Thermal transient behavior of an ANG storage during dynamic discharge phase at room temperature

Throughout this work the thermal behavior of an adsorptive natural gas (ANG) storage under dynamic discharge conditions at room temperature of 27 °C was studied. The work was conducted in a gravimetrically built experimental unit where the storage chamber was equipped with axial and radial distributed thermocouples and the storage was discharged at different discharge rates. The results demonstrated that maximum methane discharge rate of 5 L min⁻¹ in activated carbon/methane system resulted in the severest temperature drop corresponding to further drop of about 40% compared to that at 1 L min⁻¹. This extreme thermal condition claimed a reduction of 15.2% in methane dynamic delivery capacity with respect to the isothermal delivery capacity. Ethane and propane have high enthalpies of desorption, and hence high portions of these gases may influence the performance of ANG storages through their thermal impact. A gas mixture with 14.98% and 14.54% volumes of ethane and propane resulted in higher temperature drop than methane claiming a reduction of 19.4% in the dynamic delivery capacity comparing with methane delivery capacity.     

Energy and exergy analysis of timber dryer assisted heat pump

In this research, poplar and pine timbers have been dried from the moisture contents of 1.28 kg water/kg dry matter and 0.60 kg water/kg dry matter to 0.15 kg water/kg dry matter in heat pump dryer functioning on the basis of 24 h operation. The change in weight in all of the timbers was followed in the drying chamber and drying stopped when the desired weight was achieved. At 40 °C dry bulb temperature, 0.8 m/s air velocity, and initial moisture content of the poplar timbers 1.28 kg water/kg dry matter, the moisture content was reduced to 0.15 kg water/kg dry matter moisture content in 70 h, and the moisture content of the pine timbers which was 0.60 kg water/kg dry matter was reduced to the same amount in 50 h. All data collected while drying were saved on computer and analysed afterwards. For this system, energy analysis was made to determine the energy utilization. Exergy analysis was accomplished to determine of exergy losses during the drying process.     

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.     

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.     

New dry and wet Zn-polyaniline bipolar batteries and prediction of voltage and capacity by ANN

Chemically synthesized polyaniline doped with perchlorate ion was used as the electroactive material of the cathode in the construction of bipolar rechargeable batteries based on carbon doped polyethylene (CDPE) as a conductive substrate of the bipolar electrodes. A significant improvement in the originally poor adherence between the polymer foil and electroactive material layer of the anode was achieved by chemical pretreatment (etching) and single-sided metallization of the polymer foil with copper. A thin layer of optalloy was electroplated onto the surface of the copper-coated polymer foil to increase the battery overvoltage. A mixture of 1 wt% electrochemically synthesized optalloy, 92 wt% electrochemically synthesized zinc powder, 2 wt% MgO, 4 wt% ZnO and 1 wt% sodium carboxymethyl cellulose (CMC) was used as the anode mixture. Then, the electroactive mixture of the anode was coated onto the metallized surface of the CDPE. Graphite powder was used to coat the other side of the CDPE at 90 °C at 1 t cm⁻² pressure This side was coated with a cathode mixture containing 80 wt% polyaniline powder, 18 wt% graphite powder and 2 wt% acetylene black. The battery electrolyte contained 1 M Zn(ClO₄)₂ and 0.5 M NH₄ClO₄ and 1.0 × 10⁻⁴ M Triton X-100 at pH 3.2. Both 3.2 V dry and wet bipolar batteries were constructed using a bipolar electrode and tested successfully during 200 charge–discharge cycles. The battery possessed a high capacitance of 130 mAh g⁻¹ and close to 100% columbic efficiency. The loss of capacity during charge–discharge cycles for the wet bipolar battery was less than that for the dry bipolar battery. Self-discharge of the dry and wet batteries during a storage time of 30 days was about 0.64% and 0.45% per day, respectively. An artificial neural network (ANN) was used to model the voltage and battery available capacity (BAC) only for the dry bipolar battery at different currents and different times of discharge.     

