Direct Production of High Pressure Hydrogen at Great Rate from Glycerol/Water/Metal Mixture

One of the key issues facing the global society today is to find renewable and sustainable energy sources. Hydrogen has gained much attention in recent years since it is one of fuels for fuel cells. It emits no carbon dioxide when it is used and so on. In this study, a great rate production of high pressure hydrogen rich gas from glycerol/water/metal mixtures was developed since glycerol has become one of the enormous industrial by-products, especially from biodiesel processing plants. It was found that cobalt was the optimum metal additive among tested metals of aluminum, cobalt, magnesium and nickel in terms of a hydrogen producing rate, a hydrogen partial pressure and a conversion ratio from 50 mol% glycerol/water mixtures under an operating temperature of 723 K. Concretely, hydrogen rich gas with concentration about 64%H2 and high partial pressure about 4 MPaN,H2 could be produced at the great producing rate of 42.9 LN,H2 dm-2min-1 and high conversion ratio about 60%H2. All the produced hydrogen rich gases from glycerol/water/metal mixtures were by no means inferior to pure hydrogen as a fuel for the polymer elec-trolyte fuel cell.

Evaluation of the Characteristic of Adsorption in a Double-Effect Adsorption Chiller with FAM-Z01

Here, we propose a double-effect adsorption chiller with a zeolite adsorbent (FAM-Z01) for utilization of waste heat. The FAM-Z01 adsorbent has the potential to recover waste heat in low temperatures ranging from 353 to 333 K and shows good potential in the adsorption chiller in terms of the high cooling output. A double-effect adsorption chiller could provide a higher Coefficient Of Performance (COP) than that of a single-effect chiller. In this paper, we developed a measuring method for the amount of adsorption in the first and second adsorber in a double-effect adsorption chiller and measured the adsorption and desorption rate based on the volumetric method. We calculated the COP of the adsorption chiller with the quantity of adsorbent obtained in the experiment. In the experiments, the quantity of adsorbent in the first adsorber was 0.14 g-H2O/g-Ads at the pressure 20 kPa and a desorption temperature over 100℃. The amount of adsorbent in the second adsorber was equal to that of the first adsorber. By analyzing the COP with the experimental results, the COP value was calculated to be over 1.0 (–) at any desorption temperature. The COP of the double-effect cycle was higher than that of single-effect cycle.

Thermochemical Heat Storage Performance in the Gas/Liquid-Solid Reactions of SrCl2 with NH3

Thermochemical heat storage is a promising technology for improving energy efficiency through the utilization of low-grade waste heat. The formation of a SrCl2 ammine complex was selected as the reaction system for the purpose of this study. Discharge characteristics were evaluated in a packed bed reactor for both the gas-solid reaction and the liquid-solid reaction. The average power of the gas-solid reaction was influenced by the pressure of the supplied ammonia gas, with greater powers being recorded at higher ammonia pressure. For the liquid-solid reaction, the obtained average power was comparable to that obtained for the gas-solid reaction at 0.2 MPa. Moreover, the lower heat transfer resistance in the reactor was observed, which was likely caused by the presence of liquid ammonia in the system. Finally, the short-term durability of the liquid-solid reaction system was demonstrated over 10 stable charge/discharge cycles.

Reaction Rate Characteristics of SrBr2 Hydration System for Chemical Heat Pump Cooling Mode

Here, we propose a chemical heat pump chiller with a SrBr2 hydration reaction system for utilization of waste heat. The SrBr2 hydration reaction could recover waste heat in low temperatures ranging from 373 K to 353 K, and the system showed good potential in terms of the high cooling thermal-storage density. Previous studies have given little information on the reaction characteristics of the SrBr2 hydration reaction. In this paper, we developed a measuring method for the hydration reaction equilibrium and reaction rate based on the volumetric method. We analyzed the hydration reaction rate with an unreacted-core shell model. In the experiments, the SrBr2 equilibrium temperature observed was equal to the theoretical equilibrium temperature obtained from thermodynamic databases. In addition, the hysteresis gap between the hydration and dehydration values was 2.0 K. Thus, the hysteresis effect was negligible for the chemical heat pump cooling operation. The reaction fraction of the SrBr2 hydration reached 0.7 within 20 s. By analyzing the hydration reaction rate with the unreacted-core shell model, the activation energy value was calculated to be56.6 kJ/mol. The calculation results showed good agreement with those of the experiment as the reaction fraction reached 0.7.

