An insight into hydrogen isotopic separation on iron-alumina and chromium-alumina as stationary phase in gas chromatographic method

In gas chromatographic separation of hydrogen isotopes iron-alumina as a stationary phase is conventionally used. Further, Chromium-alumina as an alternative stationary phase has also been mentioned in the literature. In this present study, a detail comparative study of both the stationary phases in terms of their hydrogen isotope separation ability has been carried out. This study shows that chromium-alumina is better alternative than iron-alumina which might be attributed to its improved resolution, higher column efficiency, easy mode of preparation and shorter retention time along with equally simple regeneration procedure for regaining the performance of column material. To understand the basis behind their difference in ability of hydrogen isotope separation, hydrogen adsorption/desorption phenomenon at experimentally condition along with different surface related properties of both stationary phases have been evaluated. These experimental findings have been correlated with hydrogen isotope separation ability in terms of its retention time and resolution obtained during hydrogen isotopic separation and it illustrates the fact that hydrogen adsorption/desorption phenomenon is one of the governing factor in deciding the performance of the column materials.     

Dynamic simulation of a cryogenic batch distillation process for hydrogen isotopes separation

The operational flexibility of cryogenic batch distillation may propel its application in the Isotope Separation System of the fusion reactor. The batch distillation, unlike continuous distillation, is not a steady-state process. In order to obtain improved separation efficiency, a reasonable dynamic model of batch distillation should be developed. In this paper, dynamic simulations of the batch distillation separation process of a hydrogen-deuterium mixture were performed utilizing Aspen Plus and Aspen Dynamics. The validity of the established simulation model was firstly verified by our experimental results. Following that, two dynamic control structures, i.e., composition control and temperature control, were added to improve the recovery efficiency of batch distillation light component products. In comparison with the distillation without dynamic control structure, the distillation with composition control and temperature control can improve the H₂ recovery ratio by 5.45% and 5.09%, respectively.     

Hydrogen isotopes separation using frontal displacement chromatography: The influences of column temperature and gas flow rate

Based on the previous study in frontal displacement chromatography (FDC) packed with Pd-Al₂O₃, two groups of separation experiments were conducted to derive the rules how the two most significant factors, temperature and gas flow rate, to influence the separation performance. Separations of the first group were carried out at the feed gas flow rate of 15 mL/min and temperature of 303–213 K, and the second group at 253 K and 10–100 mL/min, with the identical composition of feedstock ((5 ± 0.1)%H₂-(5 ± 0.1)%D₂-(90 ± 0.1)%Ar). The results indicate the derived rules are consistent with those from references: 1) the rules of temperature effects on separation efficiency lie in two aspects that the lower the temperature is, the larger the thermodynamic separation effect is, and the higher the temperature is, the quicker the hydrogen isotopes exchange dynamics becomes. As to FDC using palladium, 263–213 K will be an appropriate temperature range to have excellent separation performance achieved with the insight into these two aspects. 2) the rule of the influence of gas flow rate basically obeys the van Deemter equation, which means that it does exist an theoretically optimal gas flow rate, ū_opt, at a certain temperature and for a certain composition of feedstock, and considering the theoretics and efficiency, separations conducted at the gas flow rate of an suitable range that higher than ū_opt but less than 10ū_opt can derive good separation performance. The results and discussion have verified the imperative impact of temperature and gas flow rate on the separation performance of this FDC method, and the derived desirable temperature and gas flow rate ranges would supply valuable supports and references for future applications of FDC in hydrogen isotopes separation and tritium recovery in fusion reactors.     

Permeability,solubility and diffusivity of hydrogen isotopes in stainless steels at high gas pressures

In this report, we provide a framework for describing the permeability, solubility and diffusivity of hydrogen and its isotopes in austenitic stainless steels at temperatures and high gas pressures of engineering interest for hydrogen storage and distribution infrastructure. We demonstrate the importance of using the real gas behavior for modeling permeation and dissolution of hydrogen under these conditions. A simple one-parameter equation of state (the Abel–Noble equation of state) is shown to capture the real gas behavior of hydrogen and its isotopes for pressures less than 200 MPa and temperatures between 223 and 423 K. We use the literature on hydrogen transport in austenitic stainless steels to provide general guidance on and clarification of test procedures, and to provide recommendations for appropriate permeability, diffusivity and solubility relationships for austenitic stainless steels. Hydrogen precharging and concentration measurements for a variety of austenitic stainless steels are described and used to generate more accurate solubility and diffusivity relationships.     