Experimental investigation and theoretical analysis of the solar adsorption cooling system in a green building

A solar adsorption cooling system was constructed in the green building of Shanghai Institute of Building Science. The system consisted of evacuated tube solar collector arrays of area 150 m², two adsorption chillers with nominal cooling capacity of 8.5 kW for each and a hot water storage tank of 2.5 m³ in volume. A mathematical model of the system was established. According to experimental results under typical weather condition of Shanghai, the average cooling capacity of the system was 15.3 kW during continuous operation for 8 h. The theoretical analysis of the system was verified and found to agree well with the experimental results. The performance analysis showed that solar radiant intensity had a more distinct influence on the performance of solar adsorption cooling system as compared with ambient temperature. It was observed that the cooling capacity increased with the increase of solar collector area, whereas, solar collecting efficiency varied quite contrary. With the increase of water tank volume, cooling capacity decreased, while, the solar collecting efficiency increased. The system performances can be enhanced by increasing the height-to-diameter ratio of water tank. Additionally, it was observed that solar collecting efficiency decreased with the increase of the initial temperature of water in the tank; however, cooling capacity varied on the contrary. Also can be seen is that optimum nondimensional mass flow rate is 0.7 when the specific mass flow rate exceeds 0.012 kg/m² s.     

A new methodology of studying the dynamics of water sorption/desorption under real operating conditions of adsorption heat pumps: Experiment

In this paper we proposed and tested a new methodology of studying the kinetics of water vapour sorption/desorption under operating conditions typical for isobaric stages of sorption heat pumps. The measurements have been carried out on pellets of composite sorbent SWS-1L (CaCl₂ in silica KSK) placed on a metal plate. Temperature of the plate was changed as it takes place in real sorption heat pumps, while the vapour pressure over the sorbent was maintained almost constant (saturation pressures corresponding to the evaporator temperature of 5 °C and 10 °C and the condenser temperature of 30 °C and 35 °C). Near-exponential behaviour of water uptake on time was found for most of the experimental runs. Characteristic time τ of isobaric adsorption (desorption) was measured for one layer of loose grains having a size between 1.4 mm and 1.6 mm for different heating/cooling scenarios and boundary conditions of an adsorption heat pump. Maximum specific power estimated from the τ-values can exceed 1.0 kW/kg of dry adsorbent, that gives proof to the idea of compact adsorption units for energy transformation with loose SWS grains.     

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.     

Hydrogen production for fuel cells by autothermal reforming of methane over sulfide nickel catalyst on a gamma alumina support

Experimental and modelling studies have been conducted on catalytic autothermal reforming (ATR) of methane for hydrogen production over a sulfide nickel catalyst on a gamma alumina support. The experiments are performed with different feedstock under thermally neutral conditions. The results show that the performance of the reformer is dependent on the molar air-to-fuel ratio (A/F), the molar water-to-fuel ratio (W/F) and the flowrate of the feedstock mixture. The optimum conditions for high methane conversion and high hydrogen yield are A/F = 3–3.5, W/F = 2–2.5 and a fuel flowrate below 120–250 l h⁻¹. Under these conditions, a methane conversion of 95–99% and a hydrogen yield of 39–41% on a dry basis can be achieved and 1 mole of methane can produce 1.8 moles of hydrogen at an equilibrium reactor temperature of not exceeding 850 °C.A two-dimensional reactor model is developed to simulate the conversion behaviour of the reactor for further study of the reforming process. The model includes all aspects of the major chemical kinetics and the heat and mass transfer phenomena in the reactor. The predicted results are successfully validated with experimental data.     

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.     

