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of toxicity and 24 600 ppm per min for significant likelihood of death. In contrast to MeOH, no action has been identified in the regulation of FA to be used as fuel. 5.2 Conventional production of formic acid Formic acid can be produced via four different chemical processes: methyl formate hydrolysis, oxidation of hydrocarbons, hydrolysis of formamide, and preparation of free FA from formates. In Europe, the methyl formate hydrolysis is the most common route [121]. The hydrolysis of methyl formate is based on a two-stage process, according to Eq. (11) and Eq. (12): COCH3OHHCOOCH3 Eq. (11) HCOOCH3 H2OCH3OHHCOOH Eq. (12) In the first reaction, about 95 % of the carbon monoxide and 30 % of the methanol are converted. In the second reaction, the methyl formate is hydrolysed to form FA and MeOH, which is recycled. In order to shift the equilibrium towards FA, excess of one of the reactants is needed. This leads to higher conversions, but also causes a diluted final product. Therefore, FA needs to be separated from the excess of reactant [121]. The two main FA companies in Europe have two different licensed processes, with an identical first stage, but different strategies in the second one. In the Kemira-Leonard process, the excess of methyl formate is considered and FA is dehydrated by distillation, usually in two columns, reaching maximum concentrations of 98 wt % [121]. In the BASF process, excess of water is used, and the separation is done via liquid-liquid extraction with a secondary amide and the extract is separated via distillation [121], [123]. During the production of FA from hydrolysis of methyl formate, CO2 emissions derive from steam and synthesis gas productions. The syngas needed to obtain the CO that reacts with methanol, may come from steam reforming of light ends, as natural gas, or from partial oxidation of fossil feedstocks or gasification of coal [145],[114]. The major energy consumption step in FA synthesis is syngas production, followed by steam needs. The consumption of electricity is the lowest. To compare with the CDU process, we have considered the conventional methyl formate hydrolysis process [146], with CO synthesis from heavy fuel oil [114]. The methyl formate hydrolysis process contributes with 13.9 kg CO2/tFA, as direct process emissions. Indirect emissions of this process are due to the consumption of 0.13 MWh/tFA of electricity and 19.3 MJ/tFA of steam. Electricity needs to synthesise CO are about 1.4 MWh/tFA (note that this value is calculated from an hydrogen production process oil [114], thus, with a certain uncertainty when applied to the FA process). The consumption of heavy fuel oil is about 0.4 t/tFA. The production in conventional FA plants may range from 100 kt FA/yr to 20 kt FA/yr [121]. The new plant that is currently built in Louisiana (US) by BASF, due to low-cost shale gas availability, has a production of 50 kt FA/yr [147]. The selected scale for modelling in the current work is 12 kt FA/yr, taking into account both, conventional and electrochemical scales. Formic acid can be directly used in fuel cells. The direct formic acid fuel cell (DFAFC) is an attractive alternative for small portable fuel cell applications [148]–[150]. In 2006, BASF and Tekion (a developer of micro fuel cells for portable electronic devices) signed a joint collaboration to develop and test FA formulations [151]. However, no further information has been found regarding this project. Potentially, FA can be used as a hydrogen carrier. The so-called "hydrogen economy" aims at increasing the penetration of hydrogen by means of decreasing the use of fossil fuels. Indeed, the 46PDF Image | evaluation of CO2 utilisation for fuel production
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