Purity of hydrogen released from the Liquid Organic Hydrogen Carrier compound perhydro dibenzyltoluene by catalytic dehydrogenation

While Liquid Organic Hydrogen Carrier (LOHC) systems offer a very promising way of infrastructure-compatible storage and transport of hydrogen, the hydrogen quality released from charged LOHC compounds by catalytic dehydrogenation has been a surprisingly rarely discussed topic to date. This contribution deals, therefore, with a detailed analysis of the hydrogen purity released from the hydrogen-rich Liquid Organic Hydrogen Carrier compound perhydro dibenzyltoluene (H18-DBT). We demonstrate, that high purity hydrogen (>99.999%) with carbon monoxide levels below 0.2 ppmv can be obtained from the dehydrogenation of H18-DBT if the applied H18-DBT had been carefully pre-dried and pre-purified prior to the dehydrogenation experiment. Indeed, the largest part of relevant impurities to comply with the hydrogen quality standard for fuel cells in road vehicles (ISO 14687-2) was found to originate from water and oxygenate impurities present in the applied, technical LOHC qualities.     

Connected evaluation of polymer electrolyte membrane fuel cell with dehydrogenation reactor of liquid organic hydrogen carrier

Recently, hydrogen energy technologies attract attention as power systems. To develop hydrogen energy systems, hydrogen storage methods with high storage density and good safety are required. Liquid organic hydrogen carrier (LOHC) is one of the novel hydrogen storage technologies. LOHC has advantages of high storage density, good safety, and easy handling. In this study, a polymer electrolyte membrane fuel cell (PEMFC) stack is operated with hydrogen released from LOHC to evaluate the feasibility of the connected operation of the PEMFC stack and LOHC dehydrogenation reactor. Dibenzyltoluene (H0-DBT) is used as a LOHC material, and the dehydrogenation of perhydro dibenzyltoluene (H18-DBT) is conducted at 240–300 °C. Released hydrogen is purified by adsorbent of activated carbon to remove impurities. However, 100–1400 ppm of methane is observed after the purification, and the PEMFC stack power is reduced from 39.4 W to 39.0 W during the operation by hydrogen dilution and physical adsorption of methane. Then, to evaluate the irreversible damage, pure hydrogen was supplied to the PEMFC stack. The stack power is recovered to 39.4 W. It is concluded that the connected operation of the LOHC dehydrogenation reactor and PEMFC stack is feasible, and the activated carbon adsorbent can be a cost-effective purification method for LOHC.     

A solid oxide fuel cell operating on liquid organic hydrogen carrier-based hydrogen – A kinetic model of the hydrogen release unit and system performance

In this paper, a kinetic model for the catalytic dehydrogenation of perhydro dibenzyltoluene (H18-DBT), a well-established Liquid Organic Hydrogen Carrier (LOHC) compound, is presented. Kinetic parameters for hydrogen release at a Pt on alumina catalyst in a temperature range between 260 °C and 310 °C are presented. A Solid Oxide Fuel Cell (SOFC) system model was coupled to the hydrogen release from H18-DBT in order to validate the full sequence of LOHC-bound hydrogen-to-electric power. A system layout is described and investigated according to its transient operating behavior and its efficiency. We demonstrate that the maximum efficiency of LOHC-bound hydrogen-to-electricity is 45% at full load, avoiding any critical conditions for the system components.     

Combined dynamic operation of PEM fuel cell and continuous dehydrogenation of perhydro-dibenzyltoluene

Hydrogen storage in liquid organic hydrogen carriers (LOHC) such as the substance system dibenzyltoluene/perhydro-dibenzyltoluene (H0/H18-DBT) offers a promising alternative to conventional methods. In this contribution, we describe the successful demonstration of the dynamic combined operation of a continuously operated LOHC reactor and a PEM (polymer exchange membrane) fuel cell. The fuel cell was operated stable with fluctuating hydrogen release from dehydrogenation of H18-DBT over a total period of 4.5 h, reaching electrical stack powers of 6.6 kW. The contamination with hydrocarbons contained in the hydrogen after activated carbon filtering did not result in any detectable impairment or degradation of the fuel cell. The proposed pressure control algorithm based on a proportional integral (PI) controller proved to be a robust and easy-to-implement approach to enable the dynamic combined operation of LOHC dehydrogenation and PEM fuel cell.     

