Utilization and impacts of hydrogen in the ironmaking processes: A review from lab-scale basics to industrial practices

Hydrogen (H₂) energy is a promising candidate to replace carbon monoxide (CO) as a reductant for iron oxide reduction in revolutionary ironmaking industrial processes, and numerous studies have been conducted to intensively study the utilization and impact of H₂ in ironmaking processes. Therefore, this review first collects and compares the H₂-assisted reduction mechanism and kinetics. The impacts of H₂ on the reduction accompanying behaviors, such as the disintegration, swelling, sticking, softening, and melting of iron ores, are then summarized. Third, the performance of H₂ predicted by either mass and heat balance models or numerical simulation models in various ironmaking processes is highlighted. Finally, the different applications of hydrogen-rich materials in blast furnace and non-blast furnace ironmaking processes are further compared to illuminate H₂ utilization before our outlook on the use of H₂ in the ironmaking industry.     

Advances in biohydrogen production processes: An approach towards commercialization

Biological H₂ production has an edge over its chemical counterpart mainly because it is environmentally benign. Despite having simpler technology, higher evolution rate of H₂ and the wide spectrum of substrate utilization, the major deterrent of anaerobic dark fermentation process stems from its lower achievable yields. Theoretically, the maximum H₂ yield is 4 mol H₂/mol glucose when glucose is completely metabolized to acetate or acetone in the anaerobic process. But it is somewhat difficult to achieve the complete degradation of glucose to carbon dioxide and H₂ through anaerobic dark fermentation. Moreover, this yield appears too low to be economically viable as an alternative to the existing chemical or electrochemical processes of hydrogen generation. Intensive research studies have already been carried out on the advancement of these processes, such as the development of genetically modified microorganism, improvement of the reactor designs, use of different solid matrices for the immobilization of whole cells, development of two-stage processes, and higher H₂ production rates. Maximum H₂ yield is found to be 5.1 mol H₂/mol glucose. However, major bottlenecks for the commercialization of these processes are lower H₂ yield and rate of H₂ production. Competent microbial cultures are required to handle waste materials efficiently, which are usually complex in nature. This will serve dual purposes: clean energy generation and bioremediation. Scale-up studies on fermentative H₂ production processes have been done successfully. Pilot plant trials of the photo-fermentation processes require more attention. Use of cheaper raw materials and efficient biological H₂ production processes will surely make them more competitive with the conventional H₂ generation processes in near future.     

Influence of expander components on the processes at the negative plates of lead-acid cells on high-rate partial-state-of-charge cycling. Part II. Effect of carbon additives on the processes of charge and discharge of negative plates

Lead-acid batteries operated in the high-rate partial-state-of-charge (HRPSoC) duty rapidly lose capacity on cycling, because of sulfation of the negative plates. As the battery operates from a partially discharged state, the small PbSO₄ crystals dissolve and precipitate onto the bigger crystals. The latter have low solubility and hence PbSO₄ accumulates progressively in the negative plates causing capacity loss. In order to suppress this process, the rate of the charge process should be increased.In a previous publication of ours we have established that reduction of Pb²⁺ ions to Pb may proceed on the surface of both Pb and carbon black particles. Hence, the reversibility of the charge-discharge processes improves, which leads to improved cycle life performance of the batteries in the HRPSoC mode. However, not all carbon forms accelerate the charge processes. The present paper discusses the electrochemical properties of two groups of carbon blacks: Printex and active carbons. The influence of Vaniseprse A and BaSO₄ (the other two components of the expander added to the negative plates) on the reversibility of the charge-discharge processes on the negative plates is also considered. It has been established that lignosulfonates are adsorbed onto the lead surface and retard charging of the battery. BaSO₄ has the opposite effect, which improves the reversibility of the processes on cycling and hence prolongs battery life in the HRPSoC duty. It has been established that the cycle life of lead-acid cells depends on the type of carbon black or active carbon added to the negative plates. When the carbon particles are of nano-sizes (<180 nm), the HRPSoC cycle life is between 10,000 and 20,000 cycles. Lignosulfonates suppress this beneficial effect of carbon black and activated carbon additives to about 10,000 cycles. Cells with active carbons have the longest cycle life when they contain also BaSO₄ but no lignosulfonate. A summary of the effects of the three expander components on the elementary processes during charge of negative lead-acid battery plates is presented at the end of the paper.     

