Simultaneous production of H2 and C2 hydrocarbons by using a novel configuration solid-electrolyte + fixed bed reactor

A novel combined single chamber solid electrolyte plus fixed bed reactor configuration was developed for the simultaneous production of H₂ and C₂ hydrocarbons from a humidified CH₄ atmosphere. Hence, a Pt/YSZ/Ag solid electrolyte cell was placed on the top of an active oxidative coupling catalyst powder bed Ce–Na₂WO₄/SiO₂. H₂ was produced via steam electrolysis in a Pt cathode of the solid electrolyte cell (H₂O + 2e⁻ → H₂ + O²⁻). Simultaneously, the produced O²⁻ ions were electrochemically pumped to the Ag anode, leading to the C_2s production, via oxidative coupling of CH₄ (4CH₄ + 3O²⁻ → C₂H₄ + C₂H₆ + 3H₂O + 6e⁻). Additionally, non-reacted O²⁻ molecules desorbed to the gas phase (2O²⁻ → O₂+4e⁻) and reacted with CH₄ in the catalyst bed leading to an increase of C_2s yield. The influence of different reaction parameters was investigated together with long-term reaction experiments, confirming the stability of this configuration for its practical application. The obtained results demonstrated that the addition of an active catalyst bed strongly enhances both: the efficiency of the single chamber steam electrolysis and the oxidative coupling process.     

Synthesis of reduced graphene oxide–TiO2 nanoparticle composite systems and its application in hydrogen production

The utilization of solar energy for the conversion of water to hydrogen and oxygen has been considered to be an efficient strategy to solve crisis of energy and environment. Here, we report the synthesis of reduced graphene oxide–TiO₂ nanoparticle composite system through the photocatalytic reduction of graphite oxide using TiO₂ nanoparticles. Photoelectrochemical characterizations and hydrogen evolution measurements of these nanocomposites reveal that the presence of graphene enhances the photocurrent density and hydrogen generation rate. The optimum photocurrent density and hydrogen generation rate has been found to be 3.4 mA cm⁻² and 127.5 μmole cm⁻²h⁻¹ in 0.5 M Na₂SO₄ electrolyte solution under 1.5AM solar irradiance of white light with illumination intensity of 100 mW cm⁻². In graphene–TiO₂ nanocomposite, photogenerated electrons in TiO₂ are scavenged by graphene sheets and percolate to counter electrode to reduce H⁺ to molecular hydrogen thus increasing the performance of water-splitting reaction.     

Electrochemical hydrogen discharge of high-strength low alloy steel for high-pressure gaseous hydrogen storage tank: Effect of discharging temperature

Hydrogen discharge technique of high-strength low alloy steel for high-pressure gaseous hydrogen storage tank was developed by using an electrochemical technique. The electrochemical hydrogen discharge of high-strength low alloy steel were investigated in a deaerated borate buffer solution (0.3 M H₃BO₃ + 0.074 M N₂B₄O₇, pH = 8.4). By applying a potential of +630 mV_SCE which is higher than the hydrogen equilibrium potentials and lower than the pitting potential, the oxidation reaction of metal (Fe → Fe²⁺ + 2e⁻) is limited and oxidation reaction of the hydrogen (H₂ + 2OH⁻ → 2H₂O + 2e⁻) was induced simultaneously. Thus, the pre-charged hydrogen inside the specimen was eliminated effectively without any damage to the specimen. The electrochemical hydrogen discharge method was performed at 25 °C, 50 °C and 75 °C. The efficiency of hydrogen discharge was accelerated with increasing temperature because the exchange current density of hydrogen is increased with temperature.     

H2 production via water gas shift in a composite Pd membrane reactor prepared by the pore-plating method

In this work, H₂ production via catalytic water gas shift reaction in a composite Pd membrane reactor prepared by the ELP “pore-plating” method has been carried out. A completely dense membrane with a Pd thickness of about 10.2 μm over oxidized porous stainless steel support has been prepared. Firstly, permeation measurements with pure gases (H₂ and N₂) and mixtures (H₂ with N_2, CO or CO₂) at four different temperatures (ranging from 350 to 450 °C) and trans-membrane pressure differences up to 2.5 bar have been carried out. The hydrogen permeance when feeding pure hydrogen is within the range 2.68–3.96·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5, while it decreases until 0.66–1.35·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 for gas mixtures. Furthermore, the membrane has been also tested in a WGS membrane reactor packed with a commercial oxide Fe–Cr catalyst by using a typical methane reformer outlet (dry basis: 70%H₂–18%CO–12%CO₂) and a stoichiometric H₂O/CO ratio. The performance of the reactor was evaluated in terms of CO conversion at different temperatures (ranging from 350 °C to 400 °C) and trans-membrane pressures (from 2.0 to 3.0 bar), at fixed gas hourly space velocity (GHSV) of 5000 h⁻¹. At these conditions, the membrane maintained its integrity and the membrane reactor was able to achieve up to the 59% of CO conversion as compared with 32% of CO conversion reached with conventional packed-bed reactor at the same operating conditions.     

