Hydrogen and electricity co-production plant integrating steam-iron process and chemical looping combustion

In this paper, steam-iron process (Fe looping) and NiO-based chemical looping combustion (Ni looping) are integrated for hydrogen production with inherent separation of CO₂. An integrated combined cycle based on the Fe and Ni loopings is proposed and modeled using Aspen Plus software. The simulation results show that at Fe-SR 815 °C, Fe-FR 815 °C, Ni-FR 900 °C and Ni-AR 1050 °C without supplementary firing, the co-production plant has a net power efficiency 14.12%, hydrogen efficiency 33.61% and an equivalent efficiency 57.95% without CO₂ emission. At a supplementary firing temperature of 1350 °C, the net power efficiency, hydrogen efficiency and the equivalent efficiency are 27.47%, 23.39% and 70.75%, respectively; the CO₂ emission is 365.36 g/kWh. The plant is attractive because of high-energy conversion efficiency and relatively low CO₂ emission; moreover, the hydrogen/electricity ratio can be varied in response to demand. The influences of iron oxide recycle rate, supplementary firing temperature, inert support addition and other parameters on the system performance are also investigated in the sensitive analyses.     

Study of the reactivity by pulse of CH4 over NiO/Fe-doped MgAl2O4 oxygen carriers for hydrogen production

The reactivity of Ni-based oxygen carrier (OC) was studied by CH₄ pulse test. The MgAl₂O₄ spinel was synthesized by microwave assisted combustion method and Ni and Fe were added by wet impregnation method. The results of CH₄ pulse test revealed that the OCs were more reactive for partial oxidation reaction. The XRD analysis of OCs after the test confirms the presence of NiO and MgAl₂O₄ without the secondary phases like NiAl₂O₄ and FeAl₂O₄. Among the OCs, Ni15Fe2MA was the most reactive producing the highest amounts of H₂ and exhibiting good re-oxidation capacity, illustrating its potential for use in Chemical Looping Reforming (CLR). The high reactivity is associated to a change on the NiO-support interaction.     

Synthesis of a new self-supported Mgy(CuxNi0.6-xMn0.4)1-yFe2O4 oxygen carrier for chemical looping steam methane reforming process

Novel self-supported Mg_y(Cu_xNi_0.6-xMn_0.4)_1-yFe₂O₄ with (y = 0, 0.05, 0.1, 0.15, and x = 0, 0.15, 0.3, 0.45, 0.6) oxygen carriers (OCs) are synthesized through the co-precipitation method. The synthesized OCs’ properties are characterized by X-ray powder diffraction (XRD), Raman spectra, transform infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), and Thermogravimetric Analysis (TGA). The synthesized OCs are assessed in Chemical Looping Steam Methane Reforming (CL-SMR) process subject to different mesh sizes, reaction temperatures, Steam/Carbon (S/C) molar ratios, Mg concentrations, and Cu and Ni concentrations. The characterization of the OCs and process results indicate the contributive effect of Mg incorporation on the Cu_xNi_0.6-xMn_0.4Fe₂O₄ support structure. The redox results reveal that Mg_0.1(Cu_0.3Ni_0.3Mn_0.4)_0.9Fe₂O₄ OC is of the highest activity, even at low reduction temperatures. This OC exhibits the highest activity and stability with lowest coke deposition during 24 redox cycles at 650 °C and S/C = 2.5. The highest CH₄ conversion of about 99.4% and H₂ yield of about 84.4% are obtained.     

