Supported catalyst for hydrogen production by methanol reforming as well as preparation method and application thereof

A supported catalyst, reforming hydrogen production technology, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve catalyst activity decline, catalyst loss, process cumbersome and other problems, to achieve the effect of reduced content of active components, reduced catalyst cost, and good catalyst performance

Active Publication Date: 2012-10-10
SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The core of methanol reforming hydrogen production technology lies in catalysts. Related catalysts have been widely and deeply studied, among which copper-based catalysts are the most studied. In recent years, noble metal catalysts have attracted extensive research because of their high activity and stability. , but the selectivity needs to be further improved
According to the literature, reforming hydrogen production catalysts are mostly prepared by carbonate liquid-phase co-precipitation method. The introduction of alkali metal contamination leads to a decrease in catalyst activity

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Weigh 13.06gSiO 2 and 52.24gAl 2 o 3 SiO was prepared by extruding 2 -Al 2 o 3 Complex carrier. Accurately weigh 15.39g copper nitrate [Cu(NO 3 ) 2 ·3H 2 O], 23.76g zinc nitrate [Zn(NO 3 ) 2 ·6H 2 O], formulated as an aqueous solution, to obtain SiO 2 -Al 2 o 3 Composite (composition mass fraction is: SiO 2 =20.0%, Al 2 o 3 =80.0%) as the carrier, prepared by equal volume impregnation method, dried at 100°C for 15h, and then calcined at 540°C for 3h under nitrogen atmosphere to obtain the catalyst, the composition of which is (mass fraction): CuO 15.2%, ZnO 19.5% , Composite carrier 65.3%.

[0026] After getting 3.0g of catalyst into the reactor, pass H at 15ml / min 2 , reduced at 260°C for 2h, then stopped the hydrogen, raised the temperature to 280°C, and started the feeding reaction. At 280°C, mass space velocity 1.0h -1 , Under normal pressure, the conversion rate of methanol is 79.2%, the product hydrogen selectivity is 74.6%, and the carbon mono...

Embodiment 2

[0028] Weigh 30.85gSiO2 2 and 30.85gAl 2 o 3 SiO was prepared by extruding 2 -Al 2 o 3 Complex carrier. Accurately weigh 25.11g copper nitrate [Cu(NO 3 ) 2 ·3H 2 O], 16.45g zinc nitrate [Zn(NO 3 ) 2 ·6H 2 O], formulated as an aqueous solution, to obtain SiO 2 -Al 2 o 3 Composite (composition mass fraction is: SiO 2 =50.0%, Al 2 o 3 =50.0%) as the carrier, prepared by equal-volume impregnation method, dried at 120°C for 10h, and then calcined at 450°C for 5h under air atmosphere to obtain the catalyst, whose composition (mass fraction): CuO 24.8%, ZnO 13.5% , Composite carrier 61.7%.

[0029] After taking 3.0g of catalyst into the reactor, pass H at 30ml / min 2 , reduced at 230°C for 4h, then stopped the hydrogen, raised the temperature to 250°C, and started the feeding reaction. At 250°C, mass space velocity 2.0h -1 , 0.5MPa, the conversion rate of methanol is 85.3%, the product hydrogen selectivity is 74.7%, and the carbon monoxide selectivity is 0.33%.

Embodiment 3

[0031] Weigh 22.82gSiO2 2 and 42.38gAl 2 o 3 SiO was prepared by extruding 2 -Al 2 o 3 Complex carrier. Accurately weigh 19.74g copper nitrate [Cu(NO 3 ) 2 ·3H 2 O], 18.64g zinc nitrate [Zn(NO 3 ) 2 ·6H 2 O], formulated as an aqueous solution, to obtain SiO 2 -Al 2 o 3 Composite (composition mass fraction is: SiO 2 =35.0%, Al 2 o 3 =65.0%) as the carrier, prepared by equal-volume impregnation method, dried at 110°C for 13h, and then calcined at 350°C for 8h under air atmosphere to obtain the catalyst, the composition of which is (mass fraction): CuO 19.5%, ZnO 15.3% , Composite carrier 65.2%.

[0032] After taking 3.0g of catalyst into the reactor, pass H at 20ml / min 2 , reduced at 200°C for 6h, then stopped the hydrogen, raised the temperature to 230°C, and started the feeding reaction. At 230°C, mass space velocity 0.5h -1 , Under normal pressure, the conversion rate of methanol is 78.5%, the product hydrogen selectivity is 74.8%, and the carbon monoxide ...

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Abstract

The invention discloses a supported catalyst for hydrogen production by methanol reforming as well as a preparation method and application thereof. The supported catalyst for hydrogen production by methanol reforming comprises the following components in percentage by mass: 15.0-25.0 percent of CuO, 10.0-20.0 percent of assistants, and 60.0-75.0 percent of complex carriers.. The preparation method comprises the steps of: preparing the complex carriers from SiO2 and Al2O3 by virtue of extrusion formation, impregnating the complex carriers in an impregnating solution which is a soluble precursor water solution of copper and the assistants by using an isometric impregnating method, drying at the temperature of 100-120 DEG C for 10-15 hours, and roasting for 3-8 hours under the condition that the roasting atmosphere is nitrogen or air and the roasting temperature is between 350 and 550 DEG C to obtain a catalyst finished product. The supported catalyst for hydrogen production by methanol reforming has the advantages that because the catalyst is prepared by using the impregnating method, the process is simple and easy to control, the cost is greatly reduced, and the performance of the catalyst is good.

Description

technical field [0001] The invention belongs to the field of methanol reforming hydrogen production, and in particular relates to a supported catalyst for methanol reforming hydrogen production and its preparation method and application. Background technique [0002] As a functional material, hydrogen is widely used in petroleum refining, chemical industry, metallurgy, electronics and other industries. It is also an energy material and has great application prospects in the field of new energy, such as fuel cells. However, the transportation and storage of hydrogen are the difficulties in its application process, so it is of great significance to carry out on-site hydrogen production. [0003] There are many ways to produce hydrogen in industry, such as water electrolysis, hydrocarbon steam reforming, water gas reforming, ammonia decomposition, methanol reforming and so on. For small and medium-sized hydrogen-using enterprises, the methanol conversion method has great compe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/83B01J23/80C01B3/32
Inventor 高志贤庆绍军侯晓宁郗宏娟赵金珍谷传涛李光俊李林东胡蕴青董凌曜王海荣
Owner SHANXI INST OF COAL CHEM CHINESE ACAD OF SCI
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