CN-122006715-A - Preparation method and application of copper-based alloy photo-thermal catalyst supported by alumina carrier

Abstract

The invention belongs to the technical field of photo-thermal methanol pyrolysis hydrogen production catalysts, and discloses a preparation method and application of a copper-based alloy photo-thermal catalyst loaded by an alumina carrier. Firstly, synthesizing layered double hydroxide CuMAl-LDH (metal M is Co or Ni) nanosheets serving as precursors by a coprecipitation method, and preparing the catalyst by a gas phase thermal reduction method, namely reducing the layered double hydroxide (CuMAl-LDH) in a high-temperature tube furnace by hydrogen reduction to obtain a copper-based alloy which is loaded on alumina to obtain a photo-thermal catalyst, and applying the photo-thermal catalyst to hydrogen production by photo-thermal methanol pyrolysis.

Inventors

• SHI WEIDONG
• CHAO YANG
• HUANG YUANYONG
• XIE ZHONGKAI

Assignees

• 江苏科技大学

Dates

Publication Date

20260512

Application Date

20260407

Claims (10)

1. 1. The preparation method of the copper-based alloy photo-thermal catalyst supported by the alumina carrier is characterized by comprising the following steps: (1) Cu (NO 3 ) 3 、M(NO 3 ) 2 ·6 H 2 O and Al (NO 3 ) 3 ·9H 2 O are fully dissolved in ultrapure water to obtain a solution A; (2) Sodium carbonate Na 2 CO 3 is weighed according to a proportion and fully dissolved in ultrapure water to obtain a solution B; Weighing sodium hydroxide NaOH according to a proportion, and fully dissolving in ultrapure water to obtain a solution C; (3) Under the condition of continuously stirring and keeping a certain pH value, slowly dripping the solution A and the solution C into the solution B, heating and stirring the obtained mixed solution at 60-80 ℃ for 6-24 hours, washing and centrifuging the product by deionized water until the pH value of the supernatant is close to 7, and then drying in vacuum to obtain a precursor CuMAl-LDH; (4) And (3) calcining the precursor CuMAl-LDH obtained in the step (3) at a high temperature by introducing hydrogen-argon mixture gas into a tube furnace to obtain the copper-based alloy photo-thermal catalyst CuM-Al 2 O 3 loaded by the alumina carrier.
2. 2. The method of claim 1, wherein in step (1), M (NO 3 ) 2 ·6 H 2 O) is Co (NO 3 ) 2 ·6 H 2 O or Ni (NO 3 ) 2 ·6 H 2 O).
3. 3. The method of claim 1, wherein the molar ratio of (Cu 2+ +M 2+ ) to Al 3+ in step (1) is 2:1 or 3:1, wherein the molar ratio of Cu 2+ to M 2+ is 6:1, 4:1, 2:1, 1:1, 1:4, 1:2 or 1:6, and wherein the concentration of Al 3+ in solution A is 0.25 mol/L.
4. 4. The process according to claim 1, wherein in the step (2), the concentration of Na 2 CO 3 in the solution B is 0.0059g/mL and the concentration of NaOH in the solution C is 1.5 mol/L.
5. 5. The method of claim 1, wherein in step (3), the volume ratio of solution a, solution B and solution C is 2:18:3, and the molar ratio of na 2 CO 3 to Al 3+ is 2:1.
6. 6. The process according to claim 1, wherein in step (3), stirring is continued and the pH is maintained at 9.5.
7. 7. The method according to claim 1, wherein in the step (3), the number of revolutions of the centrifugation is 8000 r/min, and the temperature of the vacuum drying is 60℃for 12 hours.
8. 8. The method of claim 1, wherein in step (4), the hydrogen gas is present in an amount of 5% by volume.
9. 9. The method according to claim 1, wherein in the step (4), the calcination temperature is 400 to 600 ℃, the temperature rising rate is 5 ℃ per minute, the ventilation flow is 40 mL per minute, and the calcination reduction time is 1 to 5 hours.
10. 10. Use of the copper-based alloy photo-thermal catalyst CuM-Al 2 O 3 loaded by the alumina carrier prepared by the preparation method according to any one of claims 1-9 for photo-thermal methanol cracking hydrogen production.

