Oxychlorination of ethylene at high temperatures

Magistro, Angelo J.; Nicholas, Paul P.; Carroll, Richard T.

doi:10.1021/jo01254a004

Cited by 5 publications

(5 citation statements)

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“…It can be seen that without Na, the catalytic performance of the PdFeCl x /Al 2 O 3 catalyst was greatly reduced and cannot compete with that of the CuCl 2 /γ-Al 2 O 3 catalyst . Besides, the iron oxide-containing catalysts, the RhFeZnLiCl x /α-Al 2 O 3 catalyst, fly ash, IrO 2 , and RuO 2 , have been also demonstrated active for ethylene oxychlorination. However, both lower activity and EDC/VCM selectivity were observed over these catalysts than the CuCl 2 /γ-Al 2 O 3 catalyst .…”

Section: Ethylene Oxychlorination Catalystsmentioning

confidence: 99%

Critical Review of Catalysis for Ethylene Oxychlorination

Wang

et al. 2020

ACS Catal.

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Ethylene oxychlorination is the key technology in vinyl chloride (VCM, the monomer of PVC, polyvinyl chloride) production to close the chlorine loop by consuming the HCl released from the former cracking step. Due to the high demand for PVC, this leads to ethylene oxychlorination being one of the most important processes in the industry. This Review covers an indepth analysis of the dynamic nature of active sites for the main and side reactions involved in ethylene oxychlorination, featuring the findings and viewpoints from the dynamic kinetics study and analysis under industrial operating conditions. A unified picture of the mechanism of the surface reactions, and the effect of supports and promoters, has been presented based on the decoupled redoxcycle experiments, which leads to a significantly better understanding of the mechanism and provides valuable guidelines for effective catalyst design. Operando techniques and kinetic tools of the rate-diagram, as well as their application to the study of the redox-cycle in ethylene oxychlorination and kinetic models on both the main product and byproduct, are also reviewed. Perspectives on challenges and new process development and future research focus for better study of the VCM production chemistry are also proposed.

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Section: Ethylene Oxychlorination Catalystsmentioning

confidence: 99%

Critical Review of Catalysis for Ethylene Oxychlorination

Wang

et al. 2020

ACS Catal.

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“…For heterogeneous catalysis of this reaction by copper chloride, still the most widely used oxychlorination catalyst, Deacon suggested the following likely mechanism: 2C uCl2 (s) -Cu2Cl2(s) + Cl2(g) (7) Cu2Cl,(s) + V202(g) ^CuO-CuCt2(s) (8) CuO-CuCl2(s) + 2HCl(g) *=* 2CuC12(s) + H20(g)…”

Section: Oxychlorination Chemistrymentioning

confidence: 99%

“…As the temperature increases the product distribution changes from high yields of 1,2dichloroethane to a mixture of more highly chlorinated hydrocarbons 1,1,2-trichloroethane, trichloroethylene, vinyl chloride, and 1,2-dichloroethylene. It is suggested that two different mechanisms are operating to give this change in product distribution with temperature (8). At lower temperature, the addition mechanism predominates {eq 13), giving saturated product.…”

Section: Oxychlorination Chemistrymentioning

confidence: 99%

“…As the temperature increases, the radical reaction might start to compete by abstracting hydrogen to give vinyl radicals, which, by chlorine substitution, can lead to vinylic chlorides (eqs [10][11][12]. However, by use of a mixture of ethylene and per-deuterated ethylene in oxychlorination at 550 °C, Magistro et al show, by mass spectra analysis of the ratio of deuterated and undeuterated products formed, that an addition step to form saturated products from ethylene, followed by elimination of hydrogen chloride, was the mechanism that best explained the results (8). A mechanism with abstraction of a hydrogen to form vinyl radical intermediate could not explain the deuterium isotope effects on product selectivity.…”

Section: Oxychlorination Chemistrymentioning

confidence: 99%

“…In a kinetic study of ethylene oxychlorination at 350-525 °C, Gel'perin et al find the reaction to be first order in ethylene and zero order in hydrogen chloride; they also demonstrate that the mechanism is an addition reaction to form a saturated chlorinated product, followed by a consecutive reaction of catalyzed dehydrochlorination to form chloro-olefin products (9, 10). In these cases only one mechanism is needed to explain the results over the complete range of temperatures from 200-500 °C; the addition of chlorine to ethylene to form 1,2dichloroethane is shown to be the initial step over supported copper chloride catalysts, and subsequent dehydrochlorination and addition steps lead to higher chlorinated products (8)(9)(10).…”

Section: Oxychlorination Chemistrymentioning

confidence: 99%

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Oxychlorination of ethylene

Magistro¹,

Cowfer²

1986

J. Chem. Educ.

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Oxychlorination of hydrocarbons designates a chemical reaction in which oxygen and hydrogen chloride react with a hydrocarbon, in the vapor phase over a supported copper chloride catalyst, to produce a chlorinated hydrocarbon and water. The oxychlorination reaction is unique in allowing the use of hydrogen chloride instead of molecular chlorine as the chlorinating agent in the manufacture of chlorinated hydrocarbons. Therefore, a commercial operation can utilize coproduct or byproduct hydrogen chloride from another process to provide feedstock for an oxychlorination process.Although oxychlorination can be conducted with aliphatic, olefinic, acetylenic, or aromatic hydrocarbons, the reaction of greatest commercial importance is oxychlorination of ethylene to produce ethylene dichloride (EDC or 1,2-dichloroethane). EDC is the precursor for vinyl chloride monomer (VCM), which is polymerized to poly(vinyl chloride) (PVC). PVC polymer is utilized commercially in a wide variety of useful vinyl plastic products and appears in both rigid and flexible (plasticized) forms. These products include plastic pipe, vinyl house siding, flooring and wall covering, window frames, wire insulation, vinyl seat covers, recording discs, and many others.Compared with most other polymers, poly (vinyl chloride) or PVC is less sensitive to increases in the costs of hydrocarbon raw materials because it consists of 57% by weight chlorine. The inherent flame-retardant properties of PVC and its relatively low cost has enabled rigid PVC compounds also to compete effectively with metals for markets in many applications.

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