Hydrogen isotopes separation validation of frontal displacement chromatography for various compositions of feed gas and tritium extraction simulation for TBM

Based on the previous study in frontal displacement chromatography (FDC) packed with Pd-Al₂O₃, three groups of separation tests were carried out to verify the separation performance of the constituted FDC device for various compositions of feed gas and to validate the application probability of FDC in the Tritium Extraction System (TES) of ITER and China Fusion Engineering Test Reactor (CFETR). The separations were conducted by the FDC procedure with characteristics of the feed gas one-time flushing though the column and then reasonable separation performance had been obtained. The results indicate that the FDC process could be applied to deal with the desorbed gas mixtures from TES and/or further to extract and thereafter enrich the breeding tritium in ITER or CFETR, which would take the advantages of system compactness and efficiency over the present route of TES. Comparing to other related displacement chromatography procedures, the FDC process could be applied in tritium pre-enrichment for the mixtures of low tritium concentrations, which is highlighted by the outstanding merit of operation simplicity.     

A highly efficient and stable catalyst for liquid phase catalytic exchange of hydrogen isotopes in a microchannel reactor

The liquid phase catalytic exchange of hydrogen isotopes is a promising process for upgrading recycle water in nuclear power station. To facilitate the isotope catalytic reaction, a series of two-dimensional hydrophobic catalysts of Pt/modified carbon nitride (Pt/s-C₃N₄) with different Pt loadings were fabricated and applied in microchannel reactor. Their excellent catalytic performances were found in our experiments by comparing with purchased Pt/activated carbon (Pt/AC), the Turn-Over-Frequency (TOF) of Pt/s-C₃N₄ is 3 times higher than Pt/AC. Because the Pt clusters of 0.82 ± 0.08 nm were uniformly distributed on the support of two-dimensional carbon nitride (C₃N₄) to improve availability of the Pt catalyst by exposing more active sites and decreasing effect of the internal diffusion. The catalytic activity of Pt/s-C₃N₄ catalysts remained stable after 1800 min reaction, whereas Pt/AC displayed a 20% drop. Hydrophobicity of the catalyst maintained its high activity and stability in the liquid phase catalytic exchange reaction.     

Techno-economic analysis of PSA separation for hydrogen/natural gas mixtures at hydrogen refuelling stations

Logistics of hydrogen is one of the bottlenecks of a hydrogen economy. In this study, a pressure swing adsorption (PSA) system is proposed for the separation of hydrogen from natural gas, co-transported in the natural gas grid. The economic feasibility of hydrogen supplied by a PSA system at a refuelling station is assessed and compared with other alternatives. The adsorbent material is key to the design of a PSA system, which determines the operation performance and cost. It is concluded that a refuelling station with hydrogen supplied by a PSA system is economically feasible. The final hydrogen price including hydrogen supply, compression, storage, and dispensing is compared with two other hydrogen supply methods: on-site electrolysis and tube-trailer transported hydrogen. Currently, PSA supplied hydrogen is a more economical option. On-site electrolysis can become a more economical option in the future with improved cell efficiencies and reduced electricity prices. Tube-trailer transported hydrogen is highly influenced by the distance travelled. The findings of this study will help with more efficient distribution of hydrogen.     

Synthetic natural gas (SNG) liquefaction processes with hydrogen separation

The fact that synthetic natural gas (SNG) contains hydrogen has a great impact on its liquefaction process. Aiming to produce liquefied natural gas (LNG) from SNG, hydrogen separation from SNG through cryogenic processes is studied. A new separation method combining distillation and flash is developed, resulting in higher liquefaction rate than that of distillation under same operating parameters. Process simulations are performed by combining one liquefaction part (a nitrogen expansion process or a mixed refrigerant one) and one distillation part (direct flash, atmospheric distillation, pressurized distillation or the new separation method). Compared to direct flash, distillation can reduce the hydrogen content of products to a very low level, increasing the temperature of products by 8 °C and reducing the unit power consumption by 3%; and, compared to the other three separation ways, the new separation method reduces the unit power consumption by 7–10%. Both nitrogen expansion and SMR liquefaction processes can be integrated with hydrogen separation, but power consumptions for SMR processes are less than those for nitrogen expansion ones.     

