Vanadium salt hetero-support, method for preparing the same and use thereof

Abstract

The application discloses a vanadium salt hetero-support and a preparation method and application thereof, and belongs to the field of material preparation and catalysis technology. The vanadium oxide-vanadium carbide hetero-support is prepared by a precursor method, vanadium salt is uniformly mixed with an organic carbon source, stirring and dissolving are conducted, drying and filtering are conducted, and a vanadium oxide-vanadium carbide hetero-support precursor is obtained, and the precursor is calcined in an argon or nitrogen atmosphere to obtain the vanadium salt hetero-support. The raw material used is low in price, the process is simple, no flammable and explosive gas is generated in the calcination process, the safety factor is high, the target product is generated by one-step calcination, impurities are not easily introduced, and the repeatability is high. The method is based on the theory of strong and weak metal carrier interaction, and a two-component vanadium salt hetero-support is used as a catalyst base, the catalyst sintering problem caused by Ostwald ripening, particle aggregation and migration is overcome, and thus a catalyst with good stability and good catalytic performance is obtained.

Description

Technical Field

[0001] This invention belongs to the field of materials preparation and catalysis technology, specifically relating to a vanadium salt heterosupport, its preparation method, and its application. Background Technology

[0002] Hydrogen is considered one of the most promising clean energy sources due to its high energy density and zero carbon emissions. However, its reactive chemical properties pose significant safety concerns regarding storage and transportation. Recently, in-situ release of hydrogen from stable liquid fuels via efficient catalytic reactions has been reported as a potential pathway for safe, convenient, and efficient hydrogen storage. Methanol, with its high energy density, low price, and ease of storage and transportation, can serve as a hydrogen carrier and storage material. Compared to direct methanol dehydrogenation, methanol-water reforming not only reduces carbon monoxide content but also generates an additional equivalent of hydrogen.

[0003] Metal-supported catalysts have proven effective for hydrogen production from methanol-water reforming. Al₂O₃, a commonly used support in methanol-water reforming, facilitates the dissociation of OH bonds in methanol and water molecules, exhibiting excellent hydrogen production performance. However, Al₂O₃ is acidic, which negatively impacts the reaction. Furthermore, Al₂O₃ is unstable and prone to phase transformation into hydrated boehmite. Therefore, developing an effective support to improve the activity and stability of metal-supported catalysts is a significant challenge in methanol-water reforming. Metal-supported transition metal carbides forming mixed catalysts can greatly optimize catalytic performance; however, catalyst sintering problems exist, reducing catalyst stability. Based on the theory of strong metal-support interactions, a metal-supported vanadium oxide-vanadium carbide heterostructure was prepared, which significantly improves catalyst performance and anti-sintering stability during the catalytic process.

[0004] Currently, vanadium oxide-vanadium carbide can be prepared using ball milling, gas-phase reduction, and precursor methods. Ball milling uses vanadium oxide and carbon black as raw materials, employing a planetary ball mill at room temperature followed by heat treatment to synthesize vanadium oxide-vanadium carbide powder. However, this method is prone to introducing impurities and the product is difficult to separate, limiting its application in catalysis. Gas-phase reduction commonly uses a CH4 / H2 mixed gas to reduce V2O5. The first step involves the reduction of V2O5 to V2O3 by H2, and the second step involves the partial reduction and carbonization of V2O3 by CH4, ultimately yielding vanadium oxide-vanadium carbide. The limitations of this method are the use of a mixed gas as the reducing gas, relatively high production costs, and low safety, which to some extent restricts its production and application. The precursor method uses ammonium vanadate as a vanadium source and nano-carbon black as a carbon source, which are dissolved in heated propylene glycol in a certain proportion, mixed evenly, and dried to obtain a precursor powder containing vanadium and carbon sources. After calcination, vanadium oxide-vanadium carbide powder is obtained. The limitation of this method is that carbon black is not as cheap as polysaccharide compounds, and the cost is relatively high, which limits its application in the industrial field. In addition, the required reaction temperature is very high, mostly around 1100℃. Summary of the Invention

[0005] This invention addresses the issues of raw material cost and demanding reaction conditions in existing technologies for preparing vanadium oxide-vanadium carbide. It provides a vanadium salt heterosupport, its preparation method, and its application. The method is simple to operate, inexpensive, operates at low temperatures, and is safe and pollution-free. By constructing a vanadium salt heterosupport with strong and weak metal support interaction effects, the performance and stability of the catalyst can be significantly improved.

