Advances in hydrogen production by thermochemical water decomposition: A review

Hydrogen demand as an energy currency is anticipated to rise significantly in the future, with the emergence of a hydrogen economy. Hydrogen production is a key component of a hydrogen economy. Several production processes are commercially available, while others are under development including thermochemical water decomposition, which has numerous advantages over other hydrogen production processes. Recent advances in hydrogen production by thermochemical water decomposition are reviewed here. Hydrogen production from non-fossil energy sources such as nuclear and solar is emphasized, as are efforts to lower the temperatures required in thermochemical cycles so as to expand the range of potential heat supplies. Limiting efficiencies are explained and the need to apply exergy analysis is illustrated. The copper–chlorine thermochemical cycle is considered as a case study. It is concluded that developments of improved processes for hydrogen production via thermochemical water decomposition are likely to continue, thermochemical hydrogen production using such non-fossil energy will likely become commercial, and improved efficiencies are expected to be obtained with advanced methodologies like exergy analysis. Although numerous advances have been made on sulphur–iodine cycles, the copper–chlorine cycle has significant potential due to its requirement for process heat at lower temperatures than most other thermochemical processes.     

Corrosion behavior analyses of metallic membranes in hydrogen iodide environment for iodine-sulfur thermochemical cycle of hydrogen production

HI decomposition in Iodine-Sulfur (IS) thermochemical process for hydrogen production is one of the critical steps, which suffers from low equilibrium conversion as well as highly corrosive environment. Corrosion-resistant metal membrane reactor is proposed to be a process intensification tool, which can enable efficient HI decomposition by enhancing the equilibrium conversion value. Here we report corrosion resistance studies on tantalum, niobium and palladium membranes, along with their comparative evaluation. Thin layer each of tantalum, palladium and niobium was coated on tubular alumina support of length 250 mm and 10 mm OD using DC sputter deposition technique. Small pieces of the coated tubes were subject to immersion coupon tests in HI-water environment (57 wt% HI in water) at a temperature of 125–130 °C under reflux environment, and simulated HI decomposition environment at 450 °C. The unexposed and exposed cut pieces were analyzed using scanning electron microscope (SEM), energy dispersive X-ray (EDX) and secondary ion mass spectrometer (SIMS). The extent of leaching of metal into liquid HI was quantified using inductively coupled plasma-mass spectrometer (ICP-MS). Findings confirmed that tantalum is the most resistant membrane material in HI environment (liquid and gas) followed by niobium and palladium.     

Kinetics study of the copper/hydrochloric acid reaction for thermochemical hydrogen production

The exothermic reaction of hydrochloric acid with particulate copper occurs during the hydrogen production step in the thermochemical copper–chlorine water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the hydrogen conversion aspects. It is obtained that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55% and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches over 3000 W/m² when the particle shrinks to 0.1% from its initial size. The estimated Biot number varies from 0.001 to 0.1, depending on the operating conditions and the accuracy of thermophysical data of the substances. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction that models the shrinking of copper particles in the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for the estimation of the temperature of a copper particle, assumed spherical, in the radial direction on the hypothesis of large Biot numbers. For small Biot numbers, the transient heat transfer equation results in a lumped capacitance model. In all cases, the particle decomposes in about 10–20s.     

Review of thermochemical hydrogen production

The periodical World Hydrogen Energy Conference (WHEC) is an opportunity to make an updated state of the art in the development of the thermochemical method for the production of hydrogen from water. The present paper summarizes the main evolution of this new technology giving also some comments.     

The catalytic thermal decomposition of water and the production of hydrogen

Experiments have been carried out on the Pt and Ir catalyzed thermal decomposition of water. The dissociation is very rapid indeed, yielding appreciable quantities of hydrogen and oxygen at approx. 1300–1400°C. The great speed of this catalytic decomposition compensates for the small degrees of thermal decomposition in this temperature range.Two prototypes for large scale thermal hydrogen production are proposed on the basis of the experiments on the catalytic decomposition of water. These have been described and characterized in detail. A reasonable number of these prototypes can replace 1 year's supply of natural gas by hydrogen in the U.S.A. Economic aspects have also been considered.     

Efficiency of thermochemical production of hydrogen

The overall thermal efficiency of several processes in the chemical industry is calculated from production units. The individual efficiency of a step was found to be 80% or less. Assuming an average thermal efficiency for each step to be 70%. the overall efficiency of two-, three- and four-step processes are estimated to be 50, 35 and 25%, respectively. Extrapolation of these results to the thermochemical decomposition of water leads to the conclusion that the process must consist of three steps or less in order for its efficiency to exceed that of electrolysis.     