Equilibrium shift of methylcyclohexane dehydrogenation in a thermally stable organosilica membrane reactor for high-purity hydrogen production

A high-performance organosilica membrane was prepared via sol–gel processing for use in methylcyclohexane (MCH) dehydrogenation to produce high-purity hydrogen. The membrane showed a high H₂ permeance of 1.29 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹, with extremely high H₂/C₃H₈ and H₂/SF₆ selectivities of 6680 and 48,900, respectively, at 200 °C. The extraction of hydrogen from the membrane reactor led to the MCH conversion higher than the thermodynamic equilibrium, with almost pure hydrogen obtained in the permeate stream without considering the effect of carrier gas and sweep gas in the membrane reactor, and the organosilica membrane reactor was very stable under the reaction conditions employed.     

Hydrogen-methane production from pulp & paper sludge and food waste by mesophilic–thermophilic anaerobic co-digestion

The present study focused on the mesophilic anaerobic bio-hydrogen production from PPS (pulp & paper sludge) and FW (food waste), and the subsequent anaerobic digestion of the effluent for the methane production under thermophilic conditions by a two-stage process. The maximum hydrogen yield of 64.48 mL g⁻¹ VS_fed and methane yield of 432.3 mL g⁻¹ VS_fed were obtained when PPS and FW were applied with 1: 1 VS ratio as the feedstock. No VFA were cumulated in the reactor during the period of hydrogen - methane fermentation, as well as no NH₃–N and Na⁺ inhibition were found in the process. 71%–87% removal efficiencies of SCOD were attained for hydrogen and methane co-production. pH 4.8–6.4 and alkalinity 794–3316 mg CaCO₃ L⁻¹ for H₂ fermentation, as well as pH 6.5–8.8 and alkalinity 4165–4679 mg CaCO₃ L⁻¹ for CH₄ fermentation, were achieved without any adjustment. This work showed that anaerobic co-digestion of PPS and FW for hydrogen-methane co-production was a stable, reliable and effective way for energy recovery and bio-solid waste stabilization by the two-stage mesophilic–thermophilic process.     

Hydrogen production by redox of bimetal cation-modified iron oxide

Pure hydrogen can be stored and supplied directly to polymer electrolyte fuel cell by the redox of iron oxide: Fe₃O₄ + 4H₂ → 3Fe + 4H₂O and 4H₂O + 3Fe → Fe₃O₄ + 4H₂. Four bimetal-modified samples were prepared by impregnation. The hydrogen storage properties of the samples were investigated. The result shows that the Fe₂O₃–Mo–Al sample presented the most excellent catalytic activity and cyclic stability. H₂ forming temperature and H₂ forming rate could be surprisingly decreased and enhanced, respectively. The average H₂ forming temperature at the rate of 250 μmol min⁻¹·Fe-g⁻¹ for Fe₂O₃–Mo–Al in the first 4 cycles could be decreased from 469 °C before the addition of Mo–Al to 273 °C after the addition of Mo–Al. The reason for it may be that the Mo–Al additive in the sample can prevent from the sintering of the particles and accelerate the H₂O decomposition due to Mo taking part in the redox reaction. The average storage capacity of Fe₂O₃–Mo–Al was up to 4.68 wt%.     

Water handling challenge on hydrolysis of sodium borohydride in batch reactors

A study was undertaken in order to investigate the potential of hydrogen (H₂) generation by hydrolysis of solid sodium borohydride (NaBH₄) with stoichiometric amount of distilled water (from molar ratios H₂O/NaBH₄ (mol/mol) of 2 to 18), in the presence of a powder nickel-ruthenium based catalyst, reused more than 300 times. The experiments, performed in batch reactors with different free volumes and bottom shapes (flat and conical) reveal – for the conical bottom shape with any excess of water – 8.1 H₂ wt% and 92 kg H₂/m³ (materials-only basis), and a H₂ rate of 87.4 L(H₂) min⁻¹ g⁻¹ catalyst, at the moderate pressure of ∼1.2 MPa. The results presented in this work give emphasis to the importance of considering the role of reactor bottom geometry on the solid NaBH₄ hydrolysis studies performed with stoichiometric amounts of liquid water.     

