Copper-iron supported catalysts for water-gas shift reaction and their preparation method

Abstract

This invention discloses a copper-iron supported catalyst for hydrogen production via water-gas shift reaction and its preparation method. The catalyst is a Cu-Fe bimetallic catalyst prepared using SBA-15 with a high specific surface area as the support, Cu as the active component, and Fe as a promoter. In this catalyst, the Cu metal particles are small in size and uniformly dispersed on the surface of the SBA-15 support. Simultaneously, a strong synergistic effect is formed between Cu and Fe, thus exhibiting excellent water-gas shift reaction activity even with a low Cu loading.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation and heterogeneous catalysis, specifically relating to a Cu-Fe supported catalyst for water-gas shift reaction and its preparation method. Background Technology

[0002] In recent years, rapid socio-economic development has led to a surge in energy demand, with clean and efficient hydrogen resources considered one of the future alternative energy sources. Currently, hydrogen production from petrochemical resources is the main way to meet people's hydrogen energy needs. Among these, the water-gas shift (WGS, CO + H2O ⇌ CO2 + H2) reaction plays a crucial role in hydrogen production. This reaction utilizes inexpensive water vapor to significantly reduce CO concentration, resulting in substantial economic benefits.

[0003] Highly efficient water-gas shift catalysts need to meet two conditions simultaneously: (1) excellent ability to dissociate and adsorb H2O; (2) good ability to adsorb and activate CO. Cu is almost the only metal element that can simultaneously adsorb and activate H2O and CO. Compared with precious metals such as Pt and Au, Cu is abundant, inexpensive and readily available, so copper-based catalysts are still favored by researchers. Chinese patent CN 202310321951.8 discloses a method for preparing spinel-type composite oxide precursors by introducing element Al to modify CuFe2O4 by B-site doping. This method promotes the synergistic effect between metal and support in the reduction product and shows good catalytic performance in the range of 240-320 °C, but its performance is poor at low temperature (200 °C) (CO conversion rate 24.7%). Chinese patent CN 202011336250.4 discloses a method for supporting Pt-based water-gas shift reaction catalysts using α-MoC as a support. The prepared catalyst exhibits high performance in the low-temperature range, but the metal loading on the support is uneven, and the use of precious metals increases catalytic costs. Therefore, current water-gas shift catalysts mostly employ high-activity metal loadings or use precious metals as the active metal, resulting in high economic costs. Thus, researching and developing low-loading, high-performance Cu catalysts is of great significance. Summary of the Invention

[0004] To address the problem that current low-load Cu-based catalysts do not have sufficient activity, this invention selects SBA-15 with a high specific surface area as a support, uses adsorption to load active metal Cu, and introduces Fe as a promoter for modification, thereby developing a low-Cu-load, high-performance water-gas shift reaction catalyst.

[0005] To achieve the above objectives, the present invention employs the following technical steps: A copper-iron supported catalyst for water-gas shift reaction is composed of Cu as the active component, Fe as the promoter, and SBA-15 as the support.

[0006] Furthermore, in the catalyst, the proportion of active component Cu is 4-10 wt.%, and the molar ratio of auxiliary agent Fe to active component Cu is 0.2-0.4:1.

[0007] The preparation method of the copper-iron supported catalyst includes the following steps: (1) Preparation of the carrier: The surfactant was dissolved in water, acid medium was added and heated and stirred for 1 hour, then silicon precursor was added, stirred evenly and aged, and then hydrothermally heated, washed, dried and calcined to obtain SBA-15 as the carrier. (2) Carrier functionalization: (3-aminopropyl)triethoxysilane (APTES) was mixed with anhydrous ethanol, and then SBA-15 obtained in step (1) was added. After heating and reflux, washing and drying, functionalized SBA-15 was obtained. (3) Metal loading: The functionalized SBA-15 prepared in step (2) is impregnated with a mixed solution of copper salt and iron salt in equal volume, and then dried, ground and calcined to obtain CuFe / SBA-15 catalyst precursor; (4) The CuFe / SBA-15 precursor obtained in step (3) is reduced to obtain the copper-iron supported catalyst.