Exergy analysis of hydrogen production by thermochemical water decomposition using the Ispra Mark-10 Cycle

An investigation is reported of the thermodynamic performance of the Ispra Mark-10 thermochemical water decomposition process for hydrogen production. Thermochemical water decomposition has been identified as a potentially important future process for the production of hydrogen, which is currently an important industrial commodity and has significant future potential as a fuel. Exergy analysis is used since energy analysis on its own does not pinpoint true process inefficiencies, and often does not provide rational efficiencies. The analysis indicates that the principle thermodynamic losses occur in the primary water decomposition reactors and are mainly due to internal irreversibilities associated with chemical reaction and heat transfer across large temperature differences, and that the losses associated with effluents (particularly cooling water) are not that significant. Energy and exergy efficiencies are provided and are observed to depend strongly on the main external process inputs, i.e., electricity and process heat, or heat, or the raw resource from which heat and electricity are produced.     

Ni doped carbons for hydrogen production by catalytic methane decomposition

Ni doped carbons were prepared from raw coal and direct coal liquefaction residue (CLR) by KOH activation with addition of Ni(NO₃)₂, and used for catalytic methane decomposition (CMD) to produce hydrogen. The catalytic activity of the Ni doped carbon for CMD was compared with those of metal catalysts (Ni/SiO₂ and Ni/Al₂O₃), coal- and CLR-based carbons, and Ni-carbon catalysts prepared by traditional impregnation and precipitation methods. The results show that the Ni doped carbon has higher and more stable activity than the metal and carbon catalysts at 850 °C. The preparation method for Ni doped carbons can make full use of the reducibility of the carbon composition and simplify the traditional synthesis process. The Ni content and the morphology of carbon deposits produced during CMD have a great effect on the catalytic activity of the Ni doped carbon.     

Ultra-pure hydrogen production via ammonia decomposition in a catalytic membrane reactor

In this work two alternatives are presented for increasing the purity of hydrogen produced in a membrane reactor for ammonia decomposition. It is experimentally demonstrated that either increasing the thickness of the membrane selective layer or using a small purification unit in the permeate of the membranes, ultra-pure hydrogen can be produced. Specifically, the results show that increasing the membrane thickness above 6 μm ultra-pure hydrogen can be obtained at pressures below 5 bar. A cheaper solution, however, consists in the use of an adsorption bed downstream the membrane reactor. In this way, ultra-pure hydrogen can be achieved with higher reactor pressures, lower temperatures and thinner membranes, which result in lower reactor costs. A possible process diagram is also reported showing that the regeneration of the adsorption bed can be done by exploiting the heat available in the system and thus introducing no additional heat sources.     

Commercial activated carbon for the catalytic production of hydrogen via the sulfur-Iodine thermochemical water splitting cycle

Eight commercial activated carbon catalysts were examined for their catalytic activity to decompose hydroiodic acid (HI) to produce hydrogen; a key reaction in the sulfur-iodine (S-I) thermochemical water splitting cycle. Activity was examined under a temperature ramp from 473 to 773 K. No statistically significant correlation was found between the measured catalyst sample properties and catalytic activity. Four of the eight samples were examined for one week of continuous operation at 723 K. All samples appeared to be stable over the period of examination.     

Open-loop thermochemical cycles for the production of hydrogen

The concept of open-loop thermochemical cycles (cycles which have additional or other feedstocks than water and produce materials in addition to hydrogen and oxygen) is introduced. Preliminary analysis of possible feedstocks available indicates substantial quantities of hydrogen could possibly be produced through open-cycles. The advantages of open-cycles include the conversion of unwanted waste products to useful products while producing hydrogen. A compilation of open processes which would have SO₂ in addition to water as feedstock and which would produce sulfuric acid in addition to hydrogen and oxygen is given.     

