Zinc-modified copper-based catalyst for hydrogen production by steam reforming of dimethyl ether and preparation method thereof

A technology of steam reforming and copper-based catalysts, which is applied in metal/metal oxide/metal hydroxide catalysts, chemical instruments and methods, physical/chemical process catalysts, etc. It can solve the problem that the preparation conditions are not easy to control and the catalyst is stable low catalytic activity and copper species are easy to be sintered and deactivated, and achieve broad industrial application prospects, excellent catalytic activity and selectivity, and novel preparation methods

CN106492810BActive Publication Date: 2019-03-26TIANJIN UNIV
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Publication Date
2019-03-26

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Abstract

The invention relates to a zinc modified copper-based catalyst for hydrogen production by dimethyl ether steam reforming and a preparation method. The catalyst is prepared from CuO-ZnO-SiO2 / gamma-Al2O3. The mass ratio of CuO-ZnO-SiO2 to gamma-Al2O3 is (2 to 5): 1. The mass percentages of CuO, ZnO and SiO2 in CuO-ZnO-SiO2 are respectively 23 to 28 percent, 5 to 23 percent and 54 to 67 percent. The catalyst is prepared by two steps of ammonia evaporation and immersing. Regulation of the content of generated cupric silicate is realized by changing conditions such as the concentration of an amino-copper solution, the pH value, the stirring time and the ammonia evaporation temperature, and elemental zinc is introduced to modify the catalyst. The catalyst is applied to the field of hydrogen production reaction by dimethyl ether steam reforming in a fixed bed for the first time; furthermore, by the adding of the elemental zinc, carbon monoxide which is a byproduct is low in selectivity, and the hydrogen yield is high; the catalyst is high in thermal stability.
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Description

technical field

[0001] The invention relates to a catalyst for hydrogen production by steam reforming of dimethyl ether and a preparation method. The invention belongs to the technical field of hydrogen production by steam reforming of dimethyl ether. The novel catalyst has the advantages of high reactivity, low selectivity of by-product carbon monoxide, high stability and the like. Background technique

[0002] In recent years, the situation of energy shortage has become more and more serious. The use of fossil energy not only makes people face a serious energy crisis, but also has a bad impact on the environment on which human beings live. People's demand for energy has gradually shifted to new energy sources. The development of proton exchange membrane fuel cells (PEMFCs) fueled by high-purity hydrogen provides ideas for increasingly tight energy demands. However, since hydrogen is difficult to store and transport, it is necessary to develop an in situ hydrogen produc...

Examples

Embodiment 1

[0025] 1) 5.800g copper nitrate (Cu(NO 3 ) 2 ﹒ 3H 2 O) Dissolve in 80mL deionized water to prepare 0.3mol / L copper nitrate solution.

[0026] 2) At 20°C, add 25% ammonia water dropwise to the solution until the pH value of the solution is 11.8. Stir for 30 minutes to form a cuproammonia solution.

[0027] 3) 18.0 g of silica sol with a mass fraction of 25% was added dropwise to the above solution while stirring. After the dropwise addition, the suspension was sealed and mechanically stirred at 20° C. for 7 hours.

[0028] 4) Transfer the stirred suspension to an evaporator, magnetically stir in a 90°C water bath until the suspension becomes a thin paste, stop the water bath, cool to room temperature, and filter to obtain the product.

[0029] 5) The product was dried at 120° C. for 12 hours, and ground for later use.

[0030] 6) Take 1.735g zinc nitrate (Zn(NO 3 ) 2 ﹒ 6H 2 O) be dissolved in 100mL deionized water to obtain a zinc salt solution. The ground CuO-SiO 2...

Embodiment 2

[0034] According to the step of embodiment 1, the difference is that 1) get 6.940g zinc nitrate (Zn(NO 3 ) 2 ﹒ 6H 2 O) be dissolved in 100mL deionized water to obtain a zinc salt solution. The ground CuO-SiO 2 The sample was added to the solution and sonicated for 30 minutes to obtain a suspension.

Embodiment 3

[0036] According to the step of embodiment 1, the difference is that 1) get 3.470g zinc nitrate (Zn(NO 3 ) 2﹒ 6H 2 O) be dissolved in 100mL deionized water to obtain a zinc salt solution. The ground CuO-SiO 2 The sample was added to the solution and sonicated for 30 minutes to obtain a suspension.