[0008] Furthermore, the mass ratio of surfactant, silicon precursor and acid medium used in step (1) is 1:(2-3):(25-35).

[0009] Further, the surfactant mentioned in step (1) is one or more of P123, P103, and F127.

[0010] Further, the acid medium mentioned in step (1) is one or more of hydrochloric acid, nitric acid, and sulfuric acid.

[0011] Furthermore, the silicon precursor mentioned in step (1) is one or more of silica sol, tetramethoxysilane, and tetraethyl orthosilicate. Furthermore, the aging temperature in step (1) is 35 °C and the time is 20-26 h.

[0012] Furthermore, the hydrothermal temperature in step (1) is 100 °C and the time is 24 h.

[0013] Furthermore, the calcination described in step (1) is carried out under static air, with the temperature increased to 500-600 ℃ at a rate of 1-2 ℃ / min and held for 4-8 hours.

[0014] Furthermore, the mass ratio of SBA-15, (3-aminopropyl)triethoxysilane and anhydrous ethanol used in step (2) is 1:(1.5-2):(30-40).

[0015] Furthermore, the temperature of the heating reflux in step (2) is 80-110 °C, and the time is 24 h.

[0016] Furthermore, the drying temperature in step (2) is 60 °C and the time is 12 h.

[0017] Furthermore, the copper salt mentioned in step (3) includes one or more of copper nitrate, copper acetate, copper chloride, and copper sulfate.

[0018] Furthermore, the iron salt mentioned in step (3) includes one or more of ferric nitrate, ferric chloride, and ferric sulfate.

[0019] Furthermore, the time for immersion in equal volume as described in step (3) is 4-6 h.

[0020] Furthermore, the calcination described in step (3) is carried out by heating to 350-500°C at a rate of 2°C / min under static air and holding for 4 h.

[0021] Furthermore, the reduction described in step (4) is carried out in an atmosphere of 5 vol.% H2 / N2 at 300-400 °C for 2-4 hours.

[0022] The present invention has the following advantages: This invention provides a Cu-based water-gas shift catalyst with Fe as an auxiliary agent. It selects SBA-15, an ordered mesoporous silica material with a large specific surface area and good thermal stability, as a support. A silane coupling agent (APTES, H2N(CH2)3Si(OC2H5)3) is introduced and reacts with the hydroxyl groups (-OH) on the surface of SBA-15 through dehydration condensation to generate a functionalized SBA-15 with -NH2 groups. Subsequently, Cu... 2+ It binds to the amino group on SBA-15, making Cu 2+ Anchoring Cu particles to the SiO2 surface promotes dispersion and stability, thereby improving catalyst activity and stability. Simultaneously, the co-impregnation of Cu and Fe metal ions using an equal-volume impregnation method allows for the adjustment of the valence state of Cu species on the catalyst surface due to the synergistic effect between Cu and Fe. + Increasing the proportion of CO increases the adsorption sites on the catalyst, thereby promoting the conversion reaction and further improving the reaction performance. Attached Figure Description

[0023] Figure 1The small-angle XRD patterns of the SBA-15 support prepared in Example 1 and the catalyst precursors obtained in Examples 1-4 are shown. As can be seen from the figures, characteristic diffraction peaks (0.9°, 1.6°, 1.8°) belonging to the ordered mesoporous structure were observed in all samples; and the characteristic small-angle XRD peaks of SBA-15 were always present with the change of metal loading, indicating that the loading of metal on the support surface did not destroy the structure of the SBA-15 support.