Hydrogenation of liquid organic hydrogen carrier systems using multicomponent gas mixtures

The cost of industrial hydrogen production and logistics, and the purity of hydrogen produced from different technologies are two critical aspects for the success of a future hydrogen economy. Here, we present a way to charge the Liquid Organic Hydrogen Carrier (LOHC) dibenzyltoluene (H0-DBT) with industrially relevant, CO₂- and CO-containing gas mixtures. As only hydrogen binds to the hydrogen-lean carrier molecule, this process step extracts hydrogen from the gas mixture and binds it selectively to the carrier. Pd on alumina has been identified as the most promising catalyst system for successfully hydrogenating H0-DBT using model gas mixtures resembling the compositions produced in methane reforming and in industrial coke production (up to 50% CO₂ and 7% CO). Up to 80% of the hydrogen present in the feedstock mixture could be extracted during the LOHC hydrogenation process. 99.5% of the reacting hydrogen was selectively bound to the H0-DBT LOHC compound. The purity of hydrogen released from the resulting perhydro dibenzyltoluene previously charged with the hydrogen-rich gas mixture proved to be up to 99.99 mol%.     

Analysis of reaction mixtures of perhydro-dibenzyltoluene using two-dimensional gas chromatography and single quadrupole gas chromatography

Energy storage via liquid organic hydrogen carrier (LOHC) systems has gained significant attention in recent times. A dibenzyltoluene (DBT) based LOHC offers excellent properties which largely solve today's hydrogen storage challenges. Understanding the course of the dehydrogenation reaction is important for catalyst and process optimization. Therefore, reliable and exact methods to determine the degree of hydrogenation (doh) are important. We here present other possible techniques, namely: comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (2D-GC-TOF-MS) and single quadrupole-mass spectrometry gas chromatogram system (GC-SQ-MS). The 2D-GC-TOF-MS results indicate that isomer fractions lose three molecules of hydrogen, as follows: H18-DBT, H12-DBT, H6-DBT and H0-DBT, and the doh decreases with an increase in dehydrogenation temperature. ¹H NMR and GC-SQ-MS were employed as additional analytical techniques. The GC-SQ-MS was also used to analyse decomposition products that result from thermal cracking of reaction mixture molecules.     

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 kW_th, 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 kW_therm l⁻¹ based on the lower heating value of the hydrogen and a catalyst productivity of up to 0.65 g_H2 g_Pt⁻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.     

Pressurized hydrogen from charged liquid organic hydrogen carrier systems by electrochemical hydrogen compression

We demonstrate that the combination of hydrogen release from a Liquid Organic Hydrogen Carrier (LOHC) system with electrochemical hydrogen compression (EHC) provides three decisive advantages over the state-of-the-art hydrogen provision from such storage system: a) The EHC device produces reduced hydrogen pressure on its suction side connected to the LOHC dehydrogenation unit, thus shifting the thermodynamic equilibrium towards dehydrogenation and accelerating the hydrogen release; b) the EHC device compresses the hydrogen released from the carrier system thus producing high value compressed hydrogen; c) the EHC process is selective for proton transport and thus the process purifies hydrogen from impurities, such as traces of methane. We demonstrate this combination for the production of compressed hydrogen (absolute pressure of 6 bar) from perhydro dibenzyltoluene at dehydrogenation temperatures down to 240 °C in a quality suitable for fuel cell operation, e.g. in a fuel cell vehicle. The presented technology may be highly attractive for providing compressed hydrogen at future hydrogen filling stations that receive and store hydrogen in a LOHC-bound manner.     

Integration of hydrogenation and dehydrogenation based on dibenzyltoluene as liquid organic hydrogen energy carrier

The heat transfer oil dibenzyltoluene (DBT) offered an intriguing approach for the scattered storage of renewable excess energy as a novel Liquid Organic Hydrogen Carrier (LOHC). The integration of hydrogenation and dehydrogenation in H0-DBT/H18-DBT pairs demonstrated that the feasibility of hydrogenation and dehydrogenation reaction conducted in one reactor with the same catalyst, which would be proposed to simplify the hydrogen storage process. The optimal reaction temperature based on the inhibition of ring opening and cracking was investigated combined with the ¹H NMR analysis. Meanwhile, the ideal catalyst 3 wt% Pt/Al₂O₃ for high hydrogen storage efficiency was screened out. Cycle tests of hydrogenation and dehydrogenation integration reaction had shown that the hydrogen storage efficiency was 84.6% after five cycle tests. The integration of hydrogenation and dehydrogenation reaction based on DBT exhibited the ideal thermal stability, which demonstrated its potential as a reversible H₂ carrier.     