Bio-hydrogen production during acidogenic fermentation in a multistage stirred tank reactor

The objective of this study was to evaluate the production of hydrogen in a two-stage CSTR system – both reactors having the same volume – and compare its performance with a conventional one-stage process. The lab-scale two-stage and one-stage systems were operated at five pHs and five hydraulic retention time (HRTs). The maximum volumetric hydrogen productivity and yield obtained with the two-stage system were 5.8 mmol L⁻¹ h⁻¹ and 2.7 mol H₂ mol glucose⁻¹, respectively, at an HRT of 12 h and pH 5.5. Overall, the two-stage system showed, at steady state, a better performance that the one-stage system for all the evaluated pHs. However, a comparison between the one-stage system, operating at 6 h of HRT, and the first reactor of the two-stage system at the same HRT did not show any significant difference, highlighting the positive impact of having a two-stage process. The determination of the ratio between the experimental measured H₂ in the gas phase and the theoretical H₂ generated in the liquid phase (discrepancy factor) indicated that an important part of the hydrogen produced in the first reactor was transferred into the second reactor instead of being desorbed in the headspace. Therefore, the improving of hydrogen production in the two-stage system is rather attributed to the increased transfer of hydrogen from liquid to gas than an actual total hydrogen production increase.     

The role of CuO in promoting photocatalytic hydrogen production over TiO2

Low cost semiconductor photocatalysts that can efficiently harvest solar energy to generate H₂ from water or biofuels will be critical to future hydrogen economies. In this study, low cost CuO/TiO₂ photocatalysts (CuO loadings 0–15 wt.%) were prepared, characterized and evaluated for H₂ production from ethanol–water mixtures (80 vol.% ethanol, 20 vol.% H₂O) under UV excitation. TEM, XRF, EDAX, EPR, Raman, TGA, XPS and Cu L-edge NEXAFS data showed that at CuO loadings <5 wt.%, Cu(II) was highly dispersed over the TiO₂ support, possibly as a sub-monolayer CuO species. At higher loadings, CuO crystallites of diameter 1–2 nm were identified. The photocatalytic activity of CuO/TiO₂ photocatalysts was highly dependent on the CuO loading, with 1.25 wt.% CuO being optimal (H₂ production rate = 20.3 mmol g⁻¹ h⁻¹). Results suggest that sub-monolayer coverages of Cu(II) or CuO on TiO₂ are highly beneficial for H₂ generation from ethanol–water mixtures and support the development of a sustainable H₂ economy.     

Non-isothermal kinetics and in situ SR XRD studies of hydrogen desorption from dihydrides of binary Ti–V alloys

Phase transformations during dynamic dehydrogenation of Ti_1−xV_xH₂ (x = 0.1; 0.2; 0.3) were studied using in situ Synchrotron X-Ray Diffraction (SR XRD) and non-isothermal kinetics experiments. The main dehydrogenation path for γ-Ti_1−xV_xH₂ was found to be γ → δ → β → β_alloy. Body-centred tetragonal δ-hydride was found to be an intermediate phase of the γ → β transformation in Ti_0.8–0.9V_0.1–0.2H₂. TDS, in situ SR XRD and isoconversional kinetics studies showed that hydrogen desorption from Ti_1−xV_xH₂ is composed of simultaneous reactions taking place between 300 and 600 °C. The effective activation energy of hydrogen desorption depends on the vanadium contents and the reaction pathway, increasing from 21 kJ/mol H₂ (γ → δ) to 60–110 kJ/mol H₂ (δ → β).     

Solar syngas production from CO2 and H2O in a two-step thermochemical cycle via Zn/ZnO redox reactions: Thermodynamic cycle analysis

Solar syngas production from CO₂ and H₂O is considered in a two-step thermochemical cycle via Zn/ZnO redox reactions, encompassing: 1) the ZnO thermolysis to Zn and O₂ using concentrated solar radiation as the source of process heat, and 2) Zn reacting with mixtures of H₂O and CO₂ yielding high-quality syngas (mainly H₂ and CO) and ZnO; the ZnO is recycled to the first, solar step, resulting in net reaction βCO₂ + (1 − β)H₂O → βCO + (1 − β)H₂. Syngas is further processed to liquid hydrocarbon fuels via Fischer-Tropsch or other catalytic processes. Second-law thermodynamic analysis is applied to determine the cycle efficiencies attainable with and without heat recuperation for varying molar fractions of CO₂:H₂O and solar reactor temperatures in the range 1900-2300 K. Considered is the energy penalty of using Ar dilution in the solar step below 2235 K for shifting the equilibrium to favor Zn production.     

