Liquid Organic Hydrogen Carrier Systems Research Articles

Pt/Al2O3 as efficient catalyst for the dehydrogenation of Dodecahydro-N-ethylcarbazole

The use of dodecahydro-N-ethylcarbazole in hydrogen storage for liquid organic hydrogen carrier systems holds potential for achieving large-scale application. In order to investigate the relationship between dodecahydro-N-ethylcarbazole dehydrogenation performance and Pt particles size, a series of monometallic Pt/Al2O3 catalysts with different Pt particles size from 0.70 nm to 5.12 nm were controlled synthesized by a simple impregnation method. The obtained catalysts are systematically characterized via XRD, 27Al MAS NMR, SEM-EDS, TEM, N2-adsorption, CO-IR, H2-TPR and NH3-TPD analyses, which provide essential micro-structure of these catalysts. The dehydrogenation of dodecahydro-N-ethylcarbazole over Pt/Al2O3 is a typical consecutive reaction, which follows a reaction sequence of dodecahydro-N-ethylcarbazole → octahydro-N-ethylcarbazole → tetrahydro-N-ethylcarbazole → N-ethylcarbazole. These dehydrogenation steps are quite sensitive to the Pt particle size. Large Pt particle can greatly enhance the reaction rates in octahydro-N-ethylcarbazole → tetrahydro-N-ethylcarbazole and tetrahydro-N-ethylcarbazole → N-ethylcarbazole steps. However, these two steps are difficult to take place in small Pt particles. The high performance of large Pt particle in dehydrogenation can be ascribed to its highly exposed (111) crystal face. The optimized catalyst Pt5.0/γ-Al2O3 with Pt average size of 4.63 nm demonstrated exceptional performance in dodecahydro-N-ethylcarbazole dehydrogenation at 180 °C and 101 kPa, and the dodecahydro-N-ethylcarbazole conversion of 100 %, N-ethylcarbazole selectivity of 96.44 % and dehydrogenation efficiency of 98.73 % can be achieved. These results provide valuable insights for the development of efficient metal-based catalysts for liquid organic hydrogen carriers hydrogen storage system.

Benzyl-methylbenzyl-benzene: Improving hydrogen storage and release performance of dibenzyltoluene based liquid organic hydrogen carrier

Liquid organic hydrogen carrier (LOHC) technology enables the safe, easy, and cost-effective storage and transportation of large quantities of hydrogen using inexpensive and mass-produced compounds. The LOHC materials play a crucial role in hydrogen storage capacity, reaction kinetics, reaction temperature, and reversibility. However, the development and optimization of LOHC materials is limited due to using of mass-produced materials for bulk hydrogen logistics. Herein, we propose a molecular engineering approach to overcome the limitations of commercial dibenzyltoluene (DBT)-based LOHC systems, considered one of the most promising LOHC materials based on the heat transfer oil, Marlotherm SH (MSH), owing to its superior physical properties (wide liquid range, and non-flammable properties), low price, and low toxicity. We devised a new chemical structure, benzyl-methylbenzyl-benzene (BMB), with highly improved dehydrogenation/hydrogenation performance achieved by rearranging the methyl group of DBT to overcome the limitations of slow reaction kinetics in terms of its chemical structure. The BMB exhibits a 150 % faster hydrogenation than MSH at 150 °C, and it releases 170 % more hydrogen compared to DBT at 270 °C. In addition, we analyzed the dehydrogenation/hydrogenation pathways according to the structures of DBT and BMB. Furthermore, we found that BMB (27 %) is inevitably generated in the MSH synthesis process alongside DBT (73 %). Based on this, we propose a streamlined and sustainable engineered method for improved MSH material manufacturing with a high BMB ratio (∼70 %). The scientific findings provide a fundamental understanding of DBT-based LOHC systems and new insights into the design of novel LOHC candidates.

Recent Advances in Reversible Liquid Organic Hydrogen Carrier Systems: From Hydrogen Carriers to Catalysts.

