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%.     

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.     

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.     

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.     

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.     

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.     

Solid oxide fuel cell operating on liquid organic hydrogen carrier-based hydrogen – making full use of heat integration potentials

Our contribution demonstrates the technological potential of coupling Liquid Organic Hydrogen Carrier (LOHC)-based hydrogen storage and hydrogen-based Solid Oxide Fuel Cell (SOFC) operation. As SOFC operation creates waste heat at a temperature level of more than 600 °C, clever heat transfer from the SOFC operation to the LOHC dehydrogenation process is possible and results in an overall efficiency of 45% (electric output of SOFC vs. lower heating value of LOHC-bound hydrogen). Moreover, we demonstrate that LOHC vapour does not harm the operational stability of a typical 150 W SOFC short stack. By operating the stack with LOHC-saturated hydrogen, operation times of more than 10 years have been simulated without noticeable degradation of SOFC performance.     

Benzyltoluene/dibenzyltoluene-based mixtures as suitable liquid organic hydrogen carrier systems for low temperature applications

In this contribution we propose mixtures of the two LOHC systems benzyltoluene (H0-BT)/perhydro benzyltoluene (H12-BT) and dibenzyltoluene (H0-DBT)/perhydro dibenzyltoluene (H18-DBT) as promising hydrogen storage media for technical applications at temperatures below ambient. The mixing of the two LOHC systems provides the advantage of a reduced viscosity of the hydrogen-rich system, for example a 20 wt% addition of H12-BT to H18-DBT reduces the viscosity at 10 °C by 80%. Interestingly, it is also found that the dehydrogenation of such mixture provides a hydrogen release productivity that is 12–16% higher compared to pure H18-DBT dehydrogenation under otherwise identical conditions. This enhanced rate is attributed to a combination of reduced hydrogen partial pressure in the reactor (due to the higher H12-BT vapor pressure), preferred H12-BT dehydrogenation (due to faster H12-BT diffusion) and effective transfer hydrogenation between the two LOHC systems.     

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.     

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.     

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.     

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.     

Enhancing selectivity and reducing cost for dehydrogenation of dodecahydro-N-ethylcarbazole by supporting platinum on titanium dioxide

N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NECZ/12H-NECZ) was a promising system for hydrogen storage applications. 1.0 wt% Pt/TiO₂ was regarded as the optimal loading in Pt/TiO₂ catalyst applied in the 12H-NECZ dehydrogenation reaction. The hydrogen release amount, selectivity to NECZ and TOF of 12H-NECZ dehydrogenation are 5.75 wt %, 98% and 229.73 min⁻¹ at 453 K. Compared with the commercial 5.0 wt% Pd and Pt-based catalysts, it exhibited very high activity, selectivity and stability for 12H-NECZ dehydrogenation with low Pt loading. Combined with the XRD, XPS, HRTEM, TPR analysis, it was indicated that the enhanced catalytic performance was due to the SMSI (strong metal-supporting interaction) between Pt and TiO₂ support, which accelerated the rate-limiting step and enhanced the whole dehydrogenation reaction. This work may be beneficial for the commercial application of Pt/TiO₂ catalysts in the Liquid Organic Hydrogen Carrier (LOHC) system.     

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.     

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.     

Liquid Organic Hydrogen Carrier (LOHC) – Assessment based on chemical and economic properties

Hydrogen can be transported via long distances based on Liquid Organic Hydrogen Carriers (LOHC). Such a transport is realized based on a two-step cycle: (1) loading/storage of hydrogen (hydrogenation) into the LOHC molecule and (2) unloading/release of hydrogen (de-hydrogenation). During the storage period, hydrogen is covalently bound to the respective LOHC. Since the (optimal) LOHC is liquid at ambient conditions and shows similar properties as crude oil based liquids (e.g. diesel, gasoline), it can easily be handled, transported and stored; thus a stepwise implementation using the existing crude oil based infrastructure would be possible. Against this background this paper reviews the current knowledge in hydrogenation and de-hydrogenation of various LOHC. Therefore, a variety of LOHC is evaluated based on their properties and compared to each other. By applying different evaluation criteria representing the requirements of the three different application areas (energy-storage, energy-transport, mobility application), the LOHCs can be assigned to a field they suit best. The analysis shows that the most promising LOHC candidates to date are dibenzyltoluene for energy-transport and energy-storage as well as N-ethylcarbazole for mobility applications. In addition, a use of toluene in the transport sector is also conceivable. Methanol can potentially be applied in all three application fields due to its properties if a compromise between de-hydrogenation temperature and gas flow can be achieved based on further R&D-activities. For future implementation phenazine and formic acid show great potential, but also additional R&D especially regarding catalysis and solvents is necessary.     

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.     

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.     

LOHC-bound hydrogen for catalytic NOx reduction from O2-rich exhaust gas

The present study demonstrates a novel method for the NO_x reduction by H₂ in lean exhaust gases using H₂ released from a Liquid Organic Hydrogen Carrier (LOHC). The concept implies the simultaneous H₂ production and H₂-deNO_x reaction, which both take place on the same catalyst. In a first approach, the catalyst was suspended in the LOHC, while the exhaust flowed through the slurry. The experiments performed with a O₂-rich model exhaust and perhydro dibenzyltoluene as LOHC as well as Pd/C, Pt/C and Pt/Al₂O₃ catalysts evidenced the feasibility of this transfer hydrogenation. As a result, the Pd/C catalyst revealed best H₂-deNO_x performance providing NO_x conversions up to 98% above 200 °C with almost selective N₂ formation. The characterization of the catalysts by temperature-programmed desorption of CO suggested that the superiority of the Pd/C sample is associated with its pronounced number of active Pd sites. Furthermore, the investigations also showed some LOHC degradation during the exposure to the lean model exhaust yielding CO, CO₂ and hydrocarbons.     

Enhanced reversibility of fluorine substituted bis-BN cyclohexane for hydrogen storage: A first-principles approach

Liquid organic hydrogen carrier (LOHC) technology, in which hydrogen is captured in a liquid-phase compound, is a key enabler in realizing hydrogen economy. Among the LOHC materials, bis-BN cyclohexane is thermodynamically stable at 150°C and does not release detectable volatile contaminants during catalytic dehydrogenation at room temperature. In this study, we identified other potential bis-BN cyclohexane-based hydrogen storage materials with improved dehydrogenation efficiency and reversibility using density functional theory (DFT) calculations. The dehydrogenation mechanisms of bis-BN cyclohexane with and without functional group (F, Cl, NH₂, CH₃, and CN) substitutions were investigated by calculating the reaction enthalpies and free energies. With the Pt catalyst surface, F-bis-BN cyclohexane has slightly lower dehydrogenation reaction efficiency than the existing bis-BN cyclohexane; however, it was found that the efficiency of the reverse reaction of hydrogenation is significantly improved owing to the F substitution in bis-BN cyclohexane. Therefore, F-bis-BN cyclohexane can exhibit enhanced reversible dehydrogenation–hydrogenation cycles in the presence of a Pt catalyst and is expected to be suitable as an alternative hydrogen carrier. Details of dehydrogenation reaction pathways with activation energies and electronic properties of the dehydrogenation mechanisms have also been discussed herein.