Understanding the kinetics of coal electrolysis at intermediate temperatures

The kinetics of coal electrolysis was studied on a bench continuous coal electrolytic cell setup at intermediate temperatures by applying galvanostatic polarization techniques. The results showed that coal oxidation takes place during the contact of the coal particles with the electrode and it is directly related to electrode composition and the presence of Fe(III) ions in the slurry solution. Coal electro-oxidation by Fe(III) is the limiting step in the oxidation of a 0.02 g mL⁻¹ coal slurry containing 100 mM Fe(II)/Fe(III) at high currents (100 mA) at 108 °C with a 65 mL min⁻¹ flow rate. The study suggests that the films that grow at the surface of the coal particles limit the coal conversion. A mechanism is proposed to describe the coal oxidation process.     

Characteristics and anode reaction of organic wastewater-assisted coal electrolysis for hydrogen production

Electrolytic hydrogen production has the advantages of distributed on-demand hydrogen production, high purity and facile coupling with renewable energy sources, but this process is very energy intensive. In this study, the organic wastewater-assisted coal electrolysis process for hydrogen production was studied in an H-type electrolytic cells. Part of the energy can come from the carbon sources in coal and wastewater to reduce power consumption. Linear sweep voltammetry and potentiostatic techniques were used to study the electrolysis characteristics and anode reaction of the wastewater coal slurry. The results showed that the difference in the composition of the wastewater made the electrolysis characteristics quite different. The gas washing water, sulfur water and slag water produced by coal conversion could significantly increase the current density of coal slurry electrolysis. As for the gas washing water, it has no obvious effect on the catalytic effect of Fe³⁺, and the increase in current density was mainly due to the effects of organic matter and chloride. With increasing voltage, the main anode reaction of the wastewater coal slurry was divided into three stages, namely oxidation of coal particles (0.7–1.0 V), oxidation of organic matter in wastewater (1.0–1.5 V) and oxidation of chloride ions (1.5–2.0 V). Below the chlorine oxidation potential, chloride ions could also promote the oxidation of coal particles. The oxidation mechanism of coal slurry in the presence of wastewater was proposed.     

On-board hydrogen storage and production: An application of ammonia electrolysis

On-board hydrogen storage and production via ammonia electrolysis was evaluated to determine whether the process was feasible using galvanostatic studies between an ammonia electrolytic cell (AEC) and a breathable proton exchange membrane fuel cell (PEMFC). Hydrogen-dense liquid ammonia stored at ambient temperature and pressure is an excellent source for hydrogen storage. This hydrogen is released from ammonia through electrolysis, which theoretically consumes 95% less energy than water electrolysis; 1.55 Wh g⁻¹ H₂ is required for ammonia electrolysis and 33 Wh g⁻¹ H₂ for water electrolysis. An ammonia electrolytic cell (AEC), comprised of carbon fiber paper (CFP) electrodes supported by Ti foil and deposited with Pt-Ir, was designed and constructed for electrolyzing an alkaline ammonia solution. Hydrogen from the cathode compartment of the AEC was fed to a polymer exchange membrane fuel cell (PEMFC). In terms of electric energy, input to the AEC was less than the output from the PEMFC yielding net electrical energies as high as 9.7 ± 1.1 Wh g⁻¹ H₂ while maintaining H₂ production equivalent to consumption.     

Thermodynamic modeling and assessment of a combined coal gasification and alkaline water electrolysis system for hydrogen production

The performance of a clean energy system that combines the coal gasification and alkaline water electrolyzer concepts to produce hydrogen is evaluated through thermodynamic modeling and simulations. A parametric study is conducted to determine the effect of water ratio in coal slurry, gasifier temperature, effectiveness of carbon dioxide removal, and hydrogen recovery efficiency of the pressure swing adsorption unit on the system hydrogen production. The exergy efficiency and exergy destruction in each system component are also evaluated. The results reveal that the overall energy and exergy efficiencies of this system are ∼58% and ∼55%, respectively. The weight ratio of the hydrogen yielded to the coal fed to this system is ∼0.126. Although this system produces hydrogen from coal, the greenhouse gases emitted from this system are fairly low.     

