Analysis of suitability of TPP ash-slag waste as materials for hydrogen fuel storage

The current trends in energy were described, the main of which is the use of alternative energy sources, especially hydrogen. The most common methods of hydrogen accumulation were proposed: accumulation of compressed gaseous hydrogen in high-pressure tanks; accumulation of liquid hydrogen in cryogenic tanks; storing hydrogen in a chemically bound state; accumulation of gaseous hydrogen in carriers with a high specific surface area. Based on the combination of advantages and disadvantages, the most promising methods of accumulation were selected: storage of liquid hydrogen and storage of hydrogen in carriers with a high specific surface area. The main requirement for materials for hydrogen storage by these methods was revealed – a high specific surface area. Prospects for the development of waste-free low-emission technologies due to the recycling of secondary raw materials and the development of low-temperature technologies for the synthesis of functional and structural materials were substantiated. The applicability of large-scale ash and slag waste from coal-fired thermal power plants as a raw material for obtaining materials by low-temperature technologies was shown. The traditional ways of using ash and slag waste as a raw material, active additive and filler in the production of cements were described. Modern technologies for the production of innovative materials with a unique set of properties were presented, namely carbon nanotubes, silica aerogel and geopolymer materials. The prospect of using geopolymer matrices as a precursor for the synthesis of a number of materials was described; the most promising type of materials was selected – geopolymer foams, which are mainly used as sorbents for purifying liquids and gases or accumulating target products, as well as heat-insulating materials. The possibility of obtaining products of any shape and size on the basis of geopolymer matrices without high-temperature processing was shown. The special efficiency of the development of the technology of porous granules and powders obtained from a geopolymer precursor using various methods was substantiated. The obtained granules can be used in the following hydrogen storage technologies: direct accumulation of hydrogen in porous granules; creation of insulating layers for liquid hydrogen storage units.     

Modeling and optimization of composite thermal insulation system with HGMs and VDMLI for liquid hydrogen on orbit storage

The passive thermal insulation system for liquid hydrogen (LH₂) on orbit storage mainly consists of foam and variable density multilayer insulation (VDMLI) which have been considered as the most efficient and reliable thermal insulation system. The foam provides main heat leak protection on launch stage and the VDMLI plays a major role on orbit stage. However, compared with the extremely low thermal conductivity of VDMLI (1 × 10⁻⁵ W/(m·K)) at high vacuum, the foam was almost useless. Recently, based on hollow glass microspheres (HGMs) we have proposed the HGMs-VDMLI system which performs better than foam-VDMLI system. In order to improve insulation performance and balance weigh and environmental adaptability of passive insulation system, the HGMs-VDMLI insulation system should be configured optimally. In this paper, the thickness of HGMs and the number and arrangement of spacers of VDMLI were configured optimally by the “layer by layer” model. The effective thicknesses of HGMs were 25 mm for 60 layers MLI and 20 mm for 45 layers VDMLI. Compared with 35 mm foam and 45 layers VDMLI system, the heat flux of 20 mm HGMs and 45 layers VDMLI system was reduced by 11.97% with the same weight, or the weight of which was reduced by 9.91% with the same heat flux. Moreover, the effects of warm boundary temperature (WBT) and vacuum pressure on thermal insulation performance of the system were also discussed.     

Thermal design analysis of a 1 L cryogenic liquid hydrogen tank for an unmanned aerial vehicle

Thermal design analysis of a 1-L cryogenic liquid hydrogen storage tank without vacuum insulation for a small unmanned aerial vehicle was carried out in the present study. To prevent excess boil-off of cryogenic liquid hydrogen, the storage tank consisted of a 1-L inner vessel, an outer vessel, insulation layers and a vapor-cooled shield. For a cryogenic storage tank considered in this study, the appropriate heat inleak was allowed to supply the boil-off gas hydrogen to a proton electrolyte membrane fuel cell as fuel. In an effort to accommodate the hydrogen mass flow rate required by the fuel cell and to minimize the storage tank volume, a thermal analysis for various insulation materials was implemented here and their insulation performances were compared. The present thermal analysis showed that the Aerogel thermal insulations provided outstanding performance at the non-vacuum atmospheric pressure condition. With the Aerogel insulation, the tank volume for storing 1-L liquid hydrogen at 20 K could be designed within a storage tank volume of 7.2 L. In addition, it was noted that the exhaust temperature of boil-off hydrogen gas was mainly affected by the location of a vapor-cooled shield as well as thermal conductivity of insulation materials.     