Liquid organic hydrogen carriers (LOHCs) have gained significant attention for large-scale hydrogen storage due to their remarkable gravimetric hydrogen storage capacity (HSC) and compatibility with existing oil and gas transportation networks for long-distance transport. However, the practical application of reversible LOHC systems has been constrained by the intrinsic thermodynamic properties of hydrogen carriers and the performances of associated catalysts in the (de)hydrogenation cycles. To overcome these challenges, thermodynamically favored carriers, high-performance catalysts, and catalytic procedures need to be developed. Here, significant advances in recent years have been summarized, primarily centered on regular LOHC systems catalyzed by homogeneous and heterogeneous catalysts, including dehydrogenative aromatization of cycloalkanes to arenes and N-heterocyclics to N-heteroarenes, as well as reverse hydrogenation processes. Furthermore, with the development of metal complexes for dehydrogenative coupling, a new family of reversible LOHC systems based on alcohols is described that can release H2 under relatively mild conditions. Finally, views on the next steps and challenges in the field of LOHC technology are provided, emphasizing new resources for low-cost hydrogen carriers, high-performance catalysts, catalytic technologies, and application scenarios.

Revealing the Effects of Weak Surfactants on the Dynamics of Surface Fluctuations by Surface Light Scattering.

Surfactant monolayers at liquid interfaces induce a viscoelastic behavior that influences the dynamics of surface fluctuations probed by surface light scattering (SLS). Recent thermophysical property research on viscosity and interfacial tension of liquid organic hydrogen carrier (LOHC) systems based on diphenylmethane suggested that such viscoelastic effects may also be present here, although not being expected a priori. To prove the hypothesis that the LOHC intermediate cyclohexylphenylmethane (H6-DPM) can induce a surfactant-like behavior, binary mixtures of diphenylmethane (H0-DPM) or dicyclohexylmethane (H12-DPM) with small amounts of H6-DPM were studied by SLS in combination with conventional viscometry and tensiometry and molecular dynamics simulations between (303 and 473) K. Only in mixtures with H0-DPM which has a slightly larger surface tension than H6-DPM, the presence of the latter compound causes a significant effect on the dynamics of surface fluctuations, especially on their damping. In analogy to the concentration-dependent behavior observed for a monolayer of a highly amphiphilic ionic surfactant on the surface of water at ambient temperature, the orientation of H6-DPM molecules with respect to the surface appears to change from a preferentially perpendicular to a parallel alignment with increasing temperature. This demonstrates that viscoelastic effects including accompanied surface orientation effects can be resolved by SLS even for weakly asymmetric surface-active molecules such as H6-DPM in its diluted mixtures with very similar species.

Exploring the potential of liquid organic hydrogen carrier (LOHC) system for efficient hydrogen storage and Transport: A Techno-Economic and energy analysis perspective

Despite its potential as an environmentally clean fuel and energy source, hydrogen storage and utilization has been significantly hampered by its extremely low volumetric density (0.08988 g/L at 1 atm), making it inefficient to store and transport. Therefore, liquid organic hydrogen carrier (LOHC) systems are being recently investigated as potential alternatives for hydrogen storage and transport. However, as a budding research area, the selection of a suitable LOHC, its deployment in hydrogen fuel stations, and its economic viability are not well established. Therefore, this study proposes a comprehensive investigation of four different LOHCs [Methylcyclohexane (MCH), Dibenzyltoluene (DBT), N-ethylcarbazole (NEC) and Naphthalene (NAP)] via Aspen HYSYS simulations. The LOHCs were compared and contrasted using their physiochemical properties, techno-economic analysis and heat network integration. The techno-economic analysis revealed that NAP-based hydrogen storage has the lowest cost among the LOHC options, while NEC shows the highest cost. However, when considering the breakeven point, the order changes to DBT, MCH, NAP, and NEC with 3, 3.8, 5.1 and 5.9, respectively. This result is attributed to the different hydrogen uptakes of the LOHCs, resulting in a longer breakeven period for NEC. Internal rate of return and net present value analysis also demonstrated the superior economic feasibility of the proposed systems. In terms of heat integration, the DBT process outperformed the other LOHCs as the most heat-efficient process with 80 % utility reduction, while the NEC process exhibited the lowest heat integration potential of 66.7 % utility reduction. Combining these findings with the physiochemical properties of the LOHCs, DBT emerges as the most attractive due to its favorable performance across multiple categories, such as toxicities, prices, energy consumptions, and material handling, using a spiderweb diagram.

