Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

Enhancement of hydrogen generation rate in reaction of aluminum with water

The aim of this investigation is to enhance hydrogen generation rate in aluminum–water reaction by improving the activity of aluminum particles and using the heat released during the reaction. This was accomplished by developing fresh surfaces by milling aluminum particles together with salt. Salt particles not only serve as nano-millers, but also surround activated particles and prevent re-oxidation of bare surfaces in the air. Therefore, the activated powder can be easily stored for a long time. Immersing the powder in warm water, the salt covers are washed away and hydrogen begins to release at a high rate until efficiency of 100% is achieved. The rate of reaction depends crucially on initial temperature of water. Hence, the mass of water was reduced to employ released energy to increase water temperature and, consequently, to increase hydrogen production rate. The optimum value of salt-to-aluminum mole ratio for achieving high activation, air-storage capability and 100% efficiency was obtained to be 2. When immersed in water, at initial temperatures of 55 and 70 °C, the powder lead to average hydrogen generation rate of ∼101 and ∼210 ml/min per 1 g of Al, respectively. To increase the rate of corrosion, three different alloys/composites of aluminum were prepared by mechanical alloying and activated with optimum salt-to-aluminum mole ratio. The alloys/composites formed galvanic cells after being immersed in water. In the case of aluminum–bismuth alloy, the average hydrogen generation rate increased to ∼287 and ∼713 ml/min per 1 g of Al, respectively.     

Hydrogen generation during the corrosion of carbon steel in crotonic acid and using some organic surfactants to control hydrogen evolution

The purpose of this paper is to describe and evaluate the corrosion of carbon steel in crotonic acid for hydrogen production and using polysorbate 20 (NS), dioctyl sodium sulfosuccinate (AS) and benzalkonium chloride (CS) to control hydrogen evolution. Measurements were conducted in tested solutions using hydrogen evolution and electrochemical impedance spectroscopy (EIS) measurements and complemented by scan electron microscope (SEM) and energy dispersive X-ray (EDX) investigations. It is shown that the hydrogen generation rate obtained during the corrosion of carbon steel in crotonic acid increased with increase in acid concentration, temperature and immersion time. The addition of organic surfactants inhibits the hydrogen generation rate. The inhibition occurs through adsorption of organic surfactants on the metal surface. Adsorption processes followed the Langmuir isotherm. The order of effectiveness of the surfactants was AS > NS > CS. The values of activation energy (E_a) and heat of adsorption (Q_ads) were calculated and discussed.     

Absorption of hydrogen in tensile strained iron and high-carbon steel studied by electrochemical permeation and desorption techniques

Absorption of hydrogen in gradually tensile strained Armco iron and high-carbon steel, cathodically charged in 0.1 M NaOH solution, was studied using the electrochemical permeation and desorption techniques. Measurements of hydrogen permeation through specimens in the form of a membrane allowed determining the lattice diffusivity and concentration of hydrogen (diffusible hydrogen). The lattice diffusivity of hydrogen in iron (D = 6.2 × 10⁻⁵ cm²/s) was about 280 times higher than that in high-carbon steel (D = 2.2 × 10⁻⁷ cm²/s). In turn, a detailed analysis of the desorption rate of hydrogen from previously hydrogen charged and strained, cylindrical specimens made it possible to characterize hydrogen reversibly attached to traps. This trapped hydrogen made nearly a whole and a majority (from 70% to 85%, depending on strain) of the reversibly absorbed hydrogen in iron and high-carbon steel, respectively. In both studied materials, the amount of the trapped hydrogen strongly increased with strain. Moreover, in contrast to the diffusible hydrogen, evenly distributed in the charged specimen, the trapped hydrogen was mainly located within a subsurface region of the specimen. The estimated thickness of this subsurface region in iron was about 0.44 mm, whereas that in high-carbon steel was only about 0.017 mm. Consequently, the subsurface concentration of hydrogen in high-carbon steel was extremely high. It may be one of the reasons for more intensive hydrogen embrittlement of high-carbon (high-strength) steels in comparison with that of iron.     

Efficiently generating COx-free hydrogen by mechanochemical reaction between alkali hydrides and carbon dioxide

This article aims to investigate the mechanochemical hydrogen desorption reactions of alkali hydrides (XH: X = Li, Na, or K) with carbon dioxide. The result of this investigation shows that CO₂ can be efficiently reduced by XH (X = Na or K), generating CO_x-free hydrogen under room-temperature mechanical ball milling condition in the absence of a catalyst. The mole percentage and production rate of hydrogen in the gaseous product, which can reach 98.72% and 95.37%, respectively, depend on the milling time, rotation rate of milling and the mole ratio of XH/CO₂. During the mechanochemical reactions, carbon dioxide is fast and wholly consumed by XH, producing element carbon, alkali carbonates, and H₂. This work establishes a new, simple and efficient means for the room-temperature preparation of CO_x-free hydrogen and the elimination of CO_x contaminant in hydrogen.     

Controlled hydrogen generation by reaction of aluminum/sodium hydroxide/sodium stannate solid mixture with water

Aluminum/water reaction system has gained considerable attention for potential hydrogen storage applications. In this paper, we report a new aluminum-based hydrogen generation system that is composed of aluminum/sodium hydroxide/sodium stannate solid mixture and water. This new system is characterized by the features as follows: the combined usage of sodium hydroxide and sodium stannate promoters, the use of solid fuel in a tablet form and the direct use of water as a reaction controlling agent. The factors that influence the hydrogen generation performance of the system were investigated. The optimized system exhibits a favorable combination of high hydrogen generation rate, high fuel conversion, rapid dynamic response, which makes it promising for portable hydrogen source applications.     

Catalytic hydrolysis of hydrazine borane for chemical hydrogen storage: Highly efficient and fast hydrogen generation system at room temperature

There has been rapidly growing interest for materials suitable to store hydrogen in solid state for transportation of hydrogen that requires materials with high volumetric and gravimetric storage capacity. B-N compounds such as ammonia-triborane, ammonia-borane and amine-borane adducts are well suited for this purpose due to their light weight, high gravimetric hydrogen storage capacity and inclination for bearing protic (N-H) and hydridic (B-H) hydrogens. In addition to them, more recent study [26] has showed that hydrazine borane with a gravimetric hydrogen storage capacity of 15.4% wt needs to be considered as another B-N compound that can be used for the storage of hydrogen. Herein we report for the first time, metal catalyzed hydrolysis of hydrazine borane (N₂H₄BH₃, HB) under air at room temperature. Among the catalyst systems tested, rhodium(III) chloride was found to provide the highest catalytic activity in this reaction. In the presence of rhodium(III) chloride, the aqueous solution of hydrazine borane undergoes fast hydrolysis to release nearly 3.0 equivalent of H₂ at room temperature with previously unprecedented H₂ generation rate TOF = 12000 h⁻¹. More importantly, it was found that in the catalytic hydrolysis of hydrazine borane the reaction between hydrazine borane and water proceeds almost in stoichiometric proportion indicating that the efficient hydrogen generation can be achieved even from the highly concentrated solution of hydrazine borane or in the solid state when water added to the solid hydrazine borane. This finding is crucial especially for on-board application of the existing system. The work reported here also includes (i) finding the solubility of hydrazine borane plus its stability against self-hydrolysis in water, (ii) the definition of reaction stoichiometry and the identification of reaction products for the catalytic hydrolysis of hydrazine borane, (iii) the collection of wealthy kinetic data to demonstrate the effect of substrate and catalyst concentrations on the hydrogen generation rate and to determine the rate law for the catalytic hydrolysis of hydrazine borane, (iv) the investigation of the effect of temperature on the rate of hydrogen generation and determination of activation parameters (E_a, ΔH^#, and ΔS^#) for the catalytic hydrolysis of hydrazine borane.     