Techno-economic analysis of the Ca-Cu process integrated in hydrogen plants with CO2 capture

In this work, a techno-economic analysis of a hydrogen production plant based on the Ca-Cu process has been carried out. The simulation of the whole hydrogen production plant has been performed, including the calculation of the Ca-Cu fixed bed reactors system using a sharp front modelling approach. From the analyses carried out, it has been demonstrated that the optimal operation point from the energy performance point of view is reached when fuel needed for sorbent regeneration is entirely supplied by the off-gas from the PSA hydrogen purification unit, which corresponds to operating the plant with the minimum steam-to-carbon ratio in the reforming step. Moreover, lowering the operating pressure of the Ca-Cu system results beneficial from the hydrogen production efficiency, but the CO₂ emissions and the economics worsen.The Ca-Cu based hydrogen production plant operating at a high pressure has been demonstrated to be cost efficient with respect to a benchmark hydrogen production plant based on conventional fired tubular reformer and CO₂ capture by MDEA absorption. A hydrogen production cost of 0.178 €/Nm³ and a CO₂ avoided cost of 30.96 €/ton have been calculated for this Ca-Cu hydrogen production plant, which are respectively 8% and 52% lower than the corresponding costs of the benchmark.     

Performance of a PEMFC system integrated with a biogas chemical looping reforming processor: A theoretical analysis and comparison with other fuel processors (steam reforming,partial oxidation and auto-thermal reforming)

In this work, the performance of a PEMFC (proton exchange membrane fuel cell) system integrated with a biogas chemical looping reforming processor is analyzed. The global efficiency is investigated by means of a thermodynamic study and the application of a generalized steady-state electrochemical model. The theoretical analysis is carried out for the commercial fuel cell BCS 500W stack. From literature, chemical looping reforming (CLR) is described as an attractive process only if the system operates at high pressure. However, the present research shows that advantages of the CLR process can be obtained at atmospheric pressure if this technology is integrated with a PEMFC system. The performance of a complete fuel cell system employing a fuel processor based on CLR technology is compared with those achieved when conventional fuel processors (steam reforming (SR), partial oxidation (PO) and auto-thermal reforming (ATR)) are used. In the first part of this paper, the Gibbs energy minimization method is applied to the unit comprising the fuel- and air-reactors in CLR or to the reformer (SR, PO, ATR). The goal is to investigate the characteristics of these different types of reforming process to generate hydrogen from clean model biogas and identify the optimized operating conditions for each process. Then, in the second part of this research, material and energy balances are solved for the complete fuel cell system processing biogas, taking into account the optimized conditions found in the first part. The overall efficiency of the PEMFC stack integrated with the fuel processor is found to be dependent on the required power demand. At low loads, efficiency is around 45%, whereas, at higher power demands, efficiencies around 25% are calculated for all the fuel processors. Simulation results show that, to generate the same molar flow-rate of H₂ to operate the PEMFC stack at a given current, the global process involving SR reactor is by far much more energy demanding than the other technologies. In this case, biogas is burnt in a catalytic combustor to supply the energy required, and there is a concern with respect to CO₂ emissions. The use of fuel processors based on CLR, PO or ATR results in an auto-thermal global process. If CLR based fuel processor is employed, CO₂ can be easily recovered, since air is not mixed with the reformate. In addition, the highest values of voltage and power are achieved when the PEMFC stack is fed on the stream coming from SR and CLR fuel processors. When a H₂ mixture is produced by reforming biogas through PO and ATR technologies, the relative anode overpotential of a single cell is about 55 mV, whereas, with the use of CLR and SR processes, this value is reduced to ∼37 and 24 mV, respectively. In this way, CLR can be seen as an advantageous reforming technology, since it allows that the global process can be operated under auto-thermal conditions and, at the same time, it allows the PEMFC stack to achieve values of voltage and power closer to those obtained when SR fuel processors are used. Thus, efforts on the development of fuel processors based on CLR technology operating at atmospheric pressure can be considered by future researchers. In the case of biogas, the CO₂ captured can produce additional economical benefits in a ‘carbon market’.     

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.     