Development and test of a solar reactor for decomposition of sulphuric acid in thermochemical hydrogen production

Decomposition of sulphuric acid is a key step of sulphur based thermochemical cycles for hydrogen production by thermal splitting of water. The Hybrid Sulphur Cycle (HyS) consisting of two reaction steps is considered as one of the most promising cycles: firstly, sulphuric acid is decomposed by high temperature heat of 800–1200 °C forming sulphur dioxide, which in a second step is used to electrochemically split water. Compared to conventional water electrolysis only about a tenth of the theoretical voltage is required making the HyS one of the most efficient processes to produce hydrogen by concentrated solar radiation. As a result, this thermochemical cycle has the potential to significantly reduce the amount of energy required for water splitting and to efficiently generate hydrogen free of carbon dioxide emissions. The European research project HycycleS aims at a technical realisation of the HyS. One objective of the project is to develop and qualify a solar interface, meaning a device to couple concentrated solar radiation into the endothermal steps of the chemical process. Therefore, a test reactor for decomposition of sulphuric acid by concentrated solar radiation was developed and tested in the solar furnace of DLR in Cologne. Tests in concentrated solar radiation were carried out for temperatures of the honeycomb up to 950 °C decomposing sulphuric acid of 50 and 96 weight-percent. Mass and energy flow of the process were calculated in order to determine energy efficiency and chemical conversion. The influence of process parameters like temperature, flow rates and space velocity on chemical conversion and reactor efficiency was analysed in detail. If catalysts like iron oxide (Fe₂O₃) and mixed oxides (i.e. CuFe₂O₄) were used a conversion of SO₃ to SO₂ of more than 80% at a thermal efficiency of over 25% could be reached.     

The utilization of ZnSO4 decomposition in thermochemical hydrogen cycles

We find that the ZnSO₄ decomposition reaction can be used as the high temperature step in a number of thermochemical cycles. It is especially applicable as a substitute for the H₂SO₄ decomposition step in H₂SO₄ based cycles, and significantly improves the efficiency of such cycles. In this study, we have taken an initial look at the effects of heat-up rate on the decomposition of ZnSO₄ as it is heated through an α-β transition at 1015 K. We find that a rapid heat-up of fine ZnSO₄ particulates through this transition leads to fracturing of the ZnSO₄ crystallites and significantly enhances its subsequent decomposition rate at ～1043 K. We also find evidence for an autocatalytic decomposition process in fine ZnSO₄ particulates with either rapid or slow heat-up rates. We believe that a combination of (1) fracturing of the crystallites and (2) surface catalysis by ZnO to equilibrate the SO₃/SO₂/O₂ gaseous products contributes to the observed autocatalytic behaviour.     

Semi-continuous hydrogen production from catalytic methane decomposition using a fluidized-bed reactor

Non-oxidative, catalytic decomposition of hydrocarbons is an alternative, one-step process to produce pure hydrogen with no production of carbon oxides or higher hydrocarbons. Carbon produced from the decomposition reaction, in the form of potentially valuable carbon nanotubes, remains anchored to the active catalyst sites in a fixed bed. To facilitate periodical removal of this carbon from the reactor and to make hydrogen production continuous, a fluidized-bed reactor was envisioned. The hypothesis that the tumbling and inter-particle collisions of bed material would efficiently separate nanotubes anchored to the active catalyst sites of the bed particles was tested and shown to be invalid. However, a switching mode reaction system for the semi-continuous production of hydrogen and carbon nanotubes by periodic removal and replenishment of the catalytic bed material has been successfully demonstrated.     

Tube-wall catalytic membrane reactor for hydrogen production by low-temperature ammonia decomposition

Ammonia has attracted great interest as a chemical hydrogen carrier. However, ammonia decomposition is limited kinetically rather than thermodynamically below 400 °C. We developed a tube-wall catalytic membrane reactor that could decompose ammonia with high conversion even at temperatures below 400 °C. The reactor had excellent heat transfer characteristics, and thus nearly 100% conversion for an NH3 feed of 10 mL/min at 375 °C was achieved with a 2-μm-thick palladium composite membrane, and hydrogen removal from the decomposition side resulted in a large kinetic acceleration.     

High-purity hydrogen gas production by catalytic thermal decomposition using mechanochemical treatment

The objectives of this work, were to produce high-purity hydrogen gas from rice husk by two-step process and to study the effect of nickel hydroxide/nickel acetate/sodium acetate and calcium hydroxide on the concentration of gaseous products. The samples were characterized by X-ray diffraction (XRD) and thermogravimetry-mass spectroscopy (TG/MS). The gaseous products were analyzed by gas chromatography (GC). The results indicated that hydrogen gas was produced from the milled samples by heating at 400–600 °C with the low concentrations of methane, carbon monoxide and carbon dioxide. The highest concentration of hydrogen gas from milled samples with the catalyst, was approximately 95–97 %mol. Furthermore, the milled samples with the carbon dioxide capture agent gave the carbon dioxide concentration, was below 2 %mol.     

