Finite element simulation of heat and mass transfer in activated carbon hydrogen storage tank

A mathematical model of heat and mass transfer in activated carbon (AC) tank for hydrogen storage is proposed based on a set of partial differential equations (PDEs) controlling the balances or conservations of mass, momentum and energy in the tank. These PDEs are numerically solved by means of the finite element method using Comsol Multiphysics^TM. The objective of this paper is to establish a correct set of PDEs describing the physical system and appropriate parameters for simulating the hydrogen storage process. In this paper, we establish an axisymmetric model of hydrogen storage by adsorption on activated carbon, considering heat and mass transfer of hydrogen in storage tank during the charging process at room temperature (295 K) and the pressure of 10 MPa. To simulate the hydrogen storage process accurately, the heat capacity of adsorbed phase, the contact thermal resistance between the AC bed and the steel wall and the inertial resistance of high speed charging hydrogen gas are all taken into account in the model. The governing equations describing the hydrogen storage process by adsorption are solved to obtain the pressure changes, temperature distributions and adsorption dynamics in the storage tank. The pressure reaches a maximum value of 10 MPa at about 240 s. A small downward trend appears in the later stage of the charging process, which lasts 700 s. The temperature distribution is highest in the center of the tank. The temperature history exhibits a rapid increase initially, followed by a steady decline. A modified Dubinin–Astakhov (D–A) model is used to represent the hydrogen adsorption isotherms. The highest hydrogen uptake is 10 mol H₂/kg AC, at the entrance of hydrogen storage tank, where the temperature is lowest. The adsorption distribution at a given time is mainly determined by the temperature distribution, because the pressure is almost uniform in the tank. The adsorption history, however, is dominated by the pressure history because the pressure change is much larger than temperature change during the charging process of hydrogen storage.     

Hydrogen storage in an activated carbon bed: Effect of energy release on storage capacity of the tank

Thermal effects during dynamic charging of a two-liter, adsorbent, packed bed, hydrogen storage tank were studied through numerical modeling. For packed-bed materials having adsorption capacities smaller than 2 wt%, the conversion to heat of the mechanical work required to feed the tank produces more than 60% of the temperature increase that occurs during the charging process. However, for materials having adsorption capacities greater than 3 wt%, 60% of the heating is due to the adsorption process. The temperature increase for a material that would fulfill the DOE recommendation of 6 wt% storage capacity is 130 K. This reduces the storage capacity by 20% relative to what would be obtained from an isothermal charging process. Simulations showed that the limitation in the storage capacity can be reduced to less than 10%, if a packed bed having an effective conductivity of a few W m^?1 K^?1 can be used.     

Microstructure and low-temperature hydrogen storage capacity of ball-milled graphite

Hydrogen adsorption in ball-milled graphite is investigated in the low temperature range from 110 to 35 K and at pressures up to 20 MPa. The adsorption data are compared to the results of detailed quantitative microstructural analyses of the samples used for the adsorption experiments. The amount of hydrogen adsorbed at temperatures well below 77 K exceeds considerably that what is expected from adsorption on plane graphitic planes. The results can be explained assuming the following mechanisms: (i) adsorption in trapping states on plane surfaces at and below 110 K; (ii) adsorption in small micropores with diameter of less than 1 nm at 77 K and pressure of 10 MPa, and (iii) multilayer adsorption in mesopores at temperatures from 35 to 40 K and pressure of 2 MPa. The effects observed in the low temperature range are reversible and make the investigated material interesting as a supporting component for liquid hydrogen storage systems.     

Sorptive storage of natural gas onto dry and wet phillipsite: Study of dynamics,storage and delivery

In this work, storage of methane on phillipsite, a naturally occurring zeolite, was studied on wet and dry basis. The temperature and pressure dynamics were investigated. The temperature gradient due to the adsorption of methane on phillipsite was less than 1 °C indicating higher thermal conductivity of this material. A decreased in temperature resulted in higher adsorption capacity. Storage of methane onto phillipsite can be enhanced by wetting the bed and thus hydrate formation. The time needed to reach equilibrium depends strongly on the water content of the adsorbent. The results revealed that the total delivery capacities for dry and wet phillipsite were 32.5 V/V and 74.13 V/V, respectively. A maximum delivery capacity of 138 V/V was reached using wet phillipsite with 350 g water content. The volumetric delivery capacity results indicated that the steady state delivery is more realistic for adsorptive natural gas (ANG) systems.     