Feasibility analysis of a new thermal insulation concept of cryogenic fuel tanks for hydrogen fuel cell powered commercial aircraft

Of cryogenic liquid hydrogen tanks for future airliners, their volumetric and gravimetric efficiencies, their robustness and their environmental adaptability are all strengthened via a novel thermal insulation concept proposed in this work.A conventional cryogenic tank is insulated either purely by a layer/layers of Polyurethane (PU) foam or by a vacuum-based multilayer insulation (MLI). In the new concept, an extra layer is inserted into the PU foam. The intermediate layer can be filled with liquid nitrogen while on the ground or with ambient air during flight.By this new design, analysis shows an approximate 33% volumetric saving compared to PU insulation. Furthermore, a 6-fold amount of passive heat input during cruise flight is easily achieved compared to the rest two concepts. This showcases an increased robustness against possible failure of the tank's active heating system, and the potential for significant parasitic power loss reduction.     

Thermal analysis of coupled vapor-cooling-shield insulation for liquid hydrogen-oxygen pair storage

The long-term storage of liquid hydrogen (LH₂)-liquid oxygen (LO₂) pair with extremely low heat leakage is essential for future deep space exploration. Vapor-cooled shield (VCS) is considered an effective insulation structure that can significantly reduce the heat penetration into the LH₂ tanks, however it is relatively ineffective for the LO₂ tanks. Novel coupled VCS insulation schemes for LH₂-LO₂ bundled tanks were proposed to achieve optimal performance not only for the LH₂ but also for the LO₂ tanks. A thermodynamic model had been developed and validated by experiments. The optimal VCS location, the temperature profile within the insulation, the heat leakage reduction contributed by the VCS, and the thermal performance versus scheme structural mass had been parametrically investigated. A comparison indicated that the proposed single integrated shield configuration can reduce the heat flux of the LH₂ and the LO₂ tanks by 64.0% and 54.8%, respectively compared with the non-VCS structure. In addition, the results also confirmed that zero boil-off storage of LO₂ can be achieved by only utilizing the exhausted hydrogen vapor, with no need for an extra cryocooler.     

Development of graphite foam infiltrated with MgCl2 for a latent heat based thermal energy storage (LHTES) system

Thermal energy storage (TES) systems that are compatible with high temperature power cycles for concentrating solar power (CSP) require high temperature media for transporting and storing thermal energy. To that end, TES systems have been proposed based on the latent heat of fusion of the phase change materials (PCMs). However, PCMs have relatively low thermal conductivities. In this paper, use of high-thermal-conductivity graphite foam infiltrated with a PCM (MgCl₂) has been investigated as a potential TES system. Graphite foams with two porosities were infiltrated with MgCl₂. The infiltrated composites were evaluated for density, heat of fusion, melting/freezing temperatures, and thermal diffusivities. Estimated thermal conductivities of MgCl₂/graphite foam composites were significantly higher than those of MgCl₂ alone over the measured temperature range. Furthermore, heat of fusion, melting/freezing temperatures, and densities showed comparable values to those of pure MgCl₂. Results of this study indicate that MgCl₂/graphite foam composites show promise as storage media for a latent heat thermal energy storage system for CSP applications.     

Numerical investigations on the fast filling of hydrogen tanks

High-pressure storage of hydrogen in tanks is a promising option to provide the necessary fuel for transportation purposes. The fill process of a high-pressure tank should be reasonably short but must be designed to avoid too high temperatures in the tank. The shorter the fill should be the higher the maximum temperature in the tank climbs. For safety reasons an upper temperature limit is included in the requirements for refillable hydrogen tanks (ISO 15869) which sets the limit for any fill optimization. It is crucial to understand the phenomena during a tank fill to stay within the safety margins.The paper describes the fast filling process of hydrogen tanks by simulations based on the Computational Fluid Dynamics (CFD) code CFX. The major result of the simulations is the local temperature distribution in the tank depending on the materials of liner and outer thermal insulation. Different material combinations (type III and IV) are investigated.Some measurements from literature are available and are used to validate the approach followed in CFX to simulate the fast filling of tanks. Validation has to be continued in the future to further improve the predictability of the calculations for arbitrary geometries and material combinations.     

