CN111111669A - Medium-high temperature methane dry reforming mesoporous photo-thermal catalyst and preparation method and application thereof - Google Patents
Medium-high temperature methane dry reforming mesoporous photo-thermal catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002407 reforming Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000002153 concerted effect Effects 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000011941 photocatalyst Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 9
- 230000002195 synergetic effect Effects 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000006057 reforming reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000012855 volatile organic compound 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J35/39—
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- B01J35/393—
-
- B01J35/394—
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- B01J35/647—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a mesoporous photo-thermal catalyst for medium-high temperature methane dry reforming, a preparation method and application thereof, belongs to the field of solar photo-thermal conversion and preparation methods of photo-thermal catalysts, and adopts an impregnation method to load a thermal catalyst Ni to mesoporous TiO2Forming nano Ni particles on the surface of the photocatalyst and loading the nano Ni particles on the mesoporous TiO2Surface Ni-mesoporous TiO2A photo-thermal catalyst. The medium-high temperature methane dry reforming photo-thermal concerted catalysis provided by the inventionThe catalyst is simple to prepare and easy to operate, has good photo-thermal synergistic catalytic activity at 400-600 ℃, and has obviously improved activity compared with the traditional Ni-based thermal catalyst, so that the catalyst has higher industrial application level and prospect.
Description
Technical Field
The invention belongs to the field of solar photo-thermal conversion and a preparation method of a photo-thermal catalyst, and relates to a mesoporous photo-thermal catalyst for medium-high temperature methane dry reforming, and a preparation method and application thereof.
Background
The ever-decreasing fossil energy sources and the increasing environmental concerns have forced the search for clean renewable energy technologies. Among numerous renewable energy sources, solar energy has the advantages of being unique, namely large in total amount of resources, wide in distribution and free of the problem of resource exhaustion. Therefore, how to efficiently utilize solar energy for energy conversion becomes the research focus of many scholars.
The solar energy conversion technology comprises a photovoltaic conversion technology for directly carrying out light energy-electric energy by utilizing the photoelectric effect of semiconductor materials such as monocrystalline silicon/polycrystalline silicon and the like, and also comprises a technology for heating working media by utilizing concentrated solar energy and utilizing steam power Rankine cycle/CO2The light-heat conversion technology of light energy-internal energy-electric energy by Brayton cycle and the like also comprises the steps of utilizing solar energy as a heat source and carrying out water/CO under the action of a catalyst2Photo-chemical catalytic conversion technology for hydrocarbon decomposition. Among them, the solar photocatalytic conversion technology based on the photocatalyst is receiving more and more attention. The solar photocatalytic conversion technology can be used for the production of clean energy (such as photocatalytic water decomposition hydrogen production technology and photocatalytic CO2Decomposition recycling technology, etc.), and can also be used for VOCs and organic waste liquid catalytic decomposition environmental management technology. In any technology, the design and preparation of the photocatalyst are the key points.
At present, common catalysts for photocatalytic conversion at home and abroad comprise TiO2、C3N4The main application occasions of the method are to utilize solar ultraviolet spectrum to excite photocatalytic activity to carry out photocatalytic water decomposition hydrogen production, photocatalytic treatment on organic pollutants and the like, and the application temperature range is mostly in a room temperature environment. In addition, some researchers develop traditional thermal catalysts such as Ni-based and Ru-based catalysts, and focus on using concentrated solar energy to form a high-temperature heat source to drive the Ni-based and Ru-based thermal catalysts to realize reforming catalytic reaction of hydrocarbons to prepare the hydrocarbonsThe application temperature range of the solar fuel is mostly in medium-high temperature environment. At present, most researches are carried out on single photocatalyst or thermal catalyst, corresponding achievements are achieved, and different series of catalysts are developed. However, sunlight has a broad spectrum characteristic, and the catalytic effect of the catalyst is significantly influenced by the activity response of the catalyst to different spectral regions, and few reports have been reported on the development of a catalyst for preparing solar fuel by photo-thermal concerted catalysis for methane dry reforming by concentrated solar energy.
In conclusion, it is still a very challenging problem to develop and prepare a photo-thermal synergistic catalyst for efficient methane dry reforming reaction capable of being applied to medium-high temperature environmental conditions, and apply the photo-thermal synergistic catalyst for concentrating solar methane reforming reaction.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a mesoporous photothermal catalyst for medium-high temperature methane dry reforming, a preparation method and an application thereof, solves the problem that the conventional methane dry reforming catalyst is difficult to carry out photothermal concerted catalysis, and has Ni-based mesoporous TiO with controllable aperture2The preparation method of the photo-thermal synergistic catalyst is simple and reliable in process. The method is utilized to prepare Ni-based mesoporous TiO with excellent activity2The photo-thermal synergistic catalyst is required to show better catalytic activity in dry reforming reaction of methane compared with pure photocatalysis or thermal catalysis.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a mesoporous photo-thermal catalyst for dry reforming of medium-high temperature methane, which is Ni-mesoporous TiO2The catalyst is characterized in that the mass percent of Ni in the mesoporous photo-thermal catalyst is 2-8%.
