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Cu-Zr catalyst for steam reforming of methanol to prepare hydrogen and its prepn

A copper-zirconium catalyst, reforming hydrogen production technology, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve the problem of low actual activity and achieve stability Good performance, high hydrogen production selectivity, and good stability

Inactive Publication Date: 2006-05-17
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this type of catalyst is only suitable for the preparation of catalytic systems with low copper content (<30wt%). Although the specific activity (hydrogen production rate per unit mass of metallic copper) is slightly higher than that of traditional Cu-Zn-Al catalysts, its actual activity is much higher than that of traditional Cu-Zn-Al catalysts. Lower than traditional Cu-Zn-Al catalyst

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] 20 grams of copper nitrate (Cu(NO 3 ) 2 ·3H 2 O) and 8.9 grams of zirconium nitrate (Zr(NO 3 ) 4 ·5H 2 O) Dissolve in 200mL ethanol, add 1mol / L oxalic acid ethanol solution under vigorous stirring, centrifuge and wash to obtain a sticky light green precipitate after the precipitation is complete, then move it to an oven and dry it overnight at 100°C, and dry the dried copper The zirconium oxalate precursor is ground into powder, and then fired in sections: bake at 250°C for 1 hour, at 300°C for 1 hour, at 400°C for 1 hour, and finally keep at 550°C for 4 hours, and then press the powder into tablets Forming, grinding and sieving (40-60 mesh), the molar composition obtained is 80% CuO-20% ZrO 2 CuZrO catalyst.

[0022] The evaluation of the catalyst's hydrogen production activity by steam reforming of methanol was carried out in a constant-pressure fixed-bed continuous flow reactor system (400mm×Ф10mm), and the catalyst dosage was 1.0g. The mixture of methanol and...

Embodiment 2

[0024] 2.5 grams of copper nitrate (Cu(NO 3 ) 2 ·3H 2 O) and 40.0 grams of zirconium nitrate (Zr(NO 3 ) 4 ·5H 2 O) Dissolve in 200mL water, add 0.5mol / L oxalic acid aqueous solution, centrifuge and wash the obtained precipitate after the precipitation is complete, then move to an oven, dry at 100°C overnight, and dry the dried copper zirconium oxalate Grind the precursor into powder, then bake in sections: bake at 200°C for 1 hour, bake at 300°C for 1 hour, and finally keep at 450°C for 4 hours, then press the powder into tablets, grind and sieve (40-60 mesh) , to obtain a molar composition of 10% CuO-90% ZrO 2 CuZrO catalyst. Catalyst activity evaluation is the same as embodiment 1, in H 2 O:CH 3 OH (molar ratio) = 2.5:1, the reactor temperature is 225-300°C, the pressure is 1.0atm, and the WHSV is 2.0h -1, the methanol conversion rate reaches 92%, the hydrogen selectivity is 99%, the CO content in the tail gas is less than 0.3% (volume), and the activity does not de...

Embodiment 3

[0030] 10 grams of copper nitrate (Cu(NO 3 ) 2 ·3H 2 O), 22.2 grams of zirconium nitrate (Zr(NO 3 ) 4 ·5H 2 O) and 4.5 grams of cerium nitrate (Ce(NO 3 ) 3 ·6H 2 O) Dissolved in 200mL water, mixed with 0.5mol / L citric acid aqueous solution, stirred evenly, moved into a vacuum dryer, evaporated at 80°C to obtain a gel, then moved to an oven, and dried overnight at 100°C to obtain a dry The foam is ground into powder, and then baked in sections: baked at 200°C for 1 hour, baked at 300°C for 1 hour, and finally kept at 350°C for 4 hours, then pressed the powder into tablets, ground and sieved (40- 60 mesh), the obtained molar composition is 40% CuO-50% ZrO 2 -10%CeO 2 CuZrCeO catalyst. Catalyst activity evaluation is the same as embodiment 1, in H 2 O:CH 3 OH (molar ratio) = 2:1, the reactor temperature is 225-300°C, the pressure is 1.0atm, and the WHSV is 2.0h -1 , the methanol conversion rate reaches 100%, the hydrogen selectivity is 99%, the CO content in the tail...

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Abstract

The present invention discloses one kind of Cu-Zr catalyst for steam reforming of methanol to prepare hydrogen and its preparation process. The catalyst without Zn and Al components contains CuO10-80 mol%, ZrO2 20-90 mol% and MOx 0-20 mol%, where M is one of Ce, La, Fe, Y and Mn. The Cu-Zr catalyst is used for steam reforming of methanol to prepare hydrogen, and has high activity, high hydrogen selectivity and very high stability. Specifically, it has conversion rate in steam reforming of methanol of 90-99 %, hydrogen selectivity of 95-99 % and CO content in the product lower than 0.5 %.

Description

technical field [0001] The invention relates to methanol steam reforming hydrogen production technology, and in particular provides a zinc-aluminum component-free copper-zirconium-based multi-component methanol steam reforming hydrogen production catalyst and a preparation method thereof. technical background [0002] Hydrogen is one of the ideal clean energy sources. The biggest obstacle to its utilization lies in the difficulty of storage and distribution. Methanol is considered to be the most promising high-energy-carrying fuel. It has the advantages of cheap and easy to obtain, high energy density, low carbon content, and convenient transportation and storage. It can be used to generate hydrogen instantly through catalytic conversion, which can effectively solve the problem of hydrogen energy. There are various problems in utilization (J. Power Source, 2002, 106, 249). Catalytic hydrogen production from methanol has good application prospects, such as directly supplying...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/72B01J23/83B01J23/889C01B3/40
CPCY02P20/52
Inventor 曹勇姚成漳王路存刘咏梅范康年
Owner FUDAN UNIV
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