresponds to the catalytic activity of the sample of example 1, the sample of example 2, and the sample of example 3, respectively. From the results, it is found that the catalyst obtained has a good catalytic activity at 100 ℃ and the maximum selectivity of aniline is about 61%.
4. Transmission Electron Microscope (TEM) tests were performed on the sample of example 1 and the comparative sample, and the obtained TEM photographs are shown in fig. 4 and 5, in which fig. 4 is a TEM picture of the comparative sample and fig. 5 is a TEM picture of the sample of example 1. From fig. 4, it can be seen that the obtained Pt nanoparticles have an octahedral structure with a particle size of about 13 nm.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. Octahedral Pt nanoparticle loaded gamma-Al2O3The preparation method of the type catalyst is characterized by comprising the following steps: the Pt precursor is loaded on MIL-53(Al) by a double-solvent method, and then the catalyst Pt/gamma-Al can be prepared by reduction and calcination2O3；
The method specifically comprises the following steps:
a. pt precursor loading was performed using a two-solvent method: mixing n-hexane and MIL-53(Al), performing ultrasonic stirring to obtain MIL-53(Al) suspension, slowly dripping Pt precursor aqueous solution into the MIL-53(Al) suspension under a stirring state to obtain mixed solution, continuously stirring the obtained mixed solution for a certain time, performing solid-liquid separation treatment, and performing vacuum drying on the obtained solid at room temperature for a certain time to obtain MIL-53(Al) powder loaded with a Pt precursor;
b. Pt/MIL-53(Al) preparation: subjecting the powder obtained in step a to high temperature treatment with H2Reducing the/Ar mixed gas to obtain a Pt/MIL-53(Al) mixture;
c、Pt/γ-Al2O3preparing a catalyst: b, calcining the Pt/MIL-53(Al) mixture obtained in the step b in air at high temperature to obtain the target catalyst Pt/gamma-Al2O3；
In the step c, the calcining temperature is 600-700 ℃, and the calcining time is 3-6 h.
2. The octahedral Pt nanoparticle-loaded γ -Al of claim 12O3The preparation method of the type catalyst is characterized by comprising the following steps: in the step a, the concentration of the Pt precursor water solution is 0.004-0.104 mol/L, and the Pt precursor water solution is dropwise added into an MIL-53(Al) suspension according to the mass ratio of 0.5-2.0%.
3. The octahedral Pt nanoparticle-loaded γ -Al of claim 12O3The preparation method of the type catalyst is characterized by comprising the following steps: in the step a, normal hexane and MIL-53(Al) are taken according to the mass ratio of 66: 1-176: 1.
4. The octahedral Pt nanoparticle-loaded γ -Al of claim 12O3The preparation method of the type catalyst is characterized by comprising the following steps: in the step a, the precursor of Pt comprises K2PtCl4、K2PtCl6、H2PtCl6One kind of (1).
5. The octahedral Pt nanoparticle-loaded γ -Al of claim 12O3The preparation method of the type catalyst is characterized by comprising the following steps: in the step b, the reduction temperature is 200-500 ℃, the reduction time is 4-8H, and H is generated during reduction2The flow rate of the/Ar mixed gas is 50-300 mL/min.
6. The octahedral Pt nanoparticle-loaded γ -Al of claim 12O3The preparation method of the type catalyst is characterized by comprising the following steps: in said step b, according to H2Preparing H with Ar at a volume ratio of 1/9-1/12and/Ar mixed gas.
7. The octahedral Pt nanoparticle-loaded γ -Al of claim 12O3The preparation method of the type catalyst is characterized by comprising the following steps: the preparation method of the MIL-53(Al) comprises the following steps: taking terephthalic acid and Al (NO)3)3·9H2Mixing and stirring O and deionized water, placing at 215-225 ℃ for constant-temperature reaction for 72-96 h, cooling the mixed liquid obtained by the reaction, performing solid-liquid separation treatment, washing the obtained solid, and then placing at 280-300 ℃ for calcining for 42-50 h to obtain MIL-53(Al) powder.
8. The octahedral Pt nanoparticle-loaded γ -Al of claim 72O3The preparation method of the type catalyst is characterized by comprising the following steps: taking terephthalic acid and Al (NO) according to the weight ratio of 0.96-1.15: 4.6-5.2: 203)3·9H2O and deionized water.
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