Preferably, the mass percentage of Ni in the mesoporous photo-thermal catalyst is 4.8%.
Preferably, TiO2The pore diameter is 4-9 nm.
Further, TiO2The pore size is preferably 8.4 nm.
The invention also discloses a preparation method of the mesoporous photo-thermal catalyst for dry reforming of medium-high temperature methane, which comprises the following steps:
1) preparing a cetyl trimethyl ammonium bromide template solution with the concentration of 0.01-0.2 mol/L;
2) adding tetra-n-butyl titanate and glacial acetic acid into a cetyl trimethyl ammonium bromide template agent solution, and uniformly stirring to prepare a mixed solution A; mixing deionized water and isopropanol to prepare dropping liquid B; dripping the dripping liquid B into the mixed solution A, and stirring and reacting under a closed state until milky white gel is generated to obtain TiO2Gelling;
3) adding TiO into the mixture2After the gel is aged for at least 48 hours, the mesoporous TiO with controllable aperture is prepared by drying and roasting2Powder;
4) preparing 0.01-1% of nickel salt solution by mass percent, and preparing the mesoporous TiO prepared in the step 3)2The powder is dipped in nickel salt solution, and then the dipped product is dried and roasted to prepare the mesoporous photo-thermal catalyst for dry reforming of the medium-high temperature methane.
Further, in step 1): the solvent used for preparing the template agent solution is an alcohol solvent;
further preferably, an isopropyl alcohol solution is selected, and the template is prepared by dissolving the template in a solvent at normal temperature and mixing with stirring.
Further, in step 2): tetra-n-butyl titanate as mesoporous TiO2A precursor of a photocatalyst; the purpose of adding glacial acetic acid is to realize the pH value control of the mixed solution A.
Further, in the step 2), cetyl trimethyl ammonium bromide, tetra-n-butyl titanate, glacial acetic acid and an alcohol solvent are added according to the weight ratio of (0.1-2) g: (1-15) g: (0.1-5) mL: (10-60) preparing a solution according to the using amount ratio of mL; deionized water and isopropanol are mixed according to the ratio of (1-10): 4, preparing a dropping liquid B according to the volume ratio; the volume ratio of the mixed solution A to the dropwise addition B is 1: 1-100: 1.
Further, in step 2), the dropping method is adopted, and the dropping solution B (isopropyl alcohol solution, deionized water and isopropyl alcohol are mixed in a ratio of 3: 4) by stirring, and gelling the mixed solution of the cetyl trimethyl ammonium bromide template agent and the tetrabutyl titanate.
Further, after the mixed solution of the cetyl trimethyl ammonium bromide template agent and the tetrabutyl titanate is gelatinized in the step 2), continuously aging for more than 48 hours.
Further, in step 3), aging the obtained TiO2Placing the precursor gel in a culture dish, drying at 100 ℃ for more than 1h, further roasting in a muffle furnace at high temperature (350-450 ℃), removing the cetyl trimethyl ammonium bromide template agent in the colloid, and forming the mesoporous TiO2A photocatalyst powder.
Further, the mesoporous TiO with controllable pore structure can be realized through the research of the roasting temperature-duration process conditions2A photocatalyst process control method.
Preferably, in step 4), the mesoporous TiO is2Mixing the powder with a nickel salt solution according to the weight ratio of 1 g: (5-100) mL of the total amount of the components
Further preferably, a nickel salt solution (such as nickel nitrate, nickel chloride, nickel sulfate, etc.) with a mass fraction of 0.2% is prepared, and then the mesoporous TiO is subjected to2Soaking the powder in nickel salt solution to obtain mesoporous TiO2Mixing the powder with a nickel salt solution according to the dosage ratio of 1g/30ml, standing and soaking for at least 12 hours, drying and roasting the soaked catalyst to obtain the Ni-mesoporous TiO with the photo-thermal concerted catalysis effect2A photo-thermal catalyst.
Wherein, the thermal catalyst Ni component is derived from nickel salt solution (such as nickel nitrate solution); photocatalyst TiO2The source is prepared mesoporous TiO2A photocatalyst powder. Impregnating mesoporous TiO2The photocatalyst powder is dipped in nickel salt solution to form mixed solution. Then, the mixed solution is dried and roasted at a certain temperature to obtain the Ni-mesoporous TiO with the photo-thermal concerted catalysis effect2A photo-thermal catalyst.