Maximizing the production of hydrogen and carbon nanotubes: Effect of Ni and reaction temperature

With the objective of maximizing hydrogen and CNTs production, the catalytic cracking of naphtha has been carried out at progressive reaction temperatures i.e. from 600 to 750 °C. The ZSM-5 and nickel impregnated ZSM-5 were used as catalysts for cracking purpose in fluidization mode. The catalyst analysis imparted that impregnation of metallic nickel induces a strong adhesion on MFI structure of ZSM-5 associated with an enhancement in textural properties and acid density. In addition, the results disclose that the incorporation of nickel on ZSM-5 leads to increment in stability of catalyst which in turn pushes the yields of H₂, CNTs and conversion to greater values of 3.29%, 4.84% and 90%, respectively. The as-grown carbon structures over the catalyst surface were found to be multiwall carbon nanotubes confirmed by Raman spectra and TGA analysis where they exhibited high quality (I_D/I_G = 0.65) and purity, respectively, at 750 °C.     

Insights into the hydrogen generation from water-iron rock reactions at low temperature and the key limiting factors in the process

Hydrogen generation from water-rock reactions is mostly studied at high temperature. This study investigated the process at low temperature (5–20 °C) using both synthetic and natural iron minerals (magnetite, goethite and hematite) for a better understanding about the reaction pathway and the key factors involved. Maximum hydrogen generation detected was 6.8 μmol/g with natural goethite. Characterization of the minerals by X-ray diffraction (XRD), X-ray fluorescence (XRF), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS) and aqueous phase by Inductively coupled plasma atomic emission spectrometer (ICP-AES) and ferrozine spectrophotometry revealed hydrogen generation to be related to the composition and specific surface area of the minerals. Low concentration of methane (200 nmol/g from natural magnetite) was also detected from natural minerals, which indicated catalytic effects. The study is significant for hydrogen generation at low temperature and yield insights on fate of carbon dioxide in the underground reservoirs and a sustainable environment.     

Effects of internal hydrogen and surface-absorbed hydrogen on the hydrogen embrittlement of X80 pipeline steel

Effects of internal hydrogen and surface-absorbed hydrogen on hydrogen embrittlement (HE) of X80 pipeline steel were investigated by using different strain rate tensile test, annealing and hydrogen permeation tests. HE of X80 pipeline steel is affected by internal hydrogen and surface-absorbed hydrogen, and the latter plays a major role due to its higher effective hydrogen concentration. The HE susceptibility decreases with increasing the strain rate because it is more difficult for hydrogen to be captured by dislocations at the high strain rate. Annealing at 200 °C can weakened HE caused by internal hydrogen, while it has little effect on HE caused by surface-absorbed hydrogen. HE of X80 pipeline steel is mainly determined by the behavior of dislocation trapping hydrogen, which can be attributed to the interaction between hydrogen and dislocation.     

Hydrogen generation by mechanochemical reaction of quartz powders in water

The present work focuses on the chemical reaction of water with quartz powders undergoing mechanical activation. The reaction produces gaseous hydrogen and is accompanied by a decrease of the water pH. The observed behavior is related to the chemical reactivity of the active sites generated at the surface of quartz powders by fracture and attrition. Their apparent surface density was estimated by connecting the reaction kinetics with the specific surface area of quartz powders. The apparent surface density of the active sites generated by fracture is higher than the one of the active sites generated by attrition. Unexpectedly, it is also higher than the maximum possible surface density of dangling bonds, which suggests for the active sites generated by fracture an unusually high chemical reactivity. This can be regarded as a consequence of undisclosed mechanochemical effects.     

Characterization of water gas shift reaction in association with carbon dioxide sequestration

The characteristics of a water gas shift reaction (WGSR) in association with carbon dioxide sequestration under the effects of a high-temperature catalyst (HTC) and a low-temperature catalyst (LTC) are studied experimentally. With the condition of fixed residence time (0.1 s) for the reactants in the catalyst bed, it is found that the reaction behaviors with the HTC are inherently different from those with the LTC. Specifically, for the WGSR with the HTC, the reaction can be divided into a rapid growth regime, a progressive growth regime and a slow growth regime with increasing reaction temperature or steam/CO ratio. With regard to the WGSR with the LTC, three different regimes are also exhibited; however, they consist of a rapid growth regime, a progressive decay regime and a growth-frozen regime. According to the aforementioned characteristics, proper or better operation conditions using the HTC and the LTC for the application of fuel cells are suggested. When the product gas passes through a Ca(OH)₂ solution, the obtained results reveal that CO₂ removal efficiency increases with increasing solution concentration or steam/CO ratio for both the HTC and the LTC used in the WGSR.     

