CN116273052A - Preparation and application of transition metal supported perovskite catalyst - Google Patents
Preparation and application of transition metal supported perovskite catalyst Download PDFInfo
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- 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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
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- 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
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- 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
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Abstract
The invention discloses a method for preparing a medicine by ABO 3 A preparation method of a catalyst with a mixed metal oxide perovskite as a carrier and a transition metal with a plasma resonance effect and application of the catalyst in the field of photo-thermal catalysis of methane dry reforming. The catalyst is prepared by reacting a catalyst with a catalyst in ABO 3 M metal ion M is loaded on perovskite, and the prepared catalyst M@ABO 3 Wherein A is lanthanide series metal element, B is transition metal element, M is transition metal with plasma resonance effect in group VIII. The catalyst can effectively reduce the energy barrier of methane dry reforming reaction under the cooperation of light and heat by coupling high efficiency of thermal catalysis and low energy consumption of photocatalysis, promote activation of methane and carbon dioxide, further realize high reaction efficiency, and has the advantages of simple synthesis method, considerable yield and capability of effectively inhibiting the high temperature of the catalystThe catalyst is inactivated, shows better performance than pure photocatalysis or thermocatalysis, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalytic methane conversion, and in particular relates to a method for converting methane by using ABO 3 A preparation method of a catalyst with a mixed metal oxide perovskite as a carrier and a transition metal with a plasma resonance effect and application of the catalyst in the field of photo-thermal catalytic methane dry reforming.
Background
With the increasing depletion of fossil fuels, the simplest hydrocarbon methane (CH 4 ) Gradually log on the historical stage. CH (CH) 4 Is currently the hydrocarbon with the largest reserves in the world and widely exists in natural gas, biogas and coal mines. In addition to that, CH 4 But also can be naturally produced from biological systems or prepared from biomass by biotechnology, and is an important component of the energy market today. CH (CH) 4 The combustion products of (a) are only carbon dioxide and water, does not pollute the environment further, and is a clean energy source. However, CH 4 And CO 2 Are all key gases causing the greenhouse effect, and at present, the common means is to utilize reforming reaction to convert CH 4 And CO 2 Conversion to synthesis gas (H) 2 +CO) and further is used for synthesizing high-value hydrocarbon raw materials, which not only helps to relieve environmental problems such as greenhouse effect, but also can provide important chemical raw materials/fuels to make up for energy shortage.
Methane reforming refers to the catalysis of CH with metal catalysts at high temperature and pressure 4 With CO 2 The process of the reaction takes place. During the reaction, CH 4 Acting as a reducing agent, CO 2 Acting as an oxidizing agent. However，CH 4 And CO 2 Are thermodynamically extremely stable molecules and are difficult to activate. Thus, CH 4 The dry reforming reaction generally needs to be carried out at a high temperature of 800-1000 ℃. However, metal catalysts are susceptible to sintering, deactivation, and formation of carbon deposits in such harsh environments, thereby blocking adsorption of reactant molecules by the metal active sites, resulting in catalyst deactivation. In recent years, photo-thermal catalytic technology has proven to be effective in promoting CH 4 And (5) dry reforming. The high efficiency of the photocatalysis is combined with the low energy consumption of the photocatalysis by the photocatalysis, and ultraviolet light, visible light and infrared light in solar energy are utilized for inducing the reaction, so that the sintering of the metal catalyst is avoided. The high-efficiency methane dry reforming process can be realized under the medium-high temperature condition through photo-thermal catalysis. Based on the research background, a high-efficiency photocatalyst is developed, and CH is realized by utilizing a photo-thermal catalysis technology 4 And CO 2 The efficient transformation of (C) obviously has important research significance and practical value.
Conventional metal oxide semiconductor catalysts, e.g. TiO 2 、Ga 2 O 3 、ZrO 2 And the like, the defects of low quantum efficiency, poor light absorption performance, poor structural stability and the like often exist, and the photocatalytic efficiency is severely limited. ABO (anaerobic-anoxic-oxic) 3 The perovskite has excellent thermochemical stability and adjustable catalytic performance, and is a promising catalytic material. The catalytic activity of the perovskite can be regulated by partial substitution of cations at the a and/or B sites, and the B component can stabilize unusual oxidation states, resulting in structural defects, yielding more oxygen vacancy active sites. In view of the above problems, the present invention employs perovskite-type mixed metal oxide (ABO 3 ) Preparing a supported catalyst with high activity, high selectivity and high stability, simultaneously efficiently converting light energy into excited state carriers and heat by supporting VIII group metal nano particles with a plasma resonance effect, providing catalytic active sites for reaction and promoting CH 4 And CO 2 And realizes high reaction efficiency.