The invention also discloses application of the mesoporous photo-thermal catalyst for dry reforming of medium-high temperature methane in photo-thermal concerted catalytic reaction.
Further, the temperature of the photo-thermal concerted catalysis reaction is 400-600 ℃.
The invention also discloses application of the mesoporous photo-thermal catalyst for medium-high temperature methane dry reforming in a light-gathering type medium-high temperature solar methane dry reforming photo-thermal concerted catalytic conversion reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a mesoporous photo-thermal catalyst for dry reforming of medium-high temperature methane, which is a mesoporous TiO loaded with nano Ni particles2Surface Ni-mesoporous TiO2The content of Ni particles in the photo-thermal catalyst is large, and the mesoporous TiO in the catalyst can be known from an SEM picture2The specific surface area is larger, so that the dispersion degree of Ni particles loaded in mesopores is high, and the Ni particles and TiO2The formed heterostructure has remarkable photo-thermal synergetic catalytic activity, can improve the charge separation characteristic of a photo-generated carrier, and has higher spectral absorption response characteristic, so that the catalytic conversion activity is higher.
Furthermore, the medium-high temperature methane dry-reforming mesoporous photo-thermal synergistic catalyst has good photo-thermal synergistic catalytic activity at a reaction temperature of 400-600 ℃, and compared with a traditional Ni-based thermal catalyst, the activity of the medium-high temperature methane dry-reforming mesoporous photo-thermal synergistic catalyst is obviously improved. The catalyst has higher industrial application level and prospect.
The invention discloses a preparation method of the catalyst, which adopts an immersion method to load a thermal catalyst Ni to mesoporous TiO2Forming nano Ni particles on the surface of the photocatalyst and loading the nano Ni particles on the mesoporous TiO2Surface Ni-mesoporous TiO2A photo-thermal catalyst. In the preparation method of the catalyst, ordered mesoporous TiO2The photocatalyst is prepared by preparing TiO2The gel is obtained by aging, drying and roasting, the preparation process is simple and reliable, and the prepared ordered mesoporous TiO is2The photocatalyst has higher specific surface area, and the prepared mesoporous TiO2The powder can be used for preparing Ni-mesoporous TiO by a simple dipping method2The catalyst can further greatly improve the photoresponse area and the absorption capacity of the broad-spectrum solar energy.
Is manufactured by the methodPrepared Ni-mesoporous TiO2The photo-thermal catalyst can be applied to a light-gathering type medium-high temperature solar reactor, and comprises a Ni active center and mesoporous TiO2The photocatalyst can respectively realize the thermal catalysis and the photocatalysis effects, and the photo-thermal catalyst can realize the cooperative conversion, so that the photo-catalysis effect and the thermal conversion effect of different spectral bands in a solar spectrum can be better exerted, the activity of the catalyst is greatly improved, and the photo-thermal chemical conversion efficiency of the reactor is improved.
Drawings
FIG. 1 shows the present invention on different TiO2Ni-mesoporous TiO prepared at the roasting temperature of precursor gel2SEM picture of catalyst, a is Ni-mesoporous TiO calcined at 350 deg.C2A photo-thermal catalyst, b is TiO obtained by roasting at the temperature of 400 DEG C2Powder c is TiO2The roasting temperature of the precursor gel is 400 ℃ to prepare the obtained Ni-mesoporous TiO2A photo-thermal catalyst, d is TiO2The roasting temperature of the precursor gel is 450 ℃ to prepare the obtained Ni-mesoporous TiO2A photo-thermal catalyst;
FIG. 2 shows the Ni-mesoporous TiO with 8.4nm aperture prepared by the present invention2Comparing photo-thermal concerted catalytic activity of the catalyst with single thermal catalytic activity;
FIG. 3 shows Ni-mesoporous TiO of the present invention2The pore diameter of the catalyst is in a temperature relationship with the roasting process.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
Dissolving 0.75g of hexadecyl trimethyl ammonium bromide in 32ml of isopropanol solution at room temperature, stirring until the hexadecyl trimethyl ammonium bromide is completely dissolved, adding 5g of tetra-n-butyl titanate and 1ml of glacial acetic acid into the isopropanol solution, and stirring for 0.5h to form a uniform light yellow solution A; adding 1.5ml of deionized water into 2ml of isopropanol to form a dropping liquid B; slowly dripping the B into the A solution, stirring and reacting for a certain time at 30 ℃ in a closed state to obtain uniform milky TiO2Gelling; aging for more than 48h to obtain the mesoporous TiO2The precursor gel is placed in a culture dish and dried at the temperature of 100 ℃, as shown in figure 3, the xerogel is roasted at the temperature of 400 ℃ for 3h, and then the white mesoporous TiO is obtained2The SEM image of the powder is shown in FIG. 1-b.
