Chlorination reactions relevant to the manufacture of trichloroethene and tetrachloroethene; Part 2: Effects of chlorine supply

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

doi:10.1016/j.apcata.2013.11.030

Cited by 7 publications

(8 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reactions carried out in mild steel that involve Cl 2 may be problematic, since surface chlorination can occur, leading to a chloride surface that behaves like solid FeCl 3 . As a result, the unwanted chlorination of hydrochlorocarbons can occur; this may be accompanied by oligomerization of unsaturated species [ 35 , 36 , 37 ]. This type of behavior in the 1,1,2,2-tetrachloroethane/Cl 2 system was observed in a recent laboratory study of reactions carried out in stainless steel or Pyrex [ 36 , 37 ].…”

Section: Iron(iii) and Copper(ii) Chlorides As Chlorination Catalymentioning

confidence: 99%

“…As a result, the unwanted chlorination of hydrochlorocarbons can occur; this may be accompanied by oligomerization of unsaturated species [ 35 , 36 , 37 ]. This type of behavior in the 1,1,2,2-tetrachloroethane/Cl 2 system was observed in a recent laboratory study of reactions carried out in stainless steel or Pyrex [ 36 , 37 ]. A rather different example of over-chlorination occurred in large-scale reactions of Cl 2 with CH 2 =CH 2 and led to unwanted 1,1,2-trichloroethane in the product, 1,2-dichloroethane.…”

Section: Iron(iii) and Copper(ii) Chlorides As Chlorination Catalymentioning

confidence: 99%

See 1 more Smart Citation

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides

Lennon

Winfield

2017

Molecules

Self Cite

View full text Add to dashboard Cite

Aspects of the chemistry of selected metal fluorides, which are pertinent to their real or potential use as Lewis acidic, heterogeneous catalysts, are reviewed. Particular attention is paid to β-aluminum trifluoride, aluminum chlorofluoride and aluminas γ and η, whose surfaces become partially fluorinated or chlorinated, through pre-treatment with halogenating reagents or during a catalytic reaction. In these cases, direct comparisons with nanostructured metal fluorides are possible. In the second part of the review, attention is directed to iron(III) and copper(II) metal chlorides, whose Lewis acidity and potential redox function have had important catalytic implications in large-scale chlorohydrocarbons chemistry. Recent work, which highlights the complexity of reactions that can occur in the presence of supported copper(II) chloride as an oxychlorination catalyst, is featured. Although direct comparisons with nanostructured fluorides are not currently possible, the work could be relevant to possible future catalytic developments in nanostructured materials.

show abstract

Section: Iron(iii) and Copper(ii) Chlorides As Chlorination Catalymentioning

confidence: 99%

Section: Iron(iii) and Copper(ii) Chlorides As Chlorination Catalymentioning

confidence: 99%

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides

Lennon

Winfield

2017

Molecules

Self Cite

View full text Add to dashboard Cite

show abstract

“…It has previously been used for the manufacture of the refrigerant feedstocks trichloroethene and tetrachloroethene. 7,14 Attapulgite was selected as the support material for its suitability under large-scale fluidised bed applications, such as the oxy-chlorination of dichloroethane to produce tetrachlorethene and trichloroethene. 14 The reaction is studied here in a continuous flow reactor arrangement and its catalytic behaviour studied under laboratory conditions.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2021

Self Cite

View full text Add to dashboard Cite

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.

show abstract

“…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%

“…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%

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

et al. 2018

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Chlorination reactions relevant to the manufacture of trichloroethene and tetrachloroethene; Part 2: Effects of chlorine supply

Cited by 7 publications

References 28 publications

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides

Metal Fluorides, Metal Chlorides and Halogenated Metal Oxides as Lewis Acidic Heterogeneous Catalysts. Providing Some Context for Nanostructured Metal Fluorides

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

Contact Info

Product

Resources

About