Experimental determination of the hydrogenation/dehydrogenation - Equilibrium of the LOHC system H0/H18-dibenzyltoluene

Liquid organic hydrogen carrier (LOHC) systems store hydrogen through a catalyst-promoted exothermal hydrogenation reaction and release hydrogen through an endothermal catalytic dehydrogenation reaction. At a given pressure and temperature the amount of releasable hydrogen depends on the reaction equilibrium of the hydrogenation/dehydrogenation reaction. Thus, the equilibrium composition of a given LOHC system is one of the key parameters for the reactor and process design of hydrogen storage and release units. Currently, LOHC equilibrium data are calculated on the basis of calorimetric data of selected, pure hydrogen-lean and hydrogen-rich LOHC compounds. Yet, real reaction systems comprise a variety of isomers, their respective partially hydrogenated species as well as by-products formed during multiple hydrogenation/dehydrogenation cycles. Therefore, our study focuses on an empirical approach to describe the temperature and pressure dependency of the hydrogenation equilibrium of the LOHC system H0/H18-DBT under real life experimental conditions. Because reliable measurements of the degree of hydrogenation (DoH) play a vital role in this context, we describe in this contribution two novel methods of DoH determination for LOHC systems based on ¹³C NMR and GC-FID measurements.     

Catalytically activated stainless steel plates for the dehydrogenation of perhydro dibenzyltoluene

Hydrogen storage and transport via Liquid Organic Hydrogen Carriers (LOHC) is gaining increasing attention. In this study, we present catalytically activated stainless steel plates as a promising alternative to the commonly used pellet catalysts for the dehydrogenation of perhydro dibenzyltoluene (H18-DBT). These plate catalysts promise better heat transport to the active sites. For improved performance, we modified our Pt/alumina plate catalysts by using i) platinum sulfite impregnation and ii) post-treatment with (NH₄)₂SO₄. Post-treatment with (NH₄)₂SO₄ resulted in a less active catalyst with lower formation of high-boiling side products compared to the S-free plate catalyst. Catalysts prepared with platinum sulfite showed both >35% higher activities and 90% reduction in high-boiler formation compared to the S-free plate catalysts. Our findings pave the way for the development of catalytically activated heat transfer plates that would allow the incorporation of LOHC dehydrogenation units into the geometry of future high temperature fuel cell stacks.     

Pt/CeO2 catalyst synthesized by combustion method for dehydrogenation of perhydro-dibenzyltoluene as liquid organic hydrogen carrier: Effect of pore size and metal dispersion

Liquid organic hydrogen carrier (LOHC) is a chemical hydrogen storage method that stores hydrogen in the form of liquid organics. Dibenzyltoluene (DBT) is a promising LOHC material due to its high storage density, low ignitability, and low cost. In this study, Pt/Al₂O₃ and Pt/CeO₂ catalysts are synthesized using a combustion nanocatalyst synthesis method called the glycine nitrate process (GNP) to obtain high catalytic activity for the dehydrogenation of perhydro-dibenzyltoluene (H18-DBT). Pt/CeO₂ exhibits much faster dehydrogenation than Pt/Al₂O₃, 80.5%/2.5 h versus 3.5%/2.5 h. To investigate the causes of the difference in the dehydrogenation rates, microstructural characterization by N₂ physisorption, CO chemisorption and transmission electron microscopy analysis are conducted, and the catalytic activities are evaluated at various liquid hourly space velocities (LHSVs). The differences in dehydrogenation can be attributed to the mass transport of liquid H18-DBT into the catalyst pores being slow due to the small pores in Pt/Al₂O₃, which is a rarely addressed issue for other LOHC materials. This is because many LOHC materials are dehydrogenated at the gas phase, which has higher diffusivity than that of the liquid phase. Pt/CeO₂ synthesized by the GNP is also compared with a commercial Pt/Al₂O₃ catalyst. The commercial Pt/Al₂O₃ catalyst shows a dehydrogenation of 17.8%/2.5 h, which is much slower than that of Pt/CeO₂ synthesized by the GNP, at 80.5%/2.5 h.     

The effects of alumina morphology and Pt electron property on reversible hydrogenation and dehydrogenation of dibenzyltoluene as a liquid organic hydrogen carrier

The morphologies and the electron property of catalysts play the very important roles in the hydrogenation and dehydrogenation of liquid organic hydrogen carriers (LOHCs) such as dibenzyltoluene (DBT). The different morphologies and pore structures of γ-Al₂O₃ and Mo_xC doped γ-Al₂O₃ were synthesized as the supports for Pt catalysts. After analyzing of various characterizations and catalytic testing, it was found that the large surface area and the mesoporous structure of catalysts are beneficial to both DBT hydrogenation and perhydro-dibenzyltoluene (H18-DBT) dehydrogenation. The doping of Mo_xC promoted the formation of the smaller Pt nanoparticles and increased Pt dispersion. The forming Pt–Mo structure is beneficial to hydrogen spillover which suppress the formation of by-product. The high Pt dispersion of 0.1 wt% Mo_xC doped Pt/Al₂O₃ catalyst plays the positive roles in increasing H18-DBT dehydrogenation activity.     