[0024] Figure 2 The figures show the XRD patterns of the catalysts obtained in the reduced state in Examples 1-4. As can be seen from the figures, the catalyst obtained in Example 3 showed a weaker Cu diffraction peak at a diffraction angle of 43.3° than that in Examples 1, 2, and 4, indicating that the Cu particles in the catalyst were smaller and more uniformly dispersed in the silicon support.

[0025] Figure 3 The figures show the Cu Auger electron spectra of the catalyst precursors obtained in Examples 1 and 3. As can be seen from the figures, the introduction of Fe increases the Cu content in the catalyst. + With Cu 0 The proportion of Cu changes. 0 The proportion increased from 43.1% (Example 1) to 57.0% (Example 3). At a low vapor-to-gas ratio of 1, the dissociation of water was crucial for the reaction. Cu 0 The increase of [something] can promote the dissociation of water and enhance the activity of the water-gas shift reaction.

[0026] Figure 4 The graph shows a comparison of the activities of catalysts (a) obtained in Examples 1-4 and catalysts (b) obtained in Examples 3 and Comparative Examples 1-4. As can be seen from the graph, among the catalysts further prepared using the catalytic precursors prepared in the examples, the catalyst obtained in Example 3 has the highest catalytic activity. Detailed Implementation

[0027] A copper-iron supported catalyst for water-gas shift reaction is prepared by the following steps: (1) Preparation of the carrier: The surfactant was dissolved in water, and after adding the acid medium, it was heated and stirred for 1 hour. Then the silicon precursor was added, and after stirring evenly, it was aged at 35 °C for 20-26 hours. Then it was hydrothermally heated at 100 °C for 24 hours, washed, dried, and calcined at 500-600 °C at a rate of 1-2 °C / min under static air for 4-8 hours to obtain SBA-15 as the carrier. The mass ratio of the surfactant, silicon precursor and acid medium used was 1:(2-3):(25-35). (2) Carrier functionalization: (3-aminopropyl)triethoxysilane (APTES) was mixed with anhydrous ethanol, and then SBA-15 obtained in step (1) was added. The mixture was heated under reflux at 80-110 °C for 24 h, washed, and dried at 60 °C for 12 h to obtain functionalized SBA-15. The mass ratio of SBA-15, APTES and anhydrous ethanol used was 1:(1.5-2):(30-40). (3) Metal loading: Fe was added to the functionalized SBA-15 prepared in step (2). 3+ Cu 2+ A mixed solution of iron and copper with a molar ratio of 0.2-0.4 was impregnated in equal volumes for 4-6 h, dried, ground, and then heated to 350-500 ℃ at a rate of 2 ℃ / min under static air and calcined for 4 h to obtain the CuFe / SBA-15 catalyst precursor. (4) The CuFe / SBA-15 precursor obtained in step (3) is reduced at 300-400 °C for 2-4 h in an atmosphere of 5 vol.% H2 / N2 to obtain an iron-supported catalyst, wherein the proportion of Cu in the catalyst is 4-10 wt.%.

[0028] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.

[0029] Example 1 Weigh 8 g of P123 and dissolve it in 60 ml of water. Stir thoroughly at 35 °C until completely dissolved. Then add 240 mL of 2M HCl solution and stir for 1 h. Add 17 g of TEOS and age for 24 h. Transfer to a hydrothermal reactor and hydrothermally heat at 100 °C for 24 h. Wash several times with water and ethanol alternately, dry at 60 °C overnight, and then calcine at 500 °C for 6 h in a muffle furnace (heating rate 1.5 °C / min) to obtain the SBA-15 carrier.

[0030] Weigh 8.3 g APTES and dissolve it in 170 mL of anhydrous ethanol. Add 5 g SBA-15 and reflux at 80 °C for 24 h. Then wash with ethanol and dry at 60 °C overnight to obtain functionalized SBA-15.