Disclosure of Invention
The invention aims to provide a catalyst for photo-thermal catalysis of methane dry reformingA preparation method and application of the chemical agent. M@ABO provided by the invention 3 The perovskite catalyst can effectively reduce the energy barrier of methane dry reforming reaction under the photo-thermal synergistic condition, promote the activation of methane and carbon dioxide, realize high reaction efficiency, and simultaneously, the VIII group metal nano particles with the plasma resonance effect can effectively inhibit the high-temperature deactivation of the catalyst, thereby solving the defects of low quantum efficiency, poor light absorption performance, poor structural stability and the like of the traditional metal oxide catalyst. Meanwhile, the synthesis method of the supported catalyst is simple, the yield is considerable, and the supported catalyst has good industrial application prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
transition metal loaded ABO 3 Perovskite catalyst prepared by reacting a perovskite catalyst with a perovskite catalyst at ABO 3 The catalyst M@ABO is prepared by loading metal ions M on perovskite as a cocatalyst 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is lanthanide series metal element, B is transition metal element, M is transition metal with plasma resonance effect in group VIII. The preparation method comprises the following steps:
1) Metal nitrate A (NO) 3 ) 3 ·xH 2 O and B (NO) 3 ) 2～3 ·xH 2 O is dissolved in a certain amount of deionized water to obtain a mixed solution;
2) Adding a proper amount of citric acid into the mixed solution obtained in the step 1), and regulating the pH value to be neutral by ammonia water;
3) Placing the mixed solution obtained in the step 2) in a water bath, stirring and heating to form a sol-like product;
4) Aging the sol-like product obtained in the step 3), and then calcining at a high temperature in air;
5) Washing, drying, grinding and sieving the product obtained in the step 4) to obtain the ABO serving as a catalyst carrier 3 The size of the perovskite is 50-100 meshes.
6) ABO obtained in step 5) is added 3 Addition of perovskite to MCl.xH 2 Fully stirring, dipping and reducing the solution of O to obtain the catalyst M@ABO 3 。
Further, A (NO) used in step 1) 3 ) 3 ·xH 2 O and B (NO) 3 ) 2～3 ·xH 2 The molar ratio of O is 1:1. Said A (NO) 3 ) 3 ·xH 2 O、B(NO 3 ) 2～3 ·xH 2 O includes, but is not limited to, a nitrate. Optimally, the A (NO 3 ) 3 ·xH 2 O is La (NO) 3 ) 3 ·6H 2 O, B is Fe (NO) 3 ) 3 ·9H 2 O、Mn(NO 3 ) 2 ·4H 2 O。
Further, the amount of citric acid added in step 2) is 1 to 3 times the total molar amount of metal nitrate used in step 1). Optimally, the ratio of the molar amount of citric acid added to the total molar amount of metal nitrate is 1:1.
Further, the temperature of the water bath in the step 3) is 60-130 ℃, and the stirring speed is 100-600 rpm. Optimally, the temperature of the water bath was 70℃and the stirring rate was 400 rpm.
Further, the temperature of the aging in the step 4) is 80-160 ℃ and the time is 12 h; the calcining temperature is 300-1000 ℃, and the heating rate is 3-20 ℃ min -1 Time 4 h. Optimally, the ageing temperature is 120 ℃, the calcining temperature is 600 ℃, and the heating rate is 5 ℃ min -1 。
Further, the solvent used for cleaning in the step 5) is deionized water; the drying mode is vacuum drying.
Further, the manner of loading the metal M in step 6) includes, but is not limited to, photo-deposition, sodium borohydride reduction, hydrogen reduction, preferably sodium borohydride reduction.
Further, the catalyst M@ABO obtained 3 The loading of M is 0.5wt% to 2wt%, preferably 1wt%.
CH 4 Activation can be achieved on nano-metal particles with plasmon resonance effect while CO 2 Activation can be achieved on oxygen vacancies of perovskite mixed metal oxides, thereby ultimately producing CO and H 2 Thus, the catalyst M@ABO obtained according to the invention 3 Can be usedThe dry reforming reaction of methane is photo-thermally catalyzed. The catalyst M@ABO is prepared by taking a xenon lamp as a light source under the condition of no external heating source 3 Fully contacting with methane and carbon dioxide to carry out dry reforming reaction of the methane; the reaction temperature is 365-555 deg.c, optimized 500 deg.c.
The technical scheme of the invention has the beneficial effects that:
(1) The invention relates to perovskite type mixed metal oxide ABO 3 The transition metal nano particles M are loaded on the catalyst, so that the energy barrier of methane dry reforming can be effectively reduced, and CH is promoted 4 And CO 2 Is activated by the activation of (a).
(2) The invention utilizes the VIII group metal nano particles with LSPR effect to inhibit the high-temperature deactivation of the catalyst, thereby solving the defects of poor light absorption performance, poor structural stability and the like of the traditional metal oxide catalyst.