Chemical looping reforming of ethanol-containing organic wastewater for high ratio H2/CO syngas with iron-based oxygen carrier

This work focused on chemical looping reforming (CLR) of ethanol-containing wastewater using iron-based oxygen carrier for high ratio H₂/CO syngas. Effects of various operating parameters on CLR experiments have been investigated. High temperature promotes the reactivity of oxygen carrier and release more lattice oxygen for CLR of ethanol-containing wastewater to realize maximum carbon conversion. 5% ethanol-containing wastewater, closed to the actual concentration of alcohol distillery wastewater, favors syngas yield. Ethanol-containing wastewater CLR processes could be divided into three stages, including the catalytic cracking, combination of catalytic cracking and reforming, and mainly catalytic reforming of ethanol, corresponding to three reduction periods Fe₂O₃ → Fe₃O₄, Fe₃O₄ → Fe₂O_2.45, and Fe₂O_2.45 → FeO, respectively. The whole process of ethanol-containing organic wastewater CLR is exothermic. Reaction heat released from the oxidation process of the reduced oxygen carrier can meet heat demand for CLR process. Ethanol-containing organic wastewater CLR opens up a new direction for hydrogen generation and waste treatment.     

Thermodynamic screening of suitable oxygen carriers for a three reactor chemical looping reforming system

Hydrogen (H₂) production by using a three reactor chemical looping reforming (TRCLR) technology is an innovative process which utilizes fossil fuels as feed stocks. This process occurs in three steps by employing an oxygen carrier (OC), which is generally a transition metal. As the OC plays an important role, its selection should be done after carefully considering the chemical and physical properties of the material. In this study, various candidate materials for use in a TRCLR process, with methane (CH₄) as a fuel stock, were investigated. The results show that the iron (Fe)- and molybdenum (Mo)-based OCs oxidize CH₄ completely in the FR at low temperatures. In terms of H₂ yield, tungsten (W)-based OCs produce the highest yield, ～3.9 mol-H₂/mol-CH₄. The equilibrium oxygen partial pressures and the solid circulation rates are the highest for Fe-based OCs. The oxygen carrying capacity of Fe-based OCs is relatively high while its price is low. Therefore, among the OCs investigated, Fe-based OCs were identified as the preferred OC option for a TRCLR process.     

Novel quasi-autothermal hydrogen production process in a fixed-bed using a chemical looping approach: A numerical study

This paper presents a novel quasi-autothermal hydrogen production process. The proposed layout couples a Chemical Looping Combustion (CLC) section and a Steam Methane Reforming (SMR) one. In CLC section, four packed-beds are operated using Ni as oxygen carrier and CH₄ as fuel to continuously produce a hot gaseous mixture of H₂O and CO₂. In SMR section, two fixed-beds filled with Ni-based catalyst convert CH₄ and H₂O into a H₂-rich syngas. Four heat exchangers were employed to recover residual heat content of all the exhaust gas currents. By means of a previously developed 1D numerical model, a dynamic simulation study was carried out to evaluate feasibility of the proposed system in terms of methane conversion (100% circa), hydrogen yield (about 0.65 mol_H2/mol_CH4) and selectivity (about 70%), and syngas ratio (about 2.3 mol_H2/mol_CO). Energetic and environmental analyses of the system performed with respect to conventional steam methane reforming, highlights an energy saving of about 98% and avoided CO₂ emission of about 99%.     

Iron oxide ores as carriers for the production of high purity hydrogen from biogas by steam–iron process

Production of high purity hydrogen (<50 ppm CO) by steam–iron process (SIP) from a synthetic sweetened biogas has been investigated making use of a natural iron ore containing up to 81 wt% of hematite (Fe₂O₃) as oxygen carrier. The presence of a lab-made catalyst (NiAl₂O₄ with NiO excess above its stoichiometric composition) was required to carry out the significant transformation of mixtures of methane and carbon dioxide in hydrogen and carbon monoxide by methane dry reforming reaction. Three consecutive sub-stages have been identified along the reduction stage that comprise A) the combustion of CH₄ by lattice oxygen of NiO and Fe₂O₃, B) catalyzed methane dry reforming and C) G–G equilibrium described by the Water-Gas-Shift reaction. Oxidation stages were carried out with steam completing the cycle. Oxidation temperature was always kept constant at 500 °C regardless of the temperature used in the previous reduction to minimize the gasification of eventual carbon deposits formed along the previous reduction stage. The presence of other oxides different from hematite in minor proportions (SiO₂, Al₂O₃, CaO and MgO to name the most significant) confers it an increased thermal resistance against sintering respecting pure hematite at the expense of slowing down the reduction and oxidation rates. A “tailor made” hematite with additives (Al₂O₃ and CeO₂) in minor proportions (2 wt%) has been used to stablish comparisons in performance between natural and synthetic iron oxides. It has been investigated the effect of the reduction temperature, the proportion of methane to carbon dioxide in the feed (CH₄:CO₂ ratio) and the number of repetitive redox cycles.     