Hydrogen,nuclear energy,and the advanced high-temperature reactor

Nuclear energy has been proposed as an energy source to produce hydrogen (H₂) from water. An examination of systems issues in this paper indicates that the infrastructure of H₂ consumption is now compatible with the production of H₂ by nuclear reactors. Alternative H₂ production processes were examined to define the requirements such processes would impose on the nuclear reactor. These requirements include supplying heat at a near-constant high temperature, providing a low-pressure interface with the H₂ production processes, isolating the nuclear plant from the chemical plant, and avoiding tritium contamination of the H₂ product. A reactor concept—the advanced high-temperature reactor—was developed to match these requirements for H₂ production.     

Energy recovery from microalgal biomass via enhanced thermo-chemical process

This work showed that microalgae having low lipid content has high potential for energy recovery via thermo-chemical processes. As an example, Microcystis aeruginosa (M. aeruginosa) was considered and tested. Specifically, this work verified that the growth rate of M. aeruginosa was extremely fast compared to other microalgae (as a factor of ∼10). Moreover, this work investigated the CO₂ co-feed impact on thermo-chemical processes (pyrolysis/gasification) using M. aeruginosa. Introducing CO₂ in the thermo-chemical process as reaction media or feedstock can enhance the efficiency of thermo-chemical processes by expediting the cracking capability of condensable hydrocarbons (tar). The generation of CO was enhanced as a factor of ∼2. Further generation of H₂ could be achieved in the presence of CO₂. Thus, utilizing CO₂ as reaction media or chemical feedstock can modify the end products into environmentally benign and desirable ones. The CO₂ co-feed impact on thermo-chemical processes with lingo-cellulosic biomass can be universally applied.     

Enhanced heterogeneous ferrioxalate photo-fenton degradation of reactive orange 4 by solar light

A combined homogeneous and heterogeneous photocatalytic decolourisation and degradation of a chlorotriazine Reactive azo dye Reactive Orange 4 (RO4) have been carried out using ferrous sulphate/ ferrioxalate with H₂O₂ and TiO₂-P25 particles. Solar/ferrous/H₂O₂/TiO₂-P25 and solar/ferrioxalate/H₂O₂/TiO₂-P25 processes are found to be more efficient than the individual photo-Fenton and solar/TiO₂-P25 processes. A comparison of these two processes with UV/ferrous/H₂O₂/TiO₂-P25 and UV/ferrioxalate/H₂O₂/TiO₂-P25 reveals that ferrioxalate is more efficient in solar light whereas ferrous ion is more efficient in UV light. The experimental parameters such as pH, initial H₂O₂, Fe²⁺, ferrioxalate and TiO₂-P25 concentration strongly influenced the dye removal rate in solar processes. The optimum operating conditions of these two combined processes are reported.     

Combustion of niobium in hydrogen and nitrogen. Synthesis of niobium hydrides and hydridonitrides

This paper treats the combustion processes observed in the Nb–N–H system, and its application to the synthesis of niobium hydridonitrides. In particular the Self-Propagating high-temperature synthesis (SHS) process in Nb–H and Nb–N systems was studied. The combustion products were hydrides and nitrides, respectively. The determination of the main features of combustion process by obtaining binary compounds enabled to examine a ternary system including both N₂ and H₂ simultaneously. It was found that niobium combustion in the mixture of two reacting gases proceeded in three competetive ways, established earlier for IVA group metals. Various types of reaction occur depending on the partial pressure ratio.     

Hybrid hydrate processes for CO2/H2 mixture purification: A techno-economic analysis

In this work, hydrate based separation technique was combined with membrane separation and amine-absorption separation technologies to design hybrid processes for separation of CO₂/H₂ mixture. Hybrid processes are designed in the presence of different types of hydrate promoters. The conceptual processes have been developed using Aspen HYSYS. Proposed processes were simulated at different flow rates for the feed stream. A comprehensive cost model was developed for economic analysis of novel processes proposed in this study. Based on the results from process simulation and equipment sizing, the amount of total energy consumption, fixed cost, variable cost, and total cost were calculated per unit weight of captured CO₂ for various flow rates of feed stream and in the presence of different hydrate promoters. Results showed that combination of hydrate formation separation technique with membrane separation technology results in a CO₂ capture process with lowest energy consumption and total cost per unit weight of captured CO₂. As split fraction and heat of hydrate formation increases, the share of hydrate formation section in total energy consumption increases. When TBAB is applied as hydrate promoter, due to its higher hydrate separation efficiency, more amount of CO₂ is captured in hydrate formation section and consequently the total cost for process decreases considerably. Hybrid hydrate-membrane process in the presence of TBAB as hydrate promoter with 29.47 US$/ton CO₂ total cost is the best scheme for hybrid hydrate CO₂ capture process. Total cost for this process is lower than total cost for single MDEA-based absorption process as the mature technology for CO₂ capture.     

