Al assistant-modified CUO-ZrO2 water gas shift catalyst and preparation method thereof

Abstract

The invention discloses an Al assistant-modified CUO-ZrO2 water gas shit catalyst and a preparation method thereof, and belongs to the technical filed of water gas shift processes and catalysts. According to the preparation method, an Al assistant-modified CUO-ZrO2 carrier is obtained by dissolving an aluminum salt, a zircon salt and urea in water to form a mixed solution, performing hydrothermal treatment on the mixed solution, and washing, drying and roasting hydrothermal products; the Al assistant-modified CUO-ZrO2 carrier is dispersed into a cupric nitrate aqueous solution; the CuO-ZrO2-Al2O3 water gas shift catalyst is prepared by depositing and precipitating by using potassium hydroxide, washing, drying and roasting. The Al assistant-modified CUO-ZrO2 water gas shift catalyst prepared by the preparation method has the advantages of low activation temperature, high activity, wide activity temperature area, high selectivity and high thermal stability, and is especially suitable for the operation environment with hydrogen-rich reaction gas and low steam-to-gas ratio. The activity of the Al assistant-modified CUO-ZrO2 water gas shit catalyst is better than that of the commercial CuO-ZnO-Al2O3 low-temperature water gas shift catalyst.

Description

technical field

[0001] The invention belongs to the field of water gas shift technology and catalyst technology, in particular to CuO-ZrO modified by Al additives 2 Water gas shift catalyst and preparation method thereof. Background technique

[0002] The water gas shift reaction (CO + H 2 O → CO + H 2 ) is an extremely important reaction process in the chemical industry, and is widely used in the ammonia synthesis industry and hydrogen production industry using coal, oil and natural gas as raw materials. In recent years, with the development of vehicle-mounted proton exchange membrane fuel cell (PEMFC) technology, the water-gas shift reaction, as an important link in the PEMFC online hydrogen production system, has once again attracted widespread attention. One of the main technical issues in the commercialization of proton exchange membrane fuel cells for vehicles is how to economically and conveniently convert fossil fuels into hydrogen-rich sources that meet the requi...

Examples

Embodiment 1

[0018] 1.95g Al(NO 3 ) 3 9H 2 O, 15.08g ZrOCl 2 ·8H 2 O and 12.48g urea were dispersed in 65mL deionized water to prepare a mixed solution [ie n(Al):n(Zr)=10:90, n(Al+Zr):n(urea)=1:4]. The above mixed solution was transferred into a hydrothermal reaction kettle with a volume of 100 mL, the hydrothermal temperature was controlled at 150° C., and the hydrothermal time was 48 hours. The hydrothermal product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 250°C for 4 hours to obtain Al-modified ZrO 2 carrier. With the aid of ultrasonication, 3 g of ZrO 2 The carrier was dispersed in 200mL of 0.021mol / L Cu(NO 3 ) 2 ·3H 2 O aqueous solution, and then dropwise add 0.5mol / L KOH aqueous solution to the above solution to the terminal pH = 9.0. The obtained product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 400°C for 4 hours to obtain CuO-ZrO 2 -Al 2 o 3 Water gas shift catalyst.

Embodiment 2

[0020] 0.39g Al(NO 3 ) 3 9H 2 O, 16.41g ZrOCl 2 ·8H 2 O and 6.24g urea were dispersed in 65mL deionized water to prepare a mixed solution [ie n(Al):n(Zr)=2:98, n(Al+Zr):n(urea)=1:2]. The above mixed solution was transferred into a hydrothermal reaction kettle with a volume of 100 mL, the hydrothermal temperature was controlled at 150° C., and the hydrothermal time was 24 hours. The hydrothermal product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 250°C for 4 hours to obtain Al-modified ZrO 2 carrier. With the aid of ultrasonication, 3 g of ZrO 2 The carrier was dispersed in 200mL of 0.021mol / L Cu(NO 3 ) 2 ·3H 2 O aqueous solution, and then dropwise add 0.5mol / L KOH aqueous solution to the above solution to the terminal pH = 9.0. The obtained product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 400°C for 4 hours to obtain CuO-ZrO 2 -Al 2 o 3Water gas shift catalyst. figure 1 It is CuO-...

