Cryo-adsorptive hydrogen storage on activated carbon. II: Investigation of the thermal effects during filling at cryogenic temperatures

This paper presents an investigation of the thermal effects during high pressure filling of a cryo-adsorptive hydrogen storage tank. The adsorbent is powdered activated carbon. A two-dimensional model is formulated, which describes hydrodynamics, heat transfer and adsorption phenomena in cylindrical tanks. Experiments with a tank containing about 10 kg of adsorbent were carried out to parameterize and validate the model. Good agreement between experiments and simulations could be obtained. Numerical results are then presented concerning filling processes. Two cooling concepts are investigated: a LN₂ cooling jacket and a recirculation system which uses the hydrogen itself as the cooling fluid. The results show that short filling times can only be achieved with the recirculation system.     

Hydrogen adsorption on modified activated carbon

The aim of this work is to investigate hydrogen adsorption on prepared super activated carbon (AC). Litchi trunk was activated by potassium hydroxide under N₂ or CO₂ atmosphere. Nanoparticles of palladium were impregnated in the prepared-AC. Hydrogen adsorption was accurately measured by a volumetric adsorption apparatus at 77, 87, 90 and 303 K, up to 5 MPa. Experimental results revealed that specific surface area of the prepared-AC increased according to KOH/char ratio. The maximum specific surface area reached up to 3400 m²/g and total pore volume of 1.79 cm³/g. The maximum hydrogen adsorption capacity of 2.89 wt.% at 77 K and under 0.1 MPa, was obtained on these materials. The hydrogen adsorption capacity of the 10 wt.% Pd-AC was determined as 0.53 wt.% at 303 K and under 6 MPa. This amount is higher than that on the pristine AC (0.41 wt.%) under the same conditions.     

Automotive hydrogen storage system using cryo-adsorption on activated carbon

An integrated model of a sorbent-based cryogenic compressed hydrogen system is used to assess the prospect of meeting the near-term targets of 36 kg-H₂/m³ volumetric and 4.5 wt% gravimetric capacity for hydrogen-fueled vehicles. The model includes the thermodynamics of H₂ sorption, heat transfer during adsorption and desorption, sorption dynamics, energetics of cryogenic tank cooling, and containment of H₂ in geodesically wound carbon fiber tanks. The results from the model show that recoverable hydrogen, rather than excess or absolute adsorption, is a determining measure of whether a sorbent is a good candidate material for on-board storage of H₂. A temperature swing is needed to recover >80% of the sorption capacity of the superactivated carbon sorbent at 100 K and 100 bar as the tank is depressurized to 3–8 bar. The storage pressure at which the system needs to operate in order to approach the system capacity targets has been determined and compared with the breakeven pressure above which the storage tank is more compact if H₂ is stored only as a cryo-compressed gas. The amount of liquid N₂ needed to cool the hydrogen dispensed to the vehicle to 100 K and to remove the heat of adsorption during refueling has been estimated. The electrical energy needed to produce the requisite liquid N₂ by air liquefaction is compared with the electrical energy needed to liquefy the same amount of H₂ at a central plant. The alternate option of adiabatically refueling the sorbent tank with liquid H₂ has been evaluated to determine the relationship between the storage temperature and the sustainable temperature swing. Finally, simulations have been run to estimate the increase in specific surface area and bulk density of medium needed to satisfy the system capacity targets with H₂ storage at 100 bar.     

Finite element model for charge and discharge cycle of activated carbon hydrogen storage

One of the main challenges to introduce hydrogen on the energy market is to improve on-board hydrogen storage and develop more efficient distribution technologies to increase the amount of stored gas while lowering the storage pressure. The physisorption of hydrogen on activated carbons (AC) is being investigated as a possible route for hydrogen storage. The objective of this work is to study the performance of adsorption-based hydrogen storage units from a "systems" point of view. A realistic two-dimensional axisymmetric geometric model which couples mass, momentum and energy balances is established based on the thermodynamic conservation laws using finite element method as implemented in COMSOL Multiphysics™. We consider the charging and discharging of the storage unit at a rated pressure of 9 MPa, and at an initial temperature of 302 K. The results are compared with experimental data obtained at the Hydrogen Research Institute of the University of Quebec at Trois-Rivieres. The storage tank is cooled by ice water. Research results show that both the simulated variations of pressure and temperatures during charge and discharge processes are in good agreement with the experimental data. The temperatures in the central region of tank are higher than those at the entrance and near the wall at the end of charge time while they are lower than those at the entrance and near the wall at the end of discharge time. The velocities are largest at the entrance, and decrease gradually along the axis of the tank. Owing to thermal effects, the larger flow rates result in less amount of adsorption in the condition of the same charging pressure. Hence measures of increasing heat transfer should be adopted, such as increasing the thermal conductivity of the storage bed. From the point of view of storage capacity, it is therefore possible to realize rapid hydrogenation, which is conducive to the use of such systems for on-board hydrogen storage based on activated carbon adsorption.     