A comparative study of hydrogen generation by reaction of ball milled mixture of magnesium powder with two water-soluble salts (NaCl and KCl) in hot water

Magnesium powder was ball milled with different weight percentages of NaCl and KCl. These mixtures were added to hot water (80 °C) and the hydrogen generation rate was measured. The results show that the hydrogen generation rate increased with an increase of the presence of both salts. Moreover, increase of the time of milling increased the hydrogen generation rate. The structure of magnesium salt mixtures was further investigated using SEM and EDS and it was demonstrated that higher hydrogen generation rate is correlated with the degree of penetration of the salt into magnesium particles. In addition, we determined that for the 15 h milled composite samples, Mg–KCl mixture generates 200 mL more hydrogen than Mg–NaCl for every 1 g Mg used. These results show that KCl salt addition is promising for hydrogen generation in presented experimental system.     

Effects of supports on hydrogen production and carbon deposition of Fe-based oxygen carriers in chemical looping hydrogen generation

Chemical looping hydrogen generation (CLHG) can produce high purity hydrogen from fuel gases with inherent separation of CO₂. However, the performance of oxygen carrier in CLHG varies with the support materials. In this paper, the reactivity, carbon deposition, redox stability, hydrogen yield and purity, and sintering behavior of the Fe-based oxygen carriers were analyzed to investigate the effects of supports, i.e. Al₂O₃, SiO₂, MgAl₂O₄, ZrO₂ and YSZ (yttrium-stabilized zirconia). The results showed that the properties of the oxygen carriers, e.g. carbon deposition, reactivity and stability, mainly depended on the support and its interaction with iron oxides. The reactivity and hydrogen yield for the oxygen carriers investigated followed the order: Fe₂O₃/MgAl₂O₄ > Fe₂O₃/ZrO₂ > Fe₂O₃/YSZ > Fe₂O₃/Al₂O₃ > Fe₂O₃/SiO₂, and the order of hydrogen purity was identical with that of hydrogen yield as a result of carbon deposition. Furthermore, the hydrogen purity of the Fe-based oxygen carriers supported by MgAl₂O₄, ZrO₂, or YSZ could reach above 99.5% and Fe₂O₃/YSZ showed the lowest carbon deposition. The oxygen carriers, Fe₂O₃/MgAl₂O₄ and Fe₂O₃/SiO₂, were selected to be characterized by SEM images and XRD patterns before and after the redox cycles.     

Study on selective hydrogen sulfide removal over carbon dioxide by catalytic oxidative absorption method with chelated iron as the catalyst

H₂S is a detrimental impurity that must be removed for upgrading biogas to biomethane. H₂S removal selectivity over CO₂ employing catalytic oxidative absorption method and its influence factors were studied in this work. The desulfurization experiments were performed in a laboratory apparatus using EDTA-Fe as the catalyst and metered mixture of 60% (v/v) CH₄, 33% (v/v) CO₂ and 2000–3000 ppmv H₂S balanced by N₂ as the simulated biogas. It was found that for a given catalytic oxidative desulfurization system, it exists a critical pH, at which desulfurization selectivity achieves the highest. It was also observed that desulfurization selectivity increased along with the increase of chelated iron concentration, gas flow rate, and ratio of gas flow rate to liquid flow rate (G/L). This demonstrated that high selectivity and high efficiency for biogas desulfurization could both be achieved through optimizing these parameters. Specific to the desulfurization system of this work, when the gas flow rate was set as 1.1 L/min, after optimizing the above mentioned parameters, i.e. EDTA-Fe concentration of 0.084 mol/L, absorption solution pH of 7.8, and G/L of 55, the desulfurization selectivity factor reached 142.1 with H₂S removal efficiency attained 96.7%.     

