Evaluation of a thermally-driven metal-hydride-based hydrogen compressor

Currently, the hydrogen storage method used aboard fuel cell electric vehicles utilizes pressures up to 70 MPa. Attaining such high pressures requires mechanical gas compression or hydrogen liquefaction followed by heating to form a high-pressure gas, and these processes add to the cost and reduce the energy efficiency of a hydrogen fueling system. In previous work we have evaluated the use of high-pressure electrolysis, in which hydrogen is generated from water and the electrolyzer boosts the hydrogen pressure to values from 13 to 45 MPa. While electrolytic compression is a novel and energy efficient method to produce high-pressure hydrogen, it has several limitations at present and will require more development work. Another concept is to use hydrogen absorbing alloys that form metal hydrides, in combination with a heat engine (hot and cold reservoirs), to drive a cyclic process in which hydrogen gas is absorbed and desorbed to compress hydrogen. Furthermore, by using a thermally-driven compressor, the hot and cold reservoirs can be obtained using renewable energy such as sunlight for heating together with ambient air or water for cooling. In this work we evaluated the thermodynamics and kinetics of a prototype metal hydride hydrogen compressor (MHHC) built for us by a research group in China. The compressor utilized a hydrogen input pressure of approximately 14 MPa, and, operating between an initial temperature of approximately 300 K and a final temperature of 400 K, a pressure of approximately 41 MPa was attained. In a series of experiments with those conditions the average compression ratio for a single-stage compression was approximately three. In the initial compression cycles, up to 300 g of hydrogen was compressed for each 100 K temperature cycle. The enthalpy of the metallic-alloy-hydriding reaction was found to be approximately 20.5 kJ per mole of H₂, determined by measuring the pressure composition isotherm at three temperatures and using a Van't Hoff plot. The thermodynamic efficiency of the compressor, as measured by the value of the compression work performed divided by the heat energy added and removed in one complete cycle, was determined via first and second law analyses. The Carnot efficiency was approximately 25%, the first law efficiency was approximately 3–5%, and the second law efficiency was approximately 12–20%, depending on the idealized compression cycle used to assign a value to the compression work, as well as other assumptions. These efficiencies compare favorably with values reported for other thermally-driven compressors.     

Hydrogen physisorption in high SSA microporous materials - A comparison between AX-21_33 and MOF-177 at cryogenic conditions

The two most promising materials for a hydrogen cryo-adsorption tank, activated carbon AX-21_33 and metal-organic framework MOF-177, have been investigated in the pressure range up to 2 MPa and at temperatures from 77 K to 125 K and at room temperature. The total hydrogen storage, including adsorbed hydrogen and gaseous hydrogen, has been determined for both samples. The results were evaluated with respect to the operating conditions of a tank system at cryogenic conditions, assuming a maximum tank pressure of 2 MPa and a minimum back pressure for the hydrogen consumer of 0.2 MPa. AX-21_33 shows a usable capacity of 3.5 wt.% in the case of isothermal operation at 77 K and 5.6 wt.%, if the tank is loaded at 77 K and the temperature is increased by 40 K during unloading. Under the same conditions, MOF-177 has a usable capacity of 6.1 wt.% and 7.4 wt.%, respectively. The results show that the heat of adsorption has a high impact on the amount of hydrogen remaining in a tank after unloading and that the heat management plays a crucial role for the design of a cryogenic tank system.     

Solubility of hydrogen in ice Ih at pressures up to 8 MPa

Experimental studies of the solubility of hydrogen in ice Ih (usual low-pressure ice) at temperature −1 to −2 °C and pressures up to 8 MPa were carried out. At a pressure equal to 1.90 and 8.04 MPa, hydrogen solubility in the ice was found to be 0.15 and 1.32 cm³/g, respectively (hydrogen volume was reduced to the normal conditions).     