[0031] 0.00252 mol Cu(NO3)2·3H2O was dissolved in 8 mL of water, and 3 g of functionalized SBA-15 was added. The mixture was sonicated for 1 h to disperse it evenly, then allowed to stand for 4 h. After that, it was dried at 60 ℃ overnight, then lightly ground, and finally calcined in a muffle furnace at 350 ℃ for 4 h (heating rate 2 ℃ / min) to obtain the Cu / SBA-15 catalyst precursor, in which the Cu content was 5 wt%.

[0032] Example 2 Weigh 8 g of P123 and dissolve it in 60 ml of water. Stir thoroughly at 35 °C until completely dissolved. Then add 240 mL of 2M HCl solution and stir for 1 h. Add 17 g of TEOS and age for 24 h. Transfer to a hydrothermal reactor and hydrothermally heat at 100 °C for 24 h. Wash several times with water and ethanol alternately, dry at 60 °C overnight, and then calcine at 500 °C for 6 h in a muffle furnace (heating rate 1.5 °C / min) to obtain the SBA-15 carrier.

[0033] Weigh 8.3 g APTES and dissolve it in 170 mL of anhydrous ethanol. Add 5 g SBA-15 and reflux at 80 °C for 24 h. Then wash with ethanol and dry at 60 °C overnight to obtain functionalized SBA-15.

[0034] 0.00252 mol Cu(NO3)2·3H2O and 0.000504 mol Fe(NO3)3·9H2O were weighed and dissolved in 8 mL of water. 3 g of functionalized SBA-15 was added, and the mixture was ultrasonicated for 1 h to disperse it evenly. After standing for 4 h, it was dried at 60 °C overnight. Following slight grinding, it was calcined in a muffle furnace at 350 °C for 4 h (heating rate 2 °C / min) to obtain CuFe. 0.2 / SBA-15 catalyst precursor, wherein the Cu content is 5 wt% and Fe / Cu=0.2.

[0035] Example 3 Weigh 8 g of P123 and dissolve it in 60 ml of water. Stir thoroughly at 35 °C until completely dissolved. Then add 240 mL of 2M HCl solution and stir for 1 h. Add 17 g of TEOS and age for 24 h. Transfer to a hydrothermal reactor and hydrothermally heat at 100 °C for 24 h. Wash several times with water and ethanol alternately, dry at 60 °C overnight, and then calcine at 500 °C for 6 h in a muffle furnace (heating rate 1.5 °C / min) to obtain the SBA-15 carrier.

[0036] Weigh 8.3 g APTES and dissolve it in 170 mL of anhydrous ethanol. Add 5 g SBA-15 and reflux at 80 °C for 24 h. Then wash with ethanol and dry at 60 °C overnight to obtain functionalized SBA-15.

[0037] 0.00252 mol Cu(NO3)2·3H2O and 0.000756 mol Fe(NO3)3·9H2O were weighed and dissolved in 8 mL of water. 3 g of functionalized SBA-15 was added, and the mixture was ultrasonically dispersed for 1 h. After standing for 4 h, it was dried at 60 °C overnight. Following slight grinding, it was calcined in a muffle furnace at 350 °C for 4 h (heating rate 2 °C / min) to obtain CuFe. 0.3 / SBA-15 catalyst precursor, wherein the Cu content is 5 wt% and Fe / Cu=0.3.

[0038] Example 4 Weigh 8 g of P123 and dissolve it in 60 ml of water. Stir thoroughly at 35 °C until completely dissolved. Then add 240 mL of 2M HCl solution and stir for 1 h. Add 17 g of TEOS and age for 24 h. Transfer to a hydrothermal reactor and hydrothermally heat at 100 °C for 24 h. Wash several times with water and ethanol alternately, dry at 60 °C overnight, and then calcine at 500 °C for 6 h in a muffle furnace (heating rate 1.5 °C / min) to obtain the SBA-15 carrier.

[0039] Weigh 8.3 g APTES and dissolve it in 170 mL of anhydrous ethanol. Add 5 g SBA-15 and reflux at 80 °C for 24 h. Then wash with ethanol and dry at 60 °C overnight to obtain functionalized SBA-15.