Achieving high-efficiency hydrogen production using planar solid-oxide electrolysis stacks

Steam electrolysis in solid oxide electrolysis cells (SOECs) is considered as an effective method to achieve high-efficiency hydrogen production. In the present investigation, samples of 1-cell, 2-cell and 30-cell SOEC stacks were tested under electrolysis of steam to give a practical evaluation of the SOEC system efficiency of hydrogen production. The samples were tested at 800 °C under various operating conditions up to 500 h without significant degradation, and obtained steam conversion rates of 12.4%, 23% and 82.2% for the 1-cell, 2-cell and 30-cell stacks, respectively. System efficiencies of hydrogen production were calculated for the samples based on their real performance. A maximum efficiency value of 52.7% was achieved in the 30-cell stack.     

Chlorine-free alkaline seawater electrolysis for hydrogen production

A new process for chlorine-free seawater electrolysis is proposed in this study. The first step of the process is separation of Mg²⁺ and Ca²⁺ ions from seawater by nanofiltration. Next, the NF permeate is dosed into the electrochemical system. There it is completely split into hydrogen and oxygen gases and NaCl precipitate. The electrochemical system comprises an electrochemical cell operated at elevated temperatures (e.g. ≥ 50 °C) and a settling tank filled with aqueous NaOH solution (20–40 %wt) that operates at lower temperatures (e.g. 20–30 °C). High concentration of hydroxide ions in the electrolyzed solution prevents anodic chlorine evolution, while the accumulated NaCl precipitates in the settling tank. Batch electrolysis tests, performed in NaCl-saturated NaOH solutions, showed absolutely no chlorine formation on Ni200 and Ti/IrO₂RuO₂TiO₂ anodes at [NaOH] > 100 g/kgH₂O. Three long-term operations (9, 12 and 30 days) of the electrochemical system showed no Cl₂ or chlorate (ClO₃^?) production on both electrodes operated at current densities of 93–467 mA/cm². The Ni200 anode was corroded in the continuous operation that resulted in formation of nickel oxide on the anode surface. On the other hand, the system was successfully operated at 467 mA/cm² with Ti/IrO₂RuO₂TiO₂ electrodes in NaCl-saturated solution of NaOH (30 %wt) for 12 days. During this period no formation of Cl₂ and ClO₃^? has been observed and precipitation of NaCl occurred only in the settling tank. The performance of the system was stable during the operation as indicated by the insignificant fluctuations in the applied cell potentials and measured constant concentrations of NaOH_(aq) and NaCl_(aq) in the electrolyte solution. During 12 days of operation at ≈ 470 mA/cm² about 1.2 m³ of H₂ and ≈150 g of solid NaCl were produced in the system. Electrical energy demand of the electrolysis cell was 5.6–6.7 kWh/m³H₂ for the current density range of 187–467 mA/cm².     

Enhanced hydrogen production through alkaline electrolysis using laser-nanostructured nickel electrodes

This study describes the fabrication of ultrafast laser-induced periodic nanostructures on Nickel sheets and their use as cathodes in alkaline electrolysis. For the first time, to the best of our knowledge, laser-nanostructured Ni sheets were used as cathode electrodes in a custom-made electrolysis cell at actual, Hydrogen producing conditions, and their efficiency has been compared to the untreated Nickel sheets. The electrochemical evaluation showed higher J_peaks, lower overpotential, and enhanced double-layer capacitance for the nanostructured electrode. A decrease in the Tafel slope was also found for the nanostructured electrode. The hydrogen production efficiency was found to be 3.7 times larger for the laser-nanostructured Nickel electrode, which was also confirmed by current-time measurements during electrolysis. Also, a novel approach is proposed to improve the stability of the current density during electrolysis and, therefore, the hydrogen production process by about 10%.     