[0006] This invention discloses a method for preparing a vanadium salt heterosupport, comprising the following steps:

[0007] A method for preparing a vanadium salt heterosupport includes the following steps:

[0008] The vanadium source and organic carbon source were dissolved in a solvent, stirred and evaporated to dryness to obtain the precursor powder;

[0009] The precursor powder was calcined at high temperature under the protection of continuous inert gas to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0010] The molar ratio of the vanadium source to the organic carbon source is 1:1 to 1:1.5.

[0011] The vanadium source is one or more of ammonium metavanadate, vanadium oxalate, or vanadium oxysulfate.

[0012] The organic carbon source is one or more of glucose, sucrose, or maltose.

[0013] The solvent is propylene glycol.

[0014] The precursor powder has a mass of 1.2 to 1.8 g.

[0015] The calcination is carried out in a tubular furnace at a temperature of 700–900°C and a heating rate of 5–8°C / min. -1 The calcination time is 4 to 6 hours.

[0016] The inert gas is nitrogen or argon, and the flow rate of the inert gas is 60-100 mL / min. -1 .

[0017] The present invention also discloses a vanadium salt heterosupport prepared by the above preparation method.

[0018] The present invention also discloses the application of the above-mentioned vanadium salt heterosupport as a catalyst support in the thermocatalytic reaction for hydrogen production by methanol-water reforming.

[0019] Compared with the prior art, the present invention has the following beneficial technical effects:

[0020] The method for preparing the vanadium salt heterosupport of this invention is based on the theory of catalyst anti-sintering. Too strong a metal-support interaction triggers Ostwald ripening, while too weak an interaction stimulates particle migration and aggregation. Therefore, constructing strong and weak metal-support interactions is one way to suppress catalyst sintering; that is, the interaction between the support and the metal should not be too strong or too weak. However, this is difficult to achieve with a single-component support alone. Heterogeneous supports provide a platform to improve the stability and activity of supported catalysts. This invention uses a precursor method to prepare vanadium oxide-vanadium carbide, replacing carbon black with an inexpensive organic carbon source. A mixed solution is formed by setting the ratio of vanadium source and organic carbon source, and a one-step calcination method is used to finally obtain a vanadium salt heterosupport with both vanadium oxide and vanadium carbide components. The reaction can be controlled by adjusting the reaction temperature, the molar ratio of vanadium source and organic carbon source, the molar ratio of reactants, the reaction time, the inert gas flow rate, the heating rate, and the mass of the precursor. The raw materials used in this invention are inexpensive, and the preparation process is simple. There are no flammable or explosive gases during the calcination process, so the safety factor is high. The target product is generated by one-step calcination, which does not easily introduce impurities and has high repeatability.

[0021] Furthermore, using one of ammonium metavanadate, vanadium oxalate, or vanadium oxalate as a vanadium source to prepare vanadium salt heterosupports can form stable substances at lower temperatures, and these substances are inexpensive and readily available.

[0022] Furthermore, one of glucose, sucrose, or maltose is used as an organic carbon source, which is non-toxic and pollution-free, and can easily decompose at lower temperatures to react with the carbon source and vanadium source.

[0023] Furthermore, the molar ratio of vanadium source to organic carbon source is 1:1 to 1:1.5. If the molar ratio is less than 1:1, the carbon source is insufficient, making it difficult to generate vanadium carbide; if the molar ratio is greater than 1:1.5, the carbon source is excessive, and vanadium oxide further generates vanadium carbide.

[0024] Furthermore, using propylene glycol as a solvent is advantageous because the carbon in propylene glycol can provide a partial carbon source. Compared with water as a solvent, propylene glycol has good heat of solution and thermal conductivity, which can lower the reaction temperature.

[0025] Furthermore, the mass of the precursor is 1.2–1.8 g. If the mass of the precursor is too small, the yield of the target product will be low, which will increase the reaction cost. If the mass of the precursor is too large, the sample reaction will be incomplete and the calcination will be insufficient.

[0026] Furthermore, the calcination temperature is 700–900℃, and the calcination time is 4–6 hours. This temperature is lower than that of the conventional carbothermal reduction method. This is mainly because, during the preparation of the precursor from propylene glycol mixtures, vanadium and carbon atoms are tightly bonded together, reducing the energy required for diffusion. Additionally, the carbon from the decomposition of glucose and propylene glycol is highly reactive, ultimately lowering the reaction temperature. The heating rate is 5℃·min. -1 ~8℃·min -1 If the heating rate is less than 5℃·min -1 This will lead to low heating efficiency, prolonged reaction cycle, and thus increased reaction cost; if the heating rate is greater than 8℃·min -1 This can lead to uneven heating of the sample.

