Biogas to high purity hydrogen by methane dry reforming in TZFBR+MB and exhaustion by Steam-Iron Process. Techno-economic assessment

A techno-economic study has been carried out with the aim of analyzing the performance (product distribution and energy yields) and estimating the production costs of high purity hydrogen obtained from biogas. For such purpose and taking advantage of empirical data developed in our laboratory, it has been proposed a system consisting of a two-zone fluidized bed reactor aided by a system of permselective (Pd/Ag) metallic membranes inserted in the fluidized bed (TZFBR+MB), and a battery of several fixed bed reactors operating cycles of reduction and oxidation (Steam-Iron Process -SIP-). The feed has always been an equimolar mixture of CH4 and CO2 simulating a sweetened biogas. The first reactor (TZFBR+MB) can produce a stream of pure hydrogen (i.e. PEMFC quality) as permeated flow through the MB, and a retentate stream rich in all species resulting from the methane dry reforming reaction (MDR) and the water gas shift equilibrium (WGS). The singularity of this kind of complex reactors is that regeneration of the catalyst is performed in the same reactor and simultaneously to the MDR reaction because of the two-zone. Due to the reductive behavior of the retentate stream, it can be fed to a bed of solid where up to two different oxygen carriers (iron oxide with additives and cobalt ferrite) can be reduced to their metallic state. Once the solid has been completely reduced, it can be reoxidized with steam releasing a high purity hydrogen stream. Both reactors (i.e. TZFBR+MB and SIP) have been coupled in different degrees. A performance (hydrogen and energy yields) as well as costs analysis (fixed assets and operating costs) have been performed with the aid of Aspen HYSYS v9.0, used for dimensioning the equipment needed to process up to 1350 kg/h of biogas. On this way, the integrated process enhances the efficiencies of every single process allowing pure hydrogen yields up to 68% at 575 °C in the TZFBR+MB and an overall energy efficiency greater than 45%. Production costs have been found to be in the range from 4 to 15 €/kg, still high but not so far away from the target of DOE fixed in 2 $/kg by 2020.