CFD model for charge and discharge cycle of adsorptive hydrogen storage on activated carbon

High surface area activated carbons and other microporous adsorbents have generated a significant amount of interest over the past decade as storage media for hydrogen and natural gas, due to their high storage capacity at low temperatures and their use in gas purification processes. This paper uses computational fluid dynamics (CFD) to simulate the charging and discharging of a sorption-based hydrogen storage system. The CFD model is based on the mass, momentum and energy conservation equations of a system formed of gaseous and adsorbed hydrogen, an activated carbon bed and steel tank walls. The adsorption process is modeled using the Dubinin–Astakov adsorption isotherms extended to the supercritical regime. The model is implemented using Fluent. In our study, we can obtain accuracy peak temperature of simulation due to a non-constant isosteric heat of adsorption is used, derived from the model isotherms. We adopt piecewise heat capacity to consider the heat capacity of the adsorbed phase of hydrogen. We can make a conclusion that the simulated temperatures without consideration of heat capacity for hydrogen in adsorbed phase (c_pa), rise faster and reach higher peaks than the simulated temperatures with consideration of c_pa, and diverge more from experimental results. Also, we study the changes of temperature, pressure and adsorption during the charging and discharging processes as well as when the system is idle (which we define as dormancy) in the case of room temperature water cooling. The results are compared with experimental data from a storage unit cooled with room temperature water. The simulated pressure is in a good agreement with the experimental values. The simulated temperature profiles are also generally in good agreement with the experimental values, except close to the inlet and the wall. In addition, we have studied the effect of quality of the mesh on the accuracy and stability of the numerical computation and the influence of the mass flow rates on temperature and adsorption capacity.     

Oxygen-promoted hydrogen adsorption on activated and hybrid carbon materials

The effect of heteroatoms on hydrogen adsorption properties of activated and hybrid carbon materials is critically described. For that purpose, olive stones were activated chemically with KOH, and subsequently washed or not, and oxidised with ozone or not. Olive stones were also activated physically with CO₂. A series of activated carbons prepared by chemical activation of sucrose was also investigated for comparison. As a result, many activated carbons with different pore-size distributions, surface areas, average micropore widths, oxygen contents and amounts of mineral matter could be compared. All were thoroughly characterised by adsorption of N₂, CO₂ and H₂O, elemental analysis, XPS, thermogravimetry, and adsorption of H₂ at different pressures. Many correlations between textural parameters, composition and adsorption properties could be evidenced, and were critically discussed. We show that the hydrogen uptake at 77 K is controlled by the following parameters, listed by decreasing order of importance: specific surface area, average micropore size, surface chemistry and shape of the pore size distribution. At room temperature (i.e., at 298 K), the adsorbed hydrogen uptake was in the range of 0.19–0.42 wt %; the presence of large amounts of alkali metals can further improve the hydrogen adsorption properties, but surface chemistry still has a major influence, especially through the acidic surface functions.     

Exergy analysis of a hybrid solar hydrogen system with activated carbon storage

A proposed hybrid solar hydrogen system with activated carbon storage for residential power generation is assessed using exergy analysis. Energy and exergy balances are applied to determine exergy flows and efficiencies for individual devices and the overall system. A ‘base case’ analysis considers the proposed system without modification, while a ‘modified case’ extends the base case by considering the possibility of multiple product outputs. It is determined that solar photovoltaic-based sub-systems have the lowest exergy efficiencies (14-18%) and offer the most potential for improvement. A comparison of these two scenarios shows that the additional outputs raise the exergy efficiency of the modified case (11%) relative to the base case (4.0%). An investigation of the energy and exergy efficiencies of separate devices illustrates how energy analyses can be misleading. The hybrid system is expected to have several environmental benefits, which may offset to some degree economic barriers to implementation.     