Electrolysis of coal slurries to produce hydrogen gas: Effects of different factors on hydrogen yield

The study was aimed to investigate the effects of different factors (such as acid concentration, cell potential, temperature, coal types, and geometric area of the membrane) on the coal slurry electrolysis and hydrogen evolution. It was observed that all of the above factors affected hydrogen production upon completion of the electrolysis. The results revealed that an increase in the initial acid concentration up to 5.0 M brought about an increase in the current density and hydrogen evolution. However, the higher the acid concentration was taken (>7.0 M) then the lower the current density and hydrogen evolution were, which resulted in significant change due to the agglomeration of coal samples and stuck on the electrode surface.Furthermore, the CO₂ evolution (14 ml) was observed only at high temperature (100 °C) and high (2.0 V) cell potential when the H₂ amount was 776 ml. The coal type was observed to have influenced the electrolysis.     

Optimization of NiMo catalyst for hydrogen production in microbial electrolysis cells

Non-platinum based cathodes were recently developed by electrodepositing NiMo on carbon cloth, which demonstrated good electrocatalytic activity for hydrogen evolution in microbial electrolysis cells (MECs). To further optimize the electrodeposition condition, the effects of electrolyte bath composition, applied current density, and duration of electrodeposition were systematically investigated in this study. The developed NiMo catalysts were characterized with scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) and evaluated using chronopotentiometry and in MECs. The optimal condition for electrodeposition of NiMo on carbon cloth was determined as: a Mo/Ni mass ratio of 0.65 in electrolyte bath, an applied current density of 50 mA/cm² and electrodeposition duration of 10 min. Under this condition, the NiMo catalyst has a formula of Ni₆MoO₃ with a nodular morphology. The NiMo loading on the carbon cloth was reduced to 1.7 mg/cm² and the performance of MEC with the developed NiMo cathode was comparable to that with Pt cathode with a similar loading. This result indicates that a much lower cathode fabrication cost can be achieved compared to that using Pt catalyst, and thereby significantly enhancing the economic feasibility of the MEC technology.     

Hydrogen production via urea electrolysis using a gel electrolyte

A technology was demonstrated for the production of hydrogen and other valuable products (nitrogen and clean water) through the electrochemical oxidation of urea in alkaline media. In addition, this process remediates toxic nitrates and prevents gaseous ammonia emissions. Improvements to urea electrolysis were made through replacement of aqueous KOH electrolyte with a poly(acrylic acid) gel electrolyte. A small volume of poly(acrylic acid) gel electrolyte was used to accomplish the electrochemical oxidation of urea improving on the previous requirement for large amounts of aqueous potassium hydroxide. The effect of gel composition was investigated by varying polymer content and KOH concentrations within the polymer matrix in order to determine which is the most advantageous for the electrochemical oxidation of urea and production of hydrogen.     

Study of hydrogen production in light assisted microbial electrolysis cell operated with dye sensitized solar cell

Hydrogen production with light as an additional energy source in a microbial electrolysis cell (MEC) is described. A ruthenium-dye (N719) sensitized solar cell with an open circuit potential (V_oc) of 602 mV was connected to the MEC. Hydrogen production was carried out by irradiating the DSSC connected across the MEC with a light intensity of 40 mW/cm² and also with natural sunlight. The DSSC was stable during various batch experiments. The acetate conversion efficiency and the coulombic efficiency based on the average of first two batches were 30.5 ± 2.5% and 40 ± 2% respectively. The cathodic recovery efficiency ranged from 72% to 86% during repeated batch experiments with an average of 78 ± 2.5%.     

PEM electrolysis for production of hydrogen from renewable energy sources

PEM electrolysis is a viable alternative for generation of hydrogen from renewable energy sources. Several possible applications are discussed, including grid independent and grid assisted hydrogen generation, use of an electrolyzer for peak shaving, and integrated systems both grid connected and grid independent where electrolytically generated hydrogen is stored and then via fuel cell converted back to electricity when needed. Specific issues regarding the use of PEM electrolyzer in the renewable energy systems are addressed, such as sizing of electrolyzer, intermittent operation, output pressure, oxygen generation, water consumption and efficiency.     