Dehydrogenation of perhydro-N-ethylcarbazole under reduced total pressure

Liquid organic hydrogen carrier (LOHC) systems represent a promising storage option for hydrogen produced from renewable electricity by water electrolysis. Regarding the efficiency of the endothermal hydrogen release reaction, this technology greatly benefits from a direct heat integration with the waste heat of the energetic use of the released hydrogen, e. g. in a fuel cell. To enable such beneficial set-up, the reaction temperature of hydrogen release must be below the operation temperature of the applied fuel cell which calls for both low temperature dehydrogenation catalysis and high temperature fuel cell operation. This paper demonstrates that such combination may be suitable if reduced pressure dehydrogenation of perhydro-N-ethylcarbazole (H12-NEC) is combined with hydrogen electrification in a high temperature polymer electrolyte membrane fuel cell (HT-PEMFC). Dehydrogenation reactions of H12-NEC were carried out between 160 °C and 200 °C applying different hydrogen partial pressures in the dehydrogenation unit to mimic the effect of a sucking fuel cell operation mode, i.e. the reduction of hydrogen partial pressure in the dehydrogenation unit caused by the fuel cell operation. Our kinetic analysis reveals that a dehydrogenation temperature of 180 °C combined with 500 mbar hydrogen partial pressure represent, for example, a suitable parameter set for efficient hydrogen release.     

Assessment of system variations for hydrogen transport by liquid organic hydrogen carriers

One option to transport hydrogen over longer distances in the future is via Liquid Organic Hydrogen Carriers (LOHC). They can store 6.2 wt% hydrogen by hydrogenation. The most promising LOHCs are toluene and dibenzyltoluene. However, for the dehydrogenation of the LOHCs – to release the hydrogen again – temperatures above 300 °C are needed, leading to a high energy demand. Therefore, a Life Cycle Assessment (LCA) and Life Cycle Costing are conducted. Both assessments concentrate on the whole life cycle rather than just direct emissions and investments. In total five different systems are analysed with the major comparison between conventional transport of hydrogen in a liquefied state of matter and LOHCs. Variations include electricity supply for liquefaction, heat supply for dehydrogenation and the actual LOHC compound. The results show that from an economic point of view transport via LOHCs is favourable while from an environmental point of view transport of liquid hydrogen is favourable.     

Two-dimensional Mo2C: An efficient promoter for hydrogen storage and release from a liquid organic hydrogen carrier

Two-dimensional Mo₂C (2D-Mo₂C) is reported for the first time as an effective promoter of a Pt/Al₂O₃ catalyst for both the hydrogenation and dehydrogenation of the liquid organic hydrogen carrier (LOHC) pair, dibenzyltoluene (DBT) and perhydro-dibenzyltoluene (H18-DBT), respectively. Addition of 6.2 wt% 2D-Mo₂C to a Pt/Al₂O₃ catalyst resulted in a significant increase in both the degree of hydrogenation and dehydrogenation compared to the unpromoted catalyst. An analysis of the initial (120 min) perhydro-DBT dehydrogenation kinetics in the temperature range of 270–330 °C, resulted in a reduction in apparent activation energy from 119.5 ± 3.8 kJ/mol for the Pt/Al₂O₃ catalyst to 110.4 ± 5.6 kJ/mol for the 6.2 wt% 2D-Mo₂C/Pt/Al₂O₃ catalyst. The 6.2 wt% 2D-Mo₂C/Pt/Al₂O₃ catalyst was also more stable than the unpromoted catalyst over several consecutive cycles of hydrogenation and dehydrogenation. Catalyst characterization showed that addition of 2D-Mo₂C resulted in an increase in particle size and electron density of the Pt, which enhanced both the hydrogenation and dehydrogenation reactions, despite the fact that the 2D-Mo₂C alone was inactive for both reactions.     

