Preparation method of reverse water gas shift reaction catalyst and use of the same

Abstract

To provide a reverse water gas shift reaction catalyst which simultaneously achieves requirements such as a high CO2 conversion state, selectivity and stability.SOLUTION: A preparation method of a reverse water gas shift reaction catalyst includes: dissolving La(NO3)3 6H2O in deionized water; then adding SBA-15 thereto; setting a mass ratio of the deionized water to the SBA-15 to be 50:1; subjecting the mixture to ultrasonic dispersion, obtaining a mixed solution A and sealing the mixed solution A; subjecting the mixed solution A to stirring and drying treatments and obtaining a material A after drying; baking the material A after drying in a muffle furnace at 550°C for 6 hours; obtaining Lay / SBA-15; dispersing 1 mg / g of an RuCl3 3H2O solution in the deionized water; then adding Lay / SBA-15 thereto; subjecting the mixture to ultrasonic dispersion and obtaining a mixed solution B and sealing the mixed solution B; subjecting the mixed solution B to stirring and drying treatments and obtaining a material B after drying; baking the material B after drying in a muffle furnace at 550°C for 6 hours; reducing the material B under H2 atmosphere at 600°C for 2 hours; and obtaining a reverse water gas shift reaction catalyst Ru2 Lay / SBA-15(y=5, 10 and 15).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to the technical field of catalysis, specifically to reverse hydrolysis. property Method for preparing a gas shift reaction catalyst and Concerning its use. [Background technology]

[0002] CO 2 Examples of active precious metals used in catalytic hydrogenation reactions include Pt, Pd, Rh, and Ru. Ru is the most economical precious metal, and its catalytic activity is close to that of Pt. The size of Ru particles affects the selectivity of products from the catalytic hydrogenation of carbon dioxide, and large Ru nanoparticles The particle is CH 4 Ru single atoms or nanoclusters favor the production of CO. Therefore, by adjusting the size of Ru particles, the catalytic hydrogenation of carbon dioxide can be achieved. In addition, Ru, which has a positive valence, can improve the selectivity of CO to C during the reaction. Promotes O elimination and CH 4 This suppresses the continuous hydrogenation reaction that produces CO, which contributes to improving the selectivity of CO. Give. However, a single Ru catalyst produces high CO 2 Conversion rate, selectivity and stability requirements can be met simultaneously. It is often difficult to achieve this in practice. Constructing iridium catalysts is an effective method to achieve the above requirements. Summary of the Invention