Manipulating the hydrogen production from acetate in a microbial electrolysis cell-microbial fuel cell-coupled system

A biological hydrogen-producing system is configured through coupling an electricity-assisting microbial fuel cell (MFC) with a hydrogen-producing microbial electrolysis cell (MEC). The advantage of this biocatalyzed system is the in-situ utilization of the electric energy generated by an MFC for hydrogen production in an MEC without external power supply. In this study, it is demonstrated that the hydrogen production in such an MEC-MFC-coupled system can be manipulated through adjusting the power input on the MEC. The power input of the MEC is regulated by applying different loading resistors connected into the circuit in series. When the loading resistance changes from 10 Ω to 10 kΩ, the circuit current and volumetric hydrogen production rate varies in a range of 78 ± 12 to 9 ± 0 mA m⁻² and 2.9 ± 0.2 to 0.2 ± 0.0 mL L⁻¹ d⁻¹, respectively. The hydrogen recovery (RH₂), Coulombic efficiency (CE), and hydrogen yield (YH₂) decrease with the increase in loading resistance. Thereafter, in order to add power supply for hydrogen production in the MEC, additional one or two MFCs are introduced into this coupled system. When the MFCs are connected in series, the hydrogen production is significantly enhanced. In comparison, the parallel connection slightly reduces the hydrogen production. Connecting several MFCs in series is able to effectively increase power supply for hydrogen production, and has a potential to be used as a strategy to enhance hydrogen production in the MEC-MFC-coupled system from wastes.     

Investigation of multi-metal catalysts for stable hydrogen production via urea electrolysis

It has been shown that urea electrolysis is a viable method for wastewater remediation and simultaneous production of valuable hydrogen. Inexpensive nickel catalyst is optimal for the oxidation of urea in alkaline media but improvements are needed to minimize surface blockage and increase current density. Multi-metal catalysts were investigated by depositing platinum group metals on a nickel substrate. Rhodium and nickel proved synergistic to reduce surface blockage and increase catalyst stability. Rh-Ni electrodes reduced the overpotential for the electro-oxidation of urea and improved the current density by a factor of 200 compared to a Ni catalyst.     

Clean hydrogen production in a full biological microbial electrolysis cell

The recent interest in microbial electrolysis cell (MEC) technology has led the research platform to develop full biological MECs (bioanode-biocathode, FB-MEC). This study focused on biohydrogen production from a biologically catalyzed MEC. A bioanode and a biocathode were initially enriched in a half biological MFC (bioanode-abiocathode, HB-MFC) and a half biological MEC (abioanode-biocathode, HB-MEC), respectively. The FB-MEC was established by transferring the biocathode of the HB-MEC and the bioanode of the HB-MFC to a two-chamber MEC. The FB-MEC was operated under batch (FB-MEC-B) and recirculation batch (FB-MEC-RB) modes of operation in the anodic chamber. The FB-MEC-B reached a maximum current density of 1.5 A/m² and the FB-MEC-RB reached a maximum current density of 2.5 A/m² at a similar applied voltage while the abiotic control system showed the maximum of 0.2 A/m². Hydrogen production rate decreased in the FB-MEC compared to that of the HB-MEC. However, the cathodic hydrogen recovery increased from 42% obtained in the HB-MEC to 56% in the FB-MEC-B and 65% in the FB-MEC-RB, suggesting the efficient oxidation and reduction rates in the FB-MEC compared to the HB-MEC. The onset potential for hydrogen evolution reaction detected by linear sweep voltammetry analysis were −0.780 and −0.860 V vs Ag/AgCl for the FB-MEC-RB and the FB-MEC-B (−1.26 for the abiotic control MEC), respectively. Moreover, the results suggested that the FB-MEC worked more efficiently when the biocathode and the bioanode were enriched initially in half biological systems before transferring to the FB-MEC compared to that of the simultaneously enriched in one system.     