Embodiment 3

[0022] 1.73g Al 2 (SO 4 ) 3 18H 2 O, 21.21g Zr(NO 3 ) 4 ·5H 2 O and 6.24g urea were dispersed in 65mL deionized water to prepare a mixed solution [ie n(Al):n(Zr)=5:95, n(Al+Zr):n(urea)=1:2]. The above mixed solution was transferred into a hydrothermal reaction kettle with a volume of 100 mL, the hydrothermal temperature was controlled at 170° C., and the hydrothermal time was 24 hours. The hydrothermal product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 250°C for 4 hours to obtain Al-modified ZrO 2 carrier. With the aid of ultrasonication, 3 g of ZrO 2 The carrier was dispersed in 200mL of 0.021mol / L Cu(NO 3 ) 2 ·3H 2 O aqueous solution, and then dropwise add 0.5mol / L KOH aqueous solution to the above solution to the terminal pH = 9.0. The obtained product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 400°C for 4 hours to obtain CuO-ZrO 2 -Al 2 o 3 Water gas shift catalyst.

technical field

[0001] The invention belongs to the field of water gas shift technology and catalyst technology, in particular to CuO-ZrO modified by Al additives 2 Water gas shift catalyst and preparation method thereof. Background technique

[0002] The water gas shift reaction (CO + H 2 O → CO + H 2 ) is an extremely important reaction process in the chemical industry, and is widely used in the ammonia synthesis industry and hydrogen production industry using coal, oil and natural gas as raw materials. In recent years, with the development of vehicle-mounted proton exchange membrane fuel cell (PEMFC) technology, the water-gas shift reaction, as an important link in the PEMFC online hydrogen production system, has once again attracted widespread attention. One of the main technical issues in the commercialization of proton exchange membrane fuel cells for vehicles is how to economically and conveniently convert fossil fuels into hydrogen-rich sources that meet the requi...

Examples

Embodiment 1

[0018] 1.95g Al(NO 3 ) 3 9H 2 O, 15.08g ZrOCl 2 ·8H 2 O and 12.48g urea were dispersed in 65mL deionized water to prepare a mixed solution [ie n(Al):n(Zr)=10:90, n(Al+Zr):n(urea)=1:4]. The above mixed solution was transferred into a hydrothermal reaction kettle with a volume of 100 mL, the hydrothermal temperature was controlled at 150° C., and the hydrothermal time was 48 hours. The hydrothermal product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 250°C for 4 hours to obtain Al-modified ZrO 2 carrier. With the aid of ultrasonication, 3 g of ZrO 2 The carrier was dispersed in 200mL of 0.021mol / L Cu(NO 3 ) 2 ·3H 2 O aqueous solution, and then dropwise add 0.5mol / L KOH aqueous solution to the above solution to the terminal pH = 9.0. The obtained product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 400°C for 4 hours to obtain CuO-ZrO 2 -Al 2 o 3 Water gas shift catalyst.

Embodiment 2

[0020] 0.39g Al(NO 3 ) 3 9H 2 O, 16.41g ZrOCl 2 ·8H 2 O and 6.24g urea were dispersed in 65mL deionized water to prepare a mixed solution [ie n(Al):n(Zr)=2:98, n(Al+Zr):n(urea)=1:2]. The above mixed solution was transferred into a hydrothermal reaction kettle with a volume of 100 mL, the hydrothermal temperature was controlled at 150° C., and the hydrothermal time was 24 hours. The hydrothermal product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 250°C for 4 hours to obtain Al-modified ZrO 2 carrier. With the aid of ultrasonication, 3 g of ZrO 2 The carrier was dispersed in 200mL of 0.021mol / L Cu(NO 3 ) 2 ·3H 2 O aqueous solution, and then dropwise add 0.5mol / L KOH aqueous solution to the above solution to the terminal pH = 9.0. The obtained product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 400°C for 4 hours to obtain CuO-ZrO 2 -Al 2 o 3Water gas shift catalyst. figure 1 It is CuO-...

Embodiment 3

[0022] 1.73g Al 2 (SO 4 ) 3 18H 2 O, 21.21g Zr(NO 3 ) 4 ·5H 2 O and 6.24g urea were dispersed in 65mL deionized water to prepare a mixed solution [ie n(Al):n(Zr)=5:95, n(Al+Zr):n(urea)=1:2]. The above mixed solution was transferred into a hydrothermal reaction kettle with a volume of 100 mL, the hydrothermal temperature was controlled at 170° C., and the hydrothermal time was 24 hours. The hydrothermal product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 250°C for 4 hours to obtain Al-modified ZrO 2 carrier. With the aid of ultrasonication, 3 g of ZrO 2 The carrier was dispersed in 200mL of 0.021mol / L Cu(NO 3 ) 2 ·3H 2 O aqueous solution, and then dropwise add 0.5mol / L KOH aqueous solution to the above solution to the terminal pH = 9.0. The obtained product was washed to remove impurity ions, dried at 120°C for 8 hours, and then calcined at 400°C for 4 hours to obtain CuO-ZrO 2 -Al 2 o 3 Water gas shift catalyst.

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