Study about sorption in sponge and powder titanium of hydrogen isotopes obtained from a cryogenic distillation process

Currently, hydrogen may be stored as a compressed gas or as cryogenic liquid. Neither method appears to be practical for many applications in which hydrogen use would otherwise be attractive. For example, gaseous storage of stationary fuel is not feasible because of the large volume or weight of the storage vessels. Liquid hydrogen could be used extensively but the liquefaction process is relatively expensive. The hydrogen can be stored for a long term with a high separation factor, like solid metal hydride. Using hydride-forming metals and intermetallic compounds, for example, recovery, purification and storage of heavy isotopes in a tritium-containing system, can solve many problems arising in the nuclear fuel cycle. This paper presents a comparative study about hydrogen sorption obtained from a cryogenic distillation process, on two titanium structures: powder and sponge. Also presented is the characterization, by X-ray diffraction, of two structures, before and after the sorption process.     

Hydrogenation of liquid organic hydrogen carrier systems using multicomponent gas mixtures

The cost of industrial hydrogen production and logistics, and the purity of hydrogen produced from different technologies are two critical aspects for the success of a future hydrogen economy. Here, we present a way to charge the Liquid Organic Hydrogen Carrier (LOHC) dibenzyltoluene (H0-DBT) with industrially relevant, CO₂- and CO-containing gas mixtures. As only hydrogen binds to the hydrogen-lean carrier molecule, this process step extracts hydrogen from the gas mixture and binds it selectively to the carrier. Pd on alumina has been identified as the most promising catalyst system for successfully hydrogenating H0-DBT using model gas mixtures resembling the compositions produced in methane reforming and in industrial coke production (up to 50% CO₂ and 7% CO). Up to 80% of the hydrogen present in the feedstock mixture could be extracted during the LOHC hydrogenation process. 99.5% of the reacting hydrogen was selectively bound to the H0-DBT LOHC compound. The purity of hydrogen released from the resulting perhydro dibenzyltoluene previously charged with the hydrogen-rich gas mixture proved to be up to 99.99 mol%.     

Hydrogen separation from synthesis gas using silica membrane: CFD simulation

In the present article, an axisymmetric two-dimensional (2D) computational fluid dynamic (CFD) model was adapted to predict the efficiency of the silica membrane for hydrogen (H₂) separation as a renewable energy source. In this model, continuum flows on the shell and tube sides are defined through the Navier-Stokes and transport of chemical species equations. Components transfer through the silica membrane is characterized by introducing source-sink terms based on activating transport mechanisms. To validate the presented model results related to H₂ molar fraction at the retentate and permeate sides were compared with experimental data. The CFD model prognosticates the local information of velocity distribution and the molar fraction of the components. Finally, considering the effects of temperature, pressure difference, gas flow rate, and inner radius of the module on the H₂ molar fraction, silica membrane performance was investigated. Moreover, it has been shown that with increasing working temperature from 323 to 473 K, H₂ molar fraction at the shell side decreases from 59% to 28.4%, and in the tube side, it rises from 78.8% to 82.8%. On the shell side, it could be seen that H₂ permeates better for a low gas flow rate. At the tube side, this parameter has a positive effect on H₂ purification. The result of the impact of pressure differences at shell and tube sides was used to indicate the variation in the H₂ molar fraction. An increase in pressure difference causes a decrease of H₂ molar fraction at the tube side. At the shell side, H₂ molar fraction would be decreased with an addition in pressure difference from 1 to 3 bar. Any further pressure difference rise from 3 to 4 bar, make this trend ascending. Likewise, at the shell and tube sides, by enhancing the inner radius of the module, the molar fraction of H₂ increases.     

Effects of metals in wastewater on hydrogen gas production using electrohydrolysis

Hydrogen gas was produced from metal plating wastewater by electro hydrolysis. Wastewater contains chrome, copper and nickel metals which can accelerate the production of hydrogen gas. Effects of kind of metals, the voltage and reaction time on percent hydrogen gas (HGP) were investigated. After application of different DC voltages on each metallic wastewater, percent hydrogen gas (HGP), cumulative hydrogen gas volume (CHGV), hydrogen gas formation rate (HFR) and total organic carbon (TOC) removal were also evaluated. Hydrogen gas percent was obtained as %99 at 4 V for chrome plating wastewater while percent hydrogen gas was achieved as 50% H₂ gas at 4 V for copper and nickel metal plating wastewater. Maximum CHGV achieved with 4 V DC voltage for all metal plating wastewater. Maximum CHGV (4000 mL), HFR (985 mL H₂ d⁻¹) and percent hydrogen gas (99%) was observed with chrome plating wastewater at 4 V DC voltage. Hydrogen gas produced from chrome metal plating wastewater using electro hydrolysis method can be efficiently used for fuel cells as a source due to nearly pure hydrogen gas.     