Hydrogen production from bio-oil: A thermodynamic analysis of sorption-enhanced chemical looping steam reforming

The steam reforming of pyrolysis bio-oil is one proposed route to low carbon hydrogen production, which may be enhanced by combination with advanced steam reforming techniques. The advanced reforming of bio-oil is investigated via a thermodynamic analysis based on the minimisation of Gibbs Energy. Conventional steam reforming (C-SR) is assessed alongside sorption-enhanced steam reforming (SE-SR), chemical looping steam reforming (CLSR) and sorption-enhanced chemical looping steam reforming (SE-CLSR). The selected CO₂ sorbent is CaO(s) and oxygen transfer material (OTM) is Ni/NiO. PEFB bio-oil is modelled as a surrogate mixture and two common model compounds, acetic acid and furfural, are also considered. A process comparison highlights the advantages of sorption-enhancement and chemical looping, including improved purity and yield, and reductions in carbon deposition and process net energy balance.The operating regime of SE-CLSR is evaluated in order to assess the impact of S/C ratio, NiO/C ratio, CaO/C ratio and temperature. Autothermal operation can be achieved for S/C ratios between 1 and 3. In autothermal operation at 30 bar, S/C ratio of 2 gives a yield of 11.8 wt%, and hydrogen purity of 96.9 mol%. Alternatively, if autothermal operation is not a priority, the yield can be improved by reducing the quantity of OTM. The thermodynamic analysis highlights the role of advanced reforming techniques in enhancing the potential of bio-oil as a source of hydrogen.     

Chemical looping steam methane reforming using Al doped LaMnO3+δ perovskites as oxygen carriers

Chemical looping steam methane reforming (CLSMR) is capable of co-production of high-quality syngas and pure hydrogen, and it is important to develop appropriate oxygen carriers for this process. In this work, LaMn_1-xAl_xO_3+δ (x = 0, 0.1, 0.3, 0.5, 0.7) perovskites were investigated as oxygen carriers for CLSMR by means of characterizations and fixed-bed tests. The characterization and test results suggested that the substitution of Al leaded to more surface active sites and higher symmetry of crystal structure, which facilitates the activation of methane molecule on the surface and the formation of the oxygen vacancy in the bulk of the oxygen carrier particles, increasing the release rate of selective oxygen and the yield of syngas. The yield of CO₂ declined with the Al doped proportion due to the decrease of the mount of Mn⁴⁺ and surface absorbed oxygen. The substitution of Al cations could stabilize the crystal structure and prevent the destruction of perovskite structure. No carbon formed on LaMn_1-xAl_xO_3+δ with x from 0 to 0.5 and a long period of partial oxidation was achieved to produce high-quality syngas with the H₂/CO ratio of 2 and pure hydrogen, while carbon deposition occurred on the LaMn_0.3Al_0.7O_3+δ oxygen carrier. LaMn_0.5Al_0.5O_3+δ possessed the best performance with CO selectivity of 96.4%, the CO yield of 1.70 mmol·g⁻¹, the H₂ yield of 3.32 mmol·g⁻¹ in the reduction stage and the H₂ yield of 1.98 mmol·g⁻¹ in the oxidation stage on average in 20 cyclic redox tests. LaMn_0.5Al_0.5O_3+δ exhibited good thermal stability and cyclic performance. It can be deduced that LaMn_0.5Al_0.5O_3+δ perovskite is a potential oxygen carrier for cyclic CLSMR.     