[0040] 0.00252 mol Cu(NO3)2·3H2O and 0.001008 mol Fe(NO3)3·9H2O were weighed and dissolved in 8 mL of water. 3 g of functionalized SBA-15 was added, and the mixture was ultrasonicated for 1 h to disperse it evenly. After standing for 4 h, it was dried at 60 °C overnight. Following slight grinding, it was calcined in a muffle furnace at 350 °C for 4 h (heating rate 2 °C / min) to obtain CuFe. 0.4 / SBA-15 catalyst precursor, wherein the Cu content is 5 wt% and Fe / Cu=0.2.

[0041] Comparative Example 1 Weigh 8 g of P123 and dissolve it in 60 ml of water. Stir thoroughly at 35 °C until completely dissolved. Then add 240 mL of 2M HCl solution and stir for 1 h. Add 17 g of TEOS and age for 24 h. Transfer to a hydrothermal reactor and hydrothermally heat at 100 °C for 24 h. Wash several times with water and ethanol alternately, dry at 60 °C overnight, and then calcine at 500 °C for 6 h in a muffle furnace (heating rate 1.5 °C / min) to obtain the SBA-15 carrier.

[0042] Weigh out 0.00252 mol Cu(NO3)2·3H2O and 0.000756 mol Fe(NO3)3·9H2O, dissolve them in 8 mL of water, add 3 g SBA-15, sonicate for 1 h to disperse evenly, let stand for 4 h, then dry at 60 ℃ overnight, then lightly grind, and calcine in a muffle furnace at 350 ℃ for 4 h (heating rate 2 ℃ / min) to obtain CuFe. 0.3 / SBA-15-no catalyst precursor.

[0043] Comparative Example 2 Weigh 8 g of P123 and dissolve it in 60 ml of water. Stir thoroughly at 35 °C until completely dissolved. Then add 240 mL of 2M HCl solution and stir for 1 h. Add 17 g of TEOS and age for 24 h. Transfer to a hydrothermal reactor and hydrothermally heat at 100 °C for 24 h. Wash several times with water and ethanol alternately, dry at 60 °C overnight, and then calcine at 500 °C for 6 h in a muffle furnace (heating rate 1.5 °C / min) to obtain the SBA-15 carrier.

[0044] Weigh 8.3 g APTES and dissolve it in 170 mL of anhydrous ethanol. Add 5 g SBA-15 and reflux at 80 °C for 24 h. Then wash with ethanol and dry at 60 °C overnight to obtain functionalized SBA-15.

[0045] 0.00252 mol Cu(NO3)2·3H2O was dissolved in 8 mL of water, and 3 g of functionalized SBA-15 was added. The mixture was sonicated for 1 h to ensure uniform dispersion, then allowed to stand for 4 h, followed by drying at 60 ℃ overnight. Next, 0.001008 mol Fe(NO3)3·9H2O was dissolved in 8 mL of water and added to the dried sample. The mixture was sonicated for 1 h, allowed to stand for 4 h, then dried at 60 ℃ overnight. After slight grinding, the sample was calcined in a muffle furnace at 350 ℃ for 4 h (heating rate 2 ℃ / min) to obtain Fe. 0.3 -Cu / SBA-15 catalyst precursor.

[0046] Comparative Example 3 Weigh 8 g of P123 and dissolve it in 60 ml of water. Stir thoroughly at 35 °C until completely dissolved. Then add 240 mL of 2M HCl solution and stir for 1 h. Add 17 g of TEOS and age for 24 h. Transfer to a hydrothermal reactor and hydrothermally heat at 100 °C for 24 h. Wash several times with water and ethanol alternately, dry at 60 °C overnight, and then calcine at 500 °C for 6 h in a muffle furnace (heating rate 1.5 °C / min) to obtain the SBA-15 carrier.