[0003] In order to solve the above technical solutions, the present invention provides a reverse water property Method for preparing a gas shift reaction catalyst and its uses. As a technical solution of the present invention, property The method for preparing the gas shift reaction catalyst includes: S1, La(NO 3 ) 3 6H 2 After dissolving O in deionized water, SBA-15 was added and deionized. The mass ratio of water to SBA-15 is 50:1, and the mixture is dispersed ultrasonically to obtain mixed solution A. Top and S2: sealing the mixed solution A, stirring and drying the mixed solution A to obtain a dried material A; S3: After drying, material A was roasted in a muffle furnace at 550°C for 6 hours. y / SBA-15 obtained , where the values ​​of y are 5, 10, and 15. When y=5, La(NO 3 ) 3 6H 2 O and The mass ratio of SBA-15 is 0.124:1, and when y = 10, La(NO 3 ) 3 6H 2 The mass ratio of O to SBA-15 is 0.246:1, and when y = 15, La(NO 3 ) 3 6H 2 a mass ratio of O to SBA-15 of 0.372:1; S4, 1 mg / g RuCl 3 3H 2 The LaO solution was dispersed in deionized water. y / S BA-15 was added and ultrasonically dispersed to obtain mixed solution B, in which RuCl 3 3H 2 O solution and La y The mass ratio of deionized water to SBA-15 was 20:1. is 50:1, S5: sealing the mixed solution B, stirring and drying the mixed solution B to obtain a dried material B; , S6: After drying, material B is roasted in a muffle furnace at 550℃ for 6 hours, then H 2 600 under atmospheric conditions Reduce at ℃ for 2h and reverse hydrolyze property Gas shift reaction catalyst Ru 2 La y / SBA-15, wherein The steps include y values ​​of 5, 10, and 15. Description: La is supported, followed by Ru, using a stepwise impregnation method. property Gas shift reaction catalyst By preparing the catalyst, the preparation of the catalyst is more efficient than the step impregnation method in which La is supported after Ru is supported. The preparation method allows Ru and La to interact effectively and sufficiently to improve the catalytic activity of the catalyst. This can be done. According to one aspect of the present invention, in steps S3 and S6, the muffle The temperature inside the furnace is increased from 25° C. to 500° C. at a rate of 5° C. / min. Explanation: Sufficient roasting under the above conditions will cause the metal precursor to react sufficiently with air to form the metal oxide. is guaranteed to generate According to one aspect of the present invention, the method of the sealed stirring and drying treatment is carried out by using mixed solution A or mixed solution B. Solution B was sealed and stirred for 3 h, then the seal was removed and the deionized water was evaporated completely under the conditions of an 80°C water bath. After the mixture is dried, it is placed in an oven at 80°C. The method is to dry the mixture at room temperature for 12 hours at room temperature to obtain Material A or Material B after drying. Explanation: By sealing and stirring mixed solution A or mixed solution B under the above conditions and drying This effectively supported Ru or La on SBA-15, and after supporting Ru, Stepwise impregnation prevents backwatering. property To effectively improve the catalytic activity of a gas shift reaction catalyst can be done. According to one aspect of the present invention, the SBA-15 is a magnetic SBA-15, Mixed solution B is placed in a sealed environment, and a strong magnetic field is applied to mixed solution A or mixed solution B during the sealed stirring period. A magnetic field of 0.5 to 1.5 T is applied. The magnetic field has an arc length of 40 to 60 degrees and is distributed symmetrically around the center of the circle of the sealed stirring bottle. It is a magnetic field applied by using an arc-shaped electromagnet with an oscillation frequency of 20 to 40 seconds per cycle. The magnetic field strength of the arc-shaped electromagnet is 0.5 to 1.5T. Description: Under the above conditions, magnetic SBA-15 was used as the carrier, and the magnetic field was used to This allows Ru or La to be more uniformly supported on SBA-16, and Ru and La are effectively and sufficiently supported. Interacts with each other in reverse hydrolysis property The catalytic activity of the gas shift reaction catalyst can be effectively improved. do. According to another aspect of the present invention, the present invention provides a method for producing a reverse hydrolysis property Further applications of the gas shift reaction catalyst are provided. , said backwater property CO using gas shift reaction catalyst 2 The hydrogenation reaction is thermally catalyzed to produce CO. Reverse water before reaction property The gas shift reaction catalyst is H 2 The mixture was reduced under atmospheric pressure for 1 h, where H 2 The flow rate of The flow rate is 30 mL / min and the temperature is 600°C. Description: The above conditions were used, and the reaction was carried out property The gas shift reaction catalyst is H 2 Reduce in the atmosphere This causes backflow property The gas shift reaction catalyst can be effectively activated. According to another aspect of the present invention, the reverse water property CO using gas shift reaction catalyst 2 Hydrogenation reaction The method for producing CO by thermal catalysis is as follows: property Gas Shift Reaction After adding the catalyst, CO 2 , H 2 and N 2 were mixed at a flow rate ratio of 1:4:1 and aerated into a fixed bed reactor. The reaction was carried out continuously with the air flow rate of the mixed gas being 43200 mL h -1 g -1 in The reaction temperature is 300°C to 600°C, and the heating rate is 5°C / min, and the reaction temperature is 25°C to 30°C. The temperature is raised from 0℃ to 600℃. Description: Using the above conditions, CO 2 By producing CO through thermal catalysis of hydrogenation reaction, Reverse water produced property CO using gas shift reaction catalyst 2 can be effectively converted to CO 2 conversion This can improve efficiency and reduce costs, contributing to increased economic profits. The present invention has the following beneficial effects: (1) The present invention relates to a method for the reverse hydrolysis of a ruthenium-lanthanum bimetallic catalyst. property Gas shift reaction catalyst preparation A method was provided to effectively introduce La and Ru onto the surface of SBA-15 by stepwise impregnation, and the high Supported ruthenium-lanthanum bimetallic catalysts were prepared by the steps of calcination at high temperature and reduction at high temperature. La is a rare earth element and is used as a catalyst auxiliary to adjust the interaction between the metal and the support. It is used as a catalyst to affect the dispersion and valence of the active metals and to sinter the active metals at high temperatures. The supported ruthenium-lanthanum bimetallic catalyst of the present invention is capable of suppressing the formation of rings. The synergistic effect of Ru and La can suppress the serious aggregation phenomenon of Ru. (2) The present invention relates to a method for preventing reverse water flow. property The present invention provides a method for producing a ruthenium oxide-containing gas shift reaction catalyst. CO using a lanthanum-lanthanum bimetallic catalyst 2 High reaction activity and thermal catalyst for hydrogenation reaction It has excellent stability and can achieve both low CO and 100% CO selectivity. [Brief description of the drawings]

