《International Journal of Hydrogen Energy》2019,44(13):6491-6504

CeO₂-supported Fe₂O₃ is a satisfactory oxygen carrier for chemical looping hydrogen generation (CLHG). However, the sintering problem restrains its further improvement on redox reactivity and stability. In the present work, a core-shell-structured Fe₂O₃/CeO₂ (labeled Fe₂O₃@CeO₂) oxygen carrier prepared by the sol-gel method was studied in a fixed bed. The effect of the core-shell structure on the sintering resistance and redox performance was investigated with a homogenous composite sample of Fe₂O₃/CeO₂ as a reference. The results showed that the Fe₂O₃@CeO₂ exhibited much higher redox reactivity and stability than the Fe₂O₃/CeO₂ with no CO or CO₂ observed in the generated hydrogen, while the hydrogen yield for Fe₂O₃/CeO₂ decreased with redox cycles due to serious sintering. The satisfactory performance of Fe₂O₃@CeO₂ can be ascribed to its high sintering resistance, since the core-shell structure suppressed the outward migration of Fe cations from the bulk to the surface of the particles. On the other hand, the migration of Fe cations and their subsequent enrichment on the particle surface led to the serious sintering of Fe₂O₃/CeO₂. The crystallite size evolution of Fe₂O₃ and CeO₂ in redox cycles further demonstrated the higher sintering resistance of Fe₂O₃@CeO₂. Further, the particle size distribution (PSD) results indicated the agglomeration of Fe₂O₃/CeO₂ after cycles. In addition, the CeO₂ shell could facilitate the transport of oxygen ions between the iron oxide nanoparticle core and the shell surface. Therefore, the coating of nanoscale Fe₂O₃ with a CeO₂ shell did not reduce the redox reactivity and stability of Fe₂O₃@CeO₂, but rather promoted it, though less oxygen-ionic-conductive CeFeO₃ was generated.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(56):29743-29751

Operational rules and control strategies of the chemically recuperated gas turbine (CRGT) in the marine propulsion are investigated in this paper. The Minimization of Gibbs free energy method is used to calculate the diesel-steam reforming reaction which products synthetic hydrogen rich fuels, and a universal model of the chemical regenerator which is easily applied to different application environments is created. The hydrogen production and hydrogen molar fraction are investigated to verify that the CRGT improve the combustion performances under low working conditions. Off-design calculations are performed to derive proper operational rules, and transient calculations are performed to investigate the best control strategies for the systems. The modelling approach of the chemical regenerator can be generally used in the chemically recuperated gas turbine. The elaborate operational rules can greatly improve the thermal efficiencies under every working condition. The system using synchronous control strategies have better regulation speed and operation stability than that using asynchronous control strategies.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(26):13175-13184

Iron oxide has been widely studied in chemical looping hydrogen generation (CLHG) process as an oxygen carrier, but fast decline of its activity in redox cycles due to sintering and agglomeration is one of the main drawbacks. In this work, the colloidal crystal templated (CCT) method was applied to synthesize Fe₂O₃/CeO₂ oxygen carrier and the mole ratio of Fe/Ce was 8:2, aiming to inhibit adjacent grains from agglomerating and improve the contact between the fuel gas and the oxygen carrier. The redox performances were evaluated with CO as fuel in a batch fixed bed reactor for 20 redox cycles, with oxygen carriers prepared by co-precipitation (CP) and sol-gel (SG) methods as references. X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), and H₂-temperature programmed reduction (H₂-TPR) were used for characterization. The results showed that the calcination temperature lower than 750 °C was suitable for the CCT. The redox experiments showed that the H₂ yield and the redox stability for the oxygen carrier prepared by CCT were higher than those by co-precipitation and sol-gel methods. The H₂ yield of CCT oxygen carrier kept stable from the 3rd cycle and was 8.5 mmol/gOC in the 20th cycle. The pore structures resulting from CCT were different from another two oxygen carriers before and after the cycles, but maintained well through SEM images, leading to high activity and stability during redox cycles. The crystallite sizes of Fe₂O₃ and CeO₂ before and after redox cycles were the smallest for the CCT oxygen carrier from XRD patterns. In addition, H₂-TPR demonstrated that CCT oxygen carrier exhibited the highest reactivity.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(33):18214-18224