Recovery of flakey cobalt from aqueous Co(II) with simultaneous hydrogen production in microbial electrolysis cells

Flakey cobalt was successfully recovered from aqueous Co(II) with simultaneous hydrogen production in microbial electrolysis cells (MECs). At applied voltages of 0.3–0.5 V, the yields of 0.81 mol Co/mol COD and 1.21 ± 0.03–1.49 ± 0.11 mol H₂/mol COD were achieved while the energy efficiency relative to the electrical input was 22.5 ± 0.1–43.2 ± 0.7% (cobalt) and 170 ± 12–262 ± 7% (hydrogen), and the overall energy efficiency relative to both the electrical input and the energy of the anodic substrate averaged 9.4% (cobalt) and 62.8% (hydrogen). Cathode accumulated flakey crystals were verified as cobalt using both a scanning electron microscope capable of energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction analysis (XRD). Dominant bacteria on the anodes and known as exoelectrogens or recalcitrant substance degraders included Geobacter uraniireducens, Comamonas nitrativorans, uncultured Geobacter sp., Acidovorax caeni, Pseudorhodoferax caeni, and Diaphorobacter nitroreducens. The evidence of influence factors including applied voltage, pH, solution conductivity, temperature and type of buffer can contribute to improving understanding of and optimizing cobalt recovery with simultaneous hydrogen production in MECs.     

On the production of hydrogen via alkaline electrolysis during off-peak periods

This article studies the opportunity for producing hydrogen via alkaline electrolysis from electricity consumption during off-peak periods. Two aspects will be discussed: electricity spot markets and nuclear electricity production in France.

From a market point of view, when there is a significant fluctuation in electricity prices, the use of an electrolysis installation during off-peak periods makes it possible to make quite considerable savings in production costs. Savings vary enormously from one market to the next; some highly fluctuating markets offer very low off-peak prices and allow for viable hydrogen production, even if average electricity prices first appear to be quite high. Very fluctuating spot prices market may be difficult to predict and makes operations of an electrolysis installation more complicated and risky. For other more stable markets, the use of an electrolysis installation during off-peak periods does not appear to be a relevant proposition.

From the point of view of French electricity production, the availability of current nuclear power plants and the estimation of available energy for mass production of hydrogen show that the installations studied would not be viable. For “peak period” use, it would certainly be more useful to have electrolysers with a lower investment proportion, even if this means slightly higher operating costs. Research into large-capacity electrolysers should, therefore, both develop low-production-cost electrolysers, for use in base load mode where dedicated production means are concerned, and highly flexible electrolysers, with low investment costs, which could easily be viable with low rates of use.     

Direct electrolysis of bunsen reaction product for hydrogen production: The continuous-flow operation

Hydrogen sulfide (H₂S) emitted from oil industry's hydrotreating processes can be converted into hydrogen and used back to the same processes through a H₂S splitting cycle, where the Bunsen reaction and HI decomposition are two participating reactions. To overcome the difficulties and complications posted in the scaling up of the cycle, direct electrolysis of the Bunsen reaction product solution was proposed and has been studied in a batch electrolysis cell in our earlier work. This paper studies the direct electrolysis using a customer-made, continuous-flow electrolysis cell. The effects of the operating parameters including the current density, the entering HI concentration and flow rate of the anolyte, the toluene to aqueous phase ratio and stirring speed in anolyte cell, the H₂SO₄ concentration and circulation rate of the catholyte on the performing parameters such as the conversion of iodide ions, the yield of iodine transferred to toluene, and the anodic and cathodic current efficiencies for iodide conversion and hydrogen production were carefully investigated. The results show that the cathodic current efficiency for hydrogen production is nearly 100% for all the runs and that the anodic current efficiency for iodide ion conversion to iodine is relatively low (20%–70%) and varies with the changes in operating parameters. Running at high levels of the current density, the volumetric ratio of toluene to aqueous phase in anolyte, or the stirring speed in anolyte, and low levels of the entering concentration of I^? in anolyte or the flow rate of anolyte in electrolysis operation are in favor of having a high iodide conversion and high I₂-toluene yield. Iodide anions at a few mmol L^?1 level (a few thousandths of the entering concentration) are found in the cathodic chamber caused by its diffuse against the electric field and the proton exchange membrane. The continuous, direct electrolysis of the Bunsen product solution can be considered being adapted in the sulfur-iodine (S–I) water splitting cycle for hydrogen production.