[0004]

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[0005] [Explanation of symbols] 1 sealed mixing bottle 11 Sealing cover 2. Arc-shaped electromagnet 21 Inclined guide groove 3 Motor 4 Stirring rods 5 Annular frame 51 Guide block 52 Support plate 6 Telescopic Rod 7. First airbag rod 8 Threaded Rod 81 Agitating blade 9. Second airbag rod 10 Water bottle DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] In order to better illustrate the advantages of the present invention, the following detailed description will be given with reference to specific embodiments. This will be explained in more detail. Example 1 backwater property The gas shift reaction catalyst is Ru 2 La 10 / SBA-15, The above reverse water property Gas shift reaction catalyst Ru 2 La 10 The method for preparing SBA-15 is as follows: S1, La(NO 3 ) 3 6H 2 After dissolving O in deionized water, SBA-15 was added and the mixture was sonicated. Mixture A was obtained by wave dispersion, where La(NO 3 ) 3 6H 2 Mass ratio of O to SBA-15 is 0.246:1, and the mass ratio of deionized water to SBA-15 is 50:1. and, S2: Mixture A was sealed and stirred for 3 h, then the seal was removed and the mixture was placed in a water bath at 80 °C with deionized water. The mixture was stirred continuously until all of the solvent was evaporated, and the dried material was obtained. The dried material was then placed in an oven. and drying the mixture at 80°C for 12 hours to obtain dried material A. S3: After drying, material A was roasted in a muffle furnace at 550°C for 6 hours. 10 / SBA-15 The temperature in the muffle furnace was increased from 25°C to 550°C at a rate of 5°C / min. and S4, 1 mg / g RuCl 3 3H 2 The LaO solution was dispersed in deionized water. 10 / SBA-15 was added and ultrasonically dispersed to obtain mixed solution B, in which RuCl 3 3H 2 O melt Liquid and La 10 The mass ratio of deionized water to SBA-15 was 20:1. The ratio of the amounts is 50:1. S5. Mixture B was sealed and stirred for 3 h, then the seal was removed and the mixture was placed in a water bath at 80°C to remove the deionized water. Stir continuously until all the water has evaporated to obtain a dried material, then place the dried material in an oven. and drying the mixture at 80°C for 12 hours to obtain dried material B. S6: After drying, material B is roasted in a muffle furnace at 550℃ for 6 hours, then cooled to 30℃ and heated. 2 The temperature in the muffle furnace was increased from 30°C to 600°C at a rate of 5°C / min under atmospheric conditions. Heat and reduce at 600℃ for 2 hours. property Gas shift reaction catalyst Ru 2 La 10 / SBA-1 and obtaining 5. Ru prepared by the stepwise impregnation method of Example 1 above 2 La 10 / SBA-15 Parallel experimental measurements were carried out, and the following comparative examples were carried out: 1) Comparative Example 1: This comparative example shows the preparation of Ru by the impregnation method. 2 / Describes the process of preparing SBA-15 death, 1mg / g RuCl 3 3H 2 The RuClO solution and SBA-15 were added to deionized water. 3 3H 2 The mass ratio of the O solution to SBA-15 was 20:1, and the mixture of deionized water and SBA-15 was The mass ratio was 50:1, and the mixture was dispersed ultrasonically to obtain a mixed solution. The mixed solution was then stirred for 3 h in a sealed state. The container was then unsealed and placed in a water bath at 80°C, with continuous stirring until all the water had evaporated. The mixture was stirred and placed in an oven to dry at 80°C for 12 hours to obtain a dried material. The dried material was then placed on a mat. The mixture was transferred to a furnace and roasted at 550℃ for 6 hours. 2 The temperature in the muffle furnace was increased to 5 The mixture was heated from 30°C to 600°C at a rate of 100°C / min, and reduced at 600°C for 2 hours. The temperature inside the muffle furnace is increased from 25°C to 550°C at a rate of 5°C / min. 2) Comparative Example 2: This comparative example shows the impregnation method using La 10 The process of preparing SBA-15 is described below. Posted, La(NO 3 ) 3 6H 2 O and SBA-15 were added to deionized water, and La(NO 3 ) 3 6H 2 The mass ratio of O to SBA-15 was 0.246:1, and the mass ratio of deionized water to SBA-15 was The ratio was 50:1, and the mixture was dispersed ultrasonically to obtain a mixed solution. The mixed solution was then stirred for 3 hours in a sealed container, and then The deionized water was then stirred continuously at 80°C in a water bath until all the water had evaporated. The dried material was then placed in a muffle furnace and dried at 80℃ for 12 hours to obtain the dried material. Roasted at 550℃ for 6 hours, and finally, 2 The temperature in the muffle furnace was increased at 5°C / min under atmospheric pressure. The mixture was heated from 30°C to 600°C at a rate of 100°C, and reduced at 600°C for 2 hours. The temperature inside is increased from 25°C to 550°C at a rate of 5°C / min. 3) Comparative Example 3: This comparative example shows the stepwise impregnation method for seq-Ru 2 La 10 / SBA-15 The process for preparing 1mg / g RuCl 3 3H 2 The RuClO solution and SBA-15 were added to deionized water. 