Mechanistic origin of the diverging selectivity patterns in catalyzed ethane and ethene oxychlorination

Scharfe, Matthias; Zichittella, Guido; Kondratenko, Vita A.; Kondratenko, Evgenii V.; López, Núria; Pérez‐Ramírez, Javier

doi:10.1016/j.jcat.2019.07.021

Cited by 10 publications

(13 citation statements)

References 42 publications

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“…Thereason for the hampered production of C 2 H 3 Cl stems from the kinetically hindered activation of intermediate C 2 H 4 as long as C 2 H 6 is present in the reaction atmosphere. [9] In particular, it was shown that the activation of the alkane leads to depletion of active sites that are responsible for the further conversion of C 2 H 4 into C 2 H 3 Cl over an iron phosphate catalyst. While variable in strength, the phenomenon of C 2 H 3 Cl suppression was observed over aw ide range of oxychlorination catalysts, including LaOCl and Cu-based systems.…”

Section: Introductionmentioning

confidence: 99%

“…While variable in strength, the phenomenon of C 2 H 3 Cl suppression was observed over aw ide range of oxychlorination catalysts, including LaOCl and Cu-based systems. [9] Alternatively, conversion of C 2 H 6 could target the generation of 1,2-C 2 H 4 Cl 2 in order to circumvent the hindered generation of C 2 H 3 Cl. However,f ormation of dichloroethane is limited (< 10 %s electivity) at the high temperatures (!…”

Section: Introductionmentioning

confidence: 99%

“…Since Dow's discovery in 2010, [7a] no major breakthroughs have been reported, highlighting the challenge of converting this alkane into the desired chlorocarbon. The reason for the hampered production of C 2 H 3 Cl stems from the kinetically hindered activation of intermediate C 2 H 4 as long as C 2 H 6 is present in the reaction atmosphere [9] . In particular, it was shown that the activation of the alkane leads to depletion of active sites that are responsible for the further conversion of C 2 H 4 into C 2 H 3 Cl over an iron phosphate catalyst.…”

Section: Introductionmentioning

confidence: 99%

“…In particular, it was shown that the activation of the alkane leads to depletion of active sites that are responsible for the further conversion of C 2 H 4 into C 2 H 3 Cl over an iron phosphate catalyst. While variable in strength, the phenomenon of C 2 H 3 Cl suppression was observed over a wide range of oxychlorination catalysts, including LaOCl and Cu‐based systems [9] . Alternatively, conversion of C 2 H 6 could target the generation of 1,2‐C 2 H 4 Cl 2 in order to circumvent the hindered generation of C 2 H 3 Cl.…”

Section: Introductionmentioning

confidence: 99%

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Ethane‐Based Catalytic Process for Vinyl Chloride Manufacture

Zichittella

Pérez‐Ramírez

2021

Angew Chem Int Ed

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The use of ethane as ap latform molecule for the manufacture of polyvinyl chloride (PVC) is al ongstanding challenge,whichwould allowtoreduce the raw material costs and CO 2 emissions to produce this plastic.Herein, we discover that rare earth oxychlorides catalyzeinaselective (up to 90 %) and stable (> 50 ho ns tream) manner the reaction of ethane and molecular chlorine into 1,2-dichloroethane,w hich, upon established cracking, will translate into an order of magnitude higher vinyl chloride productivity compared to ethane oxychlorination technologies.Inaddition, representative europium oxychloride was supported on suitable carriers and was demonstrated to be selective (up to 90 %) and stable (> 40 h on stream) in extrudate form. These findings bring the ethanebased production of PVC one step closer to implementation.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Ethane‐Based Catalytic Process for Vinyl Chloride Manufacture

