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Hydrogenious Technologies partners with United Hydrogen Group (UHG) to bring novel LOHC H2 storage system to US market

One of Anglo American Platinum’s investments, Hydrogenious Technologies, a German hydrogen storage startup, has launched its first commercial hydrogen storage and logistics system using its innovative Liquid Organic Hydrogen Carrier (LOHC) technology.

Hydrogenious Technologies is a spin-off from the University of Erlangen- Nuremberg (Germany), which also holds a stake in the company, and the Bavarian Hydrogen Center. Instead of storing hydrogen either under high pressure of up to 700 bar or in liquid form at –253 °C, Hydrogenious’ technology catalytically binds and releases the hydrogen molecules to liquid organic hydrogen carriers (LOHCs). (Earlier post.)

Liquid organic hydrogen carriers (LOHCs) are an interesting option for the storage of hydrogen. The concept of LOHC is based on the reversible hydrogenation of an unsaturated, usually aromatic, compound. This reaction forms a saturated compound, which is the hydrogen-rich form of the carrier. In a dehydrogenation reaction, the hydrogenated (i.e., hydrogen rich) form releases the hydrogen for further utilization. The hydrogen uptake in the hydrogenation reaction requires elevated pressures of about 30 to 50 bar. The dehydrogenation on the other hand can be operated at ambient pressure but necessitates high temperatures of up to 300 °C. However, during storage time, ambient conditions can be applied to the carrier, without any negative influence on storage density or losses during storage time. This is one of the most important advantages compared to most other hydrogen storage technologies.

—Müller et al.

Hydrogenation of the Hydrogenious LOHC, which occurs via the catalytic reaction at 50 bar pressure, is an exothermal process with 10kWhth/kg H2 usable heat @ 150 °C. The reactor design allows for a continuous hydrogenation process.

The storage medium is dibenzyltoluene—a liquid organic hydrocarbon that maintains a liquid state in a broad temperature range between -39°C to 390°C and ambient pressure. It is low flammability and non-explosive, even when loaded with hydrogen. There is no evaporation of stored hydrogen—multi-month storage is possible without any losses.

The proposed LOHC compounds have many physico-chemical similarities to diesel. Thus, LOHCs could make use of the existing energy infrastructure (e.g. tank ships, storage tanks or fueling stations) and enable a slow and step-wise replacement of the existing hydrocarbon fuels by alternative LOHC fuels.

The release of hydrogen molecules from the liquid carrier medium also occurs via catalytic reaction. This is an endothermic process with 10kWhth/kg H2 @ ~300°C.

News2

The system features various new technologies, including a Polymer Electrolyte Membrane (PEM) electrolyzer that generates hydrogen using solar power and a Hydrogenious “StorageBOX” that uses LOHC technology to enable storage without any losses for extended periods of time.

Hydrogenious Technologies recently signed a deal with United Hydrogen Group (UHG), a hydrogen distribution company based in the United States, to supply two LOHC systems, one StorageBOX and one ReleaseBOX. The technology will increase delivery ranges and decrease the operating costs of hydrogen logistics for UHG.

Further, the agreement enables Hydrogenious Technologies to enter the US market, which represents over 50% of the global hydrogen market, and will support the rollout of hydrogen refueling infrastructure for Fuel Cell Electric Vehicles (FCEVs.)

Hydrogenious Technologies recently was awarded with the prestigious German Industry Innovation Award.

Hydrogenious Technologies’ manufacturing plant in Erlangen, Germany, was formally inaugurated at an event attended by key government and business officials in the country including Ilse Aigner (Bavarian State Minister of Economic Affairs and Media, Energy and Technology), Prof. Joachim Hornegger (President of FAU Erlangen-Nuremberg), Dr. Katharina Beumelburg (CEO Siemens Hydrogen Solutions) and Frank Sreball (CEO H2 Mobility).

The investment in Hydrogenious Technologies forms part of Anglo American Platinum’s commitment to support early stage technologies and innovative industrial applications that use or enable the use of platinum group metals. Anglo American Platinum invested in Hydrogenious Technologies’ first financing round in 2014.

Resources

  • Karsten Müller, Katharina Stark, Vladimir N. Emel’yanenko, Mikhail A. Varfolomeev, Dzmitry H. Zaitsau, Evgeni Shoifet, Christoph Schick, Sergey P. Verevkin, and Wolfgang Arlt (2015) “Liquid Organic Hydrogen Carriers: Thermophysical and Thermochemical Studies of Benzyl- and Dibenzyl-toluene Derivatives” Industrial & Engineering Chemistry Research 54 (32), 7967-7976 doi: 10.1021/acs.iecr.5b01840

Comments

HarveyD

This technology could have major impacts on fixed H2 storage stations, for lower cost large storage units.