3 3H 2 The mass ratio of the O solution to SBA-15 was 20:1, and the mixture of deionized water and SBA-15 was The mass ratio was 50:1, and the mixture was dispersed ultrasonically to obtain a mixed solution. The mixed solution was then stirred for 3 h in a sealed state. The container was then unsealed and placed in a water bath at 80°C, with continuous stirring until all the water had evaporated. The mixture was then placed in an oven and dried at 80°C for 12 hours to obtain the dried material. The dried material was then placed in a muffler. The mixture was transferred to a furnace and roasted at 550℃ for 6 hours. 2 / SBA-15 was obtained, La(NO 3 ) 3 6H 2 O and Ru 2 / SBA-15 was added to deionized water and La(NO 3 ) 3 6H 2 The mass ratio of O to SBA-15 was 0.246:1. The mass ratio of was 50:1, and the mixture was dispersed ultrasonically to obtain a mixed solution, which was then stirred for 3 h in a sealed state. After that, the container was unsealed and placed in a water bath at 80°C and stirred continuously until all the deionized water had evaporated. The mixture was stirred and placed in an oven to dry at 80°C for 12 hours to obtain a dried material. The dried material was then placed on a mat. The mixture was roasted in a furnace at 550℃ for 6 hours, and then heated in a H 2 The temperature in the muffle furnace was increased to 5°C / m The mixture was heated from 30°C to 600°C at a heating rate of 1000 rpm, and reduced at 600°C for 2 hours. The temperature in the full furnace was raised from 25°C to 550°C at a rate of 5°C / min. Backflow property Gas shift reaction catalyst seq-Ru 2 La 10 / SBA-15 can be obtained do. Ru prepared by impregnation method 2 / SBA-15, La 10 / SBA-15, stepwise impregnation method Prepared by Ru 2 La 10 / SBA-15 and seq-Ru 2 La 10 / SB The XRD pattern of A-15 is shown in Figure 1. The broad peak at around 23° is amorphous. It comes from Susilika. 2 / SBA-15 and Ru 2 La 10 About SBA-15 The characteristic peaks at 38.4, 42.2, 44.0 and 58.3° are due to Ru. , Ru 2 The signal of / SBA-15 is strong, which is due to the reverse hydrolysis. property The Ru content in the gas shift reaction catalyst is high. The latter peak intensity is significantly weaker, indicating that the nanoparticles are larger and have better crystallinity. This is because the addition of La contributes to dispersing Ru and suppressing its aggregation. 2 La 10 / SBA-15, the Ru diffraction signal becomes weaker, and the stepwise impregnation time "Ru," La" order, and the later impregnated La covers most of the Ru.10 / SBA- For SBA-15, the presence of peaks related to La was not clearly observed, indicating that La is highly dispersed in SBA -15. Ru / SBA-15 prepared by the impregnation method and 2 Ru / La / SBA-15 prepared by the stepwise impregnation method Ru 2 La 10 The TEM images of Ru / La / SBA-15 are shown in Fig. 2. For Ru / SBA-15, 2 on the surface, an aggregated structure exceeding 100 nm formed by the deposition of a large number of Ru nanoparticles was observed, indicating that after high-temperature treatment, Ru undergoes significant migration and aggregation on the surface of SBA-15. For Ru / La / SBA-15, a similar structure was not clearly observed, and the formed nanoparticles were dispersed on the surface of SBA-15 with a relatively uniform size, indicating that the addition of La has an effect of appropriately suppressing the aggregation of Ru. Ru 2 La 10 / SBA-15, a similar structure was not clearly observed, and the formed nanoparticles were dispersed on the surface of SBA-15 with a relatively uniform size, indicating that the addition of La has an effect of appropriately suppressing the aggregation of Ru. For Ru / SBA-15 prepared by the impregnation method and Ru / La / SBA-15 prepared by the stepwise impregnation method, the XPS spectra in the Ru 3p region and the table of the relative content of Ru valence 2 are shown in Fig. 3 and Table 1 below, respectively. The peaks at 461 and 483 V in Fig. 3 Ru 2 La 10 / SBA-15 belong to zero-valent Ru, and the peaks at 463 and 485 eV belong to positively charged Ru(n+ , 0 < n < 2), and the peak areas symbolize the relative content of Ru with different valences. As can be seen from Fig. 3, compared with Ru / SBA-15, Ru / La / SBA-15 has more Ru species, indicating that between ruthenium-lanthanum bimetals, from Ru As can be seen from Fig. 3, compared with Ru / SBA-15, Ru / La / SBA-15 2 has more Ru species, indicating that between ruthenium-lanthanum bimetals, from Ru 2 La 10 / SBA-15 has more Ru n+ species, indicating that between ruthenium-lanthanum bimetals, from Ru This suggests that there is an electron transfer to La. 2 / Ru in SBA-15 n+ Seed Pi The peak is due to the oxidation of some of the Ru by air. Table 1. Relative content of Ru valence TIFF2025021375000022.tif52144