A transient thermodynamic analysis is reported of a novel chemical hydrogen storage system using energy and exergy approaches. The hydrogen is stored chemically in ammonia using the proposed hydrogen storage system and recovered via the electrochemical decomposition of ammonia through an ammonia electrolyzer. The proposed hydrogen storage system is based on a novel subzero ammonia production reactor. A single stage refrigeration system maintains the ammonia production reactor at a temperature of −10 °C. The energy and exergy efficiencies of the proposed system are 85.6% and 85.3% respectively. The proposed system consumes 34.0 kJ of work through the process of storing 1 mol of hydrogen and recovering it using the ammonia electrolyzer. The system is simulated for filling 30,000 L of ammonia at a pressure of 5 bar, and the system was able to store 7500 kg of ammonia in a liquid state (1% vapor) in 1500 s. The system consumes nearly 45.3 GJ of energy to store the 7500 kg of ammonia and to decompose it to reproduce the stored hydrogen during the discharge phase.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(33):17823-17834

Chemical looping gasification (CLG) of sewage sludge (SS) using calcined copper slag as an oxygen carrier (OC) represents a novel approach for achieving the comprehensive use of two wastes (SS and copper slag), where the SS is converted into syngas through the oxidation of calcined copper slag. The effect of the calcined temperature on the reactivity of copper slag was first studied. The results show that the copper slag calcined at 1100 °C (1100CS) exhibits excellent performance for SS gasification. Using 1100CS as an OC, the effect of the mass ratio of OC and SS (OC/SS), steam content, oxygen source and cycle number on the SS CLG were investigated in detail in a fixed bed reactor. OC/SS and steam content are determined at 5 and 33.33% for obtaining a relatively high carbon conversion and an acceptable energy recovery during the SS CLG, respectively. The 1100CS is similar to steam, which can provide an oxygen source for SS conversion, and it can catalyze the cracking of tar. The conversion of SS undergoes a slight increase with the cycle number due to the prolongation of the gas-solid mean residence time (R_t) and the deposition of alkali or alkaline earth metals on the surface of the OC particles. Phosphorus eventually appears in the form of water-soluble phosphate during the SS CLG, benefiting its recovery. Thus, CLG with 1100CS as an OC is one of good option for sludge treatment.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(39):21251-21263

In this work, a novel hydrogen production process (Integrated Chemical Looping Water Splitting “ICLWS”) has been developed. The modelled process has been optimised via heat integration between the main process units. The effects of the key process variables (i.e. the oxygen carrier-to-fuel ratio, steam flow rate and discharged gas temperature) on the behaviour of the reducer and oxidiser reactors were investigated. The thermal and exergy efficiencies of the process were studied and compared against a conventional steam-methane reforming (SMR) process. Finally, the economic feasibility of the process was evaluated based on the corresponding CAPEX, OPEX and first-year plant cost per kg of the hydrogen produced. The thermal efficiency of the ICLWS process was improved by 31.1% compared to the baseline (Chemical Looping Water Splitting without heat integration) process. The hydrogen efficiency and the effective efficiencies were also higher by 11.7% and 11.9%, respectively compared to the SMR process. The sensitivity analysis showed that the oxygen carrier–to-methane and -steam ratios enhanced the discharged gas and solid conversions from both the reducer and oxidiser. Unlike for the oxidiser, the temperature of the discharged gas and solids from the reducer had an impact on the gas and solid conversion. The economic evaluation of the process indicated hydrogen production costs of $1.41 and $1.62 per kilogram of hydrogen produced for Fe-based oxygen carriers supported by ZrO₂ and MgAl₂O₄, respectively - 14% and 1.2% lower for the SMR process H₂ production costs respectively.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(39):21290-21302