Engine characteristics of emissions and performance using mixtures of natural gas and hydrogen

An evaluation was performed on the efficiency and emissions from an engine fuelled with compressed natural gas (CNG) and a mixture of natural gas and hydrogen, respectively. The mixtures of CNG and hydrogen were named HCNG.     

An evaluation of hydrogen production from the perspective of using blast furnace gas and coke oven gas as feedstocks

Blast furnace (BF) is a large-scale reactor for producing hot metal where coke and coal are consumed as reducing agent and fuel, respectively. As a result, a large amount of CO₂ is liberated into the atmosphere. The blast furnace gas (BFG) and coke oven gas (COG) from the ironmaking process can be used for H₂ production in association with carbon capture and storage (CCS), thereby reducing CO₂ emissions. In this study thermodynamic analyses are performed to evaluate the feasibility of H₂ production from BFG and COG. Through the water gas shift reaction (WGSR) of BFG, almost all CO contained in BFG can be converted for H₂ production if the steam/CO (S/C) ratio is no less than unity and the temperature is at 200 °C, regardless of whether CO₂ is captured or not. The maximum H₂ production from WGSR is around 0.21 Nm³ (Nm³ BFG)⁻¹. Regarding H₂ production from COG, a two-stage reaction of partial oxidation (POX) followed by WGSR is carried out. It is found the proper conditions for syngas formation from the POX of COG is at the oxygen/fuel (O/F) ratio of 0.5 and the temperature range of 1000-1750 °C where the maximum syngas yield is 2.83 mol (mol hydrocarbons)⁻¹. When WGSR is subsequently applied, the maximum H₂ production from the two-stage reaction can reach 0.83 Nm³ (Nm³ COG)⁻¹.     

A fresh look at thermal cycling absorption process for hydrogen isotopes separation by dynamic simulation: Initial feeding process and total reflux mode

Thermal Cycling Absorption Process (TCAP) is an important method to separate hydrogen isotopes for the production and engineering application of tritium. There are so many influencing factors that it is difficult to fully understand the influence mechanisms only through experiments. A new simulation model of TCAP was developed. Using the simulation model, the influencing trend and optimized value of parameters of initial feeding process and total reflux mode in TCAP are obtained as follows. (1) The temperatures of initial feeding and the cold cycle are not the lower the better as commonly assumed but exists an optimal value of 30 °C in initial feeding and -20 °C in the cold cycle. (2) The heating rate and cooling rate also exist optimal values of 45 ^°C/min and 55 ^°C/min (3) Lower feeding rate is conducive to a better separation effect of hydrogen isotopes. (4) Increasing the reflux ratio benefits the enrichment of heavy hydrogen isotope at the product side but not the light hydrogen isotope at the tail side. (5) It needs more cycles to achieve the same isotope abundance in D/T separation than H/D separation and the separation degree of hydrogen isotopes exists a maximum value after multiple cycles. The findings can provide references for the process optimization and the device design of TCAP, and also can shed new light on the understanding of the basic physical and chemical process of TCAP.     

Effect on performance and emissions of a dual fuel diesel engine using hydrogen and producer gas as secondary fuels

