A method for photocatalytic hydrogen production from methyl formate
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-09
- Publication Date
- 2026-08-14
AI Technical Summary
[0003]本发明的目的在于提供一种光催化甲酸甲酯制氢的方法，解决甲酸甲酯在脱氢需要较高的反应温度，能耗较高的问题
[0013]本发明的有益效果在于：本申请可高效，低能耗，高稳定的生产氢气，氢气产率在800 mmol/g/h以上，催化剂具有较高的稳定性，20小时内没有明显衰减，没有烧结、积碳等现象。此外，该催化剂还可以用于甲醇、甲酸的蒸汽重整，整个过程生产周期短，反应条件温和，催化剂可重复使用，反应物来源广泛，反应过程简单等优点，为甲酸甲酯蒸汽重整制氢提供新的路径，具有广阔的工业应用前景。
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Abstract
Description
Technical Field
[0001] This invention relates to the field of photocatalysis technology, specifically to a method for photocatalytic hydrogen production from methyl formate. The method utilizes two-dimensional nanosheet-like TiO2 as a support and K2PdCl6 as a precursor, achieving highly dispersed loading through an impregnation method for photocatalytic hydrogen production from methyl formate. Background Technology
[0002] The large-scale use of fossil fuels has led to excessive CO2 emissions into the atmosphere, causing global warming. Hydrogen, with its zero-carbon emissions during use, is considered the most promising clean energy source. However, due to the risks associated with hydrogen transportation, some have proposed using liquid hydrogen carriers for long-distance transport. Commonly used liquid hydrogen carriers, such as methanol, are toxic, and formic acid is prone to decomposition and catalyst corrosion. Methyl formate, on the other hand, has excellent hydrogen storage capacity, stable physicochemical properties, and a simple and environmentally friendly synthesis route, making it an excellent liquid hydrogen carrier. Furthermore, the steam reforming used in traditional liquid hydrogen carrier dehydrogenation requires high reaction temperatures, reducing system sustainability and increasing dehydrogenation energy consumption. Summary of the Invention
[0003] The purpose of this invention is to provide a method for photocatalytic hydrogen production from methyl formate, which solves the problem that methyl formate dehydrogenation requires high reaction temperatures and high energy consumption.
[0004] To achieve the above objectives, the present invention provides the following technical solution:
[0005] A photocatalytic method for producing hydrogen from methyl formate, the method comprising: using anatase TiO2 as a support and Pd as a catalyst, in a reaction vessel, under light irradiation, converting an aqueous solution of methyl formate under alkaline conditions into H2, CO, and CO2.
[0006] Furthermore, the alkaline methyl formate aqueous solution refers to 3.2 mL methyl formate, 1.8 mL deionized water, and 0.4 g KOH, with the volume ratio of methyl formate to deionized water being 3.2:1.8.
[0007] Furthermore, the support is anatase phase TiO2 synthesized from tetrabutyl titanate, and Pd is loaded through the precursor K2PdCl6 with a loading amount of 3 wt%.
[0008] Furthermore, the illuminance under the aforementioned lighting conditions is 0.6–1.2 mW / cm². 2 The light source for the illumination conditions is a xenon lamp.
[0009] Furthermore, the reactor is a glass reactor.
[0010] Furthermore, the reaction was carried out under a vacuum of 30 kPa.
[0011] Furthermore, the reaction temperature is 20–80 °C, and the reaction time is 30–90 minutes.
[0012] Further, the catalyst preparation process is as follows: 100 mg TiO2 and 20 mL deionized water are added to a 50 mL glass beaker and sonicated for 20 min. Then, 3 mL of 10 mmol / L K2PdCl6 solution and 0.05 mL of ammonia water are added. The mixture is stirred in a closed state at 30 °C for 3 hours. The resulting mixture is centrifuged at 8000 rpm for 5 min to obtain a precipitate. After washing with deionized water, the precipitate is dried, ground, and the resulting sample is calcined at 250 °C for 2 hours in a 7% H2 / 93% Ar atmosphere (heating rate 5 °C / min). -1 Finally, the mixture was cooled to room temperature to obtain a Pd / TiO2 catalyst with a Pd loading of approximately 3 wt%.