Effective thermal conductivity of insulation materials for cryogenic LH2 storage tanks: A review

An accurate estimation of the effective thermal conductivity of various insulation materials is essential in the evaluation of heat leak and boil-off rate from liquid hydrogen storage tanks. In this work, we review the existing experimental data and various proposed correlations for predicting the effective conductivity of insulation systems consisting of powders, foams, fibrous materials, and multilayer systems. We also propose a first principles-based correlation that may be used to estimate the dependence of the effective conductivity as a function of temperature, interstitial gas composition, pressure, and structural properties of the material. We validate the proposed correlation using available experimental data for some common insulation materials. Further improvements and testing of the proposed correlation using laboratory scale data obtained using potential LH₂ tank insulation materials are also discussed.     

The influence of inner material with different average thermal conductivity on the performance of whole insulation system for liquid hydrogen on orbit storage

At present, several composite insulation systems were proposed that can be used for passive insulation systems, including foam-variable density multilayer insulation (VDMLI), aerogel-VDMLI and hollow glass microspheres (HGMs)-VDMLI. The passive insulation systems with different inner material (IM) showed different performances. However, the relationship between the average thermal conductivity of IM and the insulation performance of the whole system has rarely been investigated. It is of great significance for efficient configuration and matching of the passive insulation system. In this paper, a series of average thermal conductivity of IM were assumed to predict the insulation performance of the whole system at 20 K–300 K and high vacuum. In order to further illustrate the relationship between IM and MLI/VDMLI, the foam was replaced by the HGMs as 5 mm a unit forming a series of HGMs-foam-MLI/VDMLI insulation systems. The performance of the systems was investigated. After the foam was completely replaced by the HGMs, the performance of MLI and VDMLI systems was improved 33% and 13%, respectively. Moreover, each mode of heat transfer including solid conduction, radiation, and gas conduction for foam-MLI/VDMLI and HGMs-MLI/VDMLI insulation systems were calculated and analyzed.     

Development potentials for small mobile storage tanks with vacuum powder insulations

Vehicle cryofuel tanks for LNG and liquid hydrogen are currently multilayer vacuum superinsulated (MLVSI). MLVSI are known for thermal conductivities as low as 10⁻⁶W(mK)⁻¹ at cryogenic temperatures. Due to high system costs, these tanks burden the economy of cryofueled vehicles. In search of low tank costs, powdrous load-bearing insulations, applied to large storage and transport vessels today, were examined for their MLVSI-replacement potential.Thermal conductivities of some popular powders were measured to about 2–8 mW (m K)⁻¹ at zero and full external loads representing vacuum pressure enforced on the insulation layer. Furthermore, a transient simulation program was written to examine the influence of various operational parameters on powder insulated cryofuel tanks onboard passenger cars and trucks. The results were interpreted mainly for LNG fuel tanks with perspectives for liquid hydrogen.     

有空气保温层的蒸汽直埋管道保温厚度计算与分析

对不同介质温度条件下有空气保温层的"钢套钢"蒸汽直埋管保温结构厚度进行了数值计算,并将计算结果与无空气保温层的保温结构厚度进行了比较.计算结果若用于实际工程,可在确保保温效果的前提下,减小保温层厚度和外套钢管的使用量,以达到减少材料的使用、节约投资的目的.     

Field measurements on a district heating pipe with vacuum insulation panels

In Swedish district heating networks, around 10% of the supplied thermal energy is lost in the distribution system. One solution to decrease the losses is to use hybrid insulation district heating pipes, a concept where the innermost part of the thermal insulation consists of vacuum insulation panels, held in place by polyurethane foam. One problem with vacuum insulation panels are their sensitivity to high temperatures. This paper presents field measurements on a hybrid insulation district heating pipe where the temperatures have been measured continuously at various positions of a pipe section. The measurements show consistency and a large difference between hybrid insulation parts and reference parts without vacuum insulation panels. A superposition model has been used to calculate the temperature in a point and compare it to the measurement. The results are compared to the same calculation on the results from finite element simulations. The results show clearly that the vacuum panels in the pipes have not collapsed. A slow deterioration of the panels is harder to find with this model. Changes in the system, such as a return temperature which decreases over time, can give a larger impact, concealing the change in the panel performance.     