Then adding TiO2Soaking in 0.2 wt% nickel nitrate solution, drying at 100 deg.C for 2 hr, and calcining at 500 deg.C for 5 hr to obtain Ni-mesoporous TiO with 5.8nm pore diameter2The photothermal catalyst is shown in the SEM image of FIG. 1-c.
Example 2
As shown in FIG. 3, the same as example 1 except that mesoporous TiO was controlled2The roasting temperature of the precursor gel is 350 ℃, and the Ni-mesoporous TiO with the aperture of 4.6nm is obtained2The photothermal catalyst is shown in the SEM image of FIG. 1-a.
Example 3
As shown in FIG. 3, the same as example 1 except that the control mediumPorous TiO2The roasting temperature of the precursor gel is 450 ℃, and the Ni-mesoporous TiO with the aperture of 8.4nm is obtained2The photothermal catalyst is shown in the SEM image in FIG. 1-d.
Example 4
Ni-mesoporous TiO with a pore diameter of 5.8nm prepared in example 1 above2The photo-thermal catalyst is used for methane dry reforming photo-thermal concerted catalysis reaction. 0.1g of Ni-mesoporous TiO is taken2The photo-thermal catalyst is put into a micro photo-thermal reaction fixed bed reactor and H is introduced2The air in the reactor was replaced, and catalyst activation was performed. Close H2Valve, let in N2Purge replacement H2Then turn off N2And (4) a valve. Turning on a heater for heating, turning on a simulated light source when the temperature in the reactor rises to 500 ℃, and introducing CH4/CO2The reaction was started with mixed gas (1:1, 20 ml/min). The reaction product was passed to a gas chromatograph for analysis. Analysis of the product showed that the reaction temperature was 500 ℃ and that H in the product was thermally catalyzed alone2The mole fraction is 5.0 percent to 6.9 percent, and the mole fraction of CO is 9.6 percent to 11.3 percent; photo-thermal concerted catalysis of H in product27.7 to 8.1 percent of mol fraction and 12.7 to 13.5 percent of CO mol fraction. Photo-thermal concerted catalysis of H in product2The production rate is 11.6-20.0 mmol/(h.g), and the CO mole fraction is 18.3-23.6 mmol/(h.g).
Example 5
The same as example 4, except that the reaction was carried out while controlling the reaction temperature to 550 ℃ in the case of the H in the product by thermal catalysis alone2The mole fraction is 11.3% -15.6%, and the mole fraction of CO is 19.2% -22.8%; photo-thermal concerted catalysis of H in product2The mole fraction is 11.5-18.3%, and the mole fraction of CO is 18.3-13.6%. Photo-thermal concerted catalysis of H in product2The production rate is 19.9-30.2 mmol/(h.g), and the CO mole fraction is 40.8-48.5 mmol/(h.g).
Example 6
Same as example 4, except that the Ni-mesoporous TiO with a pore size of 4.6nm prepared in example 2 was used2The photo-thermal catalyst is used for the characterization of catalytic activity, and the experimental result shows that H in the photo-thermal concerted catalysis product2The generation rate is 14.0-16.3 mmol/(h.g), CO molThe fraction is 24.3 to 27.5 mmol/(h.g).
Example 7
Same as example 4, except that the Ni-mesoporous TiO with the pore diameter of 8.4nm prepared in example 3 was used2The photo-thermal catalyst is used for the characterization of catalytic activity, and the experimental result shows that H in the photo-thermal concerted catalysis product2The production rate is 19.6-21.1 mmol/(h.g), and the CO mole fraction is 31.5-32.6 mmol/(h.g).
From the above examples, it can be seen that the catalysts prepared by this method with different calcination temperatures are active for dry reforming of methane at different medium and high temperature reaction temperatures. Ni-mesoporous TiO with the aperture of 8.4nm obtained by roasting at 450 DEG C2The photo-thermal catalyst just completely removes the cetyl trimethyl ammonium bromide template by roasting at the roasting temperature, and TiO is not caused by overhigh temperature2The particles are too large, so that the hole collapse is caused, the specific surface area is reduced, higher activity is shown in the reaction process, and the hydrogen production rate and the CO production rate are obviously higher than those of other two catalysts with the hole diameters. The invention is not limited to the above examples, and the catalyst can achieve good effect on dry reforming reaction of methane under medium-high temperature condition by changing different component distribution ratio, process preparation condition and reaction condition of the catalyst.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The mesoporous photo-thermal catalyst for dry reforming of medium-high temperature methane is characterized by being Ni-mesoporous TiO2The catalyst is characterized in that the mass percent of Ni in the mesoporous photo-thermal catalyst is 2-8%.