Influence of dissolved hydrogen on the viscosity and interfacial tension of the liquid organic hydrogen carrier system based on diphenylmethane by surface light scattering and molecular dynamics simulations

In hydrogenation and dehydrogenation processes of liquid organic hydrogen carriers (LOHCs), molecular hydrogen (H₂) is present, but its influence on the thermophysical properties of the LOHC compounds is still hardly known. This study provides experimental results from surface light scattering and predictions from molecular dynamics simulations on the influence of dissolved H₂ on the liquid viscosity, interfacial tension, and liquid density of the LOHC system based on diphenylmethane at varying degree of hydrogenation, process-relevant temperatures up to 573 K, and pressures up to 7 MPa. First-time measurements of the viscosity of bicyclic hydrocarbon compounds in the presence of dissolved H₂ at saturation conditions reveal a negligible effect of pressure. The interfacial tension decreases independently of the LOHC composition by about 6% at 7 MPa. The simulations can adequately represent the effect of H₂ on the interfacial tension and evidence a weak enrichment of H₂ at the interface.     

Evaluation of catalyst activity for release of hydrogen from liquid organic hydrogen carriers

This contribution investigate the effect of parameters for production of hydrogen by catalytic dehydrogenation of perhydrodibenzyltoluene (H18-DBT). The sensitivity of the dehydrogenation reaction to temperature (290–320 °C) is justified by an increase in degree of dehydrogenation (DoD) from 40 to 90% when using 1 wt % Pt/Al₂O₃ catalyst. However, the increase in temperature increases the hydrogen production rate and decreases the hydrogen purity by increasing the formation of by-products. In addition, the DoD of 96% is obtained when 2 wt % Pt/Al₂O₃ is used at 320 °C. The DoD obtained for Pd, Pt, and Pt–Pd catalysts is 11, 82 and 6%, respectively. Therefore, Pd is not a metal of choice for dehydrogenation of H18-DBT, in both monometallic and bimetallic system. The ab-initio density functional theory (DFT) calculations are consistent with this observation. Furthermore, dehydrogenation of H18-DBT followed 1st order reaction kinetics and the activation energies for 1 wt % Pt/Al₂O₃, 1 wt % Pd/Al₂O₃ and 1:1 wt % Pt–Pd/Al₂O₃ catalysts are: 205, 84 and 66 kJ/mol, respectively.     

High active pd@mil-101 catalyst for dehydrogenation of liquid organic hydrogen carrier

Highly dispersed Pd nanoparticles immobilized in MIL-101 (Pd@MIL-101) were prepared and used for the catalytic dehydrogenation of Liquid organic hydrogen carriers (LOHC). The as-synthesized catalysts were characterized and it was found that 3 wt% of Pd@MIL-101 embodied smaller and highly dispersed Pd NPs. The catalytic activities of as-synthesized catalysts were investigated by the dehydrogenation of a representative LOHC compound, perhydro-N-propylcarbazole (12H-NPCZ). The results indicated that 3 wt% Pd@MIL-101 catalyst exhibited good catalytic activity and good reusability for the dehydrogenation of 12H-NPCZ, which is superior to that of commercial 5 wt% Pd/Al₂O₃ catalyst. This study demonstrates that Pd@MIL-101 is a promising dehydrogenation catalyst for the application of LOHC technology.     

A parametric study of dehydrogenation of various Liquid Organic Hydrogen Carrier (LOHC) materials and its application to methanation process

Global warming is one of the arch challenges of this era mainly caused by the increasing concentration of carbon dioxide in the atmosphere. Methanation process utilizes carbon dioxide and hydrogen to produce methane gas as an energy-rich fuel. To supply the hydrogen for the methanation process, LOHC could be used as a medium for long-range hydrogen transportation. However, the heat of reaction is needed to recover hydrogen from the LOHC medium. In this study, a new method to utilize the heat from the methanation process for dehydrogenation and optimum conditions are calculated for various LOHC materials. The new process designed uses an Air-Brayton cycle to generate the required high pressure as well as compensate for the LOHC dehydrogenation thermal energy requirement using a proportionate amount of methane produced. Also, the performance of various LOHC materials is compared in the proposed process. The simulation is performed via Aspen Plus® simulator. Dibenzyltoluene is found to be the best selection among the selected LOHC materials for use in this process with a system efficiency of 46.7% with a 100% medium recovery. Pyrrole group LOHC exhibits lower dehydrogenation temperature and energy requirement however are prone to bond scission and generally toxic. Toluene has high volatility resulting in its maximum recovery limited to 96.2% at an elevated pressure of 7 bar decreasing to 84.5% at 1 bar and 30 °C with a system efficiency of 49.08% and a low CVA of 36.74%, while NEC has 63.78% CVA with 55.64% efficiency and DBT has 54.12% CVA with 47.99% efficiency.