Phosgene formation via carbon monoxide and dichlorine reaction over an activated carbon catalyst: Reaction kinetics and mass balance relationships

Rossi, Giovanni E.; Winfield, John M.; Mitchell, Christopher J.; Meyer, Nathalie; Jones, Don H.; Carr, R. H.; Lennon, David

doi:10.1016/j.apcata.2020.117688

Cited by 9 publications

(36 citation statements)

References 18 publications

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“…The gaseous reactants were pumped through the system using a peristaltic pump for 242 min. IR spectra were recorded 0, 3,6,9,12,15,19,22,25,28,39,40,100,161,221,282,342, 403, 363, and 524 min (fig. S23).…”

Section: General Description Of the Flow Setupmentioning

confidence: 99%

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Novel synthetic pathway for the production of phosgene

et al. 2021

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Chloride ions are efficient catalysts for the synthesis of phosgene from carbon monoxide and elemental chlorine at room temperature and atmospheric pressure. Control experiments rule out a radical mechanism and highlight the role of triethylmethylammonium trichloride, [NEt 3 Me][Cl 3 ], as active species. In the catalytic reaction, commercially available [NEt 3 Me]Cl reacts with Cl 2 to form [NEt 3 Me][Cl 3 ], enabling the insertion of CO into an activated Cl─Cl bond with a calculated energy barrier of 56.9 to 77.6 kJ mol −1 . As [NEt 3 Me]Cl is also a useful chlorine storage medium, it could serve as a catalyst for phosgene production and as chlorine storage in a combined industrial process.

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Section: General Description Of the Flow Setupmentioning

confidence: 99%

“…The carbon-based catalysts lower the activation energy for phosgene formation to relatively low values of 32 to 56 kJ mol −1 (4,(6)(7)(8).…”

Section: Introductionmentioning

confidence: 96%

Novel synthetic pathway for the production of phosgene

et al. 2021

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“…The work also determined the rate law for phosgene synthesis over this substrate. 4 The third paper examined adsorption and desorption characteristics of reagents and product, with the work culminating in a reaction model for how CO and Cl 2 combine over activated carbon to produce phosgene at high selectivity. 5 …”

Section: Introductionmentioning

confidence: 99%

Phosgene Synthesis Catalysis: The Influence of Small Quantities of Bromine in the Chlorine Feedstream

Rossi

Winfield

Meyer

et al. 2021

Ind. Eng. Chem. Res.

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The effect of relatively low concentrations of Br 2(g) in the Cl 2(g) feedstock for phosgene synthesis catalysis via the reaction of CO (g) and Cl 2(g) over activated carbon (Donau Supersorbon K40) is explored. Under the stated reaction conditions and in the absence of a catalyst, BrCl (g) forms from the reaction of Cl 2(g) and Br 2(g) . Phosgene synthesis over the catalyst at 323 K is investigated for Br 2(g) :Cl 2(g) molar flow ratios in the range 0–1.52% (0–15,190 ppm) and shows enhanced rates of phosgene production. Maximum phosgene production is observed at a Br 2(g) :Cl 2(g) molar flow ratio of 1.52% (15,190 ppm), which corresponds to an enhancement in the rate of phosgene production of ∼227% with respect to the phosgene flow rate observed in the absence of an incident bromine co-feed. A reaction model is proposed to account for the experimental observables, where BrCl (g) is highlighted as a significant intermediate. Specifically, enhanced rates of phosgene production are associated with the dissociative adsorption of BrCl (g) that indirectly increases the pool of Cl (ad) available for reaction.

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“…The latter measurements showed a small degree of carbon retention and a greater degree of chlorine retention by the catalyst that compromised the atom economy of the phosgene synthesis process. Moreover, a rate law was determined, as represented by Equation 2 [5]:…”

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confidence: 99%

“…The current article uses this refined kinetic perspective [5] as a springboard to investigate further mechanistic issues for this commercially relevant reaction. Mechanistic insight may be gleaned from primarily kinetic studies that have been performed over the last 70 years, which are summarized below.…”

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confidence: 99%