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Thermodynamic Analysis of Hydrogen Production by a Thermochemical Cycle Based on Magnesium-Chlorine

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Thermodynamic Analysis of Hydrogen Production by a Thermochemical Cycle Based on Magnesium-Chlorine International Journal of Heat and Technology Vol. 39, No. 2, April, 2021, pp. 521-530 Journal homepage: http://iieta.org/journals/ijht Thermodynamic Analysis of Hydrogen Production by a Thermochemical Cycle Based on Magnesium-Chlorine Ahmed Bensenouci*, Mohamed Teggar, Ahmed Medjelled, Ahmed Benchatti Laboratory of Mechanics, Amar Télidji University of Laghouat, B.P. 37G Laghouat 03000, Algeria Corresponding Author Email: [email protected] https://doi.org/10.18280/ijht.390222 ABSTRACT Received: 12 July 2019 Most thermochemical cycles require complex thermal processes at very high temperatures, Accepted: 26 December 2020 which restrict the production and the use of hydrogen on a large scale. Recently, thermochemical cycles producing hydrogen at relatively low temperatures have been Keywords: developed in order to be competitive with other kinds of energies, especially those of fossil exergy analysis, hydrogen production, origin. The low temperatures required by those cycles allow them to work with heats magnesium-chlorine cycle, thermochemical recovered by thermal, nuclear and solar power plants. In this work, a new thermochemical cycle, water splitting cycle is proposed. This cycle uses the chemical elements Magnesium-Chlorine (Mg-Cl) to dissociate the water molecule. The configuration consists of three chemical reactions or three physical steps and uses mainly thermal energy to achieve its objectives. The highest temperature of the process is that of the production of hydrochloric acid, HCl, estimated between 350-450℃. A thermodynamic analysis was performed according to the first and second laws by using Engineering Equation Solver (EES) software and the efficiency of the proposed cycle was found to be 12.7%. In order to improve the efficiency of this cycle and make it more competitive, an electro-thermochemical version should be studied. 1. INTRODUCTION generation as they avoid the intermediate process of generating electricity before hydrogen is produced. Since the The rapid rising world energy demand and climate change beginning of the development of thermochemical cycles four due to greenhouse gas emissions, have motivated the public decades ago, a very long list of 280 thermochemical cycles [7] and private sectors, to seek an alternative to conventional of water decomposition has been discovered, but few of them energies and limited ecological damage. The solution to those have undergone exhaustive studies and have promising results. problems is the use of renewable energies. Currently, the Hydrogen can be produced using fossil fuels, water and world consumes about 85 million barrels of oil and 2.94 billion biomass [8]. Water is one of the most promising resources for cubic meters of natural gas a day [1], releasing greenhouse hydrogen production because of its abundance and equitable effect gases that cause global warming. Unlike fossil fuels, accessibility on the globe as well as its price which is almost hydrogen is a clean and sustainable energy carrier, which is symbolic compared to other sources of energy. Water can be widely considered the fuel of the next generation. The broken down into hydrogen and oxygen by several production of hydrogen from the dissociation of water technologies. High and low temperature electrolysis, molecule constitutes an interesting process of energy photochemical and radiochemical systems, pure and hybrid production which has the potential to be sustainable thermochemical separation cycles are prospective development. Hydrogen demand is expected to increase technologies for hydrogen production. significantly over the next decades. The hydrogen market Several types of thermochemical processes exist for the worldwide is currently growing by 10% per year, reaching production of hydrogen. The sulfur-iodine-based cycle (S-I) between 20 and 40% by the year 2020 [2]. The prevailing was proposed by General Atomics of the United States of process for hydrogen production at large scale is the steam- America in the mid-1970s. These are the three chemical reforming of methane. This technology emits huge amounts of reactions that produce the dissociation of water molecule, the carbon dioxide as the primary greenhouse effect gas. On the highest temperature of the cycle is estimated at 850℃. This other hand, the production of hydrogen based on cycle has a thermal efficiency of approximately 47% and thermochemical cycles does not emit harmful gases. The potentially reaches 60% efficiency with cogeneration of thermal energy required for the operation of these systems can hydrogen and electricity [9, 10]. The UT-3 cycle is a be supplied in abundance for large-scale capacities either by thermochemical cycle of hydrogen production initially heat recovered from thermal and nuclear power plants or developed at the University of Tokyo. This cycle is based directly by solar power plant [3, 4]. The thermochemical essentially on the chemical elements which are bromine, cycles of hydrogen