Carbonation Reaction of Lithium Hydroxide during Low Temperature Thermal Energy Storage Process

In order to apply lithium hydroxide(LiOH)as a low temperature chemical heat storage material,the carbonation reaction of LiOH and the prevention method are focused in this research.The carbonation of raw LiOH at storage and hydration condition is experimentally investigated.The results show that the carbonation reaction of LiOH with carbon dioxide(CO_(2))is confirmed during the hydration reaction.The carbonation of LiOH can be easily carried out with CO_(2) at room temperature and humidity.LiOH can be carbonated at a humidity range of 10%to 20%,a normal humidity region that air can easily be reached.Furthermore,the carbonation reaction rate has not nearly affected by the increase of reaction temperature.An improved storage method by storing LiOH at a low humidity less than 1.0%can be effectively prevented the carbonation of LiOH.The hydration reaction ratio of LiOH at the improved storage method shows a better result compared to the ordinary storage method.Therefore,the humidity should be carefully controlled during the storage of LiOH before hydration and dehydration reaction when apply LiOH as a low heat chemical storage material.

Further Stabilization and Power Density Improvement of Stack-Type Thermoelectric Power Generating Module with Biphasic Medium by Using Various Flexible Metals as Electrodes

In order to realize further stability of a stack-type thermoelectric power generating module (i.e. no electrical connections inside), flexible materials of metal springs and/or rods having restoring forces were installed between lower-temperature-sides of thermoelectric elements. These flexible materials were expected to play three important roles of interpolating different thermal expansions of the module components, enlarging heat removal area and penetration of any media through themselves. Then, a low-boiling-point medium (i.e. NOVEC manufactured by 3M Japan Ltd.) was also applied for a high-speed direct heat removal via its phase change from the lower-temperature-sides of the thermoelectric elements in the proposing stack-type thermoelectric power generating module. No electrical disconnections inside the module were confirmed for more than 9 years of use, indicating further module stability. The power generating density was improved to about 120 mW·m-2 with SUS304 springs having 0.7 mm diameter. Increasing power generating density can be expected in terms of suitable selection of flexible metal with high Vickers hardness, cavities control on the spring surface, more vigorous multiphase flow with adding powders to the medium and optimization of the module configurations according to numerical simulations.

Piezoelectric Power Harvesting Process via Phase Changes of Low-Boiling-Point Medium Together with Water for Recovering Low-Temperature Heats

Low-temperature thermal energy conversions down to exergy zero to electric power must contribute energy sustainability. That is to say, reinforcements of power harvesting technologies from extremely low temperatures less than 373 K might be at least one of minimum roles for the current generations. Then, piezoelectric power harvesting process for recovering low-temperature heats was invented by using a unique biphasic operating medium of an underlying water-insoluble/low-boiling-point medium (i.e. NOVEC manufactured by 3M Japan Ltd.) in small quantity and upper-layered water in large quantity. The higher piezoelectric power harvesting densities were naturally revealed with an increase in heating temperatures. Excessive cooling of the operating medium deteriorated the power harvesting efficiency. The denser operating medium was surpassingly helpful to the higher piezoelectric power harvesting density. Concretely, only about 5% density increase of main operating medium (i.e. water with dissolving alum at 0.10 mol/dm3) came to the champion piezoelectric power harvesting density of 92.6 pW/dm2 in this study, which was about 1.4 times compared to that with the original biphasic medium of pure water together with a small quantity of NOVEC.

Piezoelectric Power Harvesting via Acoustic-Pressure Driven by Low-Speed Wind-Force with Resonating-Tube and Wind-Collector

Wind-driven power harvestings attract attentions since their target wind speeds are quite low less than the so-called cut-in wind speed, which is generally recognized as around 3 m/s. The extant power harvestings driven by wind-induced-air-column-resonations (i.e. acoustic-pressures) are still lacking simplicity, scale flexibility and solid strategies for practical applications. Therefore, the piezoelectric power harvesters via acoustic-pressures driven by low-speedwind-forces with resonating-tubes and wind-collectors were invented so as to complement all the lacks. The wind-collector as well as the resonating-tube contributed to upraise the power harvesting density. The champion power harvesting density of 19.5 nW/dm2 could be procured at 2.3 m/s of an artificial wind and the optimal resonating-tube and wind-collector. Power harvesting proofs from the natural wind with low mean speeds down to about 0.6 m/s were successfully obtained. The cut-in wind speed of the prototype piezoelectric power harvester was found to be quite low as about 0.4 m/s, signifying its ubiquity. Finally, a multi-bundle pendant-type piezoelectric power harvester was specifically presented together with professing the solid and multiple strategies for practical applications.