Energy is an essential prerequisite for economical and social growth of any country. Skyrocketing of petroleum fuel cost s in present day has led to growing interest in alternative fuels like CNG, LPG, Producer gas, Biogas in order to provide suitable substitute to diesel for a compression ignition engine. This paper discusses some experimental investigations on dual fuel operation of a 4 cylinder (turbocharged and intercooled) 62.5 kW gen-set diesel engine with hydrogen, producer gas (PG) and mixture of producer gas and hydrogen as secondary fuels. Results on brake thermal efficiency and emissions, namely, un-burnt hydrocarbon (HC), carbon monoxide (CO), and NO_x are presented here. The paper also contains vital information relating to the performances of an engine at a wide range of load conditions with different gaseous fuel substitutions. When only hydrogen is used as secondary fuel, maximum increase in the brake thermal efficiency is 7% which is obtained with 20% of secondary fuel. When only producer gas is used as secondary fuel, maximum decrease in the brake thermal efficiency of 8% is obtained with 30% of secondary fuel. Compared to the neat diesel operation, proportion of un-burnt HC and CO increases, while, emission of NO_x reduces in all Cases. On the other hand, when 40% of mixture of producer gas and hydrogen is used (in the ratio (60:40) as secondary fuel, brake thermal efficiency reduces marginally by 3%. Further, shortcoming of low efficiency at lower load condition in a dual fuel operation is removed when a mixture of hydrogen and producer gas is used as the secondary fuel at higher than 13% load condition. Based on the performance studied, a mixture of producer gas and hydrogen in the proportion of 60:40 may be used as a supplementary fuel for diesel conservation.     

Characteristics of direct injection combustion fuelled by natural gas–hydrogen mixtures using a constant volume vessel

The effects of hydrogen addition and turbulence intensity on the natural gas–air turbulent combustion were studied experimentally using a constant volume vessel. Turbulence was generated by injecting the high-pressure fuel into the vessel. Flame propagation images and combustion characteristics via pressure-derived parameters were analyzed at various hydrogen volumetric fractions (from 0% to 40%) and the overall equivalence ratios of 0.6, 0.8 and 1.0. The results showed that the turbulent combustion rate increased remarkably with the increase of hydrogen fraction in fuel blends when hydrogen fraction is over 11%. Combustion rate was increased remarkably with the introduction of turbulence in the bomb and decreased with the decrease of turbulence intensity. The lean flammability limit of natural gas–air turbulent combustion can be extended with increasing hydrogen fraction addition. Maximum pressure and maximum rate of pressure rise increased while combustion duration decreased monotonically with the increase of hydrogen fraction in fuel blends. The sensitivity of natural gas/hydrogen hybrid fuel to the variation of turbulence intensity was decreased while increasing the hydrogen addition. Maximum pressure and maximum rate of pressure rise increased while combustion duration decreased with the increase of turbulent intensity at stoichiometric and lean-burn conditions. However, slight influence on combustion characteristics was presented with variation of hydrogen fraction at the stoichiometric equivalence ratio with and without the turbulence in the bomb.     

Simultaneous hydrogen production and pollutant degradation by photocatalysis of wastewater using liquid phase plasma

Ethanolamine released from a nuclear power plant was degraded by photocatalytic decomposition using plasma in the liquid phase with metal-incorporated photocatalysts. Metal-incorporated titanium dioxide photocatalysts were employed with carbon nanotubes and carbon nanofibers as a support. The photocatalytic decomposition of ethanol amine-contained water induced the degradation of ethanolamine and H₂ evolution, simultaneously. The degradation of ethanolamine and H₂ evolution were elevated by incorporating Ni on titanium dioxide nanocrystallites. The rate of H₂ evolution in the ethanolamine-containing water was higher than that in pure water, which was attributed to the additional H₂ evolution by the photodecomposition of ethanolamine in water.     

Modeling phase equilibrium of hydrogen and natural gas in brines: Application to storage in salt caverns

In this work, the e-PPC-SAFT equation of state has been parameterized to predict phase equilibrium of the system H₂ + CH₄ + H₂O + Na⁺Cl^? in conditions of temperature, pressure and salinities of interest for gas storage in salt caverns. The ions parameters have been adjusted to match salted water properties such as mean ionic coefficient activities, vapor pressures and molar densities. Furthermore, binary interaction parameters between hydrogen, methane, water, Na⁺ and Cl^? have been adjusted to match gas solubility data through Henry constant data. The validity ranges of this model are 0–200 °C for temperatures, 0–300 bar for pressures, and 0 to 8 mol_NaCl/kg_H2O for salinities. The e-PPC-SAFT equation of state has then been used to model gas storage in salt caverns. The performance of a storage of pure methane, pure hydrogen and a mixture methane + hydrogen have been compared. The simulations of the storage cycles show that integrating up to 20% of hydrogen in caverns does not have a major influence on temperature, pressure and water content compared to pure methane storage. They also allowed to estimate the thermodynamic properties of the system during the storage operations, like the water content in the gaseous phase. The developed model constitutes thus an interesting tool to help size surface installations and to operate caverns.