[0027] Furthermore, the flow rate of the inert gas is 60–100 mL / min. -1 If the flow rate is less than 60 mL / min -1 This will cause the gas generated by the vanadium source itself to remain in the tube furnace for a long time, affecting the crystallinity of the sample; flow rate greater than 100 mL·min -1 Too high a flow rate can cause some of the sample to be blown away, resulting in a low yield of the target product.

[0028] The vanadium salt heterosupport disclosed in this invention is used for hydrogen production via methanol-water reforming. Using the heterosupport as a substrate, its unique structure endows the heterosupport itself with strong catalytic activity. By loading other metal atoms for catalytic reactions, a strong-weak metal-support interaction is constructed, which strongly inhibits sintering problems caused by Ostwald ripening, particle migration, and aggregation. The prepared vanadium oxide-vanadium carbide heterosupport exhibits excellent hydrogen production performance and good stability in methanol-water liquid-phase reforming for hydrogen production. Attached Figure Description

[0029] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly described below:

[0030] Figure 1 The image shows the X-ray powder diffraction (XRD) pattern of the vanadium oxide-vanadium carbide heterosupport prepared in Example 1 of this invention.

[0031] Figure 2 The image shows the X-ray photoelectron spectroscopy (XPS) spectrum of the vanadium oxide-vanadium carbide heterosupport prepared in Example 1 of this invention.

[0032] Figure 3 The graphs show the performance analysis of the vanadium oxide-vanadium carbide heterosupports prepared in Examples 1-10 of this invention in methanol-water liquid-phase reforming for hydrogen production.

[0033] Figure 4 This is a stability analysis diagram of the vanadium oxide-vanadium carbide heterosupport prepared in Example 1 of the present invention in methanol-water liquid phase reforming for hydrogen production.

[0034] Figure 5 The image shows the X-ray powder diffraction (XRD) pattern of the vanadium oxide-vanadium carbide heterosupport prepared in Example 1 of this invention after undergoing a methanol-water reforming hydrogen production catalytic reaction. Detailed Implementation

[0035] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments. These descriptions are intended to explain the invention and not to limit it.

[0036] The method for preparing vanadium salt heterosupport provided by this invention includes the following steps: dissolving vanadium source and organic carbon source in a solvent, stirring and evaporating to obtain precursor powder; calcining the precursor powder at high temperature under the protection of continuous inert gas to obtain vanadium salt heterosupport with vanadium oxide-vanadium carbide coexisting components.

[0037] The molar ratio of the vanadium source to the organic carbon source is 1:1 to 1:1.5; the vanadium source is one or more of ammonium metavanadate, vanadium oxalate, or vanadium oxysulfate; the organic carbon source is one or more of glucose, sucrose, or maltose; and the solvent is propylene glycol.

[0038] The precursor powder has a mass of 1.2 to 1.8 g.

[0039] The calcination is carried out in a tubular furnace at a temperature of 700–900°C and a heating rate of 5–8°C / min. -1 The calcination time is 4 to 6 hours.

[0040] The inert gas is nitrogen or argon, and the flow rate of the inert gas is 60-100 mL / min. -1 .

[0041] The vanadium salt heterosupport prepared by the above method can be used as a catalyst support in thermocatalytic reactions.

[0042] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. For the sake of simplicity, this invention will not exhaustively list the specific point values ​​included in the range.

[0043] The raw materials used in this invention are inexpensive organic carbon sources. The preparation process is simple, there are no flammable or explosive gases during calcination, the safety factor is high, the target product is generated in one step of calcination, it is not easy to introduce impurities, and the repeatability is high.

[0044] In the following embodiments, unless otherwise specified, all materials used can be obtained through ordinary channels; the testing methods used are conventional methods in the art.