Description

Preparation method and application of copper-based alloy photo-thermal catalyst supported by alumina carrier Technical Field The invention belongs to the technical field of photo-thermal methanol cracking hydrogen production catalysts, and particularly relates to a preparation method and application of a copper-based alloy photo-thermal catalyst loaded by an alumina carrier. Background As global energy demand continues to increase, the massive consumption of traditional fossil energy causes a surge in carbon dioxide emissions, and thus environmental pollution and greenhouse effect problems are urgently needed to be solved. In this context, the construction of a new energy system that is "low carbon, safe, clean, and efficient" has become a global consensus. The hydrogen energy has the characteristics of high heat value (140 MJ/kg, about 3 times of petroleum, 4.5 times of coal, 2 times of methane and 4 times of ethanol), zero carbon emission, convenient storage and transportation, rich resources and the like, and is regarded as a key carrier for realizing energy revolution. The catalyst can be used as basic chemical raw materials for synthesizing ammonia, methanol and the like in the industrial field, and can obviously reduce carbon emission and fossil energy dependency through a fuel cell technology in the traffic field. However, the low density, high diffusivity, flammability and explosiveness of hydrogen present a significant challenge to its storage and transportation, impeding its widespread use. Breaks through the bottleneck of high-efficiency low-cost hydrogen production and safe storage and transportation technology, and is the key for realizing the large-scale application of hydrogen energy. Along with the rapid development of renewable energy sources such as wind energy, solar energy and the like and water electrolysis technologies, the renewable energy source coupling water electrolysis hydrogen production technology has become a green hydrogen production scheme with the most prospect, but the industrialization process is still subject to bottleneck problems of high energy consumption cost, large investment intensity, remarkable water resource consumption and the like. Under the background, the proposal of the concept of liquid sunshine provides an innovative solution for a hydrogen energy carrier, methanol becomes an ideal hydrogen energy carrier due to multiple advantages, and the methanol has the characteristics of abundant resources, mature synthesis process and good economy, the high hydrogen-carbon ratio (H/C) and the molecular structure without C-C bonds endow the hydrogen energy carrier with wide temperature range hydrogen production capability, and the liquid property enables the methanol to be stored and transported and filled by depending on the infrastructure of the existing gas station or realize low-cost, safe and convenient hydrogen energy transportation by pipeline transportation, and has remarkable advantages compared with the high-pressure hydrogen storage technology. Based on this, methanol hydrogen production technology capable of achieving in-situ hydrogen production is increasingly receiving academic attention. In various processes for producing hydrogen from methanol, partial oxidation of methanol and autothermal reforming of methanol are exothermic reactions, which can lead to catalyst deactivation and low hydrogen production rates. Whereas methanol steam reforming (MSR, CH 3OH + H2O → CO2 + 3H2) and methanol cracking (MD, CH 3OH → CO + 2H2) are endothermic reactions requiring additional heat input. Methanol cracking is considered one of the simplest hydrogen production processes because it does not require additional reactants, such as steam and oxygen. In addition, methanol dehydrogenation can produce synthesis gas (a mixture of hydrogen and carbon monoxide), which has a variety of applications. The synthesis gas can be used for power generation, transportation fuel production and gasoline replacement, and can also be used as an important chemical intermediate resource for producing hydrogen (through a water gas shift reaction), hydrocarbons (through Fischer-Tropsch synthesis) and high-chain alcohols/aldehydes (through an oxidation process). In recent years, the introduction of light energy in traditional thermocatalysts has become a very potential strategy. By photoinduction activating the reactants, a faster conversion rate can be achieved. Sunlight is a rich and sustainable energy source, and if it can be effectively collected and utilized, it will help reduce the dependence on polluting fossil fuels. The photocatalysis utilizes light to excite oxidation-reduction reaction to convert solar energy into chemical energy, thus opening up a new way for solar energy utilization. Compared with traditional thermocatalysis, the photocatalysis can be performed under milder conditions, thereby being beneficial to reducing energy consumption and improving product selectivity. Howe