production have received more attention calcium and iron (Br-Ca-Fe). The cycle consists of four steps because current estimates indicate that the production costs of that include only solid and gaseous components, the maximum H2 by these methods could be as low as 60% of those from temperature is about 750℃. The predicted thermal efficiency room temperature electrolysis [5, 6]. Thermochemical cycles of the UT-3 cycle varies between 35-50%, depending on the are more profitable than electrolysis on the hydrogen efficiency of the membrane separators, and whether the 521 electricity is co-generated with hydrogen or not [11-13]. analyzing thermodynamic systems from effective view point. Copper-chlorine (Cu- Cl) is identified as a promising cycle for Various evaluations are carried out using several analyzes and thermochemical hydrogen production by Atomic Energy of tools of thermodynamics and thermochemistry [20, 21]. The Canada Limited (AECL) [14, 15]. Water is decomposed into three chemical reactions of the proposed system are newly hydrogen and oxygen via copper and chlorine compounds. introduced to a thermochemical cycle and validated with This cycle is intended to operate at a temperature of 550℃. simulations and previous studies. The simulations and the The energy efficiency of the process should be around 40-45% thermodynamic modeling of the results were performed with [16, 17]. Recently, it has been upgraded to 47.4% performance the Engineering Equation Solver (EES) software [22]. This in the US Argonne National Laboratory (ANL) [18, 19]. In this work focuses on the details of the proposed Mg-Cl cycle to work, a thorough thermodynamic study of the Magnesium – identify strengths, weaknesses and gaps by developing new chlorine (Mg-Cl) cycle is performed (Figure 1). The study was methods for more efficient and cos t-effective hydrogen conducted with the aid of exergy analysis which allows production. Figure 1. Process flow diagram of the proposed Mg-Cl cycle 2. DESCRIPTION OF THE PROPOSED Table 1. Steps and reactions of the proposed cycle THERMOCHEMICAL CYCLE Temperature °C / Stage Reaction The proposed thermochemical cycle based on magnesium Pressureatm 1. Mg and and chlorine consisting of three main steps, is summarized in MgCl2(s)+ Q Cl2 300°C-400°C/ 1atm Table 1. The main chemical reaction is the reaction of →Mg(s)+Cl2(g) hydrogen production while the other reactions are for the Production 2. HCl and recycling of the chemical elements for the continuity of the Cl2 (g) +H2O(l/g)+ O2 350-450°C/1atm Q→2HCl(g)+1/2O2(g) operation of the cycle. The process is first described by a Production decomposition transformation of solid magnesium chloride at 3. H2 Mg(s)+2HCl(g) <50°C/1atm the highest cycle temperature of 350-450℃ to produce Production →MgCl2(s)+H2(g)+Q magnesium in the solid phase and chlorine gas. The second Q: Heat; g: gas; l: liquid; s: solid step is the reaction of chlorine gas and liquid water or vapor to produce two moles of HCl and one-half mole of oxygen gas. This reaction is called the inverse Deacon reaction. Mg and 3. FEASIBILITY OF THERMOCHEMICAL CYCLE HCl react in the last step to form one mole of MgCl and two STEPS moles of hydrogen H2. These chemical reactions form an internal recycling loop of elements and components in The realization of thermochemical conversion depends on continuous form. each reaction in the steps of the cycle. Therefore, it can be examined with the Gibbs function whether these reactions will 522 occur. The variation of Gibbs free energy (ΔG) at constant 1000 temperature is defined by: 0 -1000 ΔG = ΔH - T ΔS < 0 (1) -2000 G: Gibbs function, is a function of state. -3000 The previous derivation shows that at constant temperature and pressure: -4000 - if ΔG <0: the reaction is feasible and spontaneous -5000 Delta G kJ/kg - if ΔG> 0: the reaction is not feasible and non-spontaneous -6000 (the reaction is spontaneous in the opposite direction) - if ΔG = 0: the system is in equilibrium -7000 The reactions tested are: -8000 0 50 100 150 200 250 300 ReactionTemperature °C MgCl2(s)+ Q →→Mg(s)+Cl2(g) (2) Figure 4. Variation of ΔG as a function of the reaction Cl2 (g) +H2O(l/g)+ Q→2HCl(g)+1/2O2(g) (3) temperature for the third step Mg(s)+2HCl(g) +Q→MgCl2(s)+H2(g) (4) 4. THERMODYNAMIC ANALYSIS OF THE The Figures 2, 3 and 4 illustrate that all steps are feasible PROPOSED CYCLE because of their Gibbs’s functions are less than zero, it can be said that the function of Gibbs increases in the negative sense According to the principle of the conservation of the mass with the increase of the temperature that means that these for a system under a steady state the mass in term of flow reactions will be more spontaneous and more profitable in the remains constant at the entry and the exit [23-25]; temperature ranges which correspond to ΔG high in absolute value. ∑ 푚̇ = ∑ 푚̇ (5) 5000 푛 표푢푡 0 4.1 The first law analysis -5000 For an open steady-state system the variation of the total energy is zero, -10000 푑퐸푠푦푠 퐸̇푛 − 퐸̇표푢푡 = = 0 (6) -15000 푑푡 Delta G KJ/kg Energy can be conserved; -20000 퐸̇ = 퐸̇ (7) -25000 푛 표푢푡 0 100 200 300 400 500 Reaction Temperature °C For an open system, the first law of thermodynamics is written as follows; Figure 2.
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