Structural properties of CuO/TiO2 nanorod in relation to their catalytic activity for simultaneous hydrogen production under solar light

CuO was introduced into porous TiO₂ nanorod through impregnation method. Before the impregnation step, TiO₂ nanorod was hydrothermally synthesized from TiO₂ powder in aqueous NaOH solution and followed by thermal treatment at 450 °C. The structures and properties of impregnated samples were characterized using various techniques, including XRD, BET, XAS, TEM, and UV-DRS. Their photocatalytic performance on simultaneous hydrogen production from pure water and aqueous methanol solution was also investigated under solar light. It was found that CuO/TiO₂ nanorod possessed a high surface area, good photocatalytic property and excellent hydrogen generation activity. Incorporation of Cu ions into the lattice framework of anatase TiO₂ nanorod enhanced the efficiency in visible region at 438–730 nm. Moreover, the XAS results showed that some Cu ions formed solid solution in the TiO₂ nanorod (Cu_xT_1−xO₂). However, the excessive incorporation of Cu ions did not improve any ability of anatase TiO₂ nanorod for production of hydrogen from pure water splitting. This could be due to the excessive CuO agglomeration at outside-pores which blocked the sensitization of TiO₂ nanorod. Only 1% Cu/TiO₂ nanorod was found to be a remarkable and an efficient photocatalyst for hydrogen production under solar light from both pure water and sacrificial methanol splitting. The highest rate of hydrogen production of 139.03 μmol h⁻¹ g_catalyst⁻¹ was found in sacrificial methanol which was 3.24% higher than in pure water.     

Hydrogen permeation through a Pd-based membrane and RWGS conversion in H2/CO2, H2/N2/CO2 and H2/H2O/CO2 mixtures

This study investigated the effect of gases such as CO₂, N₂, H₂O on hydrogen permeation through a Pd-based membrane −0.012 m² – in a bench-scale reactor. Different mixtures were chosen of H₂/CO₂, H₂/N₂/CO₂ and H₂/H₂O/CO₂ at temperatures of 593–723 K and a hydrogen partial pressure of 150 kPa. Operating conditions were determined to minimize H₂ loss due to the reverse water gas shift (RWGS) reaction. It was found that the feed flow rate had an important effect on hydrogen recovery (HR). Furthermore, an identification of the inhibition factors to permeability was determined. Additionally, under the selected conditions, the maximum hydrogen permeation was determined in pure H₂ and the H₂/CO₂ mixtures. The best operating conditions to separate hydrogen from the mixtures were identified.     

Effects of general zero-valent metals power of Co/W/Ni/Fe on hydrogen production with H2S as a reductant under hydrothermal conditions

Hydrogen production from water with S²⁻ as a reductant under hydrothermal conditions is an effective new method, in which S²⁻ is oxidized into S₂O₃²⁻, SO₃²⁻ and SO₄²⁻. However, the reactor wall had great effect on hydrogen production as large amount hydrogen is produced with Hastelloy C-22 reactor while almost no hydrogen generated in SUS 316 reactor. Therefore, the influence of main components of Hastelloy C-22 reactor (Co/W/Ni) and SUS 316 reactor (Fe) on hydrogen production with H₂S as the reductant was investigated. The results showed that Fe had negative effect, whereas W, Co and Ni had significant positive effect on improving hydrogen production. These results provided a possible explanation for no hydrogen generated with SUS 316 reactor，and some suggestions for improving hydrogen production. The highest hydrogen production of 199 mL (2 times than the control) was obtained with 4.00 mmol Co, 4.00 mmol W, and 1.00 mmol Ni.     

Promoting hydrogen production by loading PdO and Pt on N–TiO2 under visible light

Nitrogen/titanium dioxide (N/TiO₂) visible light photocatalysts were prepared using the sol–gel method. The catalysts were characterized using transmission electron microscopy, reflective UV–visible spectroscopy, specific surface area measurements, and X-ray diffraction. The prepared catalysts were used to generate hydrogen gas through the water-splitting reaction under visible light (wavelengths greater than 400 nm). Various N/Ti addition ratios were tested, and the hydrogen generation rates were compared to determine the optimal ratio. The maximal hydrogen production rate (approximately 55 μmol h⁻¹ g⁻¹) was attained when the N/Ti ratio of N–TiO₂ was 10. When PdO and Pt were loaded onto the N–TiO₂ catalyst, the hydrogen generation rates increased to 544 and 772 μmol h⁻¹ g⁻¹, respectively. The highest hydrogen production rate (2460 μmol h⁻¹ g⁻¹) was obtained when bimetallic 0.05 wt% PdO-0.10 wt% Pt/N–TiO₂ was used. After three times use the hydrogen yield of the catalyst was maintained as 83%. A possible mechanism of water splitting catalyzed by this visible light photocatalyst is proposed.     

