CN108940308B - Preparation of platinum-cobalt composite metal photo-thermal catalyst and application of platinum-cobalt composite metal photo-thermal catalyst in methane carbon dioxide reforming - Google Patents
Preparation of platinum-cobalt composite metal photo-thermal catalyst and application of platinum-cobalt composite metal photo-thermal catalyst in methane carbon dioxide reforming Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- 238000002407 reforming Methods 0.000 title abstract description 10
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 62
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- 238000001833 catalytic reforming Methods 0.000 claims description 3
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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Abstract
The invention discloses a photothermal catalyst for preparing synthesis gas by reforming methane and carbon dioxide and application thereof. Firstly, cobalt oxide nano-particles are prepared and loaded on an alumina carrier, and then the prepared cobalt oxide nano-particles and an alumina composite metal material CoO NPs-Al are added2O3Adding platinum-containing salt solution, stirring, drying and calcining to obtain Pt/CoO-Al2O3A composite photo-thermal material. Under the light irradiation, the composite metal photo-thermal catalyst has high photo-thermal catalytic conversion efficiency on methane and carbon dioxide; successful preparation of the catalyst to methane and CO2The high-efficiency and green conversion of the mixed gas under mild conditions provides a good opportunity.
Description
Technical Field
The invention relates to a photothermal catalyst for preparing synthesis gas by reforming methane and carbon dioxide, in particular to preparation of a composite metal photothermal catalyst with platinum nanoparticles and cobalt oxide nanoparticles on an alumina carrier, and belongs to the field of preparation of binary plasma resonance photothermal coupling materials.
Background
With the increasing severity of environmental problems such as global warming, people have turned to the greenhouse gas CO2And CH4Processing and utilization is also becoming more and more of a concern. Efficient reforming of two greenhouse gases not only converts CO2The light source is recycled as a raw material, and the reaction utilizes the light source as the only energy source, so that the light source can be used for effectively converting light energy into chemical energy. The solar energy has the characteristic of inexhaustibility. If the use of solar energy to drive CH can be realized4And CO2The reforming process not only can realize the complete greening of the production of the synthesis gas, but also has the potential of capturing and fixing solar energy.
In 1928, Fischer and Tropsch studied various metals for methane and carbon dioxide reforming reactions. Since then, numerous studies have demonstrated that the group VIII transition metals are catalytically active for this reaction, and that the noble metal (Pt, Pd, Ph, Ru, Ir) catalysts have high catalytic activity and resistance to carbon deposition, with Pt being considered the best component.
The activity of the methane carbon dioxide reforming reaction is influenced by the property of the metal loaded on the catalyst, the carrier, the interaction of the metal, the carrier and the metal with the carrier and the like, and compared with other transition metals, platinum has higher reaction activity and is not easy to inactivate in the methane functionalization reaction. Although the view point of the action of the carrier is not unified, the good thermal stability and the large specific surface area are the precondition for selecting the carrier of the high-temperature reforming reaction catalyst, and the microporous and mesoporous molecular sieves have unique channel structures and generally have high stability and large specific surface area. In addition, when the carrier and the metal have strong interaction, the reaction activity and the sintering resistance of the catalyst can be greatly improved. Therefore, a carrier with large specific surface and high thermal stability loaded with a high-activity metal species platinum is selected to prepare the high-efficiency photothermal catalytic reforming reaction catalyst as a research object.
The activation of inert C-H bonds by photocatalytic means presents great thermodynamic and kinetic challenges. The cooperative catalysis process under the condition that sunlight is used as a unique energy source to simultaneously create a light field and a thermal field is a new way for effectively promoting C-H activation, and the defect of a single photocatalysis technology is overcome. Based on this, the invention establishes Pt-Co-Al2O3The multicomponent alloy strengthens the surface plasma resonance catalytic system.
Disclosure of Invention
The invention aims to provide a preparation method of a novel photo-thermal catalyst with the characteristics of good photo-thermal catalytic reforming activity, simple production process and the like in the synthesis gas prepared by reforming methane and carbon dioxide, so as to explore the realization of the photo-thermal reforming of methane and carbon dioxide by the catalyst under relatively mild conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the platinum metal loaded cobalt oxide-alumina photo-thermal catalyst comprises the following steps:
(1) preparing cobalt oxide nanoparticles:
preparing 1 mM cobalt nitrate solution, measuring 60-80 mL cobalt nitrate aqueous solution, adding 50mL ethanol solution, mixing and stirring for 10min, adding 1-5 mL dodecylamine solution, stirring for 5min, adding 50mL hexane solution, stirring for 2 min, stopping stirring, standing for 5min, taking the upper layer solution, and stirring for 30min in a 50 ℃ water bath kettle. Standing for 12 h.
(2) Cobalt oxide nanoparticle-alumina composite metal material (CoO NPs-Al)2O3) The preparation of (1):
and (2) adding 0.5-3 g of alumina powder into the solution in the step (1), stirring for 2 hours at room temperature, centrifuging, washing, drying and calcining to obtain the composite metal material with CoO NPs supported on alumina.