Thermodynamic analysis of syngas production from biodiesel via chemical looping reforming

In this study, thermodynamic analysis of the syngas production using biodiesel derived from waste cooking oil is studied based on the chemical looping reforming (CLR) process. The NiO is used as the oxygen carrier to carry out the thermodynamic analysis. Syngas with various H₂/CO ratios can be obtained by chemical looping dry reforming (CL-DR) or steam reforming (CL-SR). It is found that the syngas obtained from CL-DR is suitable for long-chain carbon fuel synthesis while syngas obtained from CL-SR is suitable for methanol synthesis. The carbon-free syngas production can be obtained when reforming temperature is higher than 700 °C for all processes. To convert the carbon resulted from biodiesel coking and operate the CLR with a lower oxygen carrier flow rate, a carbon reactor is introduced between the air and fuel reactors for removing the carbon using H₂O or CO₂ as the oxidizing agent. Because of the endothermic nature of both Boudouard and water-gas reactions, the carbon conversion in the carbon reactor increases with increased reaction temperature. High purity H₂ or CO yield can be obtained when the carbon reactor is operated with high reaction temperature and oxidizing agent flow.     

Syngas and H2 production from natural gas using CaFe2O4 – Looping: Experimental and thermodynamic integrated process assessment

Experimental methods and thermodynamic simulations were employed in this study to assess the H₂ production potential of a CaFe₂O₄ based blue H₂ production process from natural gas (NG, >90 vol%CH₄). Fixed bed reactor testing was used to verify the product outcomes. Syngas production from methane using CaFe₂O₄ was demonstrated. Stable H₂ production with high steam conversion was demonstrated with the CaFe₂O₄ when reduced with methane. The thermodynamic integrated process simulation enabled simulation of the process in two and three reactor configurations to understand the feasibility of a heat integrated system. The 2-reactor process used the generation of syngas as the prevailing mode for H₂ generation while the 3-reactor system utilized steam water splitting in a dedicated reactor as the prevailing mode to generate H₂. Simulation of the 2-reactor process's FR showed syngas generation similar to the products from fixed bed demonstrations, establishing a connection between thermodynamic simulation and experimental data. The H₂ yield potentials of the various configurations were determined and compared to steam methane reforming with capture (SMR-CCS) and a Fe₂O₃ based system from the literature. The 2-reactor process has the potential to generate 1.6–2.1 mol of H₂/mole of NG fed to the system. Three reactor configurations showed the highest potential for H₂ yield with a range of 2.2–2.56 mol of H₂/mole NG but with the need for additional CCS at the highest yield. A thermal management approach was introduced that combined the chemistries of CaFe₂O₄ and CuFeAlO₄ which enabled increasing the potential yield to 2.66 mol H₂/mol NG and enabling a system without the need for addition carbon capture to meet 90% threshold targets. The three reactor cases showed the most competitive performance in comparison to SMR-CCS with up to a 14.6% improvement in H₂ yield.     

An intelligent oxygen carrier of La2−xSrxNiO4−λ for hydrogen production by chemical looping reforming of ethanol

This work studied an intelligent perovskite of La_2?xSr_xNiO_4?λ as oxygen carrier (OC) to produce hydrogen in chemical looping reforming (CLR) process. It was prepared by co-precipitation method and investigated by XRD, TEM, ICP-OES, H₂-TPR, TGA technologies and fixed-bed experiment. The ‘intelligence’ refers to the self-regeneration ability and structural flexibility of perovskite. The former was verified by the movement that Ni ions repeatedly immerse into and out of perovskite bulk during CLR process. The movement suppressed the growth of Ni particles and maintained its high dispersion. The latter was confirmed by the addition of promoters. The insertion of Sr increased lattice oxygen mobility and greatly strengthened the reversible evolution of metallic Ni, which boosted the carbon-resistance and hold favorable stability of OC. The La_1.4Sr_0.6NiO_4?λ was the optimized composition owing to the superior activity, higher hydrogen selectivity (87%) and admirable stability. Moreover, shortened ‘dead time’ and more ideal self-regeneration property of perovskite were attained due to easier reducibility of Ni ions.