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Non-noble metal acetylene selective hydrogenation catalyst and preparation method and application thereof

A hydrogenation catalyst and non-precious metal technology, applied in the field of non-precious metal acetylene selective hydrogenation catalyst and its preparation, can solve the problems of high price of precious metal palladium, poor ethylene selectivity, poor stability, etc. The effect of efficient performance

Active Publication Date: 2019-04-16
INST OF METAL RESEARCH - CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, acetylene hydrogenation catalysts are mainly palladium-based catalysts, but due to the high price of noble metal palladium, the cost of acetylene hydrogenation catalysts is relatively high. Researchers are trying to use non-noble metals (such as iron, cobalt, nickel, etc.) The price of a hydrogenation catalyst, but these metal components alone have many problems, such as low activity, poor ethylene selectivity and poor stability caused by carbon deposition, etc.
Although Norskov predicted the excellent performance of nickel-zinc alloy catalysts in the selective hydrogenation of acetylene, the experimental results confirmed that the synthesized Ni-Zn alloy with high zinc content 5 Zn 21 The catalyst can only show an ethylene selectivity of about 50% in the hydrogenation reaction of acetylene, which is still far behind the good palladium-based catalysts reported in the literature.

Method used

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  • Non-noble metal acetylene selective hydrogenation catalyst and preparation method and application thereof
  • Non-noble metal acetylene selective hydrogenation catalyst and preparation method and application thereof
  • Non-noble metal acetylene selective hydrogenation catalyst and preparation method and application thereof

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Experimental program
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Effect test

Embodiment 1

[0028] This embodiment prepares supported Ni 3 ZnC 0.7 The catalyst process is as follows:

[0029] 1. Carbon nanotubes are first added to concentrated hydrochloric acid (37wt.%) with a feed ratio of 1g:100ml, and stirred at room temperature for 24 hours to remove residual metals; then carbon nanotubes are added to concentrated nitric acid with a feed ratio of 1g:100ml (68wt.%), reflux at 140°C for 2 hours, filter and wash until neutral to obtain oxidized carbon nanotubes (oCNT).

[0030] 2. Immersion method: Dissolve 101mg of nickel nitrate hexahydrate and 33.7mg of zinc nitrate hexahydrate in 40ml of ethanol, then add 374mg of carbon dioxide nanotubes, stir ultrasonically for about 1 hour to ensure uniform dispersion, and then remove by rotary evaporator Solvent ethanol, keep warm in oven at 100°C for 2 hours.

[0031]3. The sample treated in step 2 is subjected to reduction treatment in a mixed atmosphere of hydrogen and argon, the flow rate of the mixed gas is 100ml / min...

Embodiment 2

[0040] The Ni prepared by embodiment 1, comparative example 1-2 3 ZnC 0.7 Catalyst, Ni 3 Zn / oCNT catalysts and Ni / oCNT catalysts are used in the selective hydrogenation of acetylene. The application process is as follows:

[0041] Take Ni / oCNT, Ni / oCNT, Ni 3 Zn / oCNT and Ni 3 ZnC 0.7 The / oCNT catalyst is added into the quartz reaction tube, and the catalyst is fixed in the middle constant temperature area of ​​the reaction bed through quartz wool.

[0042] Firstly, pretreatment is carried out: the mixed gas of hydrogen and helium (hydrogen 50vol.%) is passed into the reaction tube, and the catalyst is used for reduction at 500°C for 2 hours, and the gas flow rate is controlled by a mass flow meter to be 20mL / min.

[0043] After pretreatment, it is lowered to 200°C, and then the catalyst performance is tested, specifically: the gas composition of acetylene hydrogenation reaction is: 1.5~6.0vol.%H 2 , 20vol.%C 2 h 4 , 0.5vol.%C 2 h 2 , Helium as the balance gas. The ...

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Abstract

The invention discloses a non-noble metal acetylene selective hydrogenation catalyst and a preparation method and application thereof, and belongs to the technical field of loaded nanoparticle catalysts. Nickel salt and zinc salt are loaded on a carbon material through an impregnation method, and the carbon material is firstly treated under a hydrogen atmosphere to obtain a Ni3Zn catalyst, and then is treated under an acetylene atmosphere to obtain a Ni3ZnC0.7 catalyst. A performance test of acetylene selective hydrogenation reaction shows that the catalyst exhibits excellent selectivity (about 82%) in the reaction after the introduction of carbon atoms to form a Ni3ZnC0.7 structure, and a performance test at a high conversion rate for a long time also shows that the structure and activityof the catalyst have good stability.

Description

technical field [0001] The invention relates to the technical field of supported nanoparticle catalysts, in particular to a non-noble metal acetylene selective hydrogenation catalyst and its preparation method and application. Background technique [0002] Ethylene is the cornerstone of the modern chemical industry. One of its important uses is to produce polyethylene with various structures and specifications through polymerization. The ethylene produced by the petroleum cracking industry contains a small amount of acetylene (0.5%-2%). These small amounts of acetylene Poisons Ziegler-Natta catalysts in the polymerization industry, so acetylene levels must be reduced to <5ppm levels before polymerization can occur. Based on the consideration of technical cost and efficiency at the present stage, the method adopted in industry is to convert a small amount of acetylene into ethylene through catalytic hydrogenation reaction. At present, acetylene hydrogenation catalysts are...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/22C07C11/04C07C5/09
CPCB01J27/22C07C5/09C07C11/04Y02P20/52
Inventor 张炳森牛一鸣王永钊
Owner INST OF METAL RESEARCH - CHINESE ACAD OF SCI
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