Hydrogen gas production from vinegar fermentation wastewater by electro-hydrolysis: Effects of initial COD content

Vinegar fermentation wastewater with different initial COD contents (9.66–48.6 g L⁻¹) were used for hydrogen gas production with simultaneous COD removal by electro-hydrolysis. The applied DC voltage was constant at 4 V. The highest cumulative hydrogen production (3197 ml), hydrogen yield (2766 ml H₂ g⁻¹ COD), hydrogen formation rate (799 ml d⁻¹), and percent hydrogen (99.5%) in the gas phase were obtained with the highest initial COD of 48.6 g COD L⁻¹. The highest energy efficiency (48%) was obtained with the lowest COD content of 9.66 g L⁻¹. Hydrogen gas production by water electrolysis was less than 250 ml and wastewater control resulted in less than 25 ml H₂ in 96 h. The highest (12%) percent COD removal was obtained with the lowest COD content. Hydrogen gas was produced by reaction of (H⁺) ions present in raw WW ( pH = 3.0) and protons released from acetic acid with electrons provided by electrical current. Electro-hydrolysis of vinegar wastewater was proven to be an effective method of H₂ gas production with some COD removal.     

Hydrogen production from soft-drink wastewater in an upflow anaerobic packed-bed reactor

The production of hydrogen from soft-drink wastewater in two upflow anaerobic packed-bed reactors was evaluated. The results show that soft-drink wastewater is a good source for hydrogen generation. Data from both reactors indicate that the reactor without medium containing macro- and micronutrients (R2) provided a higher hydrogen yield (3.5 mol H₂ mol⁻¹ of sucrose) as compared to the reactor (R1) with a nutrient-containing medium (3.3 mol H₂ mol⁻¹ of sucrose). Reactor R2 continuously produced hydrogen, whereas reactor R1 exhibited a short period of production and produced lower amounts of hydrogen. Better hydrogen production rates and percentages of biogas were also observed for reactor R2, which produced 0.4 L h⁻¹ L⁻¹ and 15.8% of H₂, compared to reactor R1, which produced 0.2 L h⁻¹ L⁻¹ and 2.6% of H₂. The difference in performance between the reactors was likely due to changes in the metabolic pathway for hydrogen production and decreases in bed porosity as a result of excessive biomass growth in reactor R1. Molecular biological analyses of samples from reactors R1 and R2 indicated the presence of several microorganisms, including Clostridium (91% similarity), Enterobacter (93% similarity) and Klebsiella (97% similarity).     

The size and valence state effect of Pt on photocatalytic H2 evolution over platinized TiO2 photocatalyst

Photocatalytic hydrogen production from water or organic compounds is a promising way to resolve our energy crisis and environmental problems in the near future. Over the past decades, many photocatalysts have been developed for solar water splitting. However, most of these photocatalysts require cocatalyst to facilitate H₂ evolution reaction and noble metals as key cocatalysts are widely used. Consequently, the condition of noble metal cocatalyst including the size and valence state etc plays the key role in such photocatalytic system. Here, the size and valence state effect of Pt on photocatalytic H₂ evolution over platinized TiO₂ photocatalyst were studied for the first time. Surprisingly, it was found that Pt particle size does not affect the photoreaction rate with the size range of several nanometers in this work, while it is mainly depended on the valence state of Pt particles. Typically, TOFs of TiO₂ photodeposited with 0.1–0.2 wt% Pt can exceed 3000 h⁻¹.     

Facile fabrication of visible light driven tin oxide photoanode and its photoelectrochemical water splitting properties

Photoelectrochemical water splitting is a promise way to transfer solar energy to hydrogen as chemical energy carrier. In this paper, visible light driven tin oxide based photoelectrodes were obtained through dipping SnCl₂·2H₂O EtOH solution on FTO or metal Ti substrate and with further heat treatment process. Photoelectrochemical measurements with three electrodes configuration revealed that this obtained photoelectrode showed n-type responsive properties and the photocurrent density reached mA/cm² level without any modification under visible light irradiation (λ > 420 nm). XRD, UV–Vis spectrum and control experimental results proposed that the visible light driven mechanism for the tin oxide based photoanode maybe ascribed to Sn⁴⁺/Sn²⁺ transformation and surface oxygen deficiency, and the tin oxide can be denoted as SnO_2−x.