(3) The invention is simple and easy to implement, can realize the effective methane dry reforming process without an external heat source, and is beneficial to popularization and application.
Drawings
FIG. 1 is an XRD pattern for LFO, 1wt% Ru@LFO, LMO, 1wt% Ru@LMO, LMFO, and 1wt% Ru@LMFO prepared in the examples.
FIG. 2 is a graph comparing activities of LFO, 1wt% Ru@LFO, LMO, 1wt% Ru@LMO, LMFO, 1wt% Ru@LMFO catalysts prepared in the examples.
FIG. 3 is a graph comparing the activities of Ru@LMFO catalysts at different loadings (0 wt% to 2 wt%).
FIG. 4 is an XRD pattern of a 1wt% Ru@LMFO catalyst before and after photo-thermal methane dry reforming.
FIG. 5 is a graph comparing the activities of a 1wt% Ru@LMFO catalyst under photo-thermal catalysis with thermal catalysis in a fixed bed reactor at the same temperature.
FIG. 6 is a graph comparing the activation energy of a 1wt% Ru@LMFO catalyst in a fixed bed reactor for photo-thermal catalysis with thermal catalysis.
FIG. 7 is a graph of the activity of a 1wt% Ru@LMFO catalyst in a fixed bed reactor for prolonged light.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
EXAMPLE 1 perovskite Mixed oxide ABO 3 Is prepared from
2.17 g La (NO) 3 ) 3 ·6H 2 O and 2.02 g Fe (NO) 3 ) 3 ·9H 2 O is dissolved in 10 mL deionized water, 4 g anhydrous citric acid is added after the O is fully dissolved, and ammonia water is used for adjusting the pH value to be neutral. The resulting mixed solution was placed in a 70 ℃ water bath and heated with stirring at 400 rpm until a sol-like product was formed. Aging the obtained sol product at 120deg.C for 12 h, calcining at 600deg.C under air atmosphere for 4 h at a heating rate of 5 deg.C for min -1 . Washing the obtained sample with deionized water, vacuum drying, grinding, and sieving to obtain LaFeO 3 （LFO）。
Fe (NO) 3 ) 3 ·9H 2 Equimolar or partial molar amount (40%) of O is replaced by Mn (NO) 3 ) 2 ·4H 2 O, thus obtaining LaMnO 3 (LMO) and LaFe 0.6 Mn 0.4 O 3 （LMFO）。
Example 2 M@ABO 3 Preparation of perovskite catalyst
100 mg ABO obtained in example 1 3 Dispersing in 50 mL deionized water, then adding 0.1 mL of 10mg/mL RuCl 3 ·3H 2 Mixing the solution O, stirring 5 h, dropwise adding sodium borohydride solution to obtain Ru 3+ Ions are reduced and loaded to ABO 3 Washing and drying the obtained precipitate on a carrier to obtain M@ABO with a loading capacity of 1wt% 3 A catalyst.
Example 3 M@ABO 3 Evaluation of the photo-thermal methane Dry reforming Activity of perovskite catalyst
M@ABO obtained in example 2 3 The catalyst methane dry reforming efficiency evaluation experiment was performed in a quartz reactor. The experimental process is as follows: placing catalyst into reactor, charging CH 4 /CO 2 Feed gas of 1:1 (v/v), purge air from the reactor,under the condition of no external heat source, a 300W xenon lamp is used as a light source for continuous illumination. The gas phase product of the system was analyzed qualitatively and quantitatively by Agilent 7890B gas chromatography equipped with a nickel reformer.
FIG. 1 is an XRD pattern of the prepared LFO, 1wt% Ru@LFO, LMO, 1wt% Ru@LMO, LMFO, 1wt% Ru@LMFO. As can be seen from FIG. 1, ru@ABO 3 The XRD pattern of the supported catalyst contains ABO 3 And no characteristic peak of Ru is shown in the spectrum, mainly due to the low content of Ru and small particle size.
FIG. 2 is a graph comparing activities of LFO, 1wt% Ru@LFO, LMO, 1wt% Ru@LMO, LMFO, 1wt% Ru@LMFO catalysts prepared. As can be seen from fig. 2, compared to pure ABO 3 ，Ru@ABO 3 The catalyst can obviously improve the efficiency of photo-thermal catalysis methane dry reforming, and the Ru@LMFO effect is obviously better than Ru@LFO and Ru@LMO.
Example 4 M@ABO 3 Perovskite type catalyst industrial simulation application
A quartz reaction tube filled with 50 mg of Ru@LMFO catalyst was placed in a fixed bed reactor, continuously charged with CH 4 /CO 2 =1: 1 (v/v) of a feed gas at a flow rate of 50 mL.min -1 Space velocity of 60000 mL g -1 ·h -1 . Under the condition of no external heat source, a 300W xenon lamp is used as a light source for continuous illumination.