2. The mesoporous photothermal catalyst for medium-high temperature methane dry reforming according to claim 1, wherein the TiO in the mesoporous photothermal catalyst2The pore diameter of (A) is in the range of 4-9 nm.
3. The preparation method of the mesoporous photothermal catalyst for medium-high temperature methane dry reforming according to claim 1 or 2, comprising the steps of:
1) preparing a cetyl trimethyl ammonium bromide template solution with the concentration of 0.01-0.2 mol/L;
2) adding tetra-n-butyl titanate and glacial acetic acid into a cetyl trimethyl ammonium bromide template agent solution, and uniformly stirring to prepare a mixed solution A; mixing deionized water and isopropanol to prepare dropping liquid B; dripping the dripping liquid B into the mixed solution A, and stirring and reacting under a closed state until milky white gel is generated to obtain TiO2Gelling;
3) adding TiO into the mixture2After the gel is aged for at least 48 hours, the mesoporous TiO with controllable aperture is prepared by drying and roasting2Powder;
4) preparing 0.01-1% of nickel salt solution by mass percent, and preparing the mesoporous TiO prepared in the step 3)2The powder is dipped in nickel salt solution, and then the dipped product is dried and roasted to prepare the mesoporous photo-thermal catalyst for dry reforming of the medium-high temperature methane.
4. The method for preparing the mesoporous photo-thermal catalyst for dry reforming of medium-high temperature methane according to claim 3, wherein in the step 1), an alcohol solution is used as a solvent to prepare a cetyl trimethyl ammonium bromide template solution.
5. The method for preparing the mesoporous photothermal catalyst for medium-high temperature methane dry reforming according to claim 3, wherein in the step 2), cetyl trimethyl ammonium bromide, tetra-n-butyl titanate, glacial acetic acid and an alcohol solvent are added according to the ratio of (0.1-2) g: (1-15) g: (0.1-5) mL: (10-60) preparing a solution according to the using amount ratio of mL; deionized water and isopropanol are mixed according to the ratio of (1-10): 4, preparing a dropping liquid B according to the volume ratio; the volume ratio of the mixed solution A to the dropwise addition B is 1: 1-100: 1.
6. The medium-high temperature dry methane reforming process of claim 3The preparation method of the mesoporous photo-thermal catalyst is characterized in that in the step 4), mesoporous TiO is adopted2Mixing the powder with a nickel salt solution according to the weight ratio of 1 g: (5-100) mL of the above-mentioned components in a ratio of the amount of the above-mentioned components.
7. The method for preparing the mesoporous photo-thermal catalyst for medium-high temperature methane dry reforming according to claim 3, wherein in the step 3), the drying is performed at 100 ℃ for at least 1h, and the roasting is performed at 350-450 ℃ for 2-4 h.
8. The method for preparing the mesoporous photo-thermal catalyst for medium-high temperature methane dry reforming according to claim 3, wherein in the step 4), the drying is performed at 100 ℃ for 1-3 h, and the roasting is performed at 450-600 ℃ for 4-6 h.
9. The use of the mesoporous photothermal catalyst for medium-high temperature methane dry reforming as claimed in claim 1 or 2 in photothermal concerted catalytic reaction is characterized in that the temperature of the photothermal concerted catalytic reaction is 400-600 ℃.
10. The use of the mesoporous photothermal catalyst for medium-high temperature dry methane reforming according to claim 1 or 2 in a concentrated medium-high temperature solar dry methane reforming photo-thermal concerted catalytic conversion reaction.
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| CN113941334A (en) * | 2021-11-11 | 2022-01-18 | 西南石油大学 | Solar light-gathering catalytic methane dry reforming catalyst and preparation method and application thereof |
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| CN113117672A (en) * | 2021-04-13 | 2021-07-16 | 福州大学 | Branched alkane reforming photo-thermal catalyst and preparation method and application thereof |
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| CN114377680A (en) * | 2022-01-26 | 2022-04-22 | 中国科学院上海高等研究院 | Metal-loaded TiO2Base photocatalyst, preparation method and application |
| CN115869951A (en) * | 2022-12-13 | 2023-03-31 | 鲁东大学 | Non-noble metal modified titanium dioxide catalyst and preparation method and application thereof |
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