[0007] Example 2 Reverse water prepared in Example 1 property Depending on the application of the gas shift reaction catalyst, property Gas shift reaction catalyst CO 2 It is used to produce CO by thermally catalyzing hydrogenation reactions, and reverse hydrogenation is performed before the reaction. property Gas shift The reaction catalyst is H 2 The mixture was reduced under atmospheric pressure for 1 h, where H 2 The flow rate is 30 mL / min. , the temperature is 600°C, Here, reverse water property Gas shift reaction catalyst CO 2 Produce CO by thermally catalyzing hydrogenation reactions The method comprises adding 50 mg of said backflow liquor to a fixed bed reactor. property After adding the gas shift catalyst, CO 2 , H 2 and N 2 The mixture was mixed at a flow rate ratio of 1:4:1 and reacted continuously in a fixed bed reactor by aeration. Here, the air flow rate of the mixed gas is 43200 mL h -1 g -1 The reaction temperature is 600°C. The temperature is increased from 25°C to 600°C at a rate of 5°C / min. Reverse water prepared in Example 1 and Comparative Examples 1 to 3 property Example 2: Using a gas shift reaction catalyst CO 2 The hydrogenation reaction was thermally catalyzed to produce CO. The catalyst dosage was 50 mg for all reactions. After the temperature reached 300°C, the data was recorded after stabilizing for 1 h at 50°C intervals. The results of the reaction are shown in Figure 4 and Table 2 below: Table 2 CO for each catalyst at 600℃ 2 Thermal catalytic results of hydrogenation reactions TIFF2025021375000023.tif53148 Comparing Example 1 and Comparative Examples 2 and 3, Ru 2 La 10 / SBA-15, La 10 / SBA-15 and seq-Ru 2 La 10 / All SBA-15 have 100% CO selectivity The presence of La promotes the desorption of CO, resulting in high selectivity. 2 La 10 / SBA-15 has the highest CO 2 Has a conversion rate. Comparing the Example and Comparative Example 1, Ru 2 Although SBA-15 has high catalytic activity, However, it has low selectivity for CO and generates by-products, so it cannot meet the demand. In summary, Ru 2 La 10 / SBA-15 has high CO 2 Conversion rate and 100% CO selection The reverse water gas shift reaction is ideal for simultaneously satisfying two major requirements: This is because the presence of La suppresses the aggregation of Ru and reduces the particle size. The appropriate particle size contributes to the formation of large Ru nanoparticles, and the exposed Ru active sites are Ito is CO 2 contributes to the activation of CO 2 Under the assumption of conversion rate, 100% CO Selectivity was achieved. At the same time, Ru 2 La 10To further measure the stability of the SBA-15 catalyst , Ru 2 La 10 / CO of Example 2 using SBA-15 catalyst 2 Hydrogenation reaction stability measurement The catalyst dosage was 50 mg, the reaction temperature was 600 °C, and the reaction conditions were fixed for 32 The reaction was continued for 1 h, and data was recorded every 1 h. The results of the stability measurement are shown in Figure 5 and below. As shown in Table 3: Table 3. CO at 600℃ 2 Results of thermal catalyst stability measurements for hydrogenation reactions TIFF2025021375000024.tif34145 As can be seen from the results in Table 3, Ru 2 La 10 / SBA-15 catalyst was reacted continuously for 32 hours After that, CO 2 The conversion rate remained stable at about 52%, and the CO selectivity decreased from 100% to 98.8%. It has slightly decreased to 5%. 2 La 10 / SBA-15 has good stability under high temperature conditions It was shown that there is interaction and electron transfer between Ru and La, which effectively stabilizes the active ingredient. The sintering and aggregation of Ru can be suppressed. Example 3 This embodiment differs from the first embodiment in the following respects: property The gas shift reaction catalyst is Ru 2 La 5 / S BA-15, where La(NO 3 ) 3 6H 2 The mass ratio of O to SBA-15 is 0.1 The mass ratio of deionized water to SBA-15 is 50:1. Example 4 This embodiment differs from the first embodiment in the following respects: property The gas shift reaction catalyst is Ru 2 La 15 / SBA-15, where La(NO 3 ) 3 6H 2 The mass ratio of O to SBA-15 is 0. 372:1 and the mass ratio of deionized water to SBA-15 is 50:1. The reversed water prepared in Examples 3 and 4 above property Gas shift reaction catalyst and the reverse hydrochloric acid catalyst prepared in Example 1 property gas The shift reaction catalyst was 2 It is used in the reaction to produce CO by thermally catalyzing hydrogenation. backwater property The amount of catalyst used in the gas shift reaction was 50 mg for all the reactions. The results of the catalytic reactions are shown in Figure 6 and the following. As shown in Table 4 below: Table 4. CO at 600℃ for each catalyst 2 Hydrogenation reaction thermal catalyst results TIFF2025021375000025.tif40152 As can be seen from the results in Table 4, the different ratios of Ru, La supported on SBA-15 CO 2 It has some effect on the conversion rate of the hydrogenation reaction. property CO by gas shift reaction catalyst 2 The conversion rate first increases and then decreases. In Examples 1, 3 and 4, Ru 2 La 10 / SBA-15 has the highest CO 2 touch It exhibits catalytic activity and has 100% CO selectivity. Ru 2 La 5 / SBA-15, Ru 2 La 10 / SBA-15 and Ru 2 La 15 / S As for BA-15, as can be seen from the XRD measurement results in Figure 1, the increase in La content As the La content increases, the intensity of the diffraction peaks related to Ru gradually decreases. The diffraction peak intensity is smaller, and the Ru nanoparticles are more dispersed. Ru 2 La 5 / SBA-15, Ru 2 La 10 / SBA-15 and Ru 2 La 15 / S As for BA-15, as can be seen from the XRD measurement results in Figure 1 and Table 5 below, La The addition of affects the relative content of Ru valence, and there is an electron transfer between the two elements. With increasing La content, Ru n+ The relative content of increases, promoting the desorption of CO. Move forward. Table 5. Results of relative Ru valence content TIFF2025021375000026.tif46156 Example 5 This embodiment differs from Example 1 in the following respects: SBA-15 is magnetic SBA-15, and magnetic The method for preparing SBA-15 is to add 2 g of ferrous chloride to 50 mL of water at 48°C under light-shielded conditions. 2.7 g of P123 was added and mixed uniformly to obtain a mixed solution, and 5.5 g of TE OS and 30 mL of water at 35°C were mixed uniformly and quickly added to the mixture, then stirred for 16 h. The reaction product was then transferred to a polytetrafluoroethylene reactor and heated in water at 100°C for 48 hours. After heating, cooling, filtering and drying, the mixture was placed in a muffle furnace and roasted at 550℃ for 6 hours. to obtain magnetic SBA-15, Mixed solution A or mixed solution B is placed in a sealed environment, and mixed solution A or mixed solution B is stirred for a sealed stirring period. A magnetic field of 1.2 T is applied to liquid B. 。