[0047] Weigh 8.3 g APTES and dissolve it in 170 mL of anhydrous ethanol. Add 5 g SBA-15 and reflux at 80 °C for 24 h. Then wash with ethanol and dry at 60 °C overnight to obtain functionalized SBA-15.

[0048] 0.001008 mol Fe(NO3)3·9H2O was dissolved in 8 mL of water, and 3 g of functionalized SBA-15 was added. The mixture was sonicated for 1 h to disperse it evenly, then allowed to stand for 4 h, followed by drying at 60 ℃ overnight. Next, 0.00252 mol Cu(NO3)2·3H2O was dissolved in 8 mL of water and added to the dried sample. The mixture was sonicated for 1 h, allowed to stand for 4 h, then dried at 60 ℃ overnight. After slight grinding, the sample was calcined in a muffle furnace at 350 ℃ for 4 h (heating rate 2 ℃ / min) to obtain Cu-Fe. 0.3 / SBA-15 catalyst precursor.

[0049] Comparative Example 4 Weigh 0.0063 mol Cu(NO3)2·3H2O and 0.0019 mol Fe(NO3)3·9H2O and dissolve them in 100 mL of water. Add ammonia water until the pH reaches 11. After stirring for half an hour, add 25 g of silica sol (30 wt.%) and stir overnight. Place the mixed solution in an oil bath and adjust the solution temperature to 80 °C to evaporate ammonia until the solution pH reaches 6-7. Stop evaporation and transfer the solution to a hydrothermal reactor. Hydrothermate at 200 °C for 12 h, wash with water, dry overnight, and calcine in static air at 350 °C for 4 h (heating rate 2 °C / min) to obtain CuFe. 0.3 / SiO2 catalyst precursor, wherein the Cu content is 5 wt% and Fe / Cu=0.3.

[0050] Table 1 compares the process parameters and structural parameters of the catalyst precursors prepared in the examples and comparative examples.

[0051] Table 1. Process and structural parameters for preparing catalyst precursors in the examples and comparative examples.

[0052] Table 1, comparing Examples 1-4, shows that the specific surface area of ​​the resulting catalyst precursor gradually decreases with increasing Fe addition, indicating successful metal loading onto the SBA-15 support. Furthermore, a comparison with Comparative Example 1 shows that functionalizing the support and loading metal contributes to increasing the catalyst's specific surface area. Comparisons with Comparative Examples 2 and 3 show that the order of Cu and Fe addition also affects the specific surface area and pore volume of the catalyst precursor. In addition, a comparison between Example 3 and Comparative Example 4 shows that the SBA-15 support exhibits superior specific surface area and pore structure compared to the ordinary SiO2 support.

[0053] Catalyst performance evaluation 0.5 g (40-60 mesh) of the catalyst precursors prepared in the examples and comparative examples were weighed out respectively and reduced in a fixed-bed reactor (reduction temperature 350℃, reduction time 2 h, reduction atmosphere 5 vol.% H2 / N2). Activity test conditions: dry feed gas composition 15% CO, 55% H2, 7% CO2, 23% N2 (volume fraction); water vapor to dry feed gas molar ratio 1:1; space velocity 4500 mL·g⁻¹. -1 ·h -1 The test temperature range was 200–400 °C. The catalyst activity was expressed as CO conversion rate, calculated as: CO conversion rate = (1-VCO′ / VCO) / (1+VCO′) × 100%. The activity evaluation results of the catalysts obtained in the examples and comparative examples are shown in Table 2.

[0054] Table 2. Activity evaluation results of the catalysts obtained in the examples and comparative examples.

