Maleic anhydride selective hydrogenation catalyst as well as preparation method and application method thereof

A hydrogenation catalyst and application method technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic chemistry, etc., can solve the problems of high hydrogen pressure, high application cost, loss of catalytically active components, etc. mass resistance, good catalytic performance, and the effect of improving the reactivity

Pending Publication Date: 2021-11-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the activity and selectivity are good, it is not suitable for industrialization due to problems such as high cost
The catalysts disclosed in early patents SU1541210, RU2058311, and EP0691335 are supported palladium catalysts, in which the noble metal Pd content is high (2-10wt%), the hydrogen pressure is high (4.0-6.0MPa), and the Pd loss is serious, which is not suitable for industrialization due to cost issues
In addition to noble metals, maleic anhydride hydrogenation catalysts mainly include metal nickel and copper. Compared with catalysts loaded with noble metals, supported non-noble metal catalysts are more affordable, but usually need to add other additives to improve activity and selectivity, and catalytic hydrogenation higher reaction temperature
Chinese patent CN104399469A provides a catalyst for catalyzing the hydrogenation of maleic anhydride to succinic anhydride at low temperature and low pressure, using alumina as a carrier to support 2.5-7.5% nickel, but the conversion rate and selectivity of the reaction are low
Chinese patent CN107597159A discloses a silicon carbide ordered mesoporous material loaded with 7.5-15% nickel and added with 0.2-1.2% metal additives. The content of active metal components is high, resulting in high application costs
[0006] In Chinese patent CN200910073975.6, a catalyst preparation method is protected, the catalyst Ni content is 13-20wt%, the promoter content is 1-7wt%, SiO 2 、Al 2 o 3 or SiO 2 -Al 2 o 3 The composite is used as a carrier, and under the conditions of hydrogenation temperature 60-180°C and hydrogen pressure 0.9-10MPa, it catalyzes the hydrogenation reaction of maleic anhydride, the conversion rate of maleic anhydride is >99.98%, the selectivity of succinic anhydride is >98.85%, and the content of Ni in this method is High, high price, because the catalyst contains an acid center, the maleic anhydride polymerization reaction will occur in the hydrogenation reaction of maleic anhydride, so that the product color is higher, and the carrier SiO2 used 2 、Al 2 o 3 or SiO 2 -Al 2 o 3 The complex is not stable enough under acidic conditions, resulting in the loss of catalytically active components along with the carrier, seriously affecting the catalytic performance and service life of the catalyst
Carbon materials and ceramics are acid-resistant supports, but the interaction between the support and the metal is not strong, and the catalytic active components are easy to lose
Chinese patent CN103769117A uses 10-40% nitric acid to impregnate activated carbon, then loads 1-10% cobalt or nickel, and adds 3-15% of the first additive molybdenum or tungsten, and 5-20% of the second One of the additives iron, copper, and zinc, which solves the problem of easy loss of active components when activated carbon is used as a carrier, but requires a large amount of acid to treat the carrier, which has a greater impact on the environment

Method used

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  • Maleic anhydride selective hydrogenation catalyst as well as preparation method and application method thereof
  • Maleic anhydride selective hydrogenation catalyst as well as preparation method and application method thereof
  • Maleic anhydride selective hydrogenation catalyst as well as preparation method and application method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Embodiment 1 is about Pd-Zn / NHPC catalyst

[0032] At room temperature, weigh 20g of cellulose, 60g of sodium bicarbonate and 60g of ammonium oxalate monohydrate according to the ratio of 1:3:3 and mix them. The heating rate of ℃ / min was heated to 600℃ and kept for 1h. After cooling down, the obtained sample was added to 1000mL distilled water, stirred for 24h, then filtered and washed repeatedly, and finally dried at 70℃ for 24h to obtain nitrogen-doped mesoporous The carrier composed of carbon material NHPC. The specific surface area of ​​the nitrogen-doped mesoporous carbon material NHPC is 230m 2 / g.

[0033] Weigh 1.5g of zinc nitrate, add 20mL of distilled water to dissolve it, and add it dropwise to 5g of the above-prepared carrier, and keep stirring. After all the addition is completed, stir in a 70°C water bath for 24h, then take it out and dry it in a 70°C oven for 12h Sample 1 was obtained; sample 1 was heated up to 500°C at a heating rate of 10°C / min and ...

