The Case for Hydrogen in Transport

In the last post I looked at the problem of generating electricity, and found that one of the problems is demand smoothing One approach to this is to look at the transport problem, the other major energy demand system. Currently we fill our tanks with petroleum derived products, and everything is set for that. However, battery-powered cars would remove the need for petrol, and if they were charged overnight, they would help this smoothing problem. The biggest single problem is that this cannot be done because there is not enough of some of the necessary elements to make it work. Poorer quality batteries could be made, but there is another possibility: the fuel cell.

The idea is simple. When electricity is not in high demand, the surplus is used to electrolyse water to hydrogen and oxygen. The hydrogen is stored, and when introduced to a fuel cell it burns to make water while generating electricity. Superficially, this is ideal, but there are problems. One is similar to the battery – the electrodes tend to be made of platinum, and platinum is neither cheap nor common. However, new electrodes may solve this problem. Platinum has the advantage that it is very unreactive, but the periodic servicing of the cell and the replacing of electrodes is realistic, and of course recycling can be carried out because unlike the battery, it would be possible to merely recycle the electrodes. (We could also use pressurised hydrogen in an internal combustion engine, with serious redesign, but the efficiency is simply too low.)

One major problem is storing the hydrogen. If we store it as a gas, very high pressures are needed to get a realistic mass to volume ratio, and hydrogen embrittles metals, so the tanks, etc., may need servicing as well. We could store it as a liquid, but the boiling point is -259 oC. Carting this stuff around would be a challenge, and to make matters worse, hydrogen occurs in two forms, ortho and para, which arise because the nuclear spins can be either aligned or not. Because the molecule is so small there is an energy difference between these, and the equilibrium ratio is different at liquid temperatures to room temperatures. The mix will slowly re-equilibrate at the low temperature, give off heat, boil off some hydrogen, and increase the pressure. This is less of a problem if you have a major user, because surplus pressure is relieved when hydrogen is drawn off for use, and if there is a good flow-through, no problem. It may be a problem if hydrogen is being shipped around.

The obvious alternative is not to ship it around, but ship the electricity instead. In such a scenario for smaller users, such as cars, the hydrogen is generated at the service station, stored under pressure, and more is generated to maintain the pressure. That would require a rather large tank, but it is doable. Toyota apparently think the problem can be overcome because they are now marketing the Mirai, a car powered by hydrogen fuel cells. Again, the take-up may be limited to fleet operators, who send the vehicles out of central sites. Apparently, the range is 500 km and it uses 4.6 kg of hