Copper-based catalyst, preparation method thereof and application of copper-based catalyst to furfural hydrogenation catalysis

A copper-based catalyst and catalyst technology, applied in the field of catalytic chemistry, can solve problems that need to be further improved, and achieve the effects of reproducible use of equipment corrosion, simple preparation process, and fast reaction rate

Inactive Publication Date: 2019-04-05
QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Mainly focus on chrome-free copper-based catalysts (non-supported Cu-Zn catalyst, non-supported Cu-Zn-Al catalyst, Cu / MgO catalyst, CuO / SiO 2 Catalyst, Cu-Zn / γ-Al 2 o 3 catalysts, etc.), skeleton catalysts and amorphous alloy catalysts, but the selectivity and stability of the above catalysts need to be further improved

Method used

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  • Copper-based catalyst, preparation method thereof and application of copper-based catalyst to furfural hydrogenation catalysis
  • Copper-based catalyst, preparation method thereof and application of copper-based catalyst to furfural hydrogenation catalysis
  • Copper-based catalyst, preparation method thereof and application of copper-based catalyst to furfural hydrogenation catalysis

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preparation example Construction

[0029] The preparation method of the present invention can realize the carrier ZrO by controlling the molar ratio of the solution, reaction temperature, pressure, time and other factors. 2 -M Modulation of pore diameter and pore volume. According to the requirements of the catalytic performance of furfural hydrogenation to furfuryl alcohol, the carrier ZrO 2 -M pore structure size can be adjusted within the following range: BET specific surface: 100 ~ 300m 2 g -1 ;Pore diameter: 2.5~6nm; Pore volume: 0.1~0.3cm 3 g -1 .

[0030] Compared with the prior art, the present invention has simple operation, mild preparation conditions and good controllability; the prepared product has large specific surface area and high activity; the prepared mesoporous zirconia exhibits higher activity in furfural hydrogenation reaction and selective. Under optimized conditions, complete conversion of furfural can be achieved, and the total yield of furfuryl alcohol can reach over 99%.

Embodiment 1

[0033] Under the constant temperature condition of 40℃, 2.0g P123(EO 20 PO 20 EO 20 ) was dissolved in 30g of absolute ethanol, and stirred vigorously for 3 hours to obtain solution A; another 30g of absolute ethanol was weighed, and 1.0g of acetylacetone (acac) and 6g of zirconium n-propoxide were added, which was recorded as solution B; Mix solutions A and B, add 1.5 g of deionized water, and continue stirring for 3 hours to form a milky white gel. The gel was transferred to a polytetrafluoroethylene-lined autoclave, crystallized at 45 °C for 48 h, and then treated with 0.5 mol L -1The NaOH solution was refluxed for 24 hours, cooled, filtered, washed, dried overnight at 100°C, and the powder was roasted in a muffle furnace at 550°C, and the obtained product carrier was designated as ZrO 2 -M.

[0034] Cu / ZrO 2 - Preparation of M catalyst: make copper nitrate into an aqueous solution with a mass concentration of 50 wt%. Then, the solution was impregnated with the carrie...

Embodiment 2

[0038] Under the constant temperature condition of 50℃, 1.0g P123(EO 20 PO 20 EO 20 ) was dissolved in 30g of absolute ethanol, and stirred vigorously for 4 hours to obtain solution A; another 30g of absolute ethanol was weighed, and 0.5g of acetylacetone (acac) and 8g of zirconium n-propoxide were added, which was recorded as solution B; Mix solutions A and B, add 2.0 g of deionized water, and continue stirring for 3 hours to form a milky white gel. The gel was transferred to a polytetrafluoroethylene-lined autoclave, crystallized at 50 °C for 48 h, and then treated with 0.5 mol L -1 The NaOH solution was refluxed for 24 hours, cooled, filtered, washed, dried overnight at 100°C, and the powder was roasted in a muffle furnace at 550°C, and the obtained product carrier was designated as ZrO 2 -M.

[0039] Cu / ZrO 2 - Preparation of M catalyst: make copper nitrate into an aqueous solution with a mass concentration of 25 wt%. Then, the solution was impregnated with the carri...

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Abstract

The invention discloses a copper-based catalyst taking zirconia as a carrier, a preparation method of the copper-based catalyst and an application of the copper-based catalyst to furfuryl alcohol preparation by furfural hydrogenation. The copper-based catalyst taking the zirconia as the carrier is expressed by a formula Cu/ZrO2-M, wherein Cu is an active component, active metal Cu accounts for 0.05-40% of the total weight of the catalyst, and the carrier ZrO2-M is mesoporous zirconia and accounts for 99.95-60% of the total weight of the catalyst. According to the copper-based catalyst with thezirconia carrier, precious metal is not used as an active component, the copper-based catalyst is low in cost, only contains Cu and the zirconia carrier and is free from other components and simple in preparation process, and furfural conversion rate and furfuryl alcohol selectivity can be effectively improved. Besides, a process for preparing furfuryl alcohol by furfural is mild in reaction condition and high in reaction rate. A product system is simple in separation, and the catalyst is reusable and low in corrosion to equipment. Water serves as a reaction medium, any inorganic acid and alkali are omitted in reaction, and the problem of environmental pollution in the furfural hydrogenation process is avoided.

Description

technical field [0001] The invention relates to the field of catalytic chemistry, in particular to a supported copper-based catalyst, a preparation method thereof and the use of the catalyst in preparing furfuryl alcohol by hydrogenation catalysis of furfural. Background technique [0002] Furfuryl alcohol is an important organic chemical raw material, mainly used in the production of furfural resin, furan resin, furfuryl alcohol-urea resin, phenolic resin, etc. Also used in the preparation of fruit acids, plasticizers, solvents and rocket fuel. In addition, it is also widely used in industrial sectors such as dyes, synthetic fibers, rubber, pesticides and foundry. At present, furfuryl alcohol is mostly produced by hydrogenation of furfural, which is readily available as a raw material. The catalysts for the synthesis of furfuryl alcohol in industry are mainly copper-chromium type and copper-silicon type catalyst system, but the copper-chromium type metal chromium is highl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/72C07D307/44
CPCC07D307/44B01J23/72
Inventor 郭星翠徐国强牟新东刘帅
Owner QINGDAO INST OF BIOENERGY & BIOPROCESS TECH CHINESE ACADEMY OF SCI
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