Light olefins synthesis from С<sub>1</sub>-С<sub>2</sub> paraffins via oxychlorination processes

doi:10.1007/s11705-013-1338-1

Front Chem Sci Eng

2013, Vol. 7

Issue (3) : 279-288 https://doi.org/10.1007/s11705-013-1338-1

RESEARCH ARTICLE

Light olefins synthesis from С₁-С₂ paraffins via oxychlorination processes

Anton SHALYGIN, Evgenii PAUKSHTIS, Evgenii KOVALYOV, Bair BAL’ZHINIMAEV(

)

Boreskov Institute of Catalysis, Novosibirsk 630090, Russia

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Abstract

A two-step process was employed to convert methane or ethane to light olefins via the formation of an intermediate monoalkyl halide. A novel K₄RuOCl₁₀/TiO₂ catalyst was tested for the oxidative chlorination of methane and ethane. The catalyst had high selectivity for methyl and ethyl chlorides, 80% and 90%, respectively. During the oxychlorination of ethane at T≥250°C, the formation of ethylene as a reaction product along with ethyl chloride was observed. In situ Fourier transform infrared studies showed that the key intermediate for monoalkyl chloride and ethylene formation is the alkoxy group. The reaction mechanism for the oxidative chlorination of methane and ethane over the Ru-oxychloride catalyst was proposed. The novel fiber glass catalyst was also tested for the dehydrochlorination of alkyl chlorides to ethylene and propylene. Very high selectivities (up to 94%–98%) for ethylene and propylene formation as well as high stability were demonstrated.

Keywords oxychlorination methane ethane light olefins ruthenium catalyst

Corresponding Author(s): BAL’ZHINIMAEV Bair,Email:balzh@catalysis.ru

Issue Date: 05 September 2013

Cite this article:

Anton SHALYGIN,Evgenii PAUKSHTIS,Evgenii KOVALYOV, et al. Light olefins synthesis from С₁-С₂ paraffins via oxychlorination processes[J]. Front Chem Sci Eng, 2013, 7(3): 279-288.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-013-1338-1
https://academic.hep.com.cn/fcse/EN/Y2013/V7/I3/279

Fig.1 Schematic of the catalytic setup

Fig.2 Schematic of the IR high temperature cell

Fig.3 Time dependence of the HCl conversion on the RuO/TiO and KRuOCl/TiO catalysts. Feed gas: 20% HCl in oxygen, GHSV= 750 h

Fig.4 Concentration of the reaction products in methane oxychlorination versus temperature over KRuOCl/TiO. Feed gas: 50% CH +20% HCl+10% O + the balance Ar, GHSV= 2500 h

Fig.5 Temperature dependence of the HCl and CH conversions and the CHCl selectivity in the oxidative chlorination of methane on KRuOCl/TiO. Feed gas: 50% CH +20% HCl+10% O + the balance Ar, GHSV= 2500 h

Fig.6 Effect of the feed gas oxygen concentration on the CHCl selectivity during methane conversion. Conversion was varied by increasing the temperature

Fig.7 IR spectra recorded at 300°C after 10 min of (1) methanol adsorption on the same catalyst evacuated at 300°C for 0.5 h, (2) methane interaction with the catalyst pretreated in O + HCl (1 : 1) at 300°C for 0.5 h, (3) interaction of the reaction mixture CH + HCl+ O (2 ∶ 1 ∶ 1) with the catalyst evacuated at 300°C for 0.5 h

Fig.8 Intensity of the 1270 cm peak as a function of the time after CH admission for (1) CH on the catalyst evacuated at 300°C, (2) reaction mixture CH + HCl+ O on the catalyst evacuated at 300°C, (3) CH on the catalyst pretreated in O at 300°C, (4) CH on the catalyst pretreated in HCl+ O at 300°C

Fig.9 Reaction mechanism of the methane oxidative chlorination on KRuOCl/TiO

Fig.10 Ethane and HCl conversions and selectivity for CHCl and CH versus temperature. Feed gas: 36% ethane, 13.5% HCl, 10% O, and the balance Ar, GHSV= 2500 h

Fig.11 IR spectra recorded at 200°C at different times during the ethane oxychlorination reaction of CH + HCl+ O (2 : 1 : 1) over the KRuOCl/TiO catalyst pretreated by evacuation at 300°C for 1 h.

Fig.12 Reaction mechanism of the ethane oxidative chlorination on KRuOCl/TiO

Tab.1 The performance of various catalysts in the dehydrochlorination reaction of CHCl and CHCl to light olefins (T= 450°C, feed gas: 20% CHCl+ the balance Ar, GHSV= 1000 h)

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