Effect of hydraulic oil compressibility on the volumetric efficiency of a diaphragm compressor for hydrogen refueling stations

The low volumetric efficiency of the diaphragm compressor under hydrogen refueling process, which hereby results in poor energy efficiency and high cost of hydrogen applications, should be paid attention to. This paper presents theoretical analysis and experimental investigation of the factors affecting the volumetric efficiency of the diaphragm compressor for hydrogen refueling process, focusing on the influence of hydraulic oil compressibility. A mathematical model was established to estimate the volumetric efficiency of diaphragm compressors, in which the effects of clearance volume, superheating of suction gas and pressure loss were taken into account and the emphasis was focused on the compressibility of hydraulic oil. A test rig was built to validate the theoretical model and further experimental investigations were carried out to identify the factors influencing the oil compressibility and hereby the volumetric efficiency. The volumetric efficiency was measured and compared under varied oil compressibility conditions by varying elastic modulus, oil overflow pressure and oil volume. The results indicated that the measured volumetric efficiency agrees well with the calculated value. The compression and expansion of hydraulic oil have a dominant influence on the volumetric efficiency, resulting in a loss of 37% of volumetric efficiency as compared to 2.4%, 18% and 1%, respectively for losses associated with clearance volume, superheating of suction gas and pressure loss, for a diagram compressor under refueling conditions with suction pressure of 30 MPa and discharge pressure of 90 MPa. The volumetric efficiency reduced rapidly with the increased oil overflow pressure, at a rate of 5% decrease with every 10 MPa rise in oil overflow pressure. As the oil volume increased by 100% of the stroke volume, the volumetric efficiency droped by 5.5%.     

Mixing and warming of cryogenic hydrogen releases

Laboratory measurements were made on the concentration and temperature fields of cryogenic hydrogen jets. Images of spontaneous Raman scattering from a pulsed planar laser sheet were used to measure the concentration and temperature fields from varied releases. Jets with up to 5 bar pressure, with near-liquid temperatures at the release point, were characterized in this work. This data is relevant for characterizing unintended leaks from piping connected to cryogenic hydrogen storage tanks, such as might be encountered at a hydrogen fuel cell vehicle fueling station. The average centerline mass fraction was observed to decay at a rate similar to room temperature hydrogen jets, while the half-width of the Gaussian profiles of mass fraction were observed to spread more slowly than for room temperature hydrogen. This suggests that the mixing and models for cryogenic hydrogen may be different than for room temperature hydrogen. Results from this work were also compared to a one-dimensional (streamwise) model. Good agreement was seen in terms of temperature and mass fraction. In subsequent work, a validated version of this model will be exercised to quantitatively assess the risk at hydrogen fueling stations with cryogenic hydrogen on-site.     

Demonstration of a single-stage metal hydride hydrogen compressor composed of BCC V40TiCr alloy

In this study, demonstration of a one-stage metal hydride hydrogen compressor (MH compressor) by using a BCC alloy was performed. It was estimated that V₄₀Ti₂₂Cr₃₈ could compress approximately 1.6 wt% of hydrogen from 1.0 to 10 MPa in 20–140 °C temperature range from equilibrium theory via pressure-composition-isotherm measurements. For demonstration of an actual MH compressor, a kg-scale experimental system was set up; V₄₀Ti₂₂Cr₃₈ (1.4 kg) was introduced into a 1-inch cylindrical vessel with a heat-medium flow tube outside. As a result, 1.0 MPa of hydrogen can be compressed into the hydrogen cylinder at >10 MPa by hydrogen absorption at 10 °C and desorption at 160 °C for 30 min each (1 cycle/h) to achieve a compression rate of 0.23 Nm³/h and indicate the potential of the practical MH compressors by using BCC alloy.     

Design,development, construction and operation of a novel metal hydride compressor

Metal Hydride Compressors (MHC) is a promising technology for thermal compression of hydrogen. Besides the absence of a necessity for significant mechanical or electrical energy input, this type of compressor has the advantage that no moving parts are involved. A brief review on the reported experimental set ups of metal hydride compressors is carried out and compared to the metal hydride compressor developed and constructed by HYSTORE Technologies Ltd in Cyprus. The compressor built by HYSTORE consists of 6 stages using AB₂ and AB₅ – type metal hydride alloys. The MHC is operated between 10 C and 80 °C, which is a temperature range that can be supplied by solar thermal collectors. Furthermore, the experimental results showed, that even lower temperatures of 17 C are sufficient thus reducing the demand for cooling capacity. During the operation, the compressor achieved stable compression of hydrogen from 7 bar more than 220 bar. The specific productivity of the compressor achieved values up to 67.2 l_H2 kg^?1 h^?1.     