Development research on composite adsorbents applied in adsorption heat pump

A novel adsorbent design technique base on the concept of Kelvin equation was proposed to develop hydrophilic adsorbent applicable to water vapor adsorption heat pump (AHP) for high performance. In the process, the composite adsorbent was prepared after silica gel was synthesized in the pores of activated carbons by impregnating activated carbons in sodium silicate solution. Two kinds of activated carbons were tested to produce composite adsorbent and to investigate the performance by measuring the adsorption isotherms of water vapor and pore structure characteristics. All adsorption isotherms of the silica impregnated activated carbons prepared shifted to a lower region of water vapor pressure compared to those of the raw activated carbons. The volume-based amount of adsorption in the AHP operation range (φ = 0.1–0.4) for the adsorbents prepared at sodium silicate solution concentration of 10 wt.% and impregnating time of 48 h are 5.88 and 2.62 times that of the raw activated carbons (AC1 and AC2), respectively. Based on the Kelvin equation, it is clarified that the contact angle and the volume of pore radius greater than 1.2 nm decrease with the increase of sodium silicate solution concentration for the novel composite adsorbents, which contributes the isothermals shift to lower relative pressure range.     

Modeling of adsorption storage of hydrogen on activated carbons

The storage of hydrogen on board vehicles is one of the most critical issues for the transition towards an hydrogen-based transportation system. An electric vehicle powered by a typical gasoline tank will require 3.1 kg of hydrogen (H₂) to achieve a range of 500 km. Compared to a typical gasoline tank, this would correspond to a hydrogen density of 65 kg/m³ (including the storage system) and 6.5 wt%. Presently, only liquid hydrogen (LH₂) systems with a density of 51 kg/m³ and 14 wt% is close to this target. However, LH₂ is costly and requires more complex refueling systems. The physical adsorption of hydrogen on activated carbon can reduce the pressure required to store compressed gases. Though an efficient adsorption-based storage system for vehicular use of natural gas can be achieved at room temperature, the application of this technology to hydrogen using activated carbon as the adsorbent requires its operation at cryogenic temperature. We present the results of a parametric and comparative study of adsorption and compressed gas storage of hydrogen as a function of temperature, pressure and adsorbent properties. In particular, the isothermal hydrogen storage and net storage densities for passive and active storage systems operating at 77, 150 and 293 K are compared and discussed.     

A new type adsorber for adsorption ice maker on fishing boats

A new type of adsorber for an adsorption ice maker on fishing boats, which uses a compound adsorbent (activated carbon and CaCl₂) and ammonia working pair, is designed. This type of heat pipe adsorber solves the problem of incompatibility between ammonia, copper, seawater and steel. The heating/cooling power for the adsorption/desorption process of the adsorbent, which is required to be transferred by one heat pipe in the adsorber, is computed by the test results of the adsorbent, and the heat transfer performance of one heat pipe in the adsorber is simulated according to the theory of the two phase closed thermosyphon. The heat transfer performance of the heat pipe can meet the heat demands for adsorption/desorption of the adsorbent when the evaporating temperature is −15 °C and the cycle time is 10 min. A test unit is set up to test the heating/cooling performance of the heat pipe type adsorber, and the experimental results are coincident with the simulation. The performance of a two bed adsorption ice maker with heat pipe adsorbers is predicted, and the cooling power is about 17.1–17.8 kW at the evaporating temperature of −15 °C and cycle time of 10 min with mass recovery between two 29 kg compound adsorbent beds.     