Ion dynamics in the pseudocapacitive reaction of hydrous ruthenium oxide. Effect of the temperature pre-treatment

Pseudocapacitive redox reaction of hydrous ruthenium oxide was investigated by the combined electrochemical and quartz crystal nanobalance measurements on gold support in H₂SO₄ and Na₂SO₄ solutions. The results show that the pseudocapacitance arises from at least two different Faradaic reactions with significant influence of double layer capacitance. All three processes simultaneously take place during charging/discharging reaction, but their contribution vary depending on the electrolyte used, the temperature pre-treatment and on the potential range. One Faradaic reaction releases protons during oxidation reaction resulting in the electrode mass decrease, while another Faradaic reaction results in the chemical binding of water leading to the mass gain during the oxidation reaction. The former reaction is favoured in acidic electrolyte and at lower anodic potentials, and the latter reaction proceeds predominantly in neutral media and at higher anodic potentials. The influence of annealing temperatures on the characteristics of the redox reaction of hydrous ruthenium oxide, as well as on its capacitance, was confirmed. It was demonstrated that specific capacitances of hydrous ruthenium oxide could achieve values as high as 1500 F g⁻¹, provided that conditions of good electronic conductivity among RuO₂ particles, as well as good electrical contact between gold and RuO₂, are met.     

Design of CO2 absorption plant for recovery of CO2 from flue gases of gas turbine

The ongoing human-induced emission of carbon dioxide (CO₂) threatens to change the earth's climate. A major factor in global warming is CO₂ emission from thermal power plants, which burn fossil fuels. One possible way of decreasing CO₂ emissions is to apply CO₂ removal, which involves recovering of CO₂ from energy conversion processes. This study is focused on recovery of CO₂ from gas turbine exhaust of Sarkhun gas refinery power station. The purpose of this study is to recover the CO₂ with minimum energy requirement. Many of CO₂ recovery processes from flue gases have been studied. Among all CO₂ recovery processes which were studied, absorption process was selected as the optimum one, due to low CO₂ concentration in flue gas. The design parameters considered in this regard, are: selection of suitable solvent, solvent concentration, solvent circulation rate, reboiler and condenser duty and number of stages in absorber and stripper columns. In the design of this unit, amine solvent such as, diethanolamine (DEA), diglycolamine (DGA), methyldiethanolamine (MDEA), and monoethanolamine (MEA) were considered and the effect of main parameters on the absorption and stripping columns is presented. Some results with simultaneous changing of the design variables have been obtained. The results show that DGA is the best solvent with minimum energy requirement for recovery of CO₂ from flue gases at atmospheric pressure.     

CO2 capture study in advanced integrated gasification combined cycle

This paper presents the results of technical and economic studies in order to evaluate, in the French context, the future production cost of electricity from IGCC coal power plants with CO₂ capture and the resulting cost per tonne of CO₂ avoided. The economic evaluation shows that the total cost of base load electricity produced in France by coal IGCC power plants with CO₂ capture could be increased by 39% for ‘classical’ IGCC and 28% for ‘advanced’ IGCC. The cost per tonne of avoided CO₂ is lower by 18% in ‘advanced’ IGCC relatively to ‘classical’ IGCC. The approach aimed to be as realistic as possible for the evaluation of the energy penalty due to the integration of CO₂ capture in IGCC power plants. Concerning the CO₂ capture, six physical and chemical absorption processes were modeled with the Aspen Plus™ software. After a selection based on energy performance three processes were selected and studied in detail: two physical processes based on methanol and Selexol™ solvents, and a chemical process using activated MDEA. For ‘advanced’ IGCC operating at high-pressure, only one physical process is assessed: methanol.     

