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Sustainability of (H 2 ? CH 4 ) by Anaerobic Digestion          179

            production of two high-value gases, such as hydrogen and methane, is a solution
            which leads to several energy and environmental advantages: two separate fluxes
            of high-energy value gas (H 2 and CH 4 ), optimization of the AD process for the
            treatment of refuse and its control (Monnet 2003). The produced biogas (CH 4 and/
            or H 2 ) can be used to create a source of income: biogas can be upgraded removing
            carbon dioxide and water vapor, and then, for example, used in a cogeneration unit
            as combined heat and power (CHP) to produce electricity and heat. The digestate
            either liquid or solid can instead be used as a fertilizer, or further processed into
            compost or high-value products, as bioproducts, e.g., acetic and butyric acids
            (Angenent et al. 2004).


            3.1.1 Hydrogen and Methane Production in Two-Steps AD

            Anaerobic digestion, from a biological point of view, is a multistep process that
            involves the action of various microbial species (Lyberatos and Skiadas 1999).
            Usually, such a process contains a particular step, the so-called rate-limiting step,
            which, being the slowest, limits the rate of the overall process (Hill 1977).
            However, the limiting step is not always the same over a wide range of operating
            conditions. It depends on the waste characteristics, hydraulic retention time,
            temperature, and many others (Speece 1983). The two-steps AD process is a
            process in which hydrogen and methane are produced in two separate bioreactors
            through the separation of hydrogen forming bacteria from methane forming bac-
            teria (Tommasi 2011; Gómez et al. 2011) working in different conditions such as
            pH and hydraulic retention time. This partition, optimizing the fermentation pro-
            cess, permits the production of two high-value gases by splitting acetogenesis from
            methanogenesis and increases the overall energy production (89 %) compared
            with one-step processes (only hydrogen production*33 %, only methane pro-
            duction *84 %) as can be seen in Table 1.




            Table 1 Stoichiometric energy efficiency of the reaction involved in H 2 and CH 4 production
            from AD with respect to the energy contained in 1 mol of glucose
            Theoretical reaction involved in two-stage AD process Energy yield (kJ/mol glucose)

                                                   H 2   CH 4  Total  Comparison
                                                                    (%)
            Energy content in glucose              –     –    2,872  100
            Theoretical maximum H 2 yield          2,870.4 –  2,870.4 99.9
              C 6 H 12 O 6 ? 6H 2 0 ? 12H 2 ? 6CO 2
            Maximum H 2 yield from acidogenesis (1st step)  956.8  –  965.8  33.3
              C 6 H 12 O 6 ? 2H 2 O ? 4H 2 ? 2CO 2 ? 2CH 3 COOH
            Maximum CH 4 yield from standard AD    –     2,400 2,400  83.3
              C 6 H 12 O 6 ? 3CH 4 ? 3CO 2
            Maximum yield from two-steps (H 2 ? CH 4 )  956.8  1,600 2,556.8 89
              C 6 H 12 O 6 ? 2H 2 O ? 4H 2 ? 2CH 4 ? 4CO 2
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