Simulation of heat and mass transfer in activated carbon tank for hydrogen storage

The charging process of hydrogen storage tank based on bed of activated carbon in a steel container at room temperature (295 K) and medium storage pressure (10 MPa) is simulated with an axisymmetric geometry model using the finite volume commercial solver Fluent. The mass flux profile at the entrance is established using user-defined functions (UDFs). The heat and mass transfer processes in the cylindrical steel tank packed with activated carbon are discussed considering the influence of viscous resistance and inertial resistance of the porous media. The velocity distribution and its effect on the temperature distribution are analyzed. The effects of the flow rate at the inlet and of the adsorption factor on the charging process are studied. A computational fluid dynamics (CFD) approach based on finite volume simulations is used. Results show that the temperature near the bottom of the tank is higher than that at the entrance, temperature in the center of the tank is higher than that near the wall and rises somewhat faster along the axial compared to the radial direction. The highest hydrogen absolute adsorption occurs at the entrance of the tank. A good agreement is found between the simulation results and the available experimental data. The maximum magnitude of the axial velocity is much higher than that of the radial component, resulting in more heat energy transfer along the axial direction than radial direction. In addition, the pressure reaches equilibrium earlier when the mass flow is higher, and the temperature reaches a maximum value faster.     

Determination of the enthalpy of adsorption of hydrogen in activated carbon at room temperature

The development of high-performance materials for hydrogen storage by adsorption requires detailed understanding of the adsorbate-adsorbent interactions, e.g., the enthalpy of adsorption ΔH, which measures the interaction strength. The determination of ΔH for a weakly adsorbing gas such as hydrogen in a carbonaceous porous material is difficult experimentally, normally requiring measuring two cryogenic adsorption isotherms. Here we demonstrate a calculation of ΔH based on ca. room temperature adsorption isotherms at 273 K and 296 K using the Clausius-Clapeyron equation. This requires an estimation of the volume of the adsorbed film (~40%, ~12% of the total pore volume at 77 K, 296 K, respectively) obtained from fits of the excess adsorption isotherms to an Ono-Kondo model with the auxiliary use of a fixed point corresponding to the saturation film density (estimated as 100 ± 20 g/L) which appears to be remarkably sample and temperature independent, i.e., a property of the adsorbate. The calculated room temperature enthalpy of adsorption ΔH = 8.3 ± 0.4 kJ/mol is in excellent agreement with the low-coverage cryogenic determination of ΔH. The methodology hereby proposed facilitates reliable calculations of the enthalpy of adsorption at room temperatures for weakly-adsorbing gases.     

Effect of hydrogen additive on methane decomposition to hydrogen and carbon over activated carbon catalyst

The effect of H₂ addition on CH₄ decomposition over activated carbon (AC) catalyst was investigated. The results show that the addition of H₂ to CH₄ changes both methane conversion over AC and the properties of carbon deposits produced from methane decomposition. The initial methane conversion declines from 6.6% to 3.3% with the increasing H₂ flowrate from 0 to 25 mL/min, while the methane conversion in steady stage increases first and then decreases with the flowrate of H₂, and when the H₂ flowrate is 10 mL/min, i.e. quarter flowrate of methane, the methane conversion over AC in steady stage is four times more than that without hydrogen addition. It seems that the activity and stability of catalyst are improved by the introduction of H₂ to CH₄ and the catalyst deactivation is restrained. Filamentous carbon is obtained when H₂ is introduced into CH₄ reaction gas compared with the agglomerate carbon without H₂ addition. The formation of filamentous carbon on the surface of AC and slower decrease rate of surface area and pores volume may cause the stable activity of AC during methane decomposition.     

Adsorption and compression contributions to hydrogen storage in activated anthracites

We prepared activated carbons (ACs) that are among the best adsorbents for hydrogen storage. These ACs were prepared from anthracites and have surface areas (S_BET) as high as 2772 m² g⁻¹. Anthracites activated with KOH presented the highest adsorption capacities with a maximum of 5.3 wt.% at 77 K and 4 MPa. Non-linearity between hydrogen uptake at 77 K and pore texture was confirmed, as soon as their S_BET exceeded the theoretical limiting value of (geometrical) surface area, i.e., S_BET > 2630 m² g⁻¹. We separated adsorption and compression contributions to total hydrogen storage. The amount of hydrogen stored is significantly increased by adsorption only at moderate pressure: 3 MPa and 0.15 MPa at 298 and 77 K, respectively. Hydrogen adsorption on ACs at high pressure, above 30 MPa at 298 K and 8 MPa at 77 K, has not interest because more gas can be stored by simply compression in the same tank volume.     

