Methane coupling in microwave plasma under atmospheric pressure has been investigated.The effects of molar ratio n(CH4)/n(H2),flow rate and microwave power on the reaction have been studied.(1) With the decrease of n(CH4)/n(H2) ratio,methane conversion,C2 hydrocarbon yield,energy yield and space-time yield of acetylene increased,but the yield of carbon deposit decreased.(2) With the increase of microwave power,energy yield of acetylene decreased,but space-time yield of acetylene increased.(3) With the increase of flow rate,energy yield and space-time yield of acetylene increased first and then decreased.Finally,under the reaction conditions of CH4 flow rate of 700 mL/min,n(CH4)/n(H2) ratio of 1/4 and microwave power of 400 W,the energy yield and space-time yield of acetylene could reach 0.337 mmol/kJ and 12.3 mol/(s·m3),respectively.The reaction mechanism of methane coupling in microwave plasma has been investigated based on the thermodynamics of chemical reaction.Interestingly,the acetylene yield of methane coupling in microwave plasma was much higher than the maximum thermodynamic yield of acetylene.This phenomenon was tentatively explained from non-expansion work in the microwave plasma system.