[0055] As shown in Table 2, the catalysts prepared in Examples 1-4 exhibit better performance in the water-gas shift reaction compared to Comparative Examples 1-4. Furthermore, a comparison of the results of Example 1 with Examples 2-4 shows that the introduction of Fe is beneficial to improving the catalyst activity; when an appropriate amount of Fe is introduced (the molar ratio of Fe to Cu is 0.3:1), the catalytic activity reaches its optimal level. Meanwhile, a comparison of the results of Example 3 with Comparative Example 1 shows that the catalyst prepared using a functionalized support exhibits better reaction performance in the low-temperature region than the unfunctionalized catalyst. This is attributed to the fact that functionalizing the support makes it easier to disperse and anchor metal ions. A comparison of the results of Example 3 with Comparative Examples 2 and 3 shows that the order of introduction of Cu and Fe affects the catalyst performance. When both are introduced simultaneously, Cu is better dispersed on the support, resulting in superior catalytic performance, as the functionalized SBA-15 surface groups are not destroyed. A comparison of the results of Example 3 with Comparative Example 4 shows that, compared to conventional SiO2, SBA-15 exhibits better water-gas shift performance due to its ordered pore structure and larger specific surface area.

[0056] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. The application of a copper-iron supported catalyst in water-gas shift hydrogen production, wherein the copper-iron supported catalyst comprises an active component, an additive, and a support, characterized in that, The active component is Cu, the auxiliary agent is Fe, and the support is SBA-15; wherein the active component Cu accounts for 4-10 wt.% of the catalyst, and the molar ratio of auxiliary agent Fe to active component Cu is 0.2-0.4:

1. The preparation method of the copper-iron supported catalyst includes the following steps: (1) Preparation of the carrier: The surfactant was dissolved in water, acid medium was added and heated and stirred for 1 hour, then silicon precursor was added, stirred evenly and aged, and then hydrothermally heated, washed, dried and calcined to obtain SBA-15 as the carrier. (2) Carrier functionalization: (3-aminopropyl)triethoxysilane was mixed with anhydrous ethanol, and then SBA-15 obtained in step (1) was added. After heating and reflux, washing and drying, functionalized SBA-15 was obtained. (3) Metal loading: The functionalized SBA-15 prepared in step (2) is impregnated with a mixed solution of copper salt and iron salt in equal volume, and then dried, ground and calcined to obtain CuFe / SBA-15 catalyst precursor; (4) The CuFe / SBA-15 precursor obtained in step (3) is reduced to obtain the copper-iron supported catalyst.

2. The application according to claim 1, characterized in that, The mass ratio of surfactant, silicon precursor and acid medium used in step (1) is 1:(2-3):(25-35); The surfactant is one or more of P123, P103, and F127; The silicon precursor is one or more of silica sol, tetramethoxysilane, and tetraethyl orthosilicate. The acid medium is one or more of hydrochloric acid, nitric acid, and sulfuric acid.

3. The application according to claim 1, characterized in that, In step (1), the aging temperature is 35 ℃ and the time is 20-26 h; The hydrothermal temperature was 100 ℃, and the time was 24 h; The calcination is carried out under static air, with the temperature increased to 500-600 ℃ at a rate of 1-2 ℃ / min and held for 4-8 hours.

4. The application according to claim 1, characterized in that, The mass ratio of SBA-15, (3-aminopropyl)triethoxysilane and anhydrous ethanol used in step (2) is 1:(1.5-2):(30-40).

5. The application according to claim 1, characterized in that, The temperature of the heating reflux in step (2) is 80-110℃ and the time is 24 h.

6. The application according to claim 1, characterized in that, The copper salt mentioned in step (3) includes one or more of copper nitrate, copper acetate, copper chloride, and copper sulfate; The iron salts include one or more of ferric nitrate, ferric chloride, and ferric sulfate.

7. The application according to claim 1, characterized in that, The time for immersion in equal volume as described in step (3) is 4-6 hours; The calcination is carried out by heating to 350-500 °C at a rate of 2 °C / min under static air and holding for 4 h.

8. The application according to claim 1, characterized in that, The reduction described in step (4) is carried out in an atmosphere of 5 vol.% H2 / N2 at 300-400 °C for 2-4 h.

Images