Preparation of activated rectangular polyaniline-based carbon tubes and their application in hydrogen adsorption

Porous materials, especially porous carbon materials, have the most potential as hydrogen adsorbents. In this research, a series of novel rectangular polyaniline tubes (RPTs) are synthesized using hollow carbon nanosphere (HCNS) templates. By changing mass ratios of ammonium persulfate to HCNSs, the sizes of RPTs can be controlled. Chemical activation with KOH gives rise to a large specific surface area (SSA), ranging from 1680 to 2415 m2 g⁻¹, and big pore volumes that range from 1.274 to 1.550 cm³g⁻¹. These observations demonstrate that activated rectangular polyaniline-based carbon tubes ARP-CTs are promising hydrogen adsorbents. Hydrogen uptake measurements show that the highest hydrogen adsorption reaches 5.2 wt% at 5 MPa/77 K and 0.62 wt% at 7.5 MPa/293 K respectively. Notably, the large pore volume can contribute 2.8 wt% to the total hydrogen storage which has approached 8.0 wt% at 5 MPa/77 K.     

Hydrogen storage in boron-doped carbon nanotubes: Effect of dopant concentration

Boron-doped carbon nanotubes (BCNTs) with varying B content (0–8 at%) were prepared by thermo-catalytic decomposition of ethanol in presence of boric acid at 1073 K. It was observed that hydrogen adsorption capacity improved to a critical B content of 3.86 at% and then decreased. Maximum hydrogen adsorption was found to be 0.497 wt% at 273 K and 16 bar with 3.86 at% of boron doping in CNTs. With the help of transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy, it was found that in addition to dopant concentration, dopant bonding with carbon structures, crystallinity and defects play pivotal roles in determining the extent of hydrogen adsorption by BCNTs. The thermogravimetric studies revealed the oxidation stability of the BCNTs. The hydrogen adsorption kinetics was found to follow the pseudo-second-order model. The rate constant value was minimum for the BCNT with the highest hydrogen storage capacity.     

Surface functionalization-enhanced spillover effect on hydrogen storage of Ni–B nanoalloy-doped activated carbon

Surface functionalization-enhanced spillover effect on hydrogen storage behaviors of Ni–B nanoalloy-doped activated carbon is investigated in comparison to the 3D graphene-based material. It is discovered that the hydrogen storage capacity of the activated carbon increases from Ni–B nanoalloy-doping but much less than that of graphene. After surface functionalization, although the specific surface area and micropore volume of the doped activated carbon decrease significantly, a hydrogen storage capacity is still almost as same as that of the unfunctionalized larger surface one, while showing a large desorption hysteresis. We argue that the surface functionalization greatly enhances the spillover process on carbon based adsorbents, thus playing an essential role in hydrogen storage capacity improvement.     

Conditioning of hydrogen storage by continuous solar adsorption in activated carbon AX-21 with simultaneous production

The capacity of hydrogen storage by solar adsorption in activated carbon AX-21 and filling rate with simultaneous production have been conditioned under a minimum pressure, to nullify the cost of energy supplied to compressor. A gas accumulator tank connected to electrolyzer and continuous adsorption beds have been proposed in the process scheme. Minimum pressure required for the tank at an ambient filling temperature fixed to 25 °C is only 2 bar. While at atmospheric filling pressure the corresponding value of filling temperature is found to be 5 °C. However, a cooling fluid at low temperature for adsorbent bed during the adsorption process will be an efficient way for increasing the stored amount of hydrogen. Almost 4.5 kg of hydrogen can be stored in an adsorbent mass of 200 kg. The adsorption flow rate has been also modelled to be controlled for being adapted to production rate.     