Experimental study of a solid adsorption cooling system using flat-tube heat exchangers as adsorption bed

In this paper, a solid adsorption cooling system with silica gel as the adsorbent and water as the adsorbate was experimentally studied. To reduce the manufacturing costs and simplify the construction of the adsorption chiller, a vacuum tank was designed to contain the adsorption bed and evaporator/condenser. Flat-tube type heat exchangers were used for adsorption beds in order to increase the heat transfer area and improve the heat transfer ability between the adsorbent and heat exchanger fins. Under the standard test conditions of 80 °C hot water, 30 °C cooling water, and 14 °C chilled water inlet temperatures, a cooling power of 4.3 kW and a coefficient of performance (COP) for cooling of 0.45 can be achieved. It has provided a specific cooling power (SCP) of about 176 W/(kg adsorbent). With lower hot water flow rates, a higher COP of 0.53 can be achieved.     

On thermodynamics of methane + carbonaceous materials adsorption

This study presents the theoretical frameworks for the thermodynamic quantities namely the heat of adsorption, specific heat capacity, entropy, and enthalpy for the adsorption of methane onto various carbonaceous materials. The proposed theoretical frameworks are developed from the rigor of thermodynamic property surfaces of a single component adsorbate–adsorbent system and by incorporating the micropore filling theory approach, where the effect of adsorbed phase volume is considered. The abovementioned thermodynamic properties are quantitatively evaluated from the experimental uptake data for methane adsorption onto activated carbons such as Maxsorb III at temperatures ranging from 120 to 350 K and pressures up to 25 bar. Employing the proposed thermodynamic approaches, this paper shows the thermodynamic maps of the charge and discharge processes of adsorbed natural gas (ANG) storage system for understanding the behaviors of natural gas in ANG vessel.     

A new generation cooling device employing CaCl2-in-silica gel–water system

This article presents the dynamic modelling of a single effect two-bed adsorption chiller utilizing the composite adsorbent “CaCl₂ confined to KSK silica gel” as adsorbent and water as adsorbate, which is based on the experimentally confirmed adsorption isotherms and kinetics data. Compared with the experimental data of conventional adsorption chiller based on RD silica gel + water pair, we found that the new working pair provides better cooling capacity and performances. From numerical simulation, it is also found that the cooling capacity can be increased up to 20% of the parent silica gel + water adsorption chiller and the coefficient of performance (COP) can be improved up to 25% at optimum conditions. We also demonstrate here that the best peak chilled water temperature suppression, and the maximum cooling capacity can be achieved by the optimum analysis for both cycles.     

Study of an adsorption refrigeration system powered by parabolic trough collector and coupled with a heat pipe

The aim of the current paper is to propose a study of a novel solar adsorptive cooling system, using activated carbon–ammonia pair, coupled with a parabolic trough collector (PTC) and a water-stainless steel heat pipe. A theoretical model, based on the thermodynamics of the adsorption process, heat and mass transfer within the porous medium and energy balance in the hybrid system components, is developed and a simulation code, written in FORTRAN, is carried out. This model, which has been validated by experimentation results, computes the temperature, pressure and adsorbed mass inside the adsorbent bed. The performance is assessed in terms of specific cooling power (SCP) and solar coefficient of performance (COPs). Furthermore, the effect of some important parameters on the system performance is discussed, and an optimization of these parameters is given.The simulation results have shown that there exists, for each aperture width value of the collector (W), an optimum external radius of adsorbent bed (R₂). Under the operating and design conditions of evaporation temperature T_ev = 0 °C, condensing temperature T_con = 28 °C, adsorption temperature T_ads = 24 °C, W = 0.70 m, R₂ = 0.145 m and reactor length of 0.5 m, an optimal corresponding COPs is found to be of the order of 0.18.     

A comparative study of the electrochemical hydrogen storage properties of activated carbon and well-aligned carbon nanotubes mixed with copper

We studied the electrochemical hydrogen storage properties of activated carbon (AC) material mixed with copper. The discharge capacity of AC–Cu electrode which reached 510 mAh/g after 384 cycles, is much higher than that of the CNT–Cu electrodes. The plateau of discharge potential for AC–Cu electrode was very long and flat and reached −0.88 V vs. Hg/HgO, which was far from the potential of copper oxidation. The discharge plateau gradually appeared and continually lengthened with the increase of cycle number. Cyclic voltammetric experiments showed that the adsorption and desorption of hydrogen occurred on the surface of activated carbon and the active site increased with the increase of cycle number. The mechanism for electrochemical storage of hydrogen in AC–Cu electrode may be mainly physisorption.     

