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Energies 2020, 13, 420 2 of 96 affected by intermittency and fluctuation of the energy sources that lead to both temporal and spatial discrepancy between the power supply and demand [3]. Green synthetic fuels can support the transition to a decarbonized energy system. Hydrogen and synthetic natural gas are energy carriers that can be exploited as alternative fuels to reduce GHG emissions and the depletion of fossil fuels. They enable cost-effective, long-term and high energy density storage, distribution and transport. Moreover, synthetic fuels can be converted into heat or electric power (combustion, fuel cells) during peak loads, ensuring higher flexibility of the electric and gas grid [4]. Nevertheless, hydrogen plays a primary role in the decarbonization of the road transport sector—the source of 24% of CO2 emissions, which is annually increasing by 1.6% in the past decade [5]. Indeed, the decarbonization of the mobility sector requires the combination of battery electric vehicles (BEVs), fuel-cell electric vehicles (FCEVs), biofuels, and synthetic fuels produced by non-fossil feedstock and low-carbon energy sources or through carbon capture and utilization [6]. BEVs are commercially available for short–medium distance road transportation, but the main drawbacks are related to the low energy density (low power-to-weight ratio) of batteries. Indeed, the battery size remarkably affects the battery cost, competitiveness and its applicability to heavy-duty vehicles, shipping and aviation. Hannula et al. [7] estimate that for a 135 km range, the BEVs equal-cost oil price is 66 $/bbl, which could compete with the fossil fuel price. Further, increasing the range to 500 km, the equal-cost is 243 $/bbl. Biofuels are widely available and competitive to achieve market penetration. The EU directive 2003/30/EC [8] established targets of biofuels and other renewable fuels utilization in the transport sector. Most vehicles of the European Union are capable of using low biofuel blends, and the Member States should introduce a minimum proportion of biofuels allocated for transport purposes. Targets were set to 2% by 2005 and 5.75% by 2010, and the EU directive 2009/28/EC [9] establishes the target to 10% by 2020. However, biofuels are not sufficient to sustain the transport sector decarbonization due to the relation between bioenergy and land-use change (LUC) and the competition with food production [10]. Instead, carbon-neutral synthetic fuels enable a gradual transition to the decarbonization of mobility, especially in long-distance and heavy transport because the gas storage in low volumes is more effective than electric power in batteries. FCEVs are vehicles that use the hydrogen stored in a pressurized tank to feed fuel cells for electric power generation. Driving performance and refueling time are comparable to conventional cars; therefore, fuel cell vehicles are a promising solution to substitute conventional cars by reducing GHG emissions [11]. The International Renewable Energy Agency (IRENA) [12] analyzes the hydrogen production sources and future perspective. Nowadays, approximately 120 Mtons of hydrogen are produced each year, accounting for approximately 4% of global final energy and non-energy consumption. Approximately 95% of the hydrogen produced worldwide today is derived from methane in fossil fuels without carbon capture, primarily through steam methane reforming (SMR), followed by coal and oil. Hydrogen is mainly exploited in the industrial sector for the production of ammonia and oil refining [13]. The hydrogen produced from fossil fuels is cost-effective but not environmentally sustainable since the emission factor ranges from 285 gCO2/kWh if derived from SMR to 675 gCO2/kWh from coal gasification. Further, CO2 emissions could be higher compared to direct combustion of fossil fuels due to process losses [14]. An alternative to reduce CO2 emissions is hydrogen generation from fossil fuels with carbon capture utilization and storage (CCUS), the so-called blue hydrogen, able to recover 85%–95% of the CO2 emissions [14]. Three common capture strategies are available: (i) the post-combustion carbon capture and removal at low pressure and low concentration, (ii) pre-combustion removal from syngas produced by SMR or gasification, and (iii) oxyfuel processes with recycled CO2 and steam that result in high CO2 concentration and easy removal by condensation [15]. The cleanest way to produce hydrogen is through water-splitting technologies coupled with renewable energy sources. The Hydrogen Council [16] estimated that, by 2030, a surplus of renewablePDF Image | Green Synthetic Fuels
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