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RAL proposes new efficient and low-cost process to crack ammonia for hydrogen using sodium amide; transportation applications

23 June 2014

Ja-2014-042836_0005
RAL researchers are proposing a new process for the decomposition of ammonia to release hydrogen that involves the stoichiometric decomposition and formation of sodium amide from Na metal. Credit: ACS, David et al. Click to enlarge.

Researchers at the Rutherford Appleton Laboratory (RAL) in the UK are proposing a new type of process that is an alternative to the use of rare or transition metal catalysts for the cracking of ammonia (NH3) to produce hydrogen. A paper on the process appears in the Journal of the American Chemical Society.

The new process decomposes ammonia using the concurrent stoichiometric decomposition and regeneration of sodium amide (NaNH2) via sodium metal (Na); this is a significant departure in reaction mechanism compared with traditional surface catalysts. The scientists report that in variable-temperature NH3 decomposition experiments using a simple flow reactor, the Na/NaNH2 system shows superior performance to supported nickel and ruthenium catalysts, reaching up to a 99.2% decomposition efficiency with 0.5 g of NaNH2 in a 60 sccm NH3 flow at 530 °C. As an abundant and inexpensive material, the development of NaNH2-based NH3 cracking systems may promote the utilization of NH3 for sustainable energy storage purposes, they suggest.

The Haber−Bosch process for the industrial synthesis of ammonia has, over the past century, led to a global revolution in agriculture to the extent that almost half the crops grown across the world today depend on ammonia-based fertilizers. The reverse reaction may have a similarly transformative potential, where the decomposition of ammonia into nitrogen and hydrogen enables the provision of hydrogen for a low-carbon energy economy. Indeed, high-density, affordable, and efficient hydrogen storage is one of the key steps in the realization of a hydrogen-based energy sector.

Hydrogen (H2) is an attractive chemical fuel, with very high gravimetric energy content (120 MJ/kg) and an emissions profile free from carbon dioxide. Despite these advantages, its use has been hindered by the lack of an effective and efficient method for its storage. Current high-pressure (∼700 bar) storage is expensive and energy-intensive, and imposes practical restrictions on tank dimensions. In response to this challenge, there has been a significant research effort over the past 15 years that has focused on new chemical hydrogen storage materials, particularly solid-state materials which offer impressive volumetric and gravimetric hydrogen densities. Arguably, this focus may have diminished the consideration of reversibility, cost, and practicality of use of these materials. To date, very few candidates show potential beyond that of the seminal work on titanium-doped sodium alanate.

Ammonia (NH3) has a high gravimetric (17.8 wt% H2) and volumetric (121 kg H2 m−3 in the liquid form) H2 density and is produced on an industrial scale. Furthermore, it has an existing extensive distribution network and is easily stored by liquefaction at moderate pressure (ca. 10 bar at room temperature). While both perceived and real safety risks due to the toxicity of NH3 have detracted from its appeal, its adoption as a vector for H2 has not yet been realized largely because of the absence of an efficient, low-cost method for cracking NH3 to H2 and N2.

—David et al.

Sodium amide is used extensively as a reagent in a variety of synthesis processes, but its modest hydrogen capacity and high decomposition enthalpy suggest that it would be an unattractive hydrogen storage candidate. However, the team noted, it was observed more than a century ago that NaNH2 decomposes to its constituent elements: i.e., sodium, nitrogen and hydrogen.

The bulk production of NaNH2 is by reaction of sodium metal (Na) with gaseous (or liquid) NH3. Run concurrently, the RAL team proposed, these two reactions should effect the chemical decomposition of NH3 by cycling between sodium amide and sodium metal, thusly:

Ral1

The RAL researchers performed their NH3 decomposition experiments in simple cylindrical flow reactors.

Currently, ruthenium shows the highest catalytic activity for low-temperature cracking of ammonia; the RAL results showed that the performance of as-found NaNH2 for continuous stoichiometric NH3 decomposition is as effective as a supported ruthenium catalyst—or more so. The material costs, however, are very significantly less, the team observed.

We believe this combination of high efficiency and low cost of the Na/NaNH2 system indicates the potential of this new class of NH3 decomposition catalyst, and invites reconsideration of the potential of NH3 decomposition as a viable delivery method of H2, for applications ranging from small-scale distributed power to massive grid-balancing and on-board use for transportation.

—David et al.

Low-temperature fuel cells—either alkaline fuel cells or proton exchange membrane-based fuel cells—could utilize the hydrogen produced. Given that a 1 kW fuel cell requires a H2 supply of ∼13.5 L/min, the RAL team calculated that linear scale-up of the highest production rate obtained in their work to this power output would require a reactor volume of 0.62 L, using 14.5 g of NaNH2.