[0008] Example 7 In this embodiment, the sealed mixing bottle 1 of the sixth embodiment will be described. Specifically, as shown in FIGS. As shown in FIG. 1, the arc-shaped electromagnet 2 is slidably attached to the inner wall of the sealed stirring bottle 1, and two arc-shaped The electromagnets 2 are connected by a connecting rod, and a sealed cover 11 is provided on the top of the sealed stirring bottle 1. The motor 3 is embedded in the sealed cover 11, and the stirring rod 4 is attached to the bottom of the sealed stirring bottle 1. The output shaft of the motor 3 is fixedly connected to a connecting rod and a stirring rod 4. An annular frame 5 is further provided in the sealed stirring bin 1, and the bottom surface of the annular frame 5 is a sealed stirring bin. It is connected to the inner bottom surface of the bin 1 via a plurality of telescopic rods 6 and a first airbag rod 7, An inclined guide groove 21 is provided on the side surface of the arc-shaped electromagnet 2, and an inclined A guide block 51 is provided which is slidably connected to the guide groove 21. Nine support plates 52 are provided on the inner annular surface of the annular frame 5, and nine support plates 52 are provided on the inner bottom surface of the sealed mixing bin 1. The screw rod 8 is screwed into a screw hole provided in the support plate 52. A stirring blade 81 is connected to the upper end of the screw rod 8 via a second air bag rod 9. The second airbag rod 9 penetrates the threaded rod 8 through a pipe, and the first airbag Connected with Grod 7, A water injection bottle 10 is provided in the sealed stirring bottle 1 for heating mixed solution A or mixed solution B in a water bath. The outer wall of the upper end of the sealed mixing bottle 1 is fitted with an annular tank on the inner wall of the upper end of the water pouring bottle 10. A matching ring is provided, and a commercially available heating plate and a commercially available water heater are provided in the water filling bottle 10 to control the water temperature. The sealed stirring bottle 1 is made of a thermally conductive material, specifically a commercially available polycrystalline diamond. The electromagnet 2 is made of PCD ceramic and is fitted to the inner wall of the sealed mixing bin 1. Select a commercially available product that matches your needs. The method of using the above-mentioned agitation sealed bottle 1 is as follows: Open the sealed cover 11, pour mixed solution A or mixed solution B into the sealed mixing bottle 1, and then The bar 11 is closed, the motor 3 is started, and the motor 3 operates at a preset oscillation frequency of 30 s / cycle. The two arc-shaped electromagnets 2 are controlled to oscillate with an amplitude of 130°, and the arc-shaped electromagnets 2 are excited. The magnetic field strength of the arc-shaped electromagnet 2 is controlled to 1.2 T by moving the motor 3, and the stirring rod 4 is rotated. Driven to achieve stage mixing action, During the oscillation process of the arc-shaped electromagnet 2, the inclined guide groove 21 and the guide block 5 on the annular frame 5 The synergistic action of the two components causes the annular frame 5 to reciprocate up and down. During the movement process, the first air bag rod 7 is continuously compressed so that the gas flows into the second air bag rod 7. 9 periodically, and the stirring blade 81 is moved up and down. During this time, the screw of the support plate 52 The screw rod 8 is rotated through the hole, and the annular frame 5 is rotated by two arc-shaped electromagnets 2. It exerts a step-mixing effect, improving the mixing effect of mixed solution A or mixed solution B, After the sealing and mixing is completed, the sealing cover 11 is opened, 80°C water is poured into the water injection bottle 10, and the mixture is heated. The plate is started, and the water temperature is controlled to 80°C. During this time, the stirring rod 4 is stirred in one stage, and the ring frame is The deionized water is stirred continuously in two stages until all the water has evaporated, then the mixture is placed in a sealed agitator. Remove the dried material from mixing bin 1.