Modeling of a direct solar receiver reactor for decomposition of sulfuric acid in thermochemical hydrogen production cycles

Hydrogen production thermochemical cycles, based on the recirculation of sulfur-based compounds, are among the best suited processes to produce hydrogen using concentrated solar power. The sulfuric acid decomposition section is common to each sulfur-based cycle and represents one of the fundamental steps. A novel direct solar receiver-reactor concept is conceived, conceptually designed and simulated. A detailed transport phenomena model, including mass, energy and momentum balance expressions as well as suitable decomposition kinetics, is described adopting a finite volume approach. A single unit reactor is simulated with an inlet flow rate of 0.28 kg/s (corresponding to a production of approximately 11 kg_H2/h in a Hybrid Sulfur process) and a direct solar irradiation at a constant power of 143 kW/m². Results, obtained for the high temperature catalytic decomposition of SO₃ into SO₂ and O₂, demonstrate the effectiveness of the proposed concept, operating at pressures of 14 bar. A maximum temperature of 879 °C is achieved in the reactor body, with a corresponding average SO₂ mass fraction of 27.8%. The overall pressure drop value is 1.7 bar. The reactor allows the SO₃ decomposition into SO₂ and O₂ to be realized effectively, requiring an external high temperature solar power input of 123.6 kJ/molSO2 (i.e. 123.6 kJ/mol_H2).     

Manganese oxide based thermochemical hydrogen production cycle

A MnO/NaOH based three-step thermochemical water splitting cycle was modified to improve the hydrolysis of α-NaMnO₂ (sodium manganate) and to recover Mn(III) oxides for the high-temperature reduction step. Sodium manganate forms in the reaction of NaOH with MnO that releases hydrogen. The hydrolysis of α-NaMnO₂ to manganese oxides and NaOH is incomplete even with a large excess of water and more than 10% sodium cannot be removed prior to the high-temperature reduction step.When mixed oxides of manganese with iron were used in the cycle, the NaOH recovery in the hydrolysis step improved from about 10% to 35% at NaOH concentrations above 1M. Only 60% sodium was removed at 0.5M from the mixed oxides whereas more than 80% can be recovered at the same NaOH concentration when only manganese oxides are used. A 10:1 Mn/Fe sample was cycled through all steps three times to confirm that multiple cycles are possible. The high-temperature reduction was carried out for 5h at 1773 K under vacuum and the conversion was about 65% after the 3rd cycle.Since sodium carryover into the high-temperature reduction cannot be avoided, even with the energy intensive hydrolysis step, a modified two-step cycle without low-temperature sodium recovery is proposed where α-NaMnO₂ is reduced directly to MnO at 1773 K under vacuum. On a laboratory scale, about 60% of the sodium that volatilized at the high temperatures was trapped with a water-cooled cold finger and conversions were stable at about 35% after three completed cycles.     

Solar hydrogen production using two-step thermochemical cycles

In this paper, a thermodynamic study is presented on solar hydrogen production using concentrated solar energy and two-step thermochemical cycles. After discussing the temperature availability from solar installations and temperature requirements, two-step water decomposition processes using metal/metal oxide cycles are studied in detail. Some hybrid metal/metal oxide, purely thermochemical and hybrid, metal oxide/metal sulfate cycles are also discussed. The solar high temperature heat source is briefly analyzed and interfacing problems are discussed.     

Microwave-assisted catalytic decomposition of methane over activated carbon for -free hydrogen production

The aim of this work was to combine microwave heating with the use of low-cost granular activated carbon as a catalyst for the production of CO₂-free hydrogen by methane decomposition in a fixed bed quartz-tube flow reactor. In order to compare the results achieved, conventional heating was also applied to the catalytic decomposition reaction of methane over the activated carbon. It was found that methane conversions were higher under microwave conditions than with conventional heating when the temperature measured was lower than or equal to . However, when the temperature was increased, the difference between the conversions under microwave and conventional heating was reduced. The influence of volumetric hourly space velocity (VHSV) on the conversion tests using both microwave and conventional heating was also studied. In general, there is a substantial initial conversion, which declines sharply during the first stages of the reaction but tends to stabilise with time. An increase in the VHSV has a negative effect on CH₄ conversion, and even more so in the case of microwave heating. Nevertheless, the conversions obtained in the microwave device at the beginning of the experiments are, in general, better than the conversions reported in other works which also use a carbonaceous-based catalyst. Additionally, the formation of carbon nanofibres in one of the microwave experiments is also reported.