Explosion risk assessment of a liquid organic hydrogen carrier system by using toluene–methylcyclohexane on varying hydrogen storage scenarios

The effects of phase state, delayed ignition time, mixing ratio, addition of hydrogen, and stoichiometric ratio on the explosion risk of toluene–methylcyclohexane (MCH) mixtures was investigated. Our findings indicated that the addition of 10% hydrogen to the toluene–MCH mixture exhibited a highest explosion risk, compared to other operating conditions. Gaseous toluene–MCH mixtures had a higher explosion risk than did liquid droplets of these mixtures. Of the toluene–MCH mixtures prepared in this study, that with a mass ratio of 7:3 had the highest explosion risk. Although the explosion intensities of the toluene–MCH mixtures were higher than those of their individual components, their explosion sensitivity was lower than that of MCH alone. Toluene had the lowest explosion risk. Toluene or MCH droplets can produce high-intensity explosions even in an oxygen-lean environment. These results indicate that the physical and chemical properties (and thus the combustion performance) of toluene–MCH mixtures are substantially affected by the mixing ratio and operating conditions. Overall, explosion prevention and control measures must be carefully considered when handling toluene–MCH mixtures for various hydrogen storage scenario, such as heating, mixture, or hydrogenation.

A three-phase reactor assessment for the deployment of Liquid Organic Hydrogen Carriers (LOHCs): dybenzyltoluene and indoles mixture systems as case studies

As a result of the large increase in the production of renewable energies, energy storage and energy carrier systems are required to meet the most ambitious objectives. In this area, hydrogen stands out as one of the most powerful tools. However, its low volumetric energy density and its challenging storage conditions lead to the search for new forms of storage. Liquid organic hydrogen carriers (LOHCs) are positioned as a promising option to store hydrogen using a catalytic reversible reaction at moderate temperature. Notwithstanding, although reactor technology is the core section of the LOHC process, it has not been assessed yet. Therefore, in this work, a three-phase reactor analysis is performed including mass, heat, and momentum phenomena along with kinetics. In particular, the two most important reactors for three-phase reactions are evaluated, trickle bed and slurry. And two of the most attractive LOHCs systems, dybenzyltoluene and a mixture composed of 1,2-dimethylindole and 7-ethylindole, are considered. The influence of the operating and design variables was studied. The results show that, for hydrogenation slurry reactors, a first region may be formed where gas–liquid is the main resistance (60%–95%). It eventually ends up with a second one where kinetics becomes the controlling step. At this point, a better catalyst use is expected for the first region. Alternatively, trickle bed hydrogenation reactors are largely controlled by mass transfer over almost the whole reactor length. If the dehydrogenation process is assessed, kinetics resistance is predominant. Surrogate models are developed to optimize the reactor performance and to include the full reactor operation in futures process design analysis allowing for an effective deployment of LOHCs systems.

Review on the thermal neutrality of application-oriented liquid organic hydrogen carrier for hydrogen energy storage and delivery

The depletion and overuse of fossil fuels present formidable challenge to energy supply system and environment. The human society is in great need of clean, renewable and sustainable energy which can guarantee the long-term utilization without leading to escalation of greenhouse effect. Hydrogen, as an extraordinary secondary energy, is capable of realizing the target of environmental protection and transferring the intermittent primary energy to the application terminal, while its nature of low volumetric energy density and volatility need suitable storage method and proper carrier. In this context, liquid organic hydrogen carrier (LOHC), among a series of storage methods such as compressed and liquefied hydrogen, provokes a considerable amount of research interest, since it is proven to be a suitable carrier for hydrogen with safety and stability. However, the dehydrogenation of hydrogen-rich LOHC materials is an endothermic process and needs large energy consumption, which hampers the scale up of the LOHC system. The heat issue is thus essential to be addressed for fulfilling the potential of LOHC. In this work, several strategies of heat intensification and management for LOHC system, including the microwave irradiation, circulation of exhaust heat and direct LOHC fuel cell, are summarized and analyzed to provide suggestions and directions for future research.