[0009] Example 8 This embodiment differs from the sixth embodiment in the following respects: A magnetic field is generated using arc-shaped electromagnets 2 that are distributed symmetrically around the center, and arc-shaped electromagnets 2 A magnetic field was applied at an oscillation frequency of 20 s / cycle using the arc-shaped electromagnet 2, and the magnetic field strength of the arc-shaped electromagnet 2 was 0.5 T. It is. Example 9 This embodiment differs from the sixth embodiment in the following respects: A magnetic field is generated using arc-shaped electromagnets 2 that are distributed symmetrically around the center. The magnetic field was applied at an oscillation frequency of 40 s / cycle using the arc-shaped electromagnet 2, and the magnetic field strength of the arc-shaped electromagnet 2 was 1.5 T. be. Example 10 This embodiment differs from the sixth embodiment in the following respects: A magnetic field is generated using arc-shaped electromagnets 2 that are distributed symmetrically around the center. A magnetic field was applied at an oscillation frequency of 30 s / cycle using the two arc-shaped electromagnets 2. is 140°. Example 11 This embodiment differs from the sixth embodiment in the following respects: A magnetic field is generated using arc-shaped electromagnets 2 that are distributed symmetrically around the center. A magnetic field was applied at an oscillation frequency of 30 s / cycle using the two arc-shaped electromagnets 2. is 120°. The reversed water prepared in Examples 8, 9, 10, and 11 above property Gas shift reaction catalyst and the catalyst prepared in Example 6 Reverse water property The gas shift reaction catalyst was 2 Reaction to produce CO by thermally catalyzing hydrogenation Used for backflow prevention property The amount of catalyst used in the gas shift reaction was 50 mg. The results of the catalytic reaction were as follows: As shown in Table 7 below: Table 7. Thermal catalyst CO at 600℃ for each catalyst 2 Hydrogenation reaction results TIFF2025021375000027.tif53155 As can be seen from the results in Table 7, the magnetic SBA-15, Ru, and La were sealed, stirred, and dried. Inverted water prepared by drying propertyThe gas shift reaction catalyst is CO 2 To some extent, the conversion rate of the hydrogenation reaction The oscillation frequency and magnetic field strength of the arc-shaped electromagnet or the arc length of the arc-shaped electromagnet are affected. If you change it, the water will flow backwards. property CO by gas shift reaction catalyst 2 The trend of conversion rates decreasing In Examples 6, 8, 9, 10 and 11, the reverse water property Gas shift reaction catalyst Highest CO 2 It exhibits catalytic activity and has 100% CO selectivity.

