Chlorination and dehydrochlorination reactions relevant to the manufacture of trichloroethene and tetrachloroethene

Sutherland, Iain W.; Hamilton, Neil G.; Dudman, Christopher C.; Jones, Peter N.; Lennon, David; Winfield, John M.

doi:10.1016/j.apcata.2011.02.035

Cited by 9 publications

(11 citation statements)

References 48 publications

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“…One way to improve the atom economy of the MDI manufacturing process is to utilise the Deacon process to facilitate the conversion of HCl to dichlorine. The Deacon reaction is traditionally associated with copper based catalysts, for which the reaction may be described in terms of the following reaction steps: 6,7 2Cu II Cl 2  2Cu I Cl + Cl 2 role for chlorine production by HCl oxidation in a molten chloride salt catalyst. 9 These recycle processes are not widely adopted at this time.…”

Section: Introductionmentioning

confidence: 99%

The interaction of CO with a copper(ii) chloride oxy-chlorination catalyst

et al. 2021

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The interaction of CO with an attapulgite-supported, KCl modified CuCl 2 catalyst has previously been examined using a combination of XANES, EXAFS and DFT calculations. Exposing the catalyst to CO at elevated temperatures leads to the formation of CO 2 as the only identifiable product. However, phosgene production can be induced by a catalyst pre-treatment stage, where the supported CuCl 2 sample is exposed to a diluted stream of dichlorine; subsequent CO exposure at  643 K then leads to phosgene production. This communication describes a series of FTIR based, micro-reactor measurements, coupled with characterisation measurements utilising TEM, XRD and XPS to define the nature of the catalyst at different stages of the reaction coordinate. The CuCl 2 catalyst is able to support Deacon activity (2HCl + ½ O 2  Cl 2 + H 2 O), establishing this work with the possibility of utilising the oxy-chlorination of CO to produce phosgene. However, continuous dosing of CO at elevated temperatures over the chlorine pre-dosed CuCl 2 catalyst shows diminishing phosgene production as a function of time-on-stream, indicating surface chlorine supply to be rate-limiting under the reaction conditions studied. A pictorial reaction scheme is proposed to account for the surface chemistry observed.

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Section: Introductionmentioning

confidence: 99%

The interaction of CO with a copper(ii) chloride oxy-chlorination catalyst

et al. 2021

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“…The catalyst supplied by Ineos Chlor Ltd. contains 10% CuCl 2 and 8% KCl supported on an attapulgite clay and is described elsewhere. 6,7 Before use the material was dried under a continuous stream of N 2 (BOC, 99.998%) at a owrate of 50 mL min À1 and a temperature of 110 C for 12 h. Chlorine pre-treated catalyst samples were prepared by exposing the dried catalyst to a Cl 2 /N 2 co-feed (6 mL min À1 Cl 2 , 50 mL min À1 N 2 ) for 10 min at 370 C. This chlorine exposure was repeated a further three times before reverting the carrier gas back to pure N 2 . The sample was maintained at 370 C for 30 minutes, aer which the heating was turned off and the sample allowed to cool to ambient temperature in the presence of owing nitrogen.…”

Section: Chemicals and Materialsmentioning

confidence: 99%

“…CuCl 2 (Sigma-Aldrich, 97%), CuCl 2 $H 2 O (Sigma-Aldrich, 99.99%), CuO (Acros Organics, 97%) and Cu 4 (OH) 6 Cl 2 (Supelco, #100%) were used as received. The catalyst supplied by Ineos Chlor Ltd. contains 10% CuCl 2 and 8% KCl supported on an attapulgite clay and is described elsewhere.…”

Section: Chemicals and Materialsmentioning

confidence: 99%

“…All ex situ samples were diluted with cellulose to optimize the effectiveedge step of the XAFS data and measured in transmission mode using ion-chamber detectors. Reference samples were CuO, CuCl 2 , CuCl 2 $H 2 O, and Cu 4 (OH) 6 Cl 2 . A reference spectrum of anhydrous CuCl 2 was prepared in situ by heating CuCl 2 (Sigma Aldrich 99.995%, with boron nitride) in a 3 mm O.D.…”

Section: Xafsmentioning

confidence: 99%

“…This catalyst has previously been investigated for the manufacture of trichloroethene and tetrachloroethene. 6,7 (Attapulgite is the mineralogical name for palygorskite, a porous material formed from interspersed sheets of silica and sheets of octahedrally co-ordinated cations drawn from Mg 2+ , Al 3+ and Fe 3+ .…”

Section: Introductionmentioning

confidence: 99%

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Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene

et al. 2018

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The interaction of CO with an attapulgite-supported Cu(II)Cl 2 catalyst has been examined in a micro-reactor arrangement. CO exposure to the dried, as-received catalyst at elevated temperatures leads to the formation of CO 2 as the only identifiable product.However, phosgene production can be induced by using a catalyst pre-treatment where the supported Cu(II)Cl 2 sample is exposed to a diluted stream of chlorine.Subsequent CO exposure at $370 C then leads to phosgene production. In order to investigate the origins of this atypical set of reaction characteristics, a series of X-ray absorption experiments were performed that were supplemented by DFT calculations. XANES measurements establish that at the elevated temperatures connected with phosgene formation, the catalyst is comprised of Cu + and a small amount of Cu 2+.Moreover, the data show that unique to the chlorine pre-treated sample, CO exposure at elevated temperature results in a short-lived oxidation of the copper. On the basis of calculated CO adsorption energies, DFT calculations indicate that a mixed Cu + /Cu 2+ catalyst is required to support CO chemisorption.

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Multi‐Step Consecutive Photo‐Chlorination of 1,2‐Dichloroethane: Kinetics and Reactive Distillation Experiment

Chen

Liu

et al. 2017

Chem Eng & Technol

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The development and validation of a novel kinetic model for the chlorination of 1,2‐dichloroethane to ultimately hexachloroethane catalyzed by blue light are presented. A factor (Xm) related to the chlorination depth was introduced into the kinetics model, and the results showed that the dynamic features of the photo‐chlorination are better predicted by the modified model than by the conventional one. Furthermore, to enhance the selectivity towards tetrachloroethane and pentachloroethane, a novel reactive distillation with side‐reactor configuration (SRC) for the photo‐chlorination process was proposed. In order to demonstrate the technical feasibility of the process, semi‐batch SRC experiments on the laboratory scale were carried out. Up to 96.5 wt % of tetrachloroethane and pentachloroethane with molar ratios varying from 7 to 0.7 over time were obtained in the bottom product.

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Chlorination and dehydrochlorination reactions relevant to the manufacture of trichloroethene and tetrachloroethene

Cited by 9 publications

References 48 publications

The interaction of CO with a copper(ii) chloride oxy-chlorination catalyst

The interaction of CO with a copper(ii) chloride oxy-chlorination catalyst

Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene

Multi‐Step Consecutive Photo‐Chlorination of 1,2‐Dichloroethane: Kinetics and Reactive Distillation Experiment

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