NCSU team develops catalyst for thermal hybrid water-splitting and syngas generation with exceptional conversion; H2 gas and liquid fuels
19 January 2015
Researchers at North Carolina State University have developed a highly effective new perovskite-promoted iron oxide redox catalyst for a hybrid solar-redox scheme they had proposed earlier for partial oxidation and water-splitting of methane.
In a paper published in the RSC journal Energy & Environmental Science, Feng He and Fanxing Li report that the new material—lanthanum strontium ferrite (La0.8Sr0.2FeO3-δ or LSF) supported Fe3O4—is capable of converting more than 67% steam with high redox stability. In contrast, previously reported ferrite materials typically exhibit 20% or lower steam to hydrogen conversion.
Their work indicates that a synergistic effect of reduced LSF and metallic iron phases is attributable to the exceptional steam conversion. To further enhance this effect, they proposed a layered reverse-flow reactor concept. Using this concept, they achieved more than 77% steam to hydrogen conversion is achieved at 930 °C—15% higher than the maximum conversion predicted by the second law for unpromoted iron (oxides).
He and Li and other colleagues earlier last year had proposed a hybrid solar-redox scheme for the co-production of hydrogen and liquid fuels. The hybrid solar-redox process converts solar energy and methane into separate streams of liquid fuels and hydrogen through the assistance of an oxygen carrier. The new catalyst material improves the efficiency of that process, depicted in the schematic below.
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Schematic of the hybrid process for liquid fuel and hydrogen generation. Image credit: Feng He. Click to enlarge. |
We’re excited about the new material and process because it converts water, inexpensive natural gas and clean, renewable solar energy into valuable syngas and hydrogen fuels. We’re optimistic that commercial utilization of this technique could promote the efficient usage of solar energy and domestic natural gas, produce relatively low carbon dioxide emissions while making liquid transportation fuel, and generate low cost, high purity hydrogen.
—Feng He, lead author
Researchers have long known that iron oxide can be used as a catalyst for thermal water splitting, but it is not very efficient. The addition of LSF significantly improves iron oxide’s activity, making it far more efficient. The 77% conversion of the water used (in the form of steam) into hydrogen far outpaces the prior best conversion mark for thermal water-splitting of around 20%.
In the hybrid solar-redox process, methane is injected into a reactor that is heated with solar energy. That chamber contains the catalytic composite, which reacts with the methane to produce syngas and carbon dioxide. This process “reduces” the composite particles, stripping them of oxygen. The syngas is removed from the system and the reduced composite particles are diverted into a second reactor.
High-temperature steam is then pumped into the second reactor, where it reacts with the reduced composite particles to produce hydrogen gas that is at least 97% pure. This process also reoxygenates the composite particles, which can then be re-used with the methane, starting the cycle all over again.
Initially, the steam has to be produced with an external energy source, but once the cycle is initiated the chemical reactions produce enough heat to convert water into steam without an external heat source.
We’ve created the catalytic particles and conducted every step of this process, but only in separate batches. We’re now in the process of building a circulating bed reactor to operate this entire cycle in a continuous mode in real world conditions. Next steps include fine-tuning the catalytic compound to make it better and cheaper, improving the overall process, and developing better reactors.
—Feng He
The work was supported by the National Science Foundation under grant number CBET-1254351 and the US Army Research Office under grant number 61607-CH-RIP.
Resources
Feng He and Fanxing Li (2014) “Perovskite promoted iron oxide for hybrid water-splitting and syngas generation with exceptional conversion” Energy Environ. Sci. doi: 10.1039/C4EE03431G
Feng He, James Trainham, Gregory Parsons, John S. Newman and Fanxing Li (2014) “A hybrid solar-redox scheme for liquid fuel and hydrogen coproduction” Energy Environ. Sci., 7, 2033-2042 doi: 10.1039/C4EE00038B
Would the H2 production cost drop in the same or near proportion?
Posted by: HarveyD | 19 January 2015 at 07:15 AM
"achieved at 930 °C—15% higher than the maximum conversion predicted"
This improves the process, but does not reduce the cost significantly. One of their contributions is using solar thermal heat. You can convert a lot during the day and store for use 24/7.
Posted by: SJC | 19 January 2015 at 10:41 AM
"initially, the steam has to be produced with an external energy source, but once the cycle is initiated the chemical reactions produce enough heat to convert water into steam without an external heat source."
“We’re now in the process of building a circulating bed reactor to operate this entire cycle in a continuous mode in real world conditions."
https://news.ncsu.edu/2015/01/he-syngas-2015\
This means that it can lead to a more efficient more cost effective method, a good accomplishment.
Posted by: SJC | 19 January 2015 at 05:23 PM
I would love to see analysis of:
1. Well-to-wheel energy accounting for this process
2. Carbon footprint of H2, Diesel, etc. produced.
3. $/gal cost of Diesel produced, when scaled up.
Interesting project.
Posted by: Nick Lyons | 20 January 2015 at 11:27 AM
This is an interesting method, they use the catalyst in reduction to get the synthesis gas, then they use that same catalyst for oxidation to make hydrogen. They just recycle the catalyst and start over again.
Posted by: SJC | 20 January 2015 at 12:04 PM
That's just the oxidation step. The reduction step produces "syngas and carbon dioxide". The syngas contains H2 as well as CO, and the same catalyst that converts steam to H2 will not convert H2 to water under reducing conditions. The syngas may have uses other than combustion, but that seems to be the most likely use.
What this appears to be is a potentially cheaper way of producing hydrogen from methane. It seems to have no advantage in emissions.
Posted by: Engineer-Poet | 21 January 2015 at 02:56 AM
Very interesting. Takes all kinds of energy to make our world.
"initially, the steam has to be produced with an external energy source"
Solar heat source starts and stops each day or worse, indicating the cycle does the same. "chemical reactions produce enough heat to convert water into steam without an external heat source" So system does not need solar, but adding solar gives option to syngas somewhere else part of the time, nice but more complex and capital intensive. Maybe solar's most important scontribution is to make watermelons feel good and keeps that funding source interested.
Posted by: Tim Duncan | 21 January 2015 at 11:17 AM
It would be great if they can invent a method to produce regular gasoline made synthetically at a cheaper cost than actual gasoline. That's what I put in my car and no need to change my small cheap car.
Posted by: gorr | 21 January 2015 at 05:45 PM