Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

OP-I-20GAS PHASE OXIDATION OF FORMALDEHYDE INTO FORMICACID ON A V/Ti CATALYST: 1. REACTION KINETICSE.V. Semionova, G.Ya. Popova, T.V. Andrushkevich, E.A. Ivanov,E.V. Ovchinnikova, I.A. Zolotarskii, V.N. ParmonBoreskov Institute of Catalysis SB RAS, Novosibirsk 630090, Russiae-mail: gyap@catalysis.nsk.suIntroductionFormic acid (FA) is produced commercially by a multi-stage hazardous technology.The Boreskov Institute of Catalysis has developed the one-stage gas-phase process of FAproduction by oxidation of formaldehyde (F) over the V 2 O 5 /TiO 2 catalyst. The goal of thiswork was to investigate reaction kinetics.ExperimentalKinetic experiments were performed in a differential reactor with external circulationloop providing ideal mixing regime, at ambient pressure and range temperature 100-180 °Cunder variation of concentrations of F, oxygen and steam. The catalyst fraction was 0.25-0.5 mm. V/Ti catalyst (11%V 2 O 5 /90%TiO 2 ) was used. The BET was 140 m 2 /g.Results and discussionThe products of F oxidation over V 2 O 5 /TiO 2 catalyst are FA, CO and CO 2 , and methylformate minor quantity. In the range temperature 100-180 °C parallel-consecutive network ofproducts formation is determined.r,10 -9 ,mol/m 2 *s30 T=120 o C, X=60±2%201000 2 4 6 8 101510500 20 40 60 802015100 20 40 60 80CH 2OSteady-state concentrations, C,10 -4 mol/lFig. Effect of the concentrations on FAformation rate.O 2H 2OReaction mechanism determined by IRspectroscopy and experimental kinetic dataobtained resulted in the kinetic equations for thereaction rates according to reaction network. Thekinetic parameters were calculated by minimizingthe function, which represents the differencebetween the experimental and the calculatedrates.The work was supported by the Russian Foundation for Basic Research, Grant 06-03-32473-a, Grant 06-03-08137-ofs.64