Imidazolium-Based Anion Exchange Membranes for Electrochemically Converted Liquid Organic Hydrogen Carrier

Liquid organic hydrogen carrier (LOHC) is a technology that uses renewable energy for hydrogen transportation, storage and utilization. LOHC have advantages that can store and utilize hydrogen rapidly in the lack of transportation infrastructure. A membrane-based LOHC system is a promising technology due to the dynamic operation using electrochemistry. Anion exchange membranes are widely used as electrolyte for electrochemical devices. The performance of LOHC could be determined by the properties of anion exchange membranes. Thus, high anion conducting ionomers must be developed for the superior conversion rates on the electrochemical reduction of liquid toluene to methylcyclohexane. In this study, anion exchangeable polymers containing imidazolium salt as anion-conducting group were synthesized to achieve good conduction of hydroxide ions and their chemical stability. Anion exchange membranes were prepared by a pore-filling method using porous polyethylene substrate. The pore-filling anion exchange membranes were characterized in terms of ion conductivity, areal resistance, ion exchange capacity, water uptake, swelling ratio and mechanical strength. Acknowledgment This research was supported in part by the Korea Institute of Science and Technology (No. 2E31871) and by 2021 Green Convergence Professional Manpower Training Program of the Korea Environmental Industry and Technology Institute funded by the Ministry of Environment.

Hydrodeoxygenation of Oxygen-Containing Aromatic Plastic Wastes to Liquid Organic Hydrogen Carriers.

To address the global plastic pollution issues and the challenges of hydrogen storage and transportation, we report a system, based on the hydrodeoxygenation (HDO) of oxygen-containing aromatic plastic wastes, from which organic hydrogen carriers (LOHCs) can be derived. We developed a catalytic system comprised of Ru-ReOx /SiO2 +HZSM-5 for direct HDO of polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), and their mixtures, to cycloalkanes as LOHCs, with high yields up to 99 %, under mild reaction conditions. The theoretical hydrogen storage capacity reaches ca. 5.74 wt%. The reaction pathway involves depolymerization of PC into C15 aromatics and C15 monophenols by direct hydrogenolysis of the C-O bond between the benzene ring and ester group, and subsequent parallel hydrogenation of C15 aromatics and HDO of C15 monophenols. HDO of cyclic alcohol is the rate-determining step. The active site is Ru metallic nanoparticles with partially covered ReOx species. The excellent performance is attributed to the synergetic effect of oxophilic ReOx species and Ru metallic sites for C-O hydrogenolysis and hydrogenation, and the promotion effect of HZSM-5 for dehydration of cyclic alcohol. The highly efficient and stable dehydrogenation of cycloalkanes over Pt/γ-Al2 O3 confirms that HDO products can act as LOHCs.

Hydrodeoxygenation of Oxygen‐Containing Aromatic Plastic Wastes to Liquid Organic Hydrogen Carriers

AbstractTo address the global plastic pollution issues and the challenges of hydrogen storage and transportation, we report a system, based on the hydrodeoxygenation (HDO) of oxygen‐containing aromatic plastic wastes, from which organic hydrogen carriers (LOHCs) can be derived. We developed a catalytic system comprised of Ru‐ReOx/SiO2+HZSM‐5 for direct HDO of polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), and their mixtures, to cycloalkanes as LOHCs, with high yields up to 99 %, under mild reaction conditions. The theoretical hydrogen storage capacity reaches ca. 5.74 wt%. The reaction pathway involves depolymerization of PC into C15 aromatics and C15 monophenols by direct hydrogenolysis of the C−O bond between the benzene ring and ester group, and subsequent parallel hydrogenation of C15 aromatics and HDO of C15 monophenols. HDO of cyclic alcohol is the rate‐determining step. The active site is Ru metallic nanoparticles with partially covered ReOx species. The excellent performance is attributed to the synergetic effect of oxophilic ReOx species and Ru metallic sites for C−O hydrogenolysis and hydrogenation, and the promotion effect of HZSM‐5 for dehydration of cyclic alcohol. The highly efficient and stable dehydrogenation of cycloalkanes over Pt/γ‐Al2O3 confirms that HDO products can act as LOHCs.