It could probably be fine tuned for mobile on-board H2 storage for future FCEVs. If so, it could probably reduce the total H2 cost (due to lower pressure and longer term storage ease), lower H2 tank cost and increased capacity for longer FCEV range.

H2 technologies are developing faster than batteries?

EHE

One challenge when using this technology in transportation is how to recycle the LOHCs during tanking. You would probably need one tank for hydrogenized LOHCs and one tank for the dehydrogenized LOCHs. And you have to fill up one tank and empty the other.

The article does not say anything about the storage capacity. How many kg of hydrogenized LOHCs is needed for storing 1 kg of H2?

It is very positive to get rid of the high pressure tanks, in order to get better safety, and reduce risk of hydrogen leakage. But I expect that this solution will be more expencive than using compressed hydrogen.

solarsurfer

The solar to fuels program at Caltech should match up well with this technology. Combining C02 with water to make the hydrogen and the storage material. Eliminating 70Mbar storage will make cars so much safer. I hope it comes to my hydrogen station in OC. Hopefully the doe nano catalyst will make it to market soon to make conversions cheap.

sd

Now all we need is cheap fusion power to make the H2.

sd

@solarsurfer

If you combine CO2 with water, the only thing you get is soda water.

Roger Pham

I can see many potential "show stoppers" here:

1) dibenzyltoluene has unknown carcinogenic potential, though being an aromatic compound with tri-cyclic ring is not reassuring in case of leaks or spills.

2) The thermal energy required for hydrogenation and dehydrogenation is 10 kWh per kg, which is a lot, in comparison to 1/3 required for compression to 10,000 psi, unless means for heat recycling or waste heat utilization are available.
For dehydrogenation, it takes 10 kWh of thermal energy at 300 degree C per kg of H2. PEM-FC generates waste heat at below 100 degree C, so can't be used for this purpose. So, not suitable for current FCEV tech using PEM-FC. May be for stationary single cycle gas turbine with that kind of waste heat, but not even combine-cycle gas turbine with much lower-temp waste heat.

3) The gravimetric weight percentage is 6.2% excluding the weight of container, per Wikipedia, which is not much better than Toyota's carbon fiber tanks capable of 5.7% wt percentage including container's weight, at 10,000 psi. So, the gravimetric energy density is over 2 kWh per kg.

4) With a density of 1.04 g/ml, and weight % of 6.2%, it takes 16 kg of this to carry 1 kg of H2. So, the volume will be 16 liter per kg of H2 having 33 kWh. So, the volumetric energy density is around 2 kWh/liter.
Toyota Mirai has 122-liter H2 capacity capable of 5 kg of H2 for 165 kWh, thus 1.35 kWh per liter. The circular cylinder takes up extra square space, so, at most, 1 kWh per liter.

So, this LOHC carries twice as much H2 per volume as compressed H2 at 10k psi, but this point is moot because it cannot be used in FCEV because there is no available waste heat at 300 dg C.

Though, it would be great as storage for H2 at the power station as backup means for solar and wind energy, and for H2 to be carried around in tankers over the ocean for exporting and importing. On land, H2 pipelines will be more practical and safer due to no chemical spill hazard and no conversion necessary.

gryf

@Roger,
Agree particularly on possible use as renewable energy storage where MWh are needed and the cost of the storage medium is a major factor and not the platinum catalyst necessary for conversion (which compounds the platinum needed for PEM FCEV).
LOHC could also be used for Hydrogen Combustion turbines which can then use waste heat for the Hydrogen conversion process.
I have posted many times that Hydrogen Fuel Cells may not work in transportation, though schemes that would enable a 100% renewable electric system may prove to be cost effective.

Engineer-Poet

Ammonia is roughly 3x as hydrogen-dense as this carrier.  It would be worth calculating the energy burden of decomposition of NH3 via the sodium amide process vs. dibenzyl toluene.

gryf

@E-P,
Excellent idea. Only study I have seen compares Ammonia to LOHC for transport fuels (see http://arpa-e.energy.gov/sites/default/files/Soloveichik_Intro_TransportationFuels_Workshop.pdf).
No comparison using Sodium Amide which is a new catalyst for H2 decomposition of NH3 (if you are referring to the new discovery by scientists at the UK's Science and Technology Facilities Council - http://pubs.acs.org/doi/pdf/10.1021/ja5042836).
Based on the Soloveichik work ammonia should be very cost competitive and the Sodium Amide process does not use any noble metal catalysts, so this would be a very interesting approach for static H2 renewable electric generation.