[0013] The beneficial effects of this invention are as follows: This application enables efficient, low-energy-consumption, and highly stable hydrogen production, with a hydrogen yield exceeding 800 mmol / g / h. The catalyst exhibits high stability, showing no significant degradation within 20 hours, and exhibiting no sintering or carbon deposition. Furthermore, this catalyst can also be used for the steam reforming of methanol and formic acid. The entire process has advantages such as a short production cycle, mild reaction conditions, reusable catalyst, wide availability of reactants, and a simple reaction process. It provides a new route for hydrogen production through the steam reforming of methyl formate and has broad industrial application prospects.
[0014] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings. Attached Figure Description
[0015] Figure 1 This is a graph illustrating the hydrogen yield effect of an embodiment of the present invention. Detailed Implementation
[0016] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0017] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.
[0018] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.
[0019] Furthermore, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0020] Please see Figure 1 The preferred embodiment of the present invention, which describes a light-driven vapor reforming method for producing hydrogen from methyl formate, includes: using Pd-supported TiO2 as a catalyst in a glass reaction vessel, under xenon lamp irradiation, converting an aqueous solution of methyl formate under alkaline conditions into H2, CO, and CO2.
[0021] In the method of this invention, after the reaction is complete, the hydrogen yield can be detected by conventional means, such as, but not limited to, gas chromatography. The stability of the catalyst can be assessed by long-term operation under operating conditions.
[0022] In the method of this invention, anatase TiO2 support can be purchased directly or synthesized from tetrabutyl titanate. Anatase TiO2 has a large specific surface area, numerous pores, and good stability, and is used to disperse and support Pd, prevent Pd particle agglomeration, and assist in catalysis.
[0023] Loading: Pd nanoparticles are uniformly dispersed on the TiO2 surface through methods such as impregnation, precipitation, and reduction, resulting in a tight bond between the two rather than a simple mixture. Catalyst preparation: Anatase titanium dioxide is used as a support, and palladium is the active component, with palladium loaded onto the titanium dioxide.
[0024] In the method of this invention, the mass ratio of Pd to TiO2 is 3 wt%.
[0025] In the method of this invention, the light intensity can be 0.6–1.2 mW / cm². 2 .
[0026] Catalyst preparation
[0027] The catalyst used in this invention is prepared as follows:
[0028] 100 mg TiO2 and 20 mL deionized water were added to a 50 mL glass beaker and sonicated for 20 min. Then, 3 mL of 10 mM K2PdCl6 solution and 0.05 mL of ammonia were added. The mixture was stirred in a sealed state at 30 °C for 3 hours. The resulting mixture was centrifuged at 8000 rpm for 5 min to obtain a precipitate, which was washed with deionized water, dried, and ground. The resulting sample was calcined at 250 °C for 2 hours in a 7% H2 / 93% Ar atmosphere (heating rate 5 °C / min). -1 Finally, the mixture was cooled to room temperature to obtain a Pd / TiO2 catalyst with a Pd loading of approximately 3 wt%.
[0029] Example 1
[0030] In a glass reaction vessel, 3.2 mL of methyl formate, 1.8 mL of deionized water, and 0.4 g of KOH were added. A 400 mm high glass support was erected in the reactor, and the catalyst (5 mg of catalyst dispersed in 0.4 mL of deionized water, then dropped onto a 50 mm diameter glass fiber filter and dried) was placed on top. The reaction was carried out at room temperature (approximately 25 °C) under irradiation with a 300 W xenon lamp. The product was evaluated by gas chromatography using a flame ionization detector (FID) and a thermal conductivity detector (TCD). The hydrogen production rate was detected by chromatography to be approximately 800 mmol g⁻¹ h⁻¹. Furthermore, the catalyst showed no significant performance degradation after 20 hours of operation, demonstrating potential for industrial application.