A-site effects of titanate-perovskite (ATiO3)-based catalysts on dehydrogenation of N-heterocyclic molecules

Dehydrogenation reactions in liquid organic hydrogen carrier (LOHC) systems present significant challenges, particularly when aiming for low-temperature operations while ensuring that no hydrogen remains in the substrate molecules. Enhancing catalytic performance requires modifying the adsorption behavior of the reactants and products during dehydrogenation. Perovskites have emerged as promising catalyst supports because of their ability to modify the surface chemical properties by manipulating the cations present at the A- and B- sites. This study investigated the effects of A-site cations (Ca, Sr, and Ba) in titanate-type perovskite (ATiO3)—a prototypical perovskite—on the dehydrogenation activity in LOHC systems. Remarkably, Pd/SrTiO3 exhibited outstanding performance by completely converting octahydro-N-methylindole to N-methylindole and releasing 5.76 wt% hydrogen over 8 h. Additionally, it dehydrogenated dodecahydro-N-ethylcarbazole to N-ethylcarbazole with a hydrogen release of 5.70 wt%. Furthermore, the catalyst demonstrated a stable performance after recycling tests for three times without degradation or loss of activity. The chemical state of the catalyst surface was characterized through X-ray photoelectron spectroscopy, H2-temperature programmed reduction, and chemisorption using NH3, CO2, and H2. The results revealed that the exceptional dehydrogenation activity of Pd/SrTiO3 is due to the presence of suitable surface oxygen vacancies and abundant acid–base sites.

Operational experience with a liquid organic hydrogen carrier (LOHC) system for bidirectional storage of electrical energy over 725 h

Hydrogen storage in liquid organic hydrogen carriers (LOHC) enables the utilization of renewable energy in different sectors. In this paper, we describe the operational experience with one single LOHC system for bidirectional electrical energy storage at the kW scale. The system includes a reactor for the hydrogenation and dehydrogenation of LOHC, as well as a fuel cell and an electrolyzer based on polymer electrolyte membrane (PEM) technology. The LOHC used is the substance pair dibenzyltoluene/perhydro-dibenzyltoluene. For dehydrogenation, the upflow operation with common discharge of liquid and gaseous product was found to be the preferred mode of operation. For hydrogenation, it was shown that stable operation is possible also with fluctuating hydrogen production from the electrolyzer. After operating the reactor for 725 h in the hot state, i.e., at temperatures above 150∘C, samples of the catalyst and LOHC were taken and analyzed. These showed no signs of serious degradation.

Electrochemically Activatable Liquid Organic Hydrogen Carriers and Their Applications.

Hydrogen has been chosen as an environmentally benign energy source to replace fossil-fuel-based energy systems. Since hydrogen is difficult to store and transport in its gaseous phase, thermochemical liquid organic hydrogen carriers (LOHCs) have been developed as one of the alternative technologies. However, the high temperature and pressure requirements of thermochemical LOHC systems result in huge energy waste and impracticality. This Perspective proposes electrochemical (EC)-LOHCs capable of more efficient, safer, and lower temperature and pressure hydrogen storage/utilization. To enable this technology, several EC-LOHC candidates such as isopropanol, phenolic compounds, and organic acids are described, and the latest research trends and design concepts of related homo/hetero-based electrocatalysts are discussed. In addition, we propose efficient fuel-cell-based systems that implement electrochemical (de)hydrogenation of EC-LOHCs and present prospects for relevant technologies.