Hydrogen adsorption with micro-structure deformation in nanoporous carbon under ultra-high pressure

Hydrogen adsorption with micro-structure deformation under ultra-high pressure in nanoporous carbon (NPC) has been studied. This study proposed a new ultra-high pressurization (UHP) method. It produces a gas atmosphere of over 100 MPa utilizing the cold isostatic pressing (CIP) device. NPC materials were pressurized under a hydrogen atmosphere at 100–400 MPa. NPC fabricated from rice husk via KOH activation possesses a high surface area achieving 3500 cm²/g and a micropore volume of over 2.0 cm³/g. The maximum hydrogen uptake reached 3.2 wt% (77 K, 0.1 MPa). Then, NPC materials were treated with 100–400 MPa pressurization in the hydrogen atmosphere. NPC showed a preferred deformation behavior of 1.1–1.2 nm after pressurization, which is the optimum size for hydrogen adsorption. Additionally, the maximum micropore volume increased to 2.51 cm³/g. However, the hydrogen uptake shows a slight decrease to 3.0 wt%. The isosteric heat of adsorption maintained at 8.0–10.3 kJ/mol.     

Compressor speed control design using PID controller in hydrogen compression and transfer system

Hydrogen is an energy carrier which can be processed by high pressure compressor and they can be transported, stored and converted to electricity for later use. This paper proposes a hydrogen compression model development and modeling of hydrogen transportation between two tanks using MATLAB software version 22. The proposed model provides amount of hydrogen required in volumes (m³) and compressor power required in (KW) for compressor speed of 500 rad/s, 1000 rad/s and 1500 rad/s. This model provides hydrogen volume of 1 m³ and 10 KW compressor power requirement at 500 rad/s compressor speed. For compressor speed of 1000 rad/s, the proposed model provides hydrogen volume of 10 m³and 20 KW compressor power requirements and for 1500 rad/s this model provides volume of 30 m³and 30 KW compressor power requirements which indicates that the increase in compressor speed increases hydrogen volume generated and increase the power requirement also. For maintaining compressor speed at desired value, a PID (Proportional + Integral + Derivative) controller has been designed and the results were compared with Proportional (P), PI (Proportional + Integral), and PD (Proportional + Derivative) controllers. PID controller performance can be measured using the parameters delay time and settling time. Low values of settling time and delay time indicate the better performance of PID controller. P controller achieves the desired compressor speed with delay time of 228 ms; settling time of 1250 s. PI controller achieves the desired compressor speed with delay time of 210 ms, settling time of 1210 s. PD controller achieves the desired compressor speed with delay time of 185 ms, settling time of 1280 s. PID controller provides better speed regulation with low delay time of 110 ms and settling time of 1120 s when compared with P, PI, PD controllers. From the simulation results it is observed that PID controller can be a good option for slow process like hydrogen gas flow through pipeline for effective speed regulation.     

High pressure polymer electrolyte water electrolysis: Test bench development and electrochemical analysis

A test bench for a polymer electrolyte water electrolysis (PEWE) cell for high pressure operation of up to 100 bar in differential and balanced pressure mode is described. Important aspects referring to the design, safety and operability of the test bench and the design of a small scale electrolysis cell are described. The electrolyzer cell comprises a special compression mechanism which allows accommodating porous transport layers of different thickness and setting of the compression pressure independent of the clamping pressure. In order to analyze the electrochemical results with respect to the overpotentials, a power source with integrated high frequency resistance (HFR) as well as electrochemical impedance spectroscopy (EIS) measurement capabilities is implemented. The versatility of the test environment is demonstrated by comparing the DC, HFR and EIS data as a function of operating pressure, temperature (up to 70 °C) and current density (up to 4 A/cm²). With respect to pressurized operation of PEWE cells, only the differential pressure mode (hydrogen pressurized) shows the expected isothermal compression behavior, for balanced pressure operation a different characteristic is observed.     

High-pressure torsion of TiFe intermetallics for activation of hydrogen storage at room temperature with heterogeneous nanostructure

TiFe is a potential candidate for the stationary hydrogen storage systems, but it requires initial activation to absorb hydrogen. This study shows that TiFe processed by high-pressure torsion (HPT) absorbs and desorbs 1.7 wt.% hydrogen at room temperature without activation. The absorption pressure decreases from 2 MPa in the first hydrogenation cycle to 0.7 MPa in the latter cycles. The HPT-processed TiFe exhibits heterogeneous microstructures composed of nanograins, coarse-grains, amorphous-like phases and disordered phases with a high hardness of ∼1050 Hv.     