Effect of residual gas on the dynamics of water adsorption under isobaric stages of adsorption heat pumps: Mathematical modelling

A mathematical model of the coupled heat and mass transfer in an adsorbent layer was developed to study the effect of a non-adsorbable gas (air, hydrogen) on kinetics of water adsorption on loose grains of the composite adsorbent SWS-1L (silica modified by calcium chloride). The adsorbent monolayer was placed on the surface of an isothermal metal plate at T = 60 °C and equilibrated with the mixture of water vapor at constant P = 10.3 mbar in the presence of the non-adsorbable gas at a variable partial pressure P_A = 0.06–14.3 mbar. After that the metal plate is subjected to a temperature drop down to 35 °C that initiates water adsorption. It is shown that the adsorption of water causes effective gas sweeping to the surface where it was accumulated as a gas-rich layer. This results in dramatic slowing down of the adsorption and heat transfer processes.     

Performance of a dual-purpose solar continuous adsorption system

A conceptual design and performance of a dual-purpose solar continuous adsorption system for domestic refrigeration and water heating is described. Malaysian activated carbon and methanol are used as the adsorbent–adsorbate pair. The heat rejected by the adsorber beds and condensers during the cooling process of the refrigeration part is recovered and used to heat water for the purpose of domestic consumption. In a continuous 24-h cycle, 16.9 MJ/day of heat can be recovered for heating of water in the storage tanks. In the single-purpose intermittent solar adsorption system, this heat is wasted. The total energy input to the dual-purpose system during a 24-h operation is 61.2 MJ/day and the total energy output is 50 MJ/day. The latter is made up of 44.7 MJ/day for water heating and 5.3 MJ/day for ice making. The amount of ice that can be produced is 12 kg/day. Using typical value for the efficiency of evacuated tube collector of water heating system of 65%, the following coefficient of performances (COP's) are obtained: 44% for adsorption refrigeration cycle, 73% for dual-purpose solar water heater, 9.1% for dual-purpose solar adsorption refrigeration and 82.1% for dual-purpose of both solar water heater and refrigerator.     

Performance analysis of a waste heat driven activated carbon based composite adsorbent – Water adsorption chiller using simulation model

This study aims at improving the performance of a waste heat driven adsorption chiller by applying a novel composite adsorbent which is synthesized from activated carbon impregnated by soaking in sodium silicate solution and then in calcium chloride solution. Modeling is performed to analyze the influence of the hot water inlet temperature, cooling water inlet temperature, chilled water inlet temperatures, and adsorption/desorption cycle time on the specific cooling power (SCP) and coefficient of performance (COP) of the chiller system with the composite adsorbent. The simulation calculation indicates a COP value of 0.65 with a driving source temperature of 85 °C in combination with coolant inlet and chilled water inlet temperature of 30 °C and 14 °C, respectively. The most optimum adsorption–desorption cycle time is approximately 360 s based on the performance from COP and SCP. The delivered chilled water temperature is about 9 °C under these operating conditions, achieving a SCP of 380 W/kg.     

Performance predictions for a new zeolite 13X/CaCl2 composite adsorbent for adsorption cooling systems

Composite adsorbents synthesized from zeolite 13X and CaCl₂ were investigated for applications in solar adsorption cooling systems. The effects of Ca ion exchange on the adsorption properties of zeolite 13X were studied. Ca ion exchange was found to decrease the specific surface area of the zeolite while increasing the total pore volume. Soaking zeolite 13X in 46 wt.% CaCl₂ solution for 24 h gave the optimum Ca ion exchange. The increase in the total pore volume facilitated further impregnating the zeolite with CaCl₂. In all, 41.5 mol% of CaCl₂ was impregnated in the Ca-ion-exchanged zeolite from a 40 wt.% CaCl₂ solution to form the zeolite 13X/CaCl₂ composite adsorbent. A 0.4 g/g difference in equilibrium water uptake between 25 and 75 °C at 870 Pa was recorded for the composite adsorbent. This was 420% of that of zeolite 13X under the same conditions. Numerical simulation predicts that an adsorption cooling system using the composite adsorbent could be powered by a low grade thermal energy source using the temperature range 75–100 °C. Greatly improved efficiency is predicted compared to a system using pure zeolite 13X or impregnated silica gel.     

