Alkali metal K- and/or Na-promoted FeCoCuAl catalysts were synthesized by precipitation and impregnation, and their physicochemical and catalytic performance for CO2 hydrogenation to light hydrocarbons was also investigated in the present work. The results indicate that Na and/or K introduction leads to the formation of active phase metallic Fe and Fe-Co crystals in the order Na < K < K-Na. The simultaneous introduction of Na and K causes a synergistic effect on increasing the basicity and electron-rich property, promoting the formation of active sites Fe@Cu and Fe-Co@Cu with Cu0 as a crystal core. These effects are advantageous to H2 dissociative adsorption and CO2 activation, giving a high CO2 conversion with hydrogenation. Moreover, electron-rich Fe@Cu (110) and Fe-Co@Cu (200) provide active centers for further H2 dissociative adsorption and O-C-Fe intermediate formation after adsorption of CO produced by RWGS. It is beneficial for carbon chain growth in C2+ hydrocarbons, including olefins and alkanes. FeCoCuAl simultaneously modified by K-Na exhibits the highest CO2 conversion and C2+ selectivity of 52.87 mol% and 89.70 mol%, respectively.
NiCuMoLaAl mixed oxide catalysts are prepared and applied in the steam reforming of chloroform-ethyl acetate (CHCl3-EA) mixture to syngas in the present work. The pre-introduction of Cl- ions using chloride salts as modifiers aims to improve the chlorine poisoning resistance. Catalytic tests show that KCl modification is obviously advantageous to increase the catalytic life. The destruction of catalyst structure induced by in situ produced HCl and carbon deposits that occurred on acidic sites are two key points for deactivation of reforming catalysts. The presence of Cl− ions gives rise to the formation of an Ni-Cu alloy, which exhibits a synergetic effect on catalyzing reforming along with metallic Ni crystals formed from excess nickel species, and giving an excellent catalytic stability. Less CHCl3 and more steam can also increase the catalytic stable time of KCl-modified NiCuMoLaAl reforming catalyst.
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