[0031] Example 2
[0032] The specific reaction process and detection method are the same as in Example 1, with a yield of approximately 200 mmol g⁻¹ h⁻¹ using 1 wt% loaded hydrogen and approximately 400 mmol g⁻¹ h⁻¹ using 5 wt% loaded hydrogen.
[0033] Example 3
[0034] The specific reaction process and detection method are the same as in Example 1. Without the addition of ammonia, the yield is approximately 50 mmol g⁻¹ h⁻¹, and with the addition of 3 mL of ammonia, the hydrogen yield is approximately 100 mmol g⁻¹ h⁻¹.
[0035] Example 4
[0036] The specific reaction process and detection method are the same as in Example 1, with calcination temperatures of 150 and 300°C, and a hydrogen yield of approximately 300 mmol g⁻¹ h⁻¹.
[0037] In summary, this invention provides a photocatalytic method for hydrogen production from methyl formate. This method achieves high efficiency, low energy consumption, and high stability in hydrogen production, with a hydrogen yield exceeding 800 mmol / g / h. The catalyst exhibits high stability, showing no significant degradation within 20 hours, and exhibits no sintering or carbon deposition. Furthermore, this catalyst can also be used for the steam reforming of methanol and formic acid. The entire process boasts advantages such as a short production cycle, mild reaction conditions, reusable catalyst, wide availability of reactants, and a simple reaction process. It provides a new route for hydrogen production through the steam reforming of methyl formate and has broad industrial application prospects.
[0038] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0039] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.
Claims
1. A method for photocatalytic hydrogen production from methyl formate, characterized in that, The method includes: using anatase TiO2 as a support and Pd as a catalyst, in a reaction vessel, under light irradiation, converting an aqueous solution of methyl formate under alkaline conditions into H2, CO, and CO2.
2. The method for photocatalytic hydrogen production from methyl formate as described in claim 1, characterized in that, The alkaline methyl formate aqueous solution refers to 3.2 mL methyl formate, 1.8 mL deionized water, and 0.4 g KOH, with the volume ratio of methyl formate to deionized water being 3.2:1.
8.
3. The method for photocatalytic hydrogen production from methyl formate as described in claim 1, characterized in that, The support was anatase phase TiO2 synthesized from tetrabutyl titanate, and Pd was loaded through the precursor K2PdCl6 with a loading amount of 3 wt%.
4. The method for photocatalytic hydrogen production from methyl formate as described in claim 1, characterized in that, The light intensity under the specified illumination conditions is 0.6–1.2 mW / cm². 2 The light source for the illumination conditions is a xenon lamp.
5. The method for photocatalytic hydrogen production from methyl formate as described in claim 1, characterized in that, The reactor is a glass reactor.
6. The method for photocatalytic hydrogen production from methyl formate as described in claim 1, characterized in that, The reaction was carried out under a vacuum of 30 kPa.
7. The method for photocatalytic hydrogen production from methyl formate as described in claim 1, characterized in that, The reaction temperature is 20–80 ℃, and the reaction time is 30–90 minutes.
8. The method for photocatalytic hydrogen production from methyl formate as described in claim 1, characterized in that, The catalyst preparation process is as follows: 100 mg TiO2 and 20 mL deionized water are added to a 50 mL glass beaker and sonicated for 20 min. Then, 3 mL of 10 mmol / L K2PdCl6 solution and 0.05 mL of ammonia water are added. The mixture is stirred in a closed state at 30 °C for 3 hours. The resulting mixture is centrifuged at 8000 rpm for 5 min to obtain a precipitate. After washing with deionized water, the precipitate is dried, ground, and then calcined at 250 °C for 2 hours in a 7% H2 / 93% Ar atmosphere (heating rate 5 °C / min). -1 Finally, the mixture was cooled to room temperature to obtain a Pd / TiO2 catalyst with a Pd loading of approximately 3 wt%.