Post combustion methods for control of NOx emissions

This paper is a review of stack gas treatment methods for the control of NO_x emissions. Particular emphasis is placed on status of development and factors affecting the performance of the processes. Catalytic, noncatalytic, and scrubbing processes are compared on a uniform engineering basis. Most of the active process development work is taking place in Japan. The three leading stack gas treatment techniques for NO_x control are catalytic reduction with ammonia, noncatalytic reduction with ammonia, and direct scrubbing of NO with simultaneous absorption of SO₂. The wet processes are much less developed than the dry processes.     

Synergistic effects of advanced oxidization reactions in a combination of TiO2 photocatalysis for hydrogen production and wastewater treatment applications

In this paper, the synergistic effects of advanced oxidization reactions in a combination of TiO₂ photocatalysis are comparatively investigated for hydrogen production and wastewater treatment applications. An experimental study is conducted with a photoelectrochemical reactor under a UV-light source. TiO₂ is selected as the photocatalyst due to the high corrosion resistant nature and ability to form hydroxyl radicals with the interaction with photons. The synergetic effects of advanced oxidization processes (AOPs) such as Fenton, Fenton-like, photocatalysis (TiO₂/UV) and UV photolysis (H₂O₂/UV) are investigated individually and in a combination of each other. The Fenton type reagent in the reactor is formed by anodic sacrificial of stainless-steel electrode with the presence of H₂O₂. The influences of various parameters, including pH level, type of the electrode and electrolyte and the UV light, on the performance of the combined system are also investigated experimentally. The highest chemical oxygen demand (COD) removal efficiency is observed as 97.9% for the experimental condition which combines UV/TiO₂, UV/H₂O₂ and photo-electro Fenton type processes. The maximum hydrogen production rate from the photoelectrolysis of wastewater is obtained as 7.0 mg/Wh for the experimental condition which has the highest rate of photo-electro Fenton type processes. The average enhancement with the presence of UV light on hydrogen production rates and COD removal efficiencies are further calculated to be 3% and 20%, respectively.     

Pore-scale simulation of coupled multiple physicochemical thermal processes in micro reactor for hydrogen production using lattice Boltzmann method

A general numerical scheme based on the lattice Boltzmann method (LBM) is established to investigate coupled multiple physicochemical thermal processes at the pore-scale, in which several sets of distribution functions are introduced to simulate fluid flow, mass transport, heat transfer and chemical reaction. Interactions among these processes are also considered. The scheme is then employed to study the reactive transport in a posted micro reactor. Specially, ammonia (NH₃) decomposition, which can generate hydrogen (H₂) for fuel of proton exchange membrane fuel cells (PEMFCs), is considered where the endothermic decomposition reaction takes place at the surface of posts covered with catalysts. Simulation results show that pore-scale phenomena are well captured and the coupled processes are clearly predicted. Effects of several operating and geometrical conditions including NH₃ flow rate, operating temperature, post size, post insert position, post orientation, post arrangement and post orientation on the coupled physicochemical thermal processes are assessed in terms of NH₃ conversion, temperature uniformity, H₂ flow rate and subsequent current density generated in PEMFC.     

Analysis of sulfur–iodine thermochemical cycle for solar hydrogen production. Part I: decomposition of sulfuric acid

The sulfur–iodine (S–I) thermochemical water splitting cycle is one of the most studied cycles for hydrogen (H₂) production. S–I cycle consists of four sections: (I) acid production and separation and oxygen purification, (II) sulfuric acid concentration and decomposition, (III) hydroiodic acid (HI) concentration, and (IV) HI decomposition and H₂ purification. Section II of the cycle is an endothermic reaction driven by the heat input from a high temperature source. Analysis of the S–I cycle in the past thirty years have been focused mostly on the utilization of nuclear power as the high temperature heat source for the sulfuric acid decomposition step. Thermodynamic as well as kinetic considerations indicate that both the extent and rate of sulfuric acid decomposition can be improved at very high temperatures (in excess of 1000 °C) available only from solar concentrators. The beneficial effect of high temperature solar heat for decomposition of sulfuric acid in the S–I cycle is described in this paper. We used Aspen Technologies' HYSYS chemical process simulator (CPS) to develop flowsheets for sulfuric acid (H₂SO₄) decomposition that include all mass and heat balances. Based on the HYSYS analyses, two new process flowsheets were developed. These new sulfuric acid decomposition processes are simpler and more stable than previous processes and yield higher conversion efficiencies for the sulfuric acid decomposition and sulfur dioxide and oxygen formation.     