A solar hydrogen hybrid system with activated carbon storage

A solar hydrogen hybrid system has been developed to convert, store and use energy from renewable energy sources. The theoretical model has been implemented in a dynamic model-based software environment and applied to real data. A photovoltaic sub-system drives a residential load and, if a surplus of energy is available, an electrolyzer to produce hydrogen which is stored in a cluster of nitrogen-cooled tanks filled with activated carbons; when needed, hydrogen is used in a fuel cell to supply power to the load. Hydrogen storage is achieved through physisorption at low temperature and low pressures. Physisorption storage provides safer operations along with good gravimetric and volumetric capacities at costs comparable to or smaller than compression or liquefaction storage.     

Copper-doped activated carbon from amorphous cellulose for hydrogen,methane and carbon dioxide storage

The transition away from fossil fuel and ultimately to a carbon-neutral energy sector requires new storage materials for hydrogen and methane as well as new solutions for carbon capture and storage. Among the investigated adsorbents, activated carbons are considered especially promising because they have a high specific surface area, are lightweight, thermally and chemically stable, and easy to produce. Moreover, their porosity can be tuned and they can be produced from inexpensive and environmentally friendly raw materials. This study reports on the development and characterization of activated carbons synthesized starting from amorphous cellulose with and without the inclusion of copper nanoparticles. The aim was to investigate how the presence of different concentrations of metal nanoparticles affects porosity and gas storage properties. Therefore, the research work focused on synthesis and characterization of physical and chemical properties of pristine and metal-doped activated carbons materials and on further investigation to analyze their hydrogen, methane and carbon dioxide adsorption capacity. For an optimized Cu content the microporosity is improved, resulting in a specific surface area increase of 25%, which leads to a H₂ uptake (at 77 K) higher than the theoretical value predicted by the Chahine Rule. For CH₄, the storage capacity is improved by the addition of Cu but less importantly because the size of the molecule hampers easy access of the smaller pores. For CO₂ a 26% increase in adsorption capacity compared to pure activated carbon was achieved, which translated with an absolute value of over 48 wt% at 298 K and 15 bar of pressure.     

Decomposition of hydrogen iodide via wood-based activated carbon catalysts for hydrogen production

In this study, the catalytic activity of wood-based catalysts produced by different activation methods was evaluated for the decomposition of hydrogen iodide (HI) as part of the sulfur-iodine hydrogen production process. The wood-based activated carbon catalysts showed strong improvement in the HI conversion compared to a blank, especially for carbon catalysts activated using H₃PO₄. Proximate analysis and ultimate analysis, XRD, BET, SEM, Boehm titration, TPD-MS, XPS were carried out to examine the characteristics of the catalysts. High carbon content (C_ad) seemed to favor high catalytic activity, while high ash content (A_ad) reduced catalytic activity of samples likely due to displacement of catalytically active material. Oxygen-containing groups were not directly responsible for catalytic activity. HI conversion increased as the surface area and pore diameter increased. Unsaturated carbon atoms maybe the main active constituent, therefore, low area density of oxygen [O] that was closely related to unsaturated carbon atoms was beneficial to HI conversion.     

Analysis of heat conducting enhancement measures on the composite for hydrogen storage by incorporation of activated carbon with MOFs

Experiments and numerical simulations were conducted for evaluating measures for enhancing adsorption capacity and heat conducting of an on board MOFs hydrogen storage system by cryo-adsorption. Solvothermal method was employed to synthesize MIL-101(Cr) composite by incorporating activated carbon. The composite was undergone structure characterization, structural morphology observation, thermal conductivity measurement and measurement of isotherm of hydrogen adsorption at 77.15 K within 0–6 MPa. Effect of adding expanded natural graphite (ENG) and equipping a honeycomb heat exchanging device (HHED) on mitigating the thermal effect on a 0.5 L hydrogen storage vessel packed with composite was investigated within a flow rate of hydrogen required by a ship's power unit. It shows that the sample incorporated by 1 wt% activated carbon respectively obtained about 14.5%, 26.2% and 5.7% increment in specific surface area, micropore volume and the maximum excess adsorption amount. Results also reveal that, within the flow rate 5 L·min^?1-25 L min^?1, the mean relative error between the experimental data and those from simulations is less than 1.61%, and the reduction in temperature fluctuation of the storage system is about 5 °C and 4 °C on charge and discharge process while equipping the HHED, which accordingly brought about 17%, 24.3%, 18.5% increment in accumulated amount of charge and discharge as well as the useable capacity ratio (UCR) of the system. It suggests that equipping a HHED is a more promising method for weakening the thermal effect on MOFs-hydrogen storage systems.