相变储能冷藏隔热板的应用

分析了传统冷藏集装箱的结构和传热特点,指出了传统冷藏集装箱隔热保温的局限性,提出了使用相变储能材料的隔热板能够减少冷藏车的能耗和费用。阐述了相变储能的原理,总结了相变储能材料在减少室内温度波动和节能方面的应用,提出并设计了一种使用相变储能材料的节能型冷藏集装箱隔热板,可为同类设计提供参考。     

Perspectives of high entropy alloys as hydrogen storage materials

Storage is a challenging issue that cuts across distribution, delivery, and safe end-uses of hydrogen as fuel. All the fuel cell vehicles are equipped with inefficient and unsafe high-pressure hydrogen cylinders. It is well known that storing such a highly flammable gas at high pressure is not safe. Only hydrogen can be stored safely as a form of metal hydrides, and all the investigated metal hydrides are inefficient in one way or another. Four essential hydrogen parameters for solid-state storage for fuel cell applications are high volumetric storage capacity, excellent heat transfer, and recharge time and feasible charging discharging temperatures. The available metal tanks have good gravimetric storage capacity but did not satisfy the prescribed criterion for good volumetric capacity necessary for mobile applications. Recently, some promising reports are published on the hydrogen storage properties of newly discovered High Entropy Alloys (HEAs). HEAs provide vast composition selection freedom for the formation of favorable simple solid solution phase for hydrogen storage. The four core effects of these alloys may also play a vital role in hydrogen storage properties. Here we reviewed and summarized the published results on hydrogen storage properties of HEAs to date. We underlined different essential aspects for the future development of HEAs as hydrogen storage materials. This review article discusses and describes the perspectives of HEAs in regards to the hydrogen storage applications of these alloys and will provide insight into the future development of hydrogen storage HEAs.     

Experimental investigation on sorption performance of new high–efficiency,inexpensive H2 getters in high–vacuum,variable density–multilayer insulated hydrogen storage equipment

Hydrogen (H₂) is released by the manufactured materials, which results in the deterioration of the insulation performance of liquid hydrogen (LH₂) storage tanks. The getter is found in the vacuum annular space of equipment and helps maintain the high vacuum of LH₂ tanks. Palladium oxide (PdO), an effective H₂ getter, is expensive, resource–constrained and unsuitable for the LH₂ equipment. Therefore, suitable and inexpensive alternatives were examined using LH₂ storage tanks, to maintain the insulation property of the high–vacuum variable–density multilayer insulation (VDMLI) equipment better. Eight types of H₂ getters were designed using in the LH₂ tanks, and classified into three categories, namely, chemical, physical and physico–chemical getters (PCNHG). The sorption performance of new H₂ getters was compared with that of PdO. PdO could be replaced by in the 7:1, 5:1 and 4:1 ratio by PCNHG1, PCNHG2 and CNHG in the LH₂ tanks, respectively. The results demonstrated that the sorption capacity of PCNHG1 and PCNHG2 were 1.70 and 2.14 times that of the same type of getters in the market (16.35% and 20.62% higher than that of PdO, respectively). Their average H₂ sorption efficiency was 1.17 times and 1.05 times of that of PdO, respectively. The minimum thermal conductivity exhibited by CNHG was only 6.34% of that of PdO, and the sorption capacity of CNHG was 1.82 and 1.44 times that of PCNHG1 and PCNHG2, respectively. However, the sorption capacities of PCNHG1, PCNHG2 and CNHG were belows that of PdO. These results help facilitate reduction in the expense of H₂ getters and provide an important reference to enhance the sorption performance of getters.     

Liquid hydrogen storage system for heavy duty trucks: Configuration,performance, cost,and safety

We investigate the potential of liquid hydrogen storage (LH₂) on-board Class-8 heavy duty trucks to resolve many of the range, weight, volume, refueling time and cost issues associated with 350 or 700-bar compressed H₂ storage in Type-3 or Type-4 composite tanks. We present and discuss conceptual storage system configurations capable of supplying H₂ to fuel cells at 5-bar with or without on-board LH₂ pumps. Structural aspects of storing LH₂ in double walled, vacuum insulated, and low-pressure Type-1 tanks are investigated. Structural materials and insulation methods are discussed for service at cryogenic temperatures and mitigation of heat leak to prevent LH₂ boil-off. Failure modes of the liner and shell are identified and analyzed using the regulatory codes and detailed finite element (FE) methods. The conceptual systems are subjected to a failure modes and effects analysis (FMEA) and a safety, codes, and standards (SCS) review to rank failures and identify safety gaps. The results indicate that the conceptual systems can reach 19.6% useable gravimetric capacity, 40.9 g-H₂/L useable volumetric capacity and $174–183/kg-H₂ cost (2016 USD) when manufactured 100,000 systems annually.     

