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Energies 2019, 12, 3742 2 of 15 represents a new carbon dioxide economy by producing high-value chemicals and fuels from captured CO2, including methanol, formic acid, urea, and methane [4,6]. Methanol is one of the top chemicals produced in the world [7,8] and is a widely recommended alternative chemical carrier [9] for producing a number of chemicals, such as olefins, gasoline, DME (dimethyl ether), DTBE (methyl tert-butyl ether), acetic acid, formic acid, and hydrogen [7,8,10–12]. Methanol can also be used directly as a transportation fuel in internal combustion engines [13], as a reactant for direct methanol fuel cell [14], and to produce H2 by steam reforming for fuel cell applications [7] or as fuel blend of gasoline from small concentrations as an additive to 15% (M15) and even 85% (M85) [7,9,13]. We also agree with [15] that power to fuel technologies such as fuel methanol and methane are the most interesting and feasible alternatives to producing just hydrogen and using it in a completely new infrastructure. Methane as a gas and methanol as a liquid fuel can be easily carried to the final users by using the existing infrastructure distributing natural gas and liquid fuels. This is the original motivation for studying power to methanol processes. Methanol is mostly produced from catalytic synthesis, the most developed conversion method for enhanced carbon recovery [4]. CO2 hydrogenation to synthesize methanol has been extensively studied using both homogenous and heterogeneous catalysts [4,16–21]. The heterogeneous catalyst is preferable in terms of cost, stability, separation, handling, and reuse of catalyst as well as reactor design. It is also adopted today for large-scale industrial applications to synthesize methanol from syngas [16,20]. Using CuO-ZnO-Al2O3-Cr2O3 as catalyst at 70 bar and 250 ◦C, methanol can be produced with 79% selectivity, 20% yield, and 25% CO2 conversion [22]. While with CuO-ZnO-CrO3 as the catalyst at 50 bar and 250 ◦C, methanol was produced with 57.8% selectivity, 14% yield, and 24% CO2 conversion [23]. There have been papers in literature, e.g., [19], for the design and evaluation of large-scale CO2-to-methanol system. However, CO2-to-methanol fed with renewable hydrogen derived from electrolysis technologies has not been little investigated [24,25]. The methanol synthesis through CO2 hydrogenation (CO2-to-methanol process) requires pure hydrogen. The Power-to-Hydrogen (PtH) technology can supply carbon-free hydrogen from renewable energy. The core of the PtH technology is the electrolyzer that electrochemically splits water into hydrogen and oxygen. There are mainly three available electrolysis technologies [26], alkaline electrolysis (AE), polymer electrolyte membranes electrolysis (PEME), and solid-oxide electrolysis (SOE), suitable for different applications of power-to-hydrogen process chains [27]. The SOE has been demonstrated with high electrical and system efficiency [15,26,28] due to the electrolysis at high temperature over 600 ◦C. Therefore, there is a great opportunity for integrating SOE with high-temperature processes to realize high system-level heat integration and to achieve high overall system efficiency [26,29–32]. The coupling of PtH and CO2-to-methanol might solve two crucial problems: (1) long-term and large-scale Electrical Energy Storage (EES) and (2) large-scale CCUS. Therefore, in this study, the concept of CO2-to-methanol integrated with SOE is designed and optimized from a techno-economic perspective. The key issues studied for CO2-to-methanol process integrated with SOE include: (1) system-level heat integration; (2) the impacts of operating variables on system performance, i.e., the overall system efficiency and cost. To achieve this, CO2-to-methanol process integrated with SOE has been modeled and investigated with a multi-objective optimization (MOO) platform considering heat cascade calculation. The remaining paper is organized as follows: The CO2-to-methanol conversion system is briefly described and modeled in Section 2. In Section 3, the optimization methodology and platform are briefly introduced with a detailed definition of the optimization problems. Afterward, the thermodynamic and economic performances for the case study employed are discussed comprehensively in Section 4 to support the design of such a system in the real world. Finally, the conclusions are drawn in Section 5. 2. System Description and Modeling The proposed CO2-to-methanol integrated with SOE process is illustrated in Figure 1 with steady-state simulation models developed in ASPEN PLUS. The system produces annually 100 ktonPDF Image | Optimization of CO2-to-Methanol with Solid-Oxide Electrolyzer
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