Claims

1. S1, La (NO ３ ) ３ ・6H ２ After dissolving O in deionized water, SBA-15 was added and deionized. The mass ratio of water to SBA-15 was 50:1, and the mixture was dispersed ultrasonically to obtain mixed solution A. Top and S2: sealing the mixed solution A, stirring and drying the mixed solution A to obtain a dried material A; S3: The dried material A was roasted in a muffle furnace at 550 ° C for 6 h, and La ｙ / SBA-15 obtained , where the values ​​of y are 5, 10, and 15. When y=5, La(NO ３ ) ３ ・6H ２ O and The mass ratio of SBA-15 is 0.124:1, and when y = 10, La(NO ３ ) ３ ・6H ２ The mass ratio of O to SBA-15 is 0.246:1, and when y = 15, La(NO ３ ) ３ ・6H ２ a mass ratio of O to SBA-15 of 0.372:1; S4, 1 mg / g RuCl ３ ・3H ２ The LaO solution was dispersed in deionized water. ｙ / S BA-15 was added and ultrasonically dispersed to obtain mixed solution B, in which RuCl ３ ・3H ２ O solution and La ｙ The mass ratio of deionized water to SBA-15 was 20:

1. is 50:1; S5: sealing the mixed solution B, stirring and drying the mixed solution B to obtain a dried material B; 、 S6: After drying, material B is roasted in a muffle furnace at 550 °C for 6 h, and then ２ Atmosphere: 600 The reaction mixture was reduced at 2°C for 2 hours to form the reverse water gas shift reaction catalyst Ru. ２ La ｙ / SBA-15, where y wherein the value of is 5, 10, or 15. Method for preparing the medium.

2. In steps S3 and S6, the temperature in the muffle furnace is increased by 5° C. / min.

2. The method according to claim 1, wherein the temperature is increased from 25° C. to 500° C. at a rate of n. Preparation method.

3. The method of the sealed stirring and drying treatment is to seal and stir mixed solution A or mixed solution B for 3 hours, The container was opened, and the container was continuously stirred in a water bath at 80°C until all the deionized water had evaporated, and then dried. After obtaining the dried material, the dried material was placed in an oven and dried at 80°C for 12 hours.

2. The method according to claim 1, characterized in that the method is to obtain material A or material B.

4. The SBA-15 is a magnetic SBA-15, and mixed solution A or mixed solution B is placed in a sealed environment. Then, during the sealed stirring period, a magnetic field of 0.5 to 1.5 T was applied to mixed solution A or mixed solution B. The method according to claim 3, further comprising applying

5. A use of the reverse water gas shift reaction catalyst prepared by the preparation method according to claim 1, comprising: Using the reverse water gas shift reaction catalyst, ２ Hydrogenation reaction is thermally catalyzed to produce CO, and before the reaction The reverse water gas shift reaction catalyst is ２ The mixture was reduced under atmospheric pressure for 1 h, where H ２ The flow rate is 30 mL / min and the temperature is 600°C.

6. The reverse water gas shift reaction catalyst is used to ２ Method for producing CO by thermal catalysis of hydrogenation reaction After adding 50 mg of the reverse water gas shift catalyst to a fixed bed reactor, ２ , H ２ and N ２ are mixed at a flow rate ratio of 1:4:1 and reacted continuously in a fixed bed reactor by aeration, wherein: The air flow rate of the mixed gas is 43,200 mL h －１ g －１ The reaction temperature is 300° C. to 60° C. 0°C, and the temperature is increased from 25°C to 300°C to 600°C at a rate of 5°C / min. The use according to claim 5, characterized in that

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