Evaluation of Carbon Dioxide Absorption Characteristics Lithium Ortho-Silicate in Chemical Heat Storage

We report the development of technology that may contribute to a reduction in greenhouse gas emissions and improve the energy efficiency of the CO2 capture process. Lithium ortho-silicate is a suitable solid sorbent for capturing CO2. This reversible chemical reaction is also applicable to chemical heat storage. The absorption reaction characteristics of lithium ortho-silicate were studied by a thermogravimetric method and a volumetric method that demonstrated the influence of heat and mass transfer limitations in a packed bed designed to be as small as possible. We developed a method for measuring the absorption reaction characteristics in the experiments. In the experiments, a constant conversion fraction of 60% was observed. The reaction system was stable to repetition. The CO2 absorption rate depends on the CO2 pressure and reactor temperature. The absorption rate was determined at several reactor temperatures when the conversion fraction was 0.3. In this study, the maximum absorption rate was obtained at 670oC. It was demonstrated that lithium ortho-silicate is suitable for use in a chemical heat storage system.

Characteristics of Absorption Equilibrium with HFC-134a and an Ionic Liquid Pair

Cold energy generation systems must be improved to prevent catastrophic climate change. In this study, we focused on an absorption chiller cycle with HFC-134a and an ionic liquid pair as the refrigerant and absorbent, respectively. It was expected that this absorption chiller cycle could generate cold heat below 0°C. Two liquids were selected and their absorption equilibrium with this pair was evaluated for the absorption chiller cycle. We measured the adsorbed amount at equilibrium with 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [BMIM][Tf2N] and N-trimethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide [N1113][Tf2N]. The experimental results were reproduced using the non-random two liquid (NRTL) model. This analysis model corresponded well in terms of the amount of adsorption at equilibrium with the experimental results. A Duhring diagram was also generated the NRTL model, and the absorption cycle characteristics as a function of temperature were determined. The absorption chiller cycle obtained cold heat at 10°C with a regeneration temperature of 70°C in addition to generating cold heat below 0°C.

Evaluation of Performance of Thermal and Electrical Hybrid Adsorption Chiller Cycles with Mechanical Booster Pumps

Large amounts of waste heat below 100oC from the industrial sector are re-leased into the atmosphere. It has been suggested that energy system efficiency can be increased with adsorption chillers. However, the cooling power and coefficient of performance (COP) of conventional adsorption chillers significantly decrease with the desorption temperature. In this paper, we proposed a mechanical booster pump (MBP)-assisted adsorption chiller cycle, and evaluated its performances. In the cycle, a MBP was incorporated into a zeolite-water-type adsorption chiller for facilitating water vapor transportation between an adsorber and an evaporator/condenser. We have experimentally studied the effect of the input electrical power of MBP on the performances of adsorption chiller cycle. It has been demonstrated that the heat input achieved by using MBP at the desorption temperature of 50oC was 1.6 times higher than that of without MBP at the desorption temperature of 60oC. And the increase of pump power was found to be effective in increasing the heat input. Therefore, it was confirmed that the operation range of desorption temperature, which can be generated by using the waste heat, was extended and the cooling power was increased directly by using MBP.

Long-Term Durability and Reactivation of Thermochemical Heat Storage Driven by the CaO/Ca(OH)₂Reversible Reaction

Thermochemical heat storage is a promising technology for improving thermal energy efficiency. To investigate the durability of the CaO/Ca(OH)2 reaction and develop a reactivation method, repetitive charging/discharging operation of a packed bed reactor with a thick packed bed was conducted, and variations in the discharging behavior, final conversion, and reactant activity were investigated. Owing to the formation of a deactivated sintered reactant block, the discharging time halved and the final conversion ratio decreased by the 53rd discharging operation. To enhance durability, a reactivation method using high-pressure vapor was implemented during the 54th discharging operation. Following reactivation, the final conversion increased 15%, and the discharging time tripled when compared with the discharging operation before reactivation, confirming the success of this simple reactivation method.

Chemical Heat Storage Using an SiC Honeycomb Packed with CaCl₂Powder

Chemical heat storage is a promising technology for improving thermal energy efficiency. In this study, CaCl2 and H2O were selected as a reaction system for utilization of low-grade exhaust heat that is cooler than 200°C. Heat discharging and charging were conducted through the CaCl2 hydration reaction. A silicon carbide honeycomb was adopted to improve heat transfer in the CaCl2 packed bed. The heat storage, condenser, and evaporator temperature were set at 150°C, 30°C and 90°C respectively. Repeated trials and experiments are time consuming for optimizing design of the equipment. Therefore, in this research, we constructed a simulation that can predict the performance of the device. A numerical simulation model was utilized in preparation for the design of the heat storage module. The consistency of both the simulation and the experimental results was confirmed by comparing them.