R32吸气状态对变频压缩机效率的影响

制冷剂R32作为R22热门过渡替代制冷剂,运行排气温度高严重影响压缩机长时间运行的可靠性,湿压缩方法可以降低压缩机的排气温度,但也降低了压缩机的效率。通过实验对比研究在定压比变频和定频变压比工况下,不同吸气状态对滚动转子式压缩机效率的影响,得出等熵压缩效率和容积效率与吸气状态的变化关系。实验结果表明:吸气过热时,均能保持较高的等熵压缩效率和容积效率,过热度对其影响不大,吸气带液时压缩机效率的变化趋势与吸气过热时不同,应区分开;相对x=1,x=0.9时等熵压缩效率和容积效率分别降低约7%和5%,总体降幅较小。定频下,压比越大,压缩机效率降低幅度越大,定压下,频率越高,降低幅度越小;等熵压缩效率和综合效率系数的变化趋势相同。     

Evaluation of a BCC alloy as metal hydride compressor via 100 MPa-class high-pressure hydrogen apparatus

In the study presented here, an apparatus that correctly measured pressure–composition isotherms (PCi) at high pressures (up to 100 MPa) and temperatures (up to 200 °C) was developed. The PCi characteristics of a vanadium–titanium–chromium alloy at high pressure and temperature were examined with the apparatus to develop a metal hydride (MH) compressor. It was revealed that it is possible to use a 40 V20Ti40Cr (at%) alloy with a heat source below 200 °C for hydrogen compression in the approximate range of 2.1–30.0 MPa. The compressed content reached approximately 1.8 wt%, which is almost the same as the reversible hydrogen capacity at 20 °C.     

全球加氢站产业、技术及标准进展综述

以美国、欧洲、日本、中国的加氢站作为考察对象,就产业投资运营、主要设备商、相关标准进行梳理,结果表明：在加氢站投资及运营管理方面,美国、欧洲、日本具有较为成熟的经验;在氢增压、储存、加注等技术方面,德国、日本保持领先地位。在诸多氢气和液氢的技术领域,美国保持领先地位;在一些细分技术领域,英国、法国、挪威、俄罗斯具有优势;在加氢站标准方面,美国、日本具有较为完善的标准体系。中国已解决70 MPa氢气增压、加注、储存等领域的部分技术难题,但与其他国家相比,离子液式氢压缩机、液氢泵、液氢储罐、液氢加氢枪等产品的研发仍需持续推进。     

炼厂氢气资源优化浅谈

随着炼厂氢气耗量的不断增加,需要选用低廉的制氢原料,采用合理的制氢工艺技术,满足炼厂氢气需求.比较变压吸附、膜分离、深冷分离三种氢气提纯分离技术,对加氢等装置尾气中低浓度氢进行回收利用,能够合理利用氢气资源,有效降低生产成本.某炼厂选用焦化干气制氢后,与轻油制氢相比,原料成本下降,氢气纯度提高.根据各用氢装置的用氢压力、用氢量进行匹配,采用从高压到低压的一次通过式流程,只设置一台新氢压缩机,氢气逐级利用.不仅提高了氧气资源利用率,而且有效降低了炼厂综合能耗.采用PRISM膜分离器,从高达10MPa压力的冷高压分离器排放尾气中回收提纯氧气,回收提纯的氢气再回到新氢压缩机的三级人口升压后循环使用.废氧进行胺液脱H2S处理后,采用PSA技术进行废氢回收利用,PSA副产品解吸气升压后作为制氢装置的原料,节约了生产成本.     

Performance investigation of a multi-stage sorption hydrogen compressor

Among several thermodynamic applications of metal hydrides, sorption hydrogen compressor (SHC) is more attractive for real-time application due to ease of construction and operation. In the present study, a four-stage sorption hydrogen compressor is proposed with detailed working principle for the compression output of >500 bar pressure. By adopting the screening methodology, four metal hydrides, i.e. La_0.9Ce_0.1Ni₅, Ti_0.99Zr_0.01V_0.43Fe_0.99Cr_0.05Mn_1.5, MmNi₅ and TiCrMn are selected for stages – 1, 2, 3 and 4 respectively with the supply temperature of 298 K and discharge temperatures of 373 K. The performance of sorption hydrogen compressor is estimated through finite volume approach and thermodynamic simulation in terms of variations in metal hydride bed pressure, temperature, hydrogen transmission, compressor work and efficiency. The numerical model is validated with experimentally measured metal hydride bed temperature and hydrogen concentration for single-stage hydrogen compressor, which are observed to be in good agreement. The cycle time of multi-stage SHC is predicted to be ~100 min with the maximum compression ratio of 73 with an overall efficiency of 10.62% employing 0.5 kg of each alloy and supply pressure of 9.5 bar. It is also observed that the discharge temperature greatly influences system performance. The dynamic performance of the system is also estimated with the implementation of simulation generated property data and observed that the performance parameters increased with the progression of hydrogen transmission.     