They suggested, however, that the direct combustion of NH3 might be the most attractive short-term option. Although ammonia alone is difficult to ignite, a 2.5 wt% hydrogen-in-ammonia mixture is sufficient to enable ammonia combustion. Using the current best conversion rates obtained in their experiments, they calculated that this mix could be provided, at sufficient flow rates, using a total reactor volume of 3.2 L, containing 75 g of NaNH2.

(The calculations are detailed in the paper’s Supporting Information.)

These calculations indicate that ammonia-based transportation is achievable. While advances in the containment and turnover frequency of the amide are necessary steps toward this goal, we anticipate that significant improvements in these areas will be realized through the optimization of the reactor design and materials properties of NaNH2.

—David et al.

Resources

  • William I. F. David, Joshua W. Makepeace, Samantha K. Callear, Hazel M. A. Hunter, James D. Taylor, Thomas J. Wood, and Martin O. Jones (2014) “Hydrogen Production from Ammonia Using Sodium Amide,” Journal of the American Chemical Society doi: 10.1021/ja5042836

June 23, 2014 in Ammonia, Hydrogen, Hydrogen Storage | Permalink | Comments (7) | TrackBack (0)

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Interesting that Sodium reacts violently with water to produce familiar lye (sodium hydroxide) and, you guessed it, hydrogen, to make the ammonia. The best way to produce ammonia is still the high pressure route of Haber-Bosch, but sodium which is abundant at oil refineries might be utilized to make ammonia-amino synthesis a lot less carbon intensive, with roomto use the oygen components elsewhere. No natural gas needed -- a case for nuclear!

The formation of ammonia from hydrogen and nitrogen is exothermic; obviously, the decomposition of ammonia to its chemical elements must be endothermic.  What supplies the energy to run the sodium amide reactor?

The use of H2 as a catalyst to ignite NH3 is brilliant.

You have to put in energy to get ammonia in the first place. And the hydrogen used to make ammonia comes from natural gas anyway. This is effectivelt just steam methane reformation with some extra steps added in. While ammonia is a better hydrogen carrier than actual pressurized hydrogen, the "well-to-tank" energy and financial costs of this approach will be even WORSE than pressurized hydrogen is today.

Combusting ammonia seems interesting, but what are the air pollution hazards that result? I would assume you would see a lot more NOx and ozone precursors while all the other nasties that come off of fossil fuel combustion would not be present (like PM, unburned hydrocarbons, SOx, etc.) Are there any other air quality concerns we would have to worry about? Would we be jumping from the frying pan into the fire just like we did with ethanol? And if you can just burn natural das in an engine too, why go through all the expense to get ammonia when you can save all the trouble and just use natural gas directly? (just like with a hydrogen car that uses hydrogen made from natural gas...why go through all the expense and inefficiencies just to make a fuel that is way more expensive and way less practical than it's feedstock?)

The Stranded Wind Project is working on the direct production of ammonia from electrolysis.  I question whether this works out economically, but you have to admire the effort.

I did a little bit of digging, and this is what I uncovered:

2Na + 2 NH3 -> 2 NaNH2 + H2 (350°C)

6 NaNH2 -> 2 Na + 4 NH3 + N2 (500-600°C)

It appears that this is suitable for a small recirculating reactor which converts a trickle of ammonia to sodium amide and H2 in the "cold" section, then cracks the sodium amide back to metal, NH3 and N2 in the high-temperature section.  The N2 and NH3 would be recirculated to the bottom of the cold side along with the metal.  The N2 is apparently unreactive under such conditions, so the effluent gas from the cold side would be a mixture of 1 part N2 and 3 parts H2 by volume.

Engineer-Poet

The energy comes from converting the evolved hydrogen into water in a fuel cell. The energy to run the reactor consumes a fraction of the stored chemical energy within the ammonia. The remaining energy is available to do work.

Also, NaNH2 doesn't decompose to evolve ammonia. This is a trait of only lithium amide (of the alkali metals) due to the cation size and coordination sphere limitations of the imide. As Juza first postulated, NaNH2 decomposes to give Na, N2 and H2

That's not what I found claimed in my search (I didn't save the link), but if you're correct the reactor would be even simpler.  Further, you wouldn't need any input from a fuel cell to operate it.  Combustion of a bit of hydrogen, or even raw ammonia if the right conditions can be produced, would provide the necessary process heat.  That allows the reactor to stand alone, removing a great deal of complication.

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