Adsorption cooling cycles for alternative adsorbent/adsorbate pairs working at partial vacuum and pressurized conditions

This article presents the performance analysis of both ideal single-stage and single-effect double-lift adsorption cooling cycles working at partially evacuated and pressurized conditions. Six specimens of adsorbents and refrigerant pairs, i.e., ACF (A-15)/ethanol, ACF (A-20)/ethanol, silica gel/water, Chemviron/R134a, Fluka/R134a and MaxsorbII/R134a have been investigated. The relationships between equilibrium pressures, adsorbent temperatures and equilibrium adsorption concentrations (Dühring diagram) are presented. Parametric analyses have been carried out with various regeneration (desorption) and evaporation temperatures. Theoretical analysis for adsorption cycles working in single-stage mode shows that ACF (A-20)/ethanol can achieve a specific cooling effect (SCE) of 344 kJ/kg_ads, which is followed by the silica gel/water pair with 217 kJ/kg_ads at a regeneration temperature of 85 °C. On the other hand, when the regeneration temperature is below 70 °C, single-effect double-lift cycle has a significant advantage over single-stage cycle, at which the SCE is higher due to the reduction in adsorption bed pressure in single-effect double-lift cycle.     

Year round test of a solar adsorption ice maker in Kunming,China

A solar adsorption ice maker with activated carbon–methanol adsorption pair was developed for a practical application. Its main features include utilization of a water cooled condenser and removing all valves in the refrigerant circuit except the one that is necessary for refrigerant charging. Year round performance tests of the solar ice maker were performed in Kunming, Yunnan Province, China. Test results show that the COP (coefficient of performance) of the solar ice maker is about 0.083–0.127, and its daily ice production varies within the range of 3.2–6.5 kg/m² under the climatic conditions of daily solar radiation on the surface of the adsorbent bed being about 15–23 MJ/m² and the daily average ambient temperature being within 7.7–21.1 °C. The suitable daily solar radiation under which the solar ice maker can run effectively in Kunming is above 16 MJ/m².     

Preparation and characterization of activated carbon from rubber-seed shell by physical activation with steam

The use of rubber-seed shell as a raw material for the production of activated carbon with physical activation was investigated. The produced activated carbons were characterized by Nitrogen adsorption isotherms, Scanning electron microscope, Thermo-gravimetric and Differential scanning calorimetric in order to understand the rubber-seed shell activated carbon. The results showed that rubber-seed shell is a good precursor for activated carbon. The optimal activation condition is: temperature 880 °C, steam flow 6 kg h^?1, residence time 60 min. Characteristics of activated carbon with a high yield (30.5%) are: specific surface area (S_BET) 948 m² g^?1, total volume 0.988 m³ kg^?1, iodine number of adsorbent (q_iodine) 1.326 g g^?1, amount of methylene blue adsorption of adsorbent (q_mb) 265 mg g^?1, hardness 94.7%. It is demonstrated that rubber-seed shell is an attractive source of raw material for producing high capacity activated carbon by physical activation with steam.     

Synthesis and electrochemical properties of lithium cobalt oxides prepared by molten-salt synthesis using the eutectic mixture of LiCl–Li2CO3

Lithium cobalt oxide powders have been successfully prepared by a molten-salt synthesis (MSS) method using a eutectic mixture of LiCl and Li₂CO₃ salts. The physico-chemical properties of the lithium cobalt oxide powders are investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), particle-size analysis and charge–discharge cycling. A lower temperature and a shorter time (∼700°C and 1 h) in the Li:Co=7 system are sufficient to prepare single-phase HT-LiCoO₂ powders by the MSS method, compared with the solid-state reaction method. Charge–discharge tests show that the lithium cobalt oxide prepared at 800°C has an initial discharge capacity as high as 140 mA h g⁻¹, and 100 mA h g⁻¹ after 40 cycles. The dependence of the synthetic conditions of HT-LiCoO₂ on the reaction temperature, time and amount of flux with respect to starting oxides is extensively investigated.