Hydrogen adsorption behavior of graphene above critical temperature

We evaluate the hydrogen adsorption behavior of the pristine single-layer graphene sheets in a powder form, which was performed at cryogenic and room temperatures. Only 0.4 wt.% and <0.2 wt.% hydrogen uptake was obtained at 77 K under 100 kPa and room temperature under 6 MPa, respectively, for the pristine graphene sample with a BET specific surface area of 156 m² g⁻¹. Structure/property investigations suggest that the low specific surface area and weak binding to hydrogen should be responsible for the small gravimetric uptake of pristine graphene sample.     

Assessment of thermal performance improvement of GT-MHR by waste heat utilization in power generation and hydrogen production

The Gas Turbine Modular Helium Reactor (GT-MHR) uses two compression stages to compress the helium and a pre-cooler and an intercooler to reduce the compressors inlet temperature, that dissipate around 308.36 MW_th at the design operational conditions. This dissipated thermal energy can be used as an energy source to produce hydrogen. An energy analysis is conducted for a proposed system that includes GT-MHR combined with Organic Rankine Cycle (GT-MHR/ORC) and a Proton Exchange Membrane (PEM) electrolyzer (GT-MHR/ORC-PEM) for hydrogen production. The optimum operating parameters values of the new cycle are obtained using the Engineering Equation Solver (EES) software. Thermal efficiency has been improved from 48.6% for the simple GT-MHR cycle to 49.8% for the new combined (GT-MHR/ORC-PEM) cycle including hydrogen production at a rate of 0.0644 kg/s at the same operating conditions. However, the thermal efficiency for the combined GT-MHR/ORC was higher and reaches 50.68%. Moreover, a parametric study is carried out over a wide range of some operating conditions such as turbine inlet temperature, Compressor pressure ratio and compressor inlet temperature to investigate their effect on the new cycle performance. Results revealed that increasing the low-pressure compressor inlet temperature increases the amount of hydrogen produced while decreasing thermal efficiencies for the three cycles. Furthermore, increasing compressor pressure ratio reduces the mass flow rate of hydrogen produced util it reaches a minimum value then it starts to increase slightly, on the contrary, an opposite relationship is observed between thermal efficiencies and compressor pressure ratio. Moreover, at low compressor pressure ratio, the rate of hydrogen produced increases with increasing turbine inlet temperature; however, it decreases by increasing the turbine inlet temperature at high compressor pressure ratio. Nevertheless, a direct correlation is noticed between thermal efficiencies and turbine inlet temperature.     

Scale-up activation of carbon fibres for hydrogen storage

In a previous study, we investigated, at a laboratory scale, the chemical activation of two different carbon fibres (CF), their porosity characterization, and their optimization for hydrogen storage [1]. In the present work, this study is extended to: (i) a larger range of KOH activated carbon fibres, (ii) a larger range of hydrogen adsorption measurements at different temperatures and pressures (i.e. at room temperature, up to 20 MPa, and at 77 K, up to 4 MPa), and (iii) a scaling-up activation approach in which the obtained activated carbon fibres (ACF) are compared with those from laboratory-scale activation. The prepared samples cover a large range of porosities, which is found to govern their ability for hydrogen adsorption. The hydrogen uptake capacities of all the prepared samples have been analysed both in volumetric and in gravimetric bases. Thus, maximum adsorption capacities of around 5 wt% are obtained at 77 K, and 1.1 wt% at room temperature, respectively. The packing densities of the materials have been measured, turning out to play an important role in order to estimate the total storage capacity of a tank volume. Maximum values of 17.4 g l⁻¹ at 298 K, and 38.6 g l⁻¹ at 77 K were obtained.