Abstract
Zero valent iron (Fe0) water remediation studies, over the last 40 years, have periodically reported the discovery of CnH2n+2 in the product water or product gas, where n = 1 to 20. Various theories have been proposed for the presence of these hydrocarbons. These include: (i) reductive transformation of a more complex organic chemical; (ii) hydrogenation of an organic chemical, as part of a degradation process; (iii) catalytic hydrogenation and polymerisation of carbonic acid; and (iv) redox transformation. This study uses wastewater (pyroligneous acid, (pH = 0.5 to 4.5)) from a carbonization reactor processing municipal waste to define the controls for the formation of CnH2n+2 (where n = 3 to 9), C3H4, and C3H6. A sealed, static diffusion, batch flow reactor, containing zero-valent metals [181 g m-Fe0 + 29 g m-Al0 + 27 g m-Cu0 + 40 g NaCl] L−1, was operated at two temperatures, 273–298 K and 348 K, respectively. The reactions, reactant quotients, and rate constants for the catalytic formation of H2(g), CO2(g), C3H4(g), C3H6(g), C3H8(g), C4H10(g), C5H12(g), C6H14(g,l), and C7H16(g,l), are defined as function of zero valent metal concentration (g L−1), reactor pressure (MPa), and reactor temperature (K). The produced fuel gas (422–1050 kJ mole−1) contained hydrogen + CnHy(gas), where n = 3 to 7. The gas production rate was: [1058 moles CnHy + 132 moles H2] m−3 liquid d−1 (operating pressure = 0.1 MPa; temperature = 348 K). Increasing the operating pressure to 1 MPa increased the fuel gas production rate to [2208 moles CnHy + 1071 moles H2] m−3 liquid d−1. In order to achieve these results, the Fe0, operated as a “Smart Material”, simultaneously multi-tasking to create self-assembly, auto-activated catalysts for hydrogen production, hydrocarbon formation, and organic chemical degradation (degrading carboxylic acids and phenolic species to CO2 and CO).
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