Predicting the transient response of a serpentine flow-field PEMFC: II: Normal to minimal fuel and AIR

The three-dimensional (3D) transient model presented in part I is used to study the overshoot and undershoot behavior observed in a PEMFC during operation with fixed normal stoichiometic flow rates of hydrogen and air for a 1.0 V s⁻¹ change in the load. In contrast to the behavior with excess flow shown in part I, the predictions show second-order responses for both decreases and increases in the load. That is, there is current overshoot when the load cell is decreased from 0.7 V to 0.5 V and there is current undershoot when the cell voltage is increased from 0.5 V to 0.7 V. The simulation of a 10 cm² reactive area with a serpentine flow path is used to explain this behavior in terms of the reacting gas concentrations, the flow through the gas diffusion media, the movement of water through the MEA by electro-osmotic and back diffusion forces, and the variation in the distributions of current density. The operating conditions correspond to 101 kPa, 70 °C cell temperature, anode and cathode dew-points and stoichiometries of 65 °C and 57 °C and 1.45 and 2.42 at an initial operating voltage of 0.7 V and current density of 0.33 A cm⁻². The fixed flow rates correspond to stoichiometries of 1.05 and 1.73 at 0.5 V for the 0.46 A cm⁻² predicted current density. The predictions illustrate regions where the MEA may alternate between wet and dry conditions and this may be useful to explain stability and durability of the MEA during transient operation.     

Effects of pore sizes of porous silica gels on desorption activation energy of water vapour

In this work, the effects of pore sizes of silica gel on desorption activation energy and adsorption kinetics of water vapour on the silica gels were studied. The isotherms and adsorption kinetic curves of water vapour on three kinds of silica gels with average pore diameters of 2.0 nm, 5.28 nm and 10.65 nm, respectively, were measured by the method of static adsorption, the desorption activation energies of water vapour on silica gels were estimated by using the TPD technique, and the effects of pore sizes of silica gel on adsorption kinetics and desorption activation energy were discussed. Results showed that the isotherm of water vapour on the A-type silica gel with the average pore diameter of 2 nm was of type I, which can be well described by the Langmuir model; the isotherms of water vapour on the B-type and the C-type mesoporous silica gels with the average pore diameters of 5.28 nm and 10.65 nm, respectively, were of type V; and at lower RH, the smaller the average pore size of the silica gel was, the smaller the adsorption rate constant was due to the diffusion resistance in the pores of the silica gels, while at a higher RH, the smaller the average pore size of the silica gel was, the larger the adsorption rate constant was. The desorption activation energies of water on the A-type, the B-type and the C-type silica gels were respectively 35.54 kJ/mol, 31.41 kJ/mol and 26.16 kJ/mol, which suggested that the desorption activation energy of water on the silica gels increased as the pore sizes of the silica gels decreased.     

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.     

Fuel effects on start-up energy and efficiency for automotive PEM fuel cell systems

This paper investigates the effects of various fuels on hydrogen production for automotive PEM fuel cell systems. Gasoline, methanol, ethanol, dimethyl ether and methane are compared for their effects on fuel processor size, start-up energy and overall efficiencies for 50 kW_e fuel processors. The start-up energy is the energy required to raise the temperature of the fuel processor from ambient temperature (20 °C) to that of the steady-state operating temperatures. The fuel processor modeled consisted of an equilibrium-ATR (autothermal), high-temperature water gas shift (HTS), low-temperature water gas shift (LTS) and preferential oxidation (PrOx) reactors. The individual reactor volumes with methane, dimethyl ether, methanol and ethanol were scaled relative to a gasoline-fueled fuel processor meeting the 2010 DOE technical targets. The modeled fuel processor volumes were, 25.9 L for methane, 30.8 L for dimethyl ether, 42.5 L for gasoline, 43.7 L for ethanol and 45.8 L for methane. The calculated fuel processor start-up energies for the modeled fuels were, 2712 kJ for methanol, 3423 kJ for dimethyl ether, 6632 kJ for ethanol, 7068 kJ for gasoline and 7592 kJ for methane. The modeled overall efficiencies, correcting for the fuel processor start-up energy using a drive cycle of 33 miles driven per day, were, 38.5% for dimethyl ether, 38.3% for methanol, 37% for gasoline, 34.5% for ethanol and 33.2% for methane assuming a steady-state efficiency of 44% for each fuel.     