(3) Cobalt oxide nanoparticle-alumina composite (CoO NPs-Al)2O3) Preparation of platinum nanoparticles loaded thereon (Pt NPs):
cobalt oxide nano-particles and aluminum oxide composite metal material (CoO NPs-Al) prepared in the step (2)2O3) Adding 10-90 mL of platinum-containing salt solution and stirring for 12 h, wherein the mass of platinum contained in the platinum salt solution is 1mg/mL, and then drying and calcining to obtain Pt/CoO-Al2O3A composite photo-thermal material.
The stirring speed in the step (2) is 5000 r/min, and the calcining temperature is 200-300 ℃.
The calcination temperature in the step (3) is 300-700 ℃, and the platinum metal content is 0.5-3 wt%.
Use of a photo-thermal catalyst for methane carbon dioxide reforming as described above: the CO produced by reforming synthesis gas by the composite photo-thermal catalyst under simulated sunlight reaches 6400 mu mol-1.s-1Produce H2To 7000. mu. mol.g-1.s-1。
The method for preparing the synthesis gas by methane and carbon dioxide reforming through photo-thermal catalysis comprises the following specific steps:
(1) a custom-made 3X 0.2 cm square quartz reactor was charged with 60-80 mesh Pt/CoO-Al2O3The composite metal photo-thermal catalyst is irradiated by light, and the molar content of the composite metal photo-thermal catalyst is 1:1 CH4:CO2A gas.
(2) The products of photothermocatalysis were analyzed by gas chromatography and quantified by retention time and peak area.
The invention has the following remarkable advantages:
(1) the catalyst is simple to prepare, takes solar energy as the only driving force, simultaneously realizes the reformation of two greenhouse gases, namely methane and carbon dioxide, avoids the traditional conditions of high temperature and high pressure, realizes the reformation of methane and carbon dioxide under mild conditions, and is beneficial to the sustainable development and utilization of environment and energy.
（2）Pt/CoO-Al2O3The composite metal photo-thermal catalyst has high catalytic activity, good cycle performance, simple production process, macroscopic preparation and easy recovery.
Drawings
FIG. 1 is Pt/CoO-Al2O3、Pt/Al2O3、CoO-Al2O3、Al2O3A DRS map of (1);
FIG. 2 is Pt/CoO-Al2O3XRD pattern of (a);
FIG. 3 is Pt/CoO-Al2O3The CO production activity diagram;
FIG. 4 is Pt/CoO-Al2O3Product of (H)2Activity map of (a).
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
1. Preparation of the catalyst:
(1) preparation of cobalt supported on alumina:
preparing 1 mM cobalt nitrate solution, mixing 100 mL cobalt nitrate aqueous solution and 50mL ethanol solution, stirring for 10min, adding 1 mL dodecylamine solution, stirring for 5min, adding 50mL hexane solution, stirring for 2 min, stopping stirring, standing for 5min, taking the upper layer solution, and stirring in a 50 ℃ water bath for 30 min. Standing for 12 h.
(2) Cobalt oxide nanoparticle-alumina composite metal material (CoO NPs-Al)2O3) The preparation of (1):
and (2) adding 1 g of alumina powder into the solution obtained in the step (1), stirring at room temperature for 2 h, centrifuging at the rotating speed of 5000 r/min, washing, drying and calcining to obtain the composite material with CoO NPs loaded on alumina.
(3) Cobalt oxide nanoparticle-alumina composite (CoO NPs-Al)2O3) Preparation of platinum nanoparticles loaded thereon (Pt NPs):
taking the cobalt oxide nano particles and the alumina composite material (CoO NPs-Al) prepared in the step (2)2O3) 0.5 g of platinum is added into a platinum-containing salt solution and stirred for 12 hours, the mass concentration of platinum in the platinum-containing salt solution is 1mg/mL, the addition amount is 2.5 mL, and then the mixture is dried and calcined for 4 hours at 300 ℃ to obtain Pt/CoO-Al2O3A composite photo-thermal material.
2. And (3) activity test:
(1) a custom-made 3X 0.2 cm square quartz reactor was charged with 60-80 mesh Pt/CoO-Al2O3The composite metal photo-thermal catalyst is irradiated by light and CH with the molar mass of 1:1 is introduced under normal pressure4:CO2A gas.
(2) The photothermocatalytic product was analyzed by agilent gas chromatography and quantified by retention time and peak area.
Example 2
Specific Pt/CoO-Al2O3The preparation method is basically the same as that of example 1 in this section, except that the content of platinum metal is changed to 1.0 wt% and the calcination temperature is 300 ℃.
Example 3
Specific Pt/CoO-Al2O3The preparation method is basically the same as that of example 1 in this section, except that the content of platinum metal is changed to 1.5 wt% and the calcination temperature is 400 ℃.
Example 4
Specific Pt/CoO-Al2O3The preparation method is basically the same as that of example 1 in this section, except that the content of platinum metal is changed to 2.0 wt% and the calcination temperature is 500 ℃.