FIG. 3 is a graph comparing the activities of Ru@LMFO catalysts at different loadings (0 wt% to 2 wt%) in a fixed bed reactor. As can be seen from fig. 3, the ru@lmfo catalyst with Ru loading of 1wt% has an optimal catalytic activity.
Figure 4 is an XRD pattern of the ru@lmfo catalyst before and after photo-thermal methane dry reforming. The graph shows that the supported catalyst has no obvious change after reaction and no impurity peak, and has excellent heat stability.
FIG. 5 is a graph comparing the activities of a Ru@LMFO catalyst under photo-thermal catalysis and thermal catalysis in a fixed bed reactor at the same temperature. The graph shows that under the same temperature, the efficiency of Ru@LMFO photocatalysis is 1-1.5 times of that of the photocatalysis, which indicates that the process is a photo-thermal synergistic process.
FIG. 6 is a graph comparing the activation energy of a Ru@LMFO catalyst in a fixed bed reactor under photo-thermal catalysis with that of a thermal catalyst. From the figure, the activation energy value in the thermocatalytic process is 1.5 times that of the photo-thermocatalytic process, which shows that the introduction of light effectively reduces the activation energy barrier required for the reaction.
FIG. 7 is a graph showing the activity of Ru@LMFO catalyst in a fixed bed reactor under prolonged light irradiation. From the graph, the activity of the Ru@LMFO catalyst can be kept almost unchanged in 10 h, which proves that the prepared Ru@LMFO catalyst has excellent photo-thermal stability.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. Transition metal loaded ABO 3 The preparation method of the perovskite catalyst is characterized by comprising the following steps of: by at ABO 3 The perovskite is loaded with metal ion M to prepare the catalyst M@ABO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is lanthanide series metal element, B is transition metal element, M is transition metal with plasma resonance effect in group VIII.
2. The transition metal loaded ABO of claim 1 3 The preparation method of the perovskite catalyst is characterized by comprising the following steps of: the method comprises the following steps:
1) Metal nitrate A (NO) 3 ) 3 ·xH 2 O and B (NO) 3 ) 2～3 ·xH 2 O is dissolved in a certain amount of deionized water to obtain a mixed solution;
2) Adding a proper amount of citric acid into the mixed solution obtained in the step 1), and regulating the pH value to be neutral by ammonia water;
3) Placing the mixed solution obtained in the step 2) in a water bath, stirring and heating to form a sol-like product;
4) Aging the sol-like product obtained in the step 3), and then calcining at a high temperature in air;
5) The product of step 4) is subjected to the following stepsCleaning, oven drying, grinding, and sieving to obtain ABO as catalyst carrier 3 Perovskite;
6) ABO obtained in step 5) is added 3 Addition of perovskite to MCl.xH 2 Fully stirring, dipping and reducing the solution of O to obtain the catalyst M@ABO 3 。
3. The transition metal loaded ABO of claim 2 3 The preparation method of the perovskite catalyst is characterized by comprising the following steps of: a (NO) used in step 1) 3 ) 3 ·xH 2 O and B (NO) 3 ) 2～3 ·xH 2 The molar ratio of O is 1:1.
4. The transition metal loaded ABO of claim 2 3 The preparation method of the perovskite catalyst is characterized by comprising the following steps of: the amount of citric acid added in step 2) is 1 to 3 times the total molar amount of metal nitrate used in step 1).
5. The transition metal loaded ABO of claim 2 3 The preparation method of the perovskite catalyst is characterized by comprising the following steps of: the temperature of the water bath in the step 3) is 60-130 ℃, and the stirring speed is 100-600 rpm.
6. The transition metal loaded ABO of claim 2 3 The preparation method of the perovskite catalyst is characterized by comprising the following steps of: the temperature of the aging in the step 4) is 80-160 ℃ and the time is 12 h; the calcining temperature is 300-1000 ℃, and the heating rate is 3-20 ℃ min -1 Time 4 h.
7. The transition metal loaded ABO of claim 2 3 The preparation method of the perovskite catalyst is characterized by comprising the following steps of: the solvent used for cleaning in the step (5) is deionized water; the drying mode is vacuum drying.
8. The process according to claim 2Transition metal loaded ABO 3 The preparation method of the perovskite catalyst is characterized by comprising the following steps of: the catalyst M@ABO obtained 3 The loading of M is 0.5-2 wt%.
9. Use of the catalyst prepared by the method of claim 1 in photo-thermal catalysis of methane dry reforming reaction, characterized in that: under the condition of no external heating source, a xenon lamp is used as a light source to make the catalyst M@ABO 3 Is fully contacted with methane and carbon dioxide to carry out the dry reforming reaction of methane.
10. The use according to claim 9, characterized in that: the temperature of the reaction is 365-555 ℃.
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