Recent developments in membrane-based technologies for CO2 capture

Developing new methods and technologies that compete with conventional industrial processes for CO₂ capture and recovery is a hot topic in the current research. Conventional processes do not fit with the current approach of process intensification but take advantage due to their maturity and large-scale implementation. Acting in a precombusion scenario or post-combustion scenario involves the separation of CO₂/H₂ or CO₂/N₂, respectively.     

Reactivity and characteristics of Pd/MOF and Pd/calcinated-MOF catalysts for CO oxidation reaction: Effect of oxygen and hydrogen

For the first time, the effect of calcination process on characteristics and catalytic performances of Pd supported on different MOFs (MIL-101(Cr), NH₂-MIL-101(Cr), and HKUST-1) was evaluated. Besides, the various orders of calcination process and reduction one on Pd/MOF and Pd/calcinated-MOF were studied, and their performances in CO oxidation reaction were presented to find the effect of H₂ and O₂. Results showed that the effect of calcination and reduction processes on the catalytic activities and characteristics strongly depends on the nature of MOF. Among MIL-based catalysts, the catalyst with no calcination treatment showed the best activity. Among MNH₂-based catalysts, high activity was obtained for Pd/MNH₂, Pd/MNH₂-C, and Pd/MNH₂(RC) samples and Pd/calcinated-MNH₂was the best. Catalytic activities of HKUST-1-based catalysts decreased with calcination due to high changes in their structures. The results are useful for predicting the performance of MOFs in oxidation processes, especially reactions in which high oxygen concentrations are involved.     

Synergistic catalysis of bi-metals in the reforming of biomass-derived hydrocarbons: A review

Biomass such as ethanol and glycerol has emerged as an alternative feedstock for hydrogen (H₂) production in recent years. Ethanol, which is high in H_2, can easily be derived from renewable biomass sources, whereas; glycerol is a by-product of biodiesel expected to be surplus in the coming years. Several catalytic reforming routes involving biomass such as steam, CO₂, auto thermal, partial oxidation and aqueous-phase reforming can produce syngas or H₂. Bimetallic catalysis is one of the potential solutions to reduce carbon formation and catalysts deactivation in reforming processes since it can produce more stable catalysts from the synergistic effect of the combined metals. There are many reviews on catalyst designs and reaction pathways reported in the literature; nevertheless, comparative literature is lacking on the metal configuration of bimetallic catalyst in biomass reforming particularly for ethanol and glycerol reforming reactions. Therefore, studies linked with the synergistic effects of various bi-metal combinations of catalysts used in biomass reforming processes have been reviewed in the paper. Moreover, the study provides data for the application of bimetallic catalyst for industrial biomass processes.     

Biological hydrogen production by Anabaena sp. - Yield, energy and CO2 analysis including fermentative biomass recovery

This paper presents laboratory results of biological production of hydrogen by photoautrotophic cyanobacterium Anabaena sp. Additional hydrogen production from residual Cyanobacteria fermentation was achieved by Enterobacter aerogenes bacteria. The authors evaluated the yield of H₂ production, the energy consumption and CO₂ emissions and the technological bottlenecks and possible improvements of the whole energy and CO₂ emission chain.The authors did not attempt to extrapolate the results to an industrial scale, but to highlight the processes that need further optimization.The experiments showed that the production of hydrogen from cyanobacteria Anabaena sp. is technically viable. The hydrogen yield for this case was 0.0114 kgH₂/kg_biomass which had a rough energy consumption of 1538 MJ/MJH₂ and produced 114640 gCO₂/MJH₂. The use of phototrophic residual cyanobacteria as a substrate in a dark-fermentation process increased the hydrogen yield by 8.1% but consumed 12.0% more of energy and produced 12.1% more of CO₂ showing that although the process increased the overall efficiency of hydrogen production it was not a viable energy and CO₂ emission solution. To make cyanobacteria-based biofuel production energy and environmentally relevant, efforts should be made to improve the hydrogen yield to values which are more competitive with glucose yields (0.1 kgH₂/kg_biomass). This could be achieved through the use of electricity with at least 80% of renewables and eliminating the unessential processes (e.g. pre-concentration centrifugation).