Zichittella

Pérez‐Ramírez

2021

Angew Chem Int Ed

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“…At present, in industry, VDF is usually produced via the dehydrochlorination of 1,1-difluoro-1-chloroethane (HCFC-142b) at reaction temperatures above 650 • C [3,4]. Dehydrochlorination is an efficient route for the preparation of 1, 1-dichloroethylene (VDC), vinyl chloride monomer (VCM), 2,3,3,3-tetrafluoropropene (HFO-1234yf), and ethylene oxychlorination [5][6][7][8]. As the dehydrochlorination of HCFC-142b is a highly endothermic reaction, very long reaction tubes are adopted to supply the reaction heat.…”

Section: Introductionmentioning

confidence: 99%

Facile Preparation of BaClxFy for the Catalytic Dehydrochlorination of 1-Chloro-1,1-Difluoroethane to Vinylidene Fluoride

Han

Liu

et al. 2020

Catalysts

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BaClxFy as well as BaF2 and BaClF catalysts were prepared by solid-state reaction at room temperature with Ba(OH)2 as the precursor and NH4F/NH4Cl as the F and Cl sources. The catalysts were applied for the dehydrochlorination of 1-chloro-1,1-difluoroethane to vinylidene fluoride at 350 °C. The industrial manufacture of vinylidene fluoride (VDF) is carried out at 600–700 °C, whereas the BaClxFy catalysts provided a promising pathway to produce VDF at much lower temperatures. Unfortunately, the selectivity of VDF over BaF2 decreased from 94% to 84% along with the deactivation of the BaF2 catalyst monotonically. In the presence of small amounts of Cl in BaF2, stabilized selectivity was achieved. Over BaCl0.05F0.95, BaCl0.1F0.9 and BaCl0.25F0.75, no decrease in VDF selectivity was observed. Clearly, the presence of small amounts Cl during solid-state preparation inhibited the growth of BaF2 crystalline significantly. Far smaller particles were achieved. The particle size, or more precisely, the crystal size of the barium catalyst played a major role in the catalytic performance. In addition to the crystal growth, the presence of small amounts of Cl during catalyst preparation changed the chemical state of Ba, and therefore the adsorption and activation of the C–Cl bond for HCFC-142b were altered.

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Atomic Cu‐N‐P‐C Active Complex with Integrated Oxidation and Chlorination for Improved Ethylene Oxychlorination

Zheng

Zhang

et al. 2023

Advanced Science

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Fine constructing the chemical environment of the central metal is vital in developing efficient single-atom catalysts (SACs). Herein, the atomically dispersed Cu on the N-doped carbon is modulated by introducing Cu-P moiety to Cu-N-C SAC. Through fine-tuning with another heteroatom P, the Cu SAC shows the superior performance of ethylene oxychlorination. The Cu site activity of Cu-NPC is four times higher than the P-free Cu-NC catalyst and 25 times higher than the Ce-promoted CuCl 2 /Al 2 O 3 catalyst in the long-term test (>200 h). The selectivity of ethylene dichloride can be splendidly kept at ≈99%. Combined experimental and simulation studies provide a theoretical framework for the coordination of Cu, N, and P in the complex active center and its role in effectively catalyzing ethylene oxychlorination. It integrates the oxidation and chlorination reactions with superior catalytic performance and unrivaled ability of corrosive-HCl resistance. The concept of fine constructing with another heteroatom is anticipated to provide with inspiration for rational catalyst design and expand the applications of carbon-based SACs in heterogeneous catalysis.

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Mechanistic origin of the diverging selectivity patterns in catalyzed ethane and ethene oxychlorination

Cited by 10 publications

References 42 publications

Ethane‐Based Catalytic Process for Vinyl Chloride Manufacture

Ethane‐Based Catalytic Process for Vinyl Chloride Manufacture

Facile Preparation of BaClxFy for the Catalytic Dehydrochlorination of 1-Chloro-1,1-Difluoroethane to Vinylidene Fluoride

Atomic Cu‐N‐P‐C Active Complex with Integrated Oxidation and Chlorination for Improved Ethylene Oxychlorination

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