An overview of hydrogen generation by hydrolysis of Al and its alloys with the addition of carbon-based materials

Al and its alloys are studied extensively for hydrogen generation through water splitting. Alloying Al with metal activators such as bismuth, indium, gallium, etc., leads to the formation of micro galvanic cells during hydrolysis reaction, resulting in an improved hydrogen generation rate. Activation of Al by adding carbon-based materials such as graphite, carbon nanotubes (CNTs), graphene, etc., can instantaneously generate hydrogen at room temperature. When carbon particles are desorbed from the Al matrix during hydrolysis, new Al is exposed, resulting in an increased reaction rate. In Al-Graphite composites which form core-shell structures, H₂O molecules penetrate through the graphite layers and break down the core-shell structure during hydrolysis, and the new Al surfaces are exposed to water. It was found that Al with nano bismuth and graphene nanosheets showed better hydrogen generation rate and hydrogen yield. Graphene nanosheets control the agglomeration of Al and enhance the specific surface area for hydrolysis. During the hydrolysis of Al-CNTs composites, CNTs act as a cathode, resulting in galvanic corrosion between CNTs and the Al matrix. CNTs can also effectively control the agglomeration of Al during ball milling. Spark plasma sintered Al–Bi-CNT composites showed an enhanced hydrogen generation rate during hydrolysis. This paper presents an overview of hydrogen generation by hydrolysis of Al and its alloys, emphasising the addition of carbon-based materials such as graphite, graphene, CNTs, etc.     

Evaluation of iron based chemical looping for hydrogen and electricity co-production by gasification process with carbon capture and storage

Integrated Gasification Combined Cycle (IGCC) is one of power generation technologies having the highest potential for carbon capture with low penalties in efficiency and cost. Syngas produced by gasification can be decarbonised using chemical looping methods in which an oxygen carrier (usually a metallic oxide) is recycled between the syngas oxidation reactor (fuel reactor) and the chemical agent oxidation reactor (steam reactor). In this way, the resulted carbon dioxide is inherently separated from the other products of combustion and the syngas energy is transferred to an almost pure hydrogen stream suitable to be used not only for power generation but also for transport sector (PEM fuel cells).     

Inhibition of carbon deposition using iron ore modified by K and Cu in chemical looping hydrogen generation

Chemical looping hydrogen generation based on iron is an innovative method to produce high purity hydrogen and capture CO₂ simultaneously. However, carbon deposition of iron ore limits the development. The iron ore modified by K and Cu was employed to suppress the carbon deposition. Experiments were carried out to investigate the effects of the additive amount on carbon deposition and hydrogen purity via carbon release characteristics in a batch fluidized bed. The carbon deposition ratio decreased monotonically with the increasing amount of potassium, but the excess copper loading led to a rise in the ratio of carbon deposition instead. The carbon deposition ratio decreased by up to 84% after adding K and Cu, which is speculated to be closely related to the weight ratio of Fe on the oxygen carrier surfaces. The experimental results at different temperatures demonstrated that 850°C was suitable for the inhibition of carbon deposition and sintering. In addition, the mechanism of inhibition of carbon deposition was proposed in detail and illustrated that it was correlated to the covering of active sites and the reactivity enhancement. Moreover, the carbon deposition ratio of the modified oxygen carrier maintained stable during the cyclic experiments. Therefore, it is feasible to employ the iron ore modified by K and Cu as oxygen carrier to suppress carbon deposition in the chemical looping hydrogen generation.     

The effect of various factors on the hydrogen generation by hydrolysis reaction of potassium borohydride

Potassium borohydride (KBH₄) reacted very slowly with water to liberate 4 mol of hydrogen/mol of compound at room temperature. The hydrolysis and stability conditions of KBH₄ investigated depend on KBH₄ concentrations, concentration of alkaline solutions, temperatures and electrical field intensity. Yield of produced hydrogen by self-hydrolysis of KBH₄ increases as the temperature increased and it produced 53.9% yield at the end of 300 min at 60 °C. The reaction rate order of hydrolysis of KBH₄ in aqueous solution is found at about 0.7–0.8 and the activation energy for hydrolysis is calculated as 14,700 kJ/mol. Potassium borohydride is stable both in room temperature and in aqueous alkaline solution. In this study, the electrical field that is not needed for catalytic activity was used for the hydrolysis of KBH₄ aqueous solution. It was found that 6 mol of hydrogen/mol of potassium borohydride was liberated in the presence of electrical field, whereas 4 mol of hydrogen was produced in the absence of electrical field per mol of potassium borohydride.