Henry Gibson

There is an isotope 238 that does power an automobile on Mars; Its power density is 500 watts thermal per kilogram. A kilogram or two would be enough for the average automobile use. Shielding most of the radiation from such material can be done with ultra thin stainless steel foil. ..HG..

Henry Gibson

Isotope 238 loses half its energy in 80 years. ..HG..

Engineer-Poet

You make me wonder about you, Henry.  Pu-238 (distinct from U-238) must be specially manufactured by neutron capture in neptunium-237 (it cannot be refined from other mixtures of plutonium).  Np-237 is itself a product of neutron capture starting with U-235, the bulk of which fissions when it captures a neutron, followed by another neutron capture in U-236 (which has a rather small neutron-capture cross-section) which ultimately decays to neptunium.  The upshot is that Pu-238 is going to be scarce and expensive no matter what you do.  Oh, it's EXTREMELY good (and thus worth the expense) for outer-space probes and a few other special purposes, but nobody in their right mind is going to try to run earth-bound automobiles on it.

Alain

I'd be much less troubled by a spill of NH3 (boiling point -33°C) compared to dibenzyltoluene in the environment.

Secondly, I wouldn't be so sure that the high-pressure H2 tank is such a danger. Only 4 kg of H2 gives an impressive range. Ten tanks of each 0.4 kg of H2, being 1 meter long, with consequently a very small radius, made from carbon fiber reinforced plastic will be extremely strong and never burst catastrophically (= "explode"). Even if it bursts, the internal thermal energy of 0.4kg of H2 is so low that it will not cause a lot of damage compared to a gasoline fire. A chemical explosion of H2+O2 is unlikely compared to gasoline because H2 will immediately rise to the stratosphere (again, in contrast gasoline vapor or CH4 doesn't fly up, increasing the risk that an explosive concentration is reached).
I don't think the burden of adsorption/desorption systems or carrier molecules will ever compete with simple high-pressure tanks.

Another point is that once carrier molecules are being used, distributed production will become much more difficult. With high-pressure tanks, anyone at home will be able to produce its own H2, or start a small business to produce H2 with whatever excess electricity there is available in the neighborhood. it can easily be stored in high volumes. There will never be a H2-monopoly. In contrast, with carrier molecules a complex distribution system will be necessary requiring "big H2" to take control. As H2 is environmentally completely benign, there is no concern for spills.
The car itself also becomes much simpler in design, as H2 easily flows from high to low pressure (in contrast to carrier molecules that need to be pumped, recovered, heated, cooled with all sort of additional systems to ultimately produce the H2)

gryf

@E-P,
Henry will be driving his automobile on Mars.

gryf

@Alain,
Ammonia is the second most widely produced chemical after petroleum (of course, now produced with natural gas and coal to get the hydrogen). What is needed is renewable ammonia. There is even an ammonia pipeline in the Midwest, where coincidentally is a large concentration of wind turbines. So the NH3 infrastructure already exists.
There is no H2 infrastructure except in a few places like California.

Alain

I agree that IF a carrier molecule would be advantageous (because somehow high pressure containers wouldn't be), that NH3 is most probably the best choice because of its low toxicity, environmental benign, and the waste product (N2) can be discharged in the atmosphere. (a combination of hydrocarbons - such as ethanol or methanol - and H2O would have the same advantages)

However, it still makes small-scale H2 production much more difficult, so I would prefer pure H2.

The Mirai has a fuel cell of 114 kW, and is affordable.
So, a small 2kW electrolyser should be very cheap (even with present-day technology).
Such a small electrolyser in my garage, should be enough to keep my personal reserve of 20kg of H2. If containers and pressure pumps can be made at a reasonable price, this makes lokal production very convenient. The comparatively complex transformation of H2 to NH3 is much less evident at home. In addition, the reaction H2 --> NH3 --> H2 gives an additional loss of efficiency.

kalendjay

I would imagine the dibenzyltoluene conveys interest because the hydrogenated/dehydrogenated components can mass separate (stack, like water in a hot water tank), apparently low toxicity (we know toluene, unlike benzene, can be metabolized), good heat capacity (need to efficiently utilize heat to free hydrogen), dielectric usage as a capacitor (ever consider a battery-like activated hydrogen storage system in which this fluid is a virtual electrolyte with a small heated interface?), low flammability, high boiling point, low water solubility -- all of these must be issues that have prevented the miracle H2 storage medium car from being developed.

As for the U-238 thing, thorium has been presented for a quite adequate auto energy system (beta particles split H from H2O)

Engineer-Poet

Are you aware just how grossly inefficient radiolysis is at cracking water?

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