Activation of methane: A selective industrial route to methanesulfonic acid

Abstract

Direct methane functionalization to value-added products remains a challenge because of the propensity for overoxidation in many reaction environments. Sulfonation has emerged as an attractive approach for achieving the necessary selectivity. Here, we report a practical process for the production of methanesulfonic acid (MSA) from only two reactants: methane and sulfur trioxide. We have achieved >99% selectivity and yield of MSA. The electrophilic initiator based on a sulfonyl peroxide derivative is protonated under superacidic conditions, producing a highly electrophilic oxygen atom capable of activating a C–H bond of methane. Mechanistic studies support the formation of CH3+as a key intermediate. This method is readily scalable with reactors connected in series for prospective production of up to 20 metric tons per year of MSA.

Water enables mild oxidation of methane to methanol on gold single-atom catalysts

“…For single atoms, δ = 100%. For NPs, δ was calculated using the following equations (equations [11][12][13] given by Vannice 29 :…”

“…For instance, aqueous Au-Pd colloids achieved selective oxidation of methane into methanol with H 2 O 2 as an oxidant under 30 bar of CH 4 at 50°C 10 . Methane was reported to be oxidized into methanesulfonic acid by SO 3 over an electrophilic initiator at 50°C 11 . However, these processes generally involve corrosive oxidant or expensive media, such as H 2 O 2 , oleum, trifluoroacetic acid, and hydrobromic acid, which is not suitable for commercialization [12][13][14][15] .…”

Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer

“…Fundamentally, this catalytic conversion requires low activation energy and high reactivity, in order to accommodate the low thermal energy and partial pressure of CH 4 substrate at ambient condition. Existing approaches of CH 4 functionalization usually operated at high pressure and/or elevated temperature [3][4][5][6][7][8][9][10][11][12][13][14][15][16] , involve metal-catalyzed reactions [3][4][5][6][7] , superacid-based activation 17 , or catalysis based on peroxo species for a free-radical chain mechanism [8][9][10] . For the metal-catalyzed reactions reported by Periana and others ( Fig.…”

On the Electronic Origins of the Different Behaviors of S+ and S2+/2+ in Methane Activation

“…[6] Later, Bell et al reported direct conversion of methane to methanesulfonic acid. [7] Recently, Díaz-Urrutia and Ott reported a practical process for the production of methanesulfonic acid from methane and sulfur trioxide, [8] promising in industrial application. On the other hand, however, the associated fundamental research -for example the gas-phase study on methane activation with CÀ S coupling -is lacking.…”