The use of binary oxygen carrier allows for the materials of enhanced activity or stability during chemical looping process. However, the lack of mechanical understanding of the origin of the improvements hindered the rational design and control of the doping process in the oxygen carrier production. Here, we synthesized a series of M_0.6Fe_2.4O_y (M = Ni, Cu, Co, Mn) binary spinel materials and carried out various characterization techniques to study how the dopants influenced the material phase change, the oxygen transfer as well as the chemical looping performance. The results showed the chemical looping reactivity can be related to the oxygen transformation between lattice oxygen and oxygen vacancy, which was determined by the redox properties of both dopants and iron. The metal in tetrahedral site for Cu, Mn, Ni-doped sample were relatively stable, limiting oxygen transformation ability. In comparison, Co dopant promoted the reducibility of iron in tetrahedral site as well as metals in other sites, making almost all lattice oxygen rapidly transformed to oxygen vacancy during reduction. This was the main cause for the subsequent high hydrogen production rate (average ∼0.02 mmol. g⁻¹.s⁻¹) and yield (∼15.9 mmol.g⁻¹). Upon cycling, the phase separation of single oxides from Co_0.6Fe_2.4O_y and Mn_0.6Fe_2.4O_y spinels led to the decreased ability of oxygen transformation. However, the performance was extremely stable for Cu_0.6Fe_2.4O_y with reversible phase change between spinel and (Fe, Cu) wusitite by the Cu-Fe interaction. Based on the current results, this work points to a promising Cu-Co co-doping material with both good reactivity and stability.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(54):28638-28648

Shifting chemical looping from high temperatures to intermediate temperatures could mitigate the materials from sintering and benefit for longer durability as well as process economy. However, oxygen carriers cannot perform sufficiently due to the degrading effect at lower temperatures, resulting in the decrease of hydrogen production ability. Although doping precious metals can improve the poor performance at intermediate temperatures, the high cost impeded their large-scale application. In this paper, a range of oxygen carrier materials consisted of earth abundant elements were prepared for chemical looping hydrogen production. The results indicated that CoFe₂O₄ exhibited the highest hydrogen yield of 11.9 mmol·g⁻¹ and hydrogen production rate of 0.051 mmol g⁻¹·s⁻¹ at 650 °C, which was 1.7 times higher than that of Fe₂O₃. A combined experimental and DFT calculation method was used to understand the mechanism behind the performance. The results indicated that the synergistic effect between Co and Fe increased the reactivity of the ferrite materials. The enhanced hydrogen production performance was attributed to the high reduction degree and reversible phase change. This study can be also extended to develop more active oxygen carrier for chemical looping processes at intermediate temperatures.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(57):29849-29861

Refueling costs account for much of the fuel cost for light-duty hydrogen fuel-cell electric vehicles. We estimate cost savings for hydrogen dispensing if metal hydride (MH) storage tanks are used on board instead of 700-bar tanks. We consider a low-temperature, low-enthalpy scenario and a high-temperature, high-enthalpy scenario to bracket the design space. The refueling costs are insensitive to most uncertainties. Uncertainties associated with the cooling duty, coolant pump pressure, heat exchanger (HX) fan, and HX operating time have little effect on cost. The largest sensitivities are to tank pressure and station labor. The cost of a full-service attendant, if the refueling interconnect were to prevent self-service, is the single largest cost uncertainty. MH scenarios achieve $0.71–$0.75/kg-H₂ savings by reducing compressor costs without incurring the cryogenics costs associated with cold-storage alternatives. Practical refueling station considerations are likely to affect the choice of the MH and tank design.  相似文献   

    

《International Journal of Hydrogen Energy》2019,44(59):30806-30819

Efficient non-noble metal catalysts for the oxygen evolution reaction (OER) are particularly important in the practical applications of electrocatalytic water splitting (ECWS). Herein, based on a simple quasi chemical vapor deposition (Q-CVD) method, we fabricate a newly Ni₃S₂@3-D graphene free-standing electrode for efficient OER applications. The Ni₃S₂@3-D graphene integrates the advantageous features of 3-D graphene and Ni₃S₂ towards OER, such as more interfacial catalytic sites, pore-rich structure, N-doped structure and good electrical conductivity. Benefiting from the favorable features, the Ni₃S₂@3-D graphene (especially 900 °C sample) exhibits excellent OER performances in alkaline medium, which includes a low on-set potential (1.53 V), low overpotential of 305 mV at a current density of 10 mA cm⁻², and a smaller Tafel slope (50 mV dec⁻¹). This catalyst also shows ultrahigh stability after chronoamperometry response at 10 mA cm⁻² for 48 h with 30% increase in the current density. The present work opens a new approach for the one-pot construction of hybrid materials between metal sulfide and graphene to increase the electrocatalytic activity of non-noble metal OER catalysts.  相似文献