Experimental Evaluation of the Heat Output/Input and Coefficient of Performance Characteristics of a Chemical Heat Pump in the Periodic Operation of CaCl₂Hydration

We herein evaluate the use of a chemical heat pump (CHP) for upgrading waste heat. CaCl2 was used in the system of CHP. We evaluated the heat storage and heat releasing of CHP, and confirmed the practicality from the experimental results. The reactor module employed was an aluminum plate-tube heat exchanger with corrugated fins, and the CaCl2 powder was in the form of a packed bed. Heat storage operation and heat dissipation operation are performed at the same time and supplied to the heat demand destination. At this time, an environmental heat source can be used during the heat radiation operation, and the heat output can release more heat than the heat input during heat storage. The heat discharging and charging characteristics of the reactor module were evaluated experimentally. The coefficient of performance (COP) was calculated for the heat upgrading cycle, and the heat output in the system was determined. A COP of 1.42 and output of 650 W/L, based on the heat exchanger volume, were obtained using a 600 s change time for the heat pump.

Analysis of CO₂Pressure Swing Adsorption Simulation by Considering the Transport Phenomena in the Adsorber

This study focused on CO2 separation technology with adsorption. This paper describes the analysis carried out by a CO2 pressure swing adsorption simulation to scale up the absorber. An unsteady one-dimensional balance model was constructed by considering the material, energy, and momentum. In the CO2 breakthrough test, the beginning time and CO2 concentration at outlet of CO2 breakthrough in the calculation were almost equivalent to that of experiment results. The correlation consistency of the calculation results with the analysis model and the experimental results obtained by a bench scale experiment was evaluated. The transport phenomena in the adsorber were investigated at the adsorption, rinse, and desorption steps according to the calculation results. The starting time of CO2 breakthrough obtained by the analysis is equal to that obtained by the adsorption breakthrough experiment. This confirms that the CO2 adsorption, and the temperature and velocity distribution in the adsorber, change as a function of the adsorption, rinse, and desorption steps, respectively. Additionally, the CO2 concentration of the captured gas and the amount of CO2 quantity were 93.4% per day and 2.9 ton/day, respectively. These values are equal to those obtained by the bench scale experiment.

Performance of an Activated Carbon-Ammonia Adsorption Refrigeration System

An experimental study of the adsorption performances of NH3 on several commercial activated carbons was described. Firstly, the specific surface area, pore size distribution and morphological structure of the activated carbons have been characterized by N2 adsorption, Scanning Electron Microscope (SEM), and X-ray diffraction (XRD). The adsorption capacities of four kinds of activated carbons were compared based on adsorption isotherms at 30℃. Results show that a type of activated carbon MSC30 with high adsorption capacity of NH3 is a promising adsorbent for NH3 because of its large specific surface area and high pore volume. Secondly, the effect of adsorption temperature on the adsorption capacity of NH3 on MSC30 was investigated. A modified Dubinin-Astakhov equation was employed to describe the adsorption isotherms, with the reliability and accuracy evaluation. The isosteric heat of adsorption of MSC30-NH3 as a function of the amount adsorbed was calculated applying the Clausius-Clapeyron equation with isotherms obtained at 20℃ and 30℃. Thirdly, a packed-bed type adsorber was used to evaluate the influence of cycle time on the system cooling performance (coefficient of performance, specific cooling performance, and volumetric cooling performance) of the MSC30-NH3 pair at the evaporating temperatures of 5℃, 10℃ and 15℃ with a fixed adsorption/condensing temperature and desorption temperature of 30?C and 80℃, respectively. Finally, a long term operation without degradation for MSC30-NH3 adsorption was experimentally demonstrated from the 80 consecutive adsorption-desorption cycles.

Hybrid Rubisco with Complete Replacement of Rice Rubisco Small Subunits by Sorghum Counterparts Confers C4 Plant-like High Catalytic Activity

Photosynthetic rate at the present atmospheric condition is limited by the CO2-fixing enzyme ribulose-1,5-bisphosphate carboxylase/oxygenase(Rubisco)because of its extremely low catalytic rate(kcat)and poor affinity for C02(Kc)and specificity for CO2(Sc/O).Rubisco in C4 plants generally shows higher k cat than that in C3 plants.Rubisco consists of eight large subunits and eight small subunits(RbcS).Previously,the chimeric incorporation of sorghum C4-type RbcS significantly increased the k cat of Rubisco in a C3 plant,rice.In this study,we knocked out rice RbcS multigene family using the CRISPR-Cas9 technology and completely replaced rice RbcS with sorghum RbcS in rice Rubisco.Obtained hybrid Rubisco showed almost C4 plant-like catalytic properties,i.e.,higher kcai,higher Kc,and lower Sc/O.Transgenic lines expressing the hybrid Rubisco accumulated reduced levels of Rubisco,whereas they showed slightly but significantly higher photosynthetic capacity and similar biomass production under high C 02 condition compared with wild-type rice.High-resolution crystal structural analysis of the wild-type Rubisco and hybrid Rubisco revealed the structural differences around the central pore of Rubisco and the pC-pD hairpin in RbcS.We propose that such differences,particularly in the pC-pD hairpin,may impact the flexibility of Rubisco catalytic site and change its catalytic properties.