[0045] Example 1

[0046] At room temperature, a mixed solution of ammonium metavanadate and glucose in a molar ratio of 1:1.1 was prepared in a beaker containing 60 mL of propylene glycol. The uniformly mixed substance was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0047] Weigh 1.2g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace filled with argon gas. Adjust the argon gas flow rate to 60mL·min. -1 , at 5℃·min -1 The temperature was increased to 700℃ at a certain rate and calcined for 6 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0048] Example 2

[0049] At room temperature, a mixed solution of vanadium oxalate and maltose in a molar ratio of 1:1.5 was prepared in a beaker containing 60 mL of propylene glycol. The homogeneous mixture was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0050] Weigh 1.8g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace filled with argon gas. Adjust the argon gas flow rate to 100mL·min. -1 , at 8℃·min -1 The temperature was increased to 900℃ at a certain rate and calcined for 4 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0051] Example 3

[0052] At room temperature, a mixed solution of vanadium oxysulfate and sucrose in a molar ratio of 1:1.2 was prepared in a beaker containing 60 mL of propylene glycol. The homogeneous mixture was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0053] Weigh 1.3g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace under a nitrogen atmosphere. Adjust the argon flow rate to 70mL·min. -1 , at 6℃·min -1 The temperature was increased to 800℃ at a certain rate and calcined for 5 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0054] Example 4

[0055] At room temperature, a mixed solution of ammonium metavanadate and maltose in a molar ratio of 1:1.2 was prepared in a beaker containing 60 mL of propylene glycol. The uniformly mixed substance was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0056] Weigh 1.4g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace under a nitrogen atmosphere. Adjust the argon flow rate to 80mL·min. -1 , at 7℃·min -1 The temperature was increased to 700℃ at a certain rate and calcined for 6 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0057] Example 5

[0058] At room temperature, a mixed solution of ammonium metavanadate and sucrose in a molar ratio of 1:1.2 was prepared in a beaker containing 60 mL of propylene glycol. The uniformly mixed substance was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0059] Weigh 1.5g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace filled with argon gas. Adjust the argon gas flow rate to 90mL·min. -1 , at 5℃·min -1 The temperature was increased to 700℃ at a certain rate and calcined for 6 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0060] Example 6

[0061] At room temperature, a mixed solution of vanadium oxalate and maltose in a molar ratio of 1:1.2 was prepared in a beaker containing 60 mL of propylene glycol. The homogeneous mixture was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0062] Weigh 1.6g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace filled with argon gas. Adjust the argon gas flow rate to 80mL·min. -1 , at 5℃·min -1 The temperature was increased to 700℃ at a certain rate and calcined for 6 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0063] Example 7

[0064] At room temperature, a mixed solution of vanadium oxalate and sucrose in a molar ratio of 1:1.2 was prepared in a beaker containing 60 mL of propylene glycol. The homogeneous mixture was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0065] Weigh 1.7g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace filled with argon gas. Adjust the argon gas flow rate to 60mL·min. -1 , at 5℃·min -1 The temperature was increased to 800℃ at a certain rate and calcined for 5 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0066] Example 8

[0067] At room temperature, a mixed solution of vanadium oxysulfate and glucose in a molar ratio of 1:1.2 was prepared in a beaker containing 60 mL of propylene glycol. The uniformly mixed substance was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0068] Weigh 1.2g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace filled with argon gas. Adjust the argon gas flow rate to 60mL·min. -1 , at 5℃·min -1 The temperature was increased to 800℃ at a certain rate and calcined for 6 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0069] Example 9

[0070] At room temperature, a mixed solution of vanadium oxysulfate and maltose in a molar ratio of 1:1.2 was prepared in a beaker containing 60 mL of propylene glycol. The homogeneous mixture was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0071] Weigh 1.5g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace filled with argon gas. Adjust the argon gas flow rate to 60mL·min. -1 , at 5℃·min -1 The temperature was increased to 900℃ at a certain rate and calcined for 5 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0072] Example 10

[0073] At room temperature, a mixed solution of ammonium metavanadate and glucose in a molar ratio of 1:1.2 was prepared in a beaker containing 60 mL of propylene glycol. The uniformly mixed substance was placed in a thermostatic magnetic stirrer at 80 °C and stirred until a large amount of brown flocculent material was generated. After filtration and drying, a dark brown precursor powder was obtained.

[0074] Weigh 1.5g of dark brown precursor powder and place it in a quartz crucible, then transfer it into a tube furnace filled with argon gas. Adjust the argon gas flow rate to 60mL·min. -1 , at 5℃·min -1 The temperature was increased to 800℃ at a certain rate and calcined for 5 hours to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting components.

[0075] Figure 1 The X-ray powder diffraction (XRD) pattern of the vanadium salt heterosupport prepared in Example 1 is shown. As can be seen from the figure, the diffraction peaks of the prepared product are consistent with those of the standard cards V2O3 (PDF#76-1043) and V8C7 (PDF#76-0394).