Embodiment 2

[0036] Embodiment 2 is about Pd-Zn / NHPC catalyst

[0037] At room temperature, weigh 20g of cellulose, 60g of sodium bicarbonate and 60g of ammonium oxalate monohydrate according to the ratio of 1:3:3 and mix them. The heating rate of ℃ / min was heated to 800℃ and kept for 1h. After cooling down, the obtained sample was added to 1000mL distilled water, stirred for 24h, then filtered and washed repeatedly, and finally dried at 70℃ for 24h to obtain nitrogen-doped mesoporous The carrier composed of carbon material NHPC. The specific surface area of ​​the nitrogen-doped mesoporous carbon material NHPC is 230m 2 / g.

[0038] Weigh 1.5g of zinc nitrate, add 20mL of distilled water to dissolve it, and add it dropwise to 5g of the above-prepared carrier, and keep stirring. After all the addition is completed, stir in a 70°C water bath for 24h, then take it out and dry it in a 70°C oven for 12h To obtain sample 1, the sample was heated to 500°C at a heating rate of 10°C / min under a ...

Embodiment 3

[0041] Embodiment 3 is about Pd-Zn / NHPC catalyst

[0042] At room temperature, weigh 10g of cellulose, 50g of sodium bicarbonate and 80g of ammonium oxalate monohydrate according to the ratio of 1:5:8 and mix them. The heating rate of ℃ / min was heated to 600℃ and kept for 1h. After cooling down, the obtained sample was added to 1000mL distilled water, stirred for 24h, then filtered and washed repeatedly, and finally dried at 70℃ for 24h to obtain nitrogen-doped mesoporous The carrier composed of carbon material NHPC. The specific surface area of ​​the nitrogen-doped mesoporous carbon material NHPC is 1180m 2 / g.

[0043] Weigh 1.5g of zinc nitrate, add 20mL of distilled water to dissolve it, and add it dropwise to 5g of the above-prepared carrier, and keep stirring. After all the addition is completed, stir in a 70°C water bath for 24h, then take it out and dry it in a 70°C oven for 12h To obtain sample 1, the sample was heated up to 500°C at a heating rate of 10°C / min unde...

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Abstract

The invention relates to a maleic anhydride selective hydrogenation catalyst as well as a preparation method and an application method thereof. The catalyst is a Pd-M/NHPC catalyst which is prepared by taking a nitrogen-doped mesoporous carbon material NHPC as a carrier and loading Pd-M bimetallic by adopting an impregnation method, in the catalyst, the content of the active component metal Pd is 0.1-5wt%, the content of the metal M is 0.5-10.0 wt%, and the specific surface area is 80-1000m < 2 >/g; and the metal M is one or more of iron, cobalt, zinc and copper. The catalyst is low in cost, large in specific surface area, good in catalytic stability and high in activity and selectivity in reaction for catalyzing maleic anhydride hydrogenation to prepare succinic anhydride.

Description

technical field [0001] The invention relates to a hydrogenation catalyst in the field of chemical catalysis, in particular to a maleic anhydride selective hydrogenation catalyst, a preparation method and an application method thereof. Background technique [0002] Succinic anhydride is an important organic synthesis intermediate and fine chemical raw material, which can undergo hydrolysis, alcoholysis, esterification, halogenation, acylation, reduction, etc., and is widely used in medicine, pesticides, food, petrochemicals, building materials, and synthetic resins and fuels and other fields, in the plastics industry, the polycondensation of succinic acid and 1,4-butanediol, the hydrolysis product of succinic anhydride, can be used to prepare biodegradable plastics with excellent properties - polybutylene succinate (PBS ), can be widely used in packaging, catering, cosmetic bottles, plastic films, etc., and has been listed as an industry encouraged by the state. However, the...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/24B01J35/10C07D307/60
CPCB01J27/24B01J35/1004C07D307/60
Inventor 张治国孙爱国罗梦琳石李明任其龙江鸥鲍宗必杨启炜
Owner CHINA PETROLEUM & CHEM CORP
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