Example 5
Specific Pt/CoO-Al2O3The preparation method is basically the same as that of example 1 in this section, except that the content of platinum metal is changed to 2.5 wt% and the calcination temperature is 600 ℃.
Example 6
Specific Pt/CoO-Al2O3The preparation method is basically the same as that of example 1 in this section, except that the content of platinum metal is changed to 3.0 wt% and the calcination temperature is 700 ℃.
The support (Al) can be seen from the UV-Vis-NIR characterization of the catalyst (FIG. 1)2O3) Almost no light absorption in the 400-1200 nm range, Co/Al2O3The catalyst has certain light absorption in the range of 400-1200 nm. Pt-Co/Al2O3And Pt/Al2O3The catalyst has obvious light absorption in 400-1200 nm and has a small peak package in 400-450 nm, which is characteristic absorption caused by self excitation of metal Pt;
due to Pt-Co/Al2O3The content of noble metal and cobalt metal ions in the catalyst is very low, and when the loading amount of the active component is lower than the single-layer dispersion threshold value of the carrier, the XRD representation result of figure 2 can not detect the characteristic diffraction peak of the (Pt, Co) component. This also indicates that the active component may be in Al2O3Uniformly dispersing on the substrate;
as can be seen from FIG. 3, Pt-Co/Al2O3Catalyst of photo-thermal catalysis CH4And CO2The yield of the CO produced by the synthesis gas is obviously higher than that of the CO produced by the pure thermal catalysis, and the photo-thermal concerted catalysis is at 386o C yield, thermal catalysis is 500o C can be reached;
as can be seen from FIG. 4, Pt-Co/Al2O3Catalyst of photo-thermal catalysis CH4And CO2The yield of the CO produced by the synthesis gas is obviously higher than that of the CO produced by the pure thermal catalysis, and the photo-thermal concerted catalysis is at 386o The C yield is far greater than that of thermocatalysis at 500o Yield at C;
the above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. The application of the platinum-cobalt composite metal photo-thermal catalyst is characterized in that: catalyst for preparing synthetic gas by photothermal catalytic reforming of methane and carbon dioxideIn the reaction, the catalyst is platinum nano-particle Pt NPs and cobalt oxide nano-particle CoO NPs loaded on alumina Al2O3Wherein the mass of the Pt NPs accounts for 0.5-3% of the whole catalyst; the CoO NPs account for 0.6-0.8% of the mass fraction of the whole catalyst; the preparation method of the catalyst comprises the following steps:
(1) preparing cobalt oxide nanoparticles:
preparing a cobalt nitrate solution, measuring 60-80 mL of a cobalt nitrate aqueous solution, adding 50mL of an ethanol solution, mixing and stirring for 10min, adding 1-5 mL of a dodecylamine solution, stirring for 5min, adding 50mL of a hexane solution, stirring for 2 min, stopping stirring, standing for 5min, taking an upper layer solution, stirring for 30min in a 50 ℃ water bath, and standing for 12 h;
(2) cobalt oxide nanoparticle-aluminum oxide composite metal material CoO NPs-Al2O3The preparation of (1):
adding 0.5-3 g of alumina powder into the solution obtained in the step (1), stirring for 2 hours at room temperature, centrifuging, washing, drying and calcining to obtain the cobalt oxide nanoparticle-alumina composite metal material CoO NPs-Al2O3；
(3) Preparing a platinum-cobalt composite metal photo-thermal catalyst:
cobalt oxide nano-particle-aluminum oxide composite metal material CoO NPs-Al prepared in the step (2)2O3Adding 10-90 mL of platinum-containing salt solution, stirring for 12 h, drying and calcining to obtain the platinum-cobalt composite metal photo-thermal catalyst, wherein the concentration of platinum in the platinum salt solution is 1 mg/mL.
2. The use of the platinum-cobalt composite metal photothermal catalyst according to claim 1, wherein: in the step (1), the concentration of the cobalt nitrate solution is 1 mM.
3. The use of the platinum-cobalt composite metal photothermal catalyst according to claim 1, wherein: in the step (2), the calcining temperature is 200-300 ℃, and the calcining time is 2-3 h.
4. The use of the platinum-cobalt composite metal photothermal catalyst according to claim 1, wherein: in the step (3), the calcining temperature is 300-700 ℃, and the calcining time is 4-5 h.
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| CN113522015A (en) * | 2020-04-21 | 2021-10-22 | 中国科学院广州能源研究所 | Method for quickly treating organic gas by solar photo-thermal catalysis |
| CN113117672A (en) * | 2021-04-13 | 2021-07-16 | 福州大学 | Branched alkane reforming photo-thermal catalyst and preparation method and application thereof |
| CN114471613A (en) * | 2022-02-10 | 2022-05-13 | 武汉理工大学 | Pt/Co-Al for high-efficiency photo-thermal catalysis carbon dioxide methane dry reforming2O3Catalyst and preparation method thereof |
| CN115254138B (en) * | 2022-08-17 | 2023-08-01 | 山东大学 | Preparation method and application of Ir-CoO/alumina photo-thermal catalyst |
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