The effects of operation parameter on the performance of a solar-powered adsorption chiller

A solar-powered adsorption chiller with heat and mass recovery cycle was designed and constructed. It consists of a solar water heating unit, a silica gel-water adsorption chiller, a cooling tower and a fan coil unit. The adsorption chiller includes two identical adsorption units and a second stage evaporator with methanol working fluid. The effects of operation parameter on system performance were tested successfully. Test results indicated that the COP (coefficient of performance) and cooling power of the solar-powered adsorption chiller could be improved greatly by optimizing the key operation parameters, such as solar hot water temperature, heating/cooling time, mass recovery time, and chilled water temperature. Under the climatic conditions of daily solar radiation being about 16–21 MJ/m², this solar-powered adsorption chiller can produce a cooling capacity about 66–90 W per m² collector area, its daily solar cooling COP is about 0.1–0.13.     

Hydrogen and dry ice production through phase equilibrium separation and methane reforming

A clean hydrogen (99.9999%) and dry ice production process is proposed, which is based on phase equilibrium (PE) separation and methane reforming. Heat and power integration studies are carried out for the proposed process, by formulating and solving the minimum hot/cold/electric utility cost problem for the associated heat exchange network. The optimum operating cost of the proposed process is shown to be lower than the corresponding cost of the conventional PSA (pressure swing adsorption) based process, if the produced dry ice is sold for as low as 2 cents kg-dry-ice⁻¹ or if an equivalent CO₂ sequestration credit is conceded.     

Design of solar powered adsorption heat pump with ice storage

The design and performance of a solar (and/or natural gas) powered adsorption (desiccant-vapor) heat pump for residential cooling (and heating) is described. The entire system is modeled and analyzed: adsorption heat pump itself, ice thermal storage reservoir, and solar collectors. The adsorption heat pump embodies patent pending improvements to the state-of-the-art which elevate coefficient of performance for cooling from a maximum of 1.2 reported in the literature to a conservatively predicted minimum of 1.5. The adsorption device utilizes economical, robust configurations (shell-and-tube) and components (helical annular finned tubes, multi-lumen tubes) commonly employed in heat exchangers in a manner heretofore untried, as well as other enhancements (metal wool to diffuse heat throughout the adsorbent). The vessel is all aluminum and the adsorbent-refrigerant pair is carbon-ammonia. The ice reservoir provides 24 h cooling. Two types of solar collector are determined to be satisfactory at the selected operating temperature of 170 °C: (1) compound parabolic concentrator with high concentration ratio (10+) and automatic tilt adjustment, and (2) evacuated (0.001 atm) flat panel, similar to atmospheric pressure versions employed for domestic water heating.     

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.     

Hydrothermal catalytic gasification of fermentation residues from a biogas plant

Biogas plants, increasing in number, produce a stream of fermentation residue with high organic content, providing an energy source which is by now mostly unused. We tested this biomass as a potential feedstock for catalytic gasification in supercritical water (T ≥ 374 °C, p ≥ 22 MPa) for methane production using a batch reactor system. The coke formation tendency during the heat-up phase was evaluated as well as the cleavage of biomass-bound sulfur with respect to its removal from the process as a salt. We found that sulfur is not sufficiently released from the biomass during heating up to a temperature of 410 °C. Addition of alkali salts improved the liquefaction of fermentation residues with a low content of minerals, probably by buffering the pH. We found a deactivation of the carbon-supported ruthenium catalyst at low catalyst-to-biomass loadings, which we attribute to sulfur poisoning and fouling in accordance with the composition of the fermentation residue. A temperature of 400 °C was found to maximize the methane yield. A residence time dependent biomass to catalyst ratio of 0.45 g g⁻¹ h⁻¹ was found to result in nearly full conversion with the Ru/C catalyst. A Ru/ZrO₂ catalyst, tested under similar conditions, was less active.