[0076] Figure 2 The X-ray photoelectron spectroscopy (XPS) spectrum of the vanadium salt heterosupport synthesized in Example 1 is shown. The high-resolution spectrum in the C 1s region can be convolved into three distinct components: C=C at 283.1 eV and 285.6 eV, C=O at 284.8 eV, and C=O at 288.6 eV, results consistent with the typical characteristic peaks of V8C7. In the O 1s region, the two peaks at 530.1 eV and 531.9 eV correspond to V0 and CO bonds, respectively. In the V 2p region, 525.5 eV corresponds to VV(V 2p) 1 / 2 ), at 523.8 eV (V2p 1 / 2 ), 516.3eV (V 2p) 3 / 2The peak at the binding energy corresponds to the VO bond, indicating the formation of V₂O₃. The binding energy at 517.4 eV corresponds to (V 2p) 3 / 2 ), belongs to V 4+ Ions, which may be due to a small amount of V on the surface. 3+ Oxidized to V 4+ At 521.3 eV (V2p) 1 / 2 ) and 513.7eV (V 2p 3 / 2 The binding energy corresponds to the VC bond, which in turn corresponds to the V8C7 phase. The peak appearing at 525.1 eV corresponds to VV 2p. 1 / 2 XPS plots confirmed the formation of the vanadium oxide-vanadium carbide heterostructure.

[0077] Figure 3 The hydrogen production performance and CO selectivity of the vanadium oxide-vanadium carbide heterosupports prepared in Examples 1-10 of this invention in methanol-water liquid-phase reforming are shown. It can be seen that the vanadium oxide-vanadium carbide heterosupport prepared in Example 1 has the best hydrogen production performance and CO selectivity, which are 10.52 mmol·g⁻¹, respectively. -1 ·h -1 4.7%.

[0078] Figure 4 This study examines the stability of the vanadium oxide-vanadium carbide heterosupport prepared in Example 1 of this invention during methanol-water liquid-phase reforming for hydrogen production. It can be seen that after 15 in-situ cyclic reactions, the hydrogen production performance of the prepared vanadium oxide-vanadium carbide heterosupport remained stable at 10.52 mmol·g. -1 ·h -1 about.

[0079] Figure 5 The image shows the X-ray powder diffraction (XRD) pattern of the vanadium oxide-vanadium carbide heterosupport prepared in Example 1 of this invention after methanol-water liquid-phase reforming to produce hydrogen. It can be seen from the figure that there is no obvious change in crystal form of the product after catalysis. Therefore, it can be concluded that the vanadium salt heterosupport does not undergo oxidation or destruction of its own structure during the reaction and has good stability.

[0080] It should be noted that the above description is only a part of the embodiments of the present invention, and all equivalent changes made to the system described in this invention are included within the protection scope of this invention. Those skilled in the art can make similar substitutions to the specific examples described, as long as they do not deviate from the structure of the invention or exceed the scope defined in these claims, all of which fall within the protection scope of this invention.

Claims

1. A method for preparing a vanadium salt heterosupport, characterized in that, Includes the following steps: Vanadium source and organic carbon source are dissolved in a solvent, stirred and evaporated to dryness to obtain precursor powder, wherein the solvent is propylene glycol; The precursor powder was calcined at high temperature under the protection of continuous inert gas to obtain a vanadium salt heterosupport with vanadium oxide and vanadium carbide coexisting in two components, wherein the vanadium oxide is V2O3 and the vanadium carbide is V8C7. The molar ratio of the vanadium source to the organic carbon source is 1:1 to 1:1.5; the calcination temperature is 700 to 900 ℃.

2. The method for preparing vanadium salt heterosupport according to claim 1, characterized in that, The vanadium source is one or more of ammonium metavanadate, vanadium oxalate, or vanadium oxysulfate.

3. The method for preparing vanadium salt heterosupport according to claim 1, characterized in that, The organic carbon source is one or more of glucose, sucrose, or maltose.

4. The method for preparing vanadium salt heterosupport according to claim 1, characterized in that, The precursor powder has a mass of 1.2~1.8 g.

5. The method for preparing vanadium salt heterosupport according to claim 1, characterized in that, The calcination is carried out in a tube furnace at a heating rate of 5-8 °C / min. -1 The calcination time is 4-6 hours.

6. The method for preparing vanadium salt heterosupport according to claim 1, characterized in that, The inert gas is nitrogen or argon, and the flow rate of the inert gas is 60-100 mL / min. -1 .

7. The vanadium salt heterosupport prepared by the preparation method according to any one of claims 1 to 6.

8. The vanadium salt heterosupport according to claim 7 is used as a catalyst support in the thermocatalytic reaction for hydrogen production by methanol-water reforming.

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