Preparation method for catalyst prepared from Si-based material having undergone lattice doping by metallic element, and method for oxygen-free preparation of ethylene from methane

A lattice doping, metal element technology, applied in the direction of metal/metal oxide/metal hydroxide catalyst, catalyst, carbon compound catalyst, etc., can solve the problem of short catalyst life, high selectivity of aromatic hydrocarbon products, and no large-scale application prospects, etc.

Active Publication Date: 2017-07-04
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
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  • Description
  • Claims
  • Application Information

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Problems solved by technology

For the selective oxidation of methane to produce methanol or formaldehyde, since the oxidation rate of the target product methanol and formaldehyde is much faster than that of the raw material methane, the selectivity of the reaction is low, and there is basically no prospect of large-scale application
[0008] For the method disclosed in the patent application number 201310174960.5, in the catalyst described, metal elements coexist in the Si-based material as lattice doping and surface loading, resulting in some defects in the catalyst structure, which leads to the following shortcomings in the catalyst and reaction process : (1) redox tolerance temperature is only 800-1150°C; (2) catalyst life is short (about 100 hours); (3) ethylene selectivity is low (30-90%); (4) selection of aromatic products High resistance (10-70%); (5) There is a small amount of carbon deposition in the initial stage of the reaction

Method used

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  • Preparation method for catalyst prepared from Si-based material having undergone lattice doping by metallic element, and method for oxygen-free preparation of ethylene from methane
  • Preparation method for catalyst prepared from Si-based material having undergone lattice doping by metallic element, and method for oxygen-free preparation of ethylene from methane
  • Preparation method for catalyst prepared from Si-based material having undergone lattice doping by metallic element, and method for oxygen-free preparation of ethylene from methane

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preparation example Construction

[0059] 1. Preparation of catalyst

[0060] The preparation methods of lattice-doped catalysts include solid-phase doping techniques such as chemical vapor deposition (MCVD), sol-gel doping, and porous Si compound infiltration. Catalysts are marked as:

Embodiment 1

[0063] Improved Chemical Vapor Deposition (MCVD)

[0064] Use 30mL / min of high-purity oxygen to reduce SiCl 4 Liquid, FeCl 3 Aqueous solution bubbling into high temperature MCVD, SiCl at 1600 °C 4 and FeCl 3 Oxidative deposition was performed to obtain Fe-doped SiO 2 The powder material was then melted for 3 hours at a temperature of 2200 ° C and a pure oxygen atmosphere of 2 bar, and then rapidly cooled in ice water to obtain 0.2 wt.% catalyst.

Embodiment 2

[0066] Improved Chemical Vapor Deposition (MCVD)

[0067] Use 30mL / min of high-purity oxygen to reduce SiCl 4 Liquid, CoCl 2 , NiCl 2 Aqueous solution bubbling into high temperature MCVD, SiCl at 1600 °C 4 , CoCl 2 and NiCl 2 Oxidative deposition was carried out to obtain Co, Ni doped SiO 2 The powder material was then melted for 3 hours at a temperature of 2200°C in a 2 bar pure nitrogen atmosphere, and then rapidly cooled in liquid nitrogen to obtain 0.5wt.%Co-0.5wt.% catalyst.

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Abstract

The invention relates to a preparation method for a catalyst prepared from a Si-based material having undergone lattice doping by a metallic element, and a method for oxygen-free preparation of ethylene from methane. The methods realize zero carbon formation of methane and high-selectivity synthesis of ethylene. According to the invention, in a fixed-bed reaction mode, reaction temperature is 750 to 1100 DEG C and reaction pressure is 0.1 to 0.3 Mpa; the mass space velocity of raw reaction gas is 1000 to 30000 ml / g / h; the conversion rate of methane is 10 to 60%; the selectivity of olefins is 60 to 95%; the selectivity of propylene and butylene is 5 to 25%; the selectivity of aromatic hydrocarbons is 0 to 25%; and zero carbon formation is formed. The methods provided by the invention has the characteristics of long service life (greater than 500 h) of the catalyst, good redox performance and hydro-thermal stability at a high temperature (less than 1400 DEG C) of the catalyst, high product selectivity, zero carbon formation, easy separation of products, good process repeatability, safe and reliable operation, etc., and have good industrial application prospects.

Description

technical field [0001] The invention relates to a catalyst in which a metal element lattice is doped into a Si-based material and a method for catalyzing the direct preparation of ethylene from methane under oxygen-free conditions. Background technique [0002] The development and effective utilization of natural gas (methane) resources represent the development direction of contemporary energy structure, and it is also one of the important ways to ensure sustainable development and green energy. In recent years, developed western countries have also made breakthroughs in the development of shale gas and "combustible ice", and a "shale gas revolution" has erupted. There are many types of shale gas resources in my country, and the distribution is relatively concentrated. The recoverable resource potential is 25 trillion cubic meters (excluding the Qinghai-Tibet area), which is equivalent to the conventional natural gas in my country's land area, and is similar to the 24 trill...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/745B01J23/755B01J23/58B01J21/10B01J23/02B01J23/52B01J23/89B01J23/06B01J27/22B01J27/224C07C2/76C07C11/04C07C11/06C07C11/08C07C15/04C07C15/24
CPCB01J21/10B01J23/02B01J23/06B01J23/52B01J23/58B01J23/745B01J23/755B01J23/8906B01J27/22B01J27/224C07C2/76C07C2521/10C07C2523/02C07C2523/06C07C2523/52C07C2523/58C07C2523/745C07C2523/755C07C2523/89C07C2527/22C07C2527/224C07C11/04C07C11/06C07C11/08C07C15/04C07C15/24Y02P20/52
Inventor 包信和郭晓光方光宗于琴琴谭大力
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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