Thermal management of metal hydride hydrogen storage reservoir using phase change materials

Metal hydride hydrogen storage reservoir should be carefully designed to achieve acceptable performance due to significant thermal effect on the system during hydriding/dehydriding. Phase change materials can be applied to metal hydride hydrogen storage system in order to improve the system performance. A transient two-dimensional axisymmetric numerical model for the metal hydride reservoir packed with LaNi₅ has been developed on Comsol platform, which was validated by comparing the simulation results with the experiment data from other work. Then, the performances of metal hydride hydrogen storage reservoir using phase change materials were predicted. The effects of some parameters, such as the thermal conductivity, the mass and the latent heat of fusion of the phase change materials, on the metal hydride hydrogen storage reservoir were discussed. The results shown that it was good way to improve the efficiency of the system by increasing the thermal conductivity of phase change materials and selecting a relatively larger latent heat of fusion. Due to the relatively lower thermal conductivity of phase change materials, different metal foams were composited with the phase change materials in order to improve the heat transfer from the metal hydride bed to the phase change materials and the hydrogen storage efficiency. The effect of aluminium foam on the metal hydride reservoir was studied and validated. The phase change materials composited with copper foam shown better performance than that composited with aluminium foam.     

Performance analysis of vapor-cooled shield insulation integrated with para-ortho hydrogen conversion for liquid hydrogen tanks

A composite thermal insulation system consisting of variable-density multi-layer insulation (VDMLI) and vapor-cooled shields (VCS) integrated with para-ortho hydrogen (P-O) conversion is proposed for long-term storage of liquid hydrogen. High-performance thermal insulation is realized by minimizing the thermal losses via the VDMLI design and fully recovering the cold energy released from the sensible heat and P-O conversion of the vented gas. Effects of different design considerations on the thermal insulation performance are studied. The results show that the maximum reduction of the heat leak with multiple VCSs can reach 79.9% compared to that without VCS. The heat leak with one VCS is reduced by 61.1%, and further reduced by 11.6% after adding catalysts. It is found that the deterioration of the insulation performance has an almost linear relationship with catalytic efficiency. A unified criterion with relative optimization efficiency is finally proposed to evaluate the improvement of the VCS number.     

含二氧化硅气凝胶和相变材料三层玻璃窗热性能分析

为了研究含二氧化硅气凝胶和相变材料三层玻璃窗对严寒地区建筑能耗的影响,建立了相变材料层与其他透明壁层结合发生的传热数值模型。分析了含二氧化硅气凝胶和相变材料三层玻璃窗在不同二氧化硅气凝胶厚度、导热系数和不同保温材料下的动态热调节性能,得到了含二氧化硅气凝胶和相变材料三层玻璃窗内表面热流密度和液相率随时间的变化规律。结果表明:随着二氧化硅气凝胶厚度增加,总传热量降低和液相率增加,当二氧化硅气凝胶厚度为20～30 mm时,可以实现有效的利用太阳能;随着二氧化硅气凝胶导热系数增加,总传热量升高和液相率降低;当二氧化硅气凝胶的导热系数从0.022降低到0.014 W/(m·K)时,最大液相率从0.83增加到1.00。二氧化硅作为保温层比相变材料作为保温层具有更好的保温隔热作用。     

Comparative performance investigation of integrated collector‐storage solar water heaters with various heat loss reduction strategies

A detailed comparative assessment is reported on the thermal performance of integrated collector‐storage (ICS) solar water heaters with various strategies for reducing top heat losses. The objective of this investigation is to assess and compare heat loss reduction strategies. The shape of ICS solar water heater considered in present investigation is rectangular. The thermal performance of the solar water heater is evaluated and analyzed for the following cases: (1) single glass cover without night insulation; (2) single glass cover with night insulation; (3) double glass cover without night insulation; (4) transparent insulation with single glass cover; and (5) insulating baffle plate with single glass cover. Energy balances are developed for each case and solved using a finite difference technique. The numerical assessment of the system performance is performed for a typical July day in Toronto. Each strategy is observed to be beneficial, reducing top heat losses, and improving system performance. The greatest performance enhancements are observed for the water heater with a single glass cover and night insulation and for the system with a double glass cover and without night insulation. Copyright © 2010 John Wiley & Sons, Ltd.