Metal–support interface engineering of Ni catalysts for improved H2 storage performance: Grafting alkyltriethoxysilane onto commercial alumina

Tuning metal–support interface in supported Ni catalysts is a promising approach for overcoming the agglomeration of Ni particles and the low reducibility of Ni species. This study describes a facile two-step method to produce active Ni catalysts for the hydrogenation of benzyltoluene. In the first step, alkyltriethoxysilanes (CnTES, n = 1, 3, and 8) were grafted onto the surface of commercial Al2O3. The maximum Si/Al ratio of the prepared CnTES-on-Al2O3 materials was determined to be approximately 2.9 mol.%, which can vary depending on the surface properties of Al2O3. The second step was H2 reduction of the Ni precursor loaded on the CnTES-on-Al2O3 materials to remove alkyl substituents from the grafted CnTES and form Ni particles on the surface of silica grafted onto alumina (SGA). The hydrogenation performance of the obtained Ni/SGA_CnTES catalysts was improved with increasing Si/Al ratio owing to higher Ni dispersion and more abundant metallic Ni. The activity of the Ni/SGA_2.9CnTES (Si/Al = 2.9 mol.%) catalysts exhibited a volcano-shaped relationship with the length of the alkyl substituent of grafted CnTES, reaching the maximum for C3TES. Notably, Ni/SGA_2.9C3TES showed excellent ability for the adsorption of H2 and substrate, as well as high stability, resulting from the reduced agglomeration of Ni particles and the modulated metal–support interface. Therefore, the demonstrated synthesis approach can render Ni catalysts servable to promote the commercialization of liquid organic hydrogen carrier system.

Hydrogen flow rate control in a liquid organic hydrogen carrier batch reactor for hydrogen storage

Liquid Organic Hydrogen Carriers (LOHCs) feature a highly variable rate of hydrogen release if held at constant pressure and temperature, but in real-life applications hydrogen release must be controlled to match end-user demand. The aim of this paper is to provide an overall assessment of LOHC systems’ controllability, within a general framework regardless of the specific application field. Hydrogen discharge can be controlled through the reactor pressure and temperature; thus, a PI controller is introduced acting on three control variables independently: discharge pressure; thermal fluid inlet temperature; thermal fluid mass flow rate. A quantile analysis is performed on the uncontrolled hydrogen release: practical values of the energy-to-power ratios for LOHC systems are 2–6 h. A normalised release time is introduced to assess the efficiency of the control system. Temperature control leads to the best results, with an efficiency higher than 90% for the entire load range, while pressure control leads to satisfactory performance only at low loads. The mass flow rate control is the least effective, with efficiencies always below 80%. Sensitivity analysis highlights the temperature control strategy as the best fit to enhance controllability across the whole power range. Pressure control presents a more variable trend.

Highly dispersed Pt–MnOx nanoclusters for the promoted activity of mesoporous Pt–MnOx–Al2O3 in dehydrogenation of perhydro-benzyltoluene

Pt single atom is vulnerable to sintering under endothermic reaction conditions and sometimes shows low activity in the conversion of bulky molecules, e.g., dehydrogenation of perhydro-benzyltoluene (H12-BT) for the state-of-the-art liquid organic hydrogen carrier system. Such weakness has been tackled using various approaches including Pt nanoclustering with metal oxide(s). We herein describe the excellence of mesoporous Pt–MnOx–Al2O3 (mPtMnA) in H12-BT dehydrogenation, where solvent-deficient precipitation (SDP) is employed for catalyst preparation. When prepared at the Mn/Pt molar ratio of 0.33 and the ramp of 10 °C min−1 in H2 reduction, the catalyst (named mPt0.33MnA_r10) affords the best efficiency of 94 % H2 yield. This results from highly dispersed Pt–MnOx nanoclusters generated by the surface diffusion of Pt atoms to oxophilic Mn oxides distributed homogeneously on the surface of support. Consequently, this study demonstrates that the SDP method favors Pt nanoclustering with MnOx, which will greatly impact on dehydrogenation catalysis.

Future of hydrogen economy: simulation-based comparison of LOHC systems

Hydrogen is one of the key components in renewable energy systems. Its storage and transport, however, are challenging. The Liquid Organic Hydrogen Carrier (LOHC) technology is a possible solution for this issue. With suitable organic components, hydrogen can be stored in a chemically bound form which is safer and has a higher energy density than other solutions. Furthermore, the storage and transport of the LOHC component with high hydrogen content can be provided under normal environmental conditions. The LOHC process cycle involves a catalytic hydrogenation and dehydrogenation step where the LOHC component can be recovered and recycled. The paper reviews a few relevant studies regarding the possible LOHC compound pairs, the potential catalyst systems, and the necessary equipment. Then, the paper discusses a simulation study of three LOHC systems, determining suitable operating conditions and estimating costs. The toluene-methylcyclohexane system was found to be the most promising for LOHC application. Two energy integration opportunities were also examined. The first case study was based on separate hydrogenation and dehydrogenation sites, while the second was based on one site utilization. The results show a lower energy demand in the case of a toluene system, with a reduction of 70% in heating and 45% in cooling.Graphical

Burner-heated dehydrogenation of a liquid organic hydrogen carrier (LOHC) system

For a hydrogen-based economy, safe and efficient hydrogen storage is essential. Compared to other chemical hydrogen storage technologies, such as ammonia or methanol, liquid organic hydrogen carrier (LOHC) systems allow for a reversible storage of hydrogen while being easy to handle in a diesel-like manner. In our contribution, we describe for the first time the successful utilization of the exhaust gas enthalpy of a porous media burner to directly supply the dehydrogenation heat for a kW-scale dehydrogenation of the hydrogen-rich LOHC compound perhydro dibenzyltoluene (H18-DBT). Our setup demonstrates the dynamics of the dehydrogenation unit at a realized maximum hydrogen power of 3.9 kWth, based on the lower heating value of the released hydrogen. For the intended applications with fluctuating hydrogen demand, e.g. a hydrogen refueling station (HRS) or stationary heating in buildings, a dynamic hydrogen supply from LOHC is important. Methane, e.g. from a biogas plant, is utilized in our scenario as a fuel source for the burner. Hydrogen is released within 30 min after cold start of the system. The dehydrogenation unit exhibits a power density relative to the reactor volume of about 0.5 kWtherm l−1 based on the lower heating value of the hydrogen and a catalyst productivity of up to 0.65 gH2 gPt−1 min−1 for hydrogen release from H18-DBT. An analysis of the by-products and reaction intermediates shows low by-product formation (e.g. maximum 0.6 wt.-% for high boilers and 0.9 wt.- % for low boilers) and uniform distribution of intermediates after the reaction. Thus, a relatively homogeneous temperature distribution and a uniform LOHC flow in the reaction zone can be assumed. Our findings illustrate the dynamics (heating rates of about 10 K min−1) and performance of direct heating of a release unit with a burner and represent a significant step towards LOHC-based hydrogen provisioning systems at technically relevant scales.

Thermophysical properties of the liquid organic hydrogen carrier system based on diphenylmethane with the byproducts fluorene or perhydrofluorene

Fluorene (H0-F) and perhydrofluorene (H12-F) represent process-related byproducts formed by a dehydrocyclization step in the liquid organic hydrogen carrier (LOHC) system based on diphenylmethane (H0-DPM) and dicyclohexylmethane (H12-DPM). The influence of these byproducts on the liquid viscosity, surface tension, and liquid density of the DPM-based system was experimentally determined by studying three dehydrogenated binary mixtures with H0-F mole fractions of 0.05, 0.10, and 0.20 as well as one hydrogenated binary mixture with an H12-F mole fraction of 0.10 close to 0.1 MPa from (283–573) K. The densities increase with increasing share of H0-F or H12-F by around 1% per added byproduct mole fraction of 0.1. For the surface tension, an increase relative to the values of H0-DPM or H12-DPM by up to 6% is found. The addition of H0-F to H0-DPM or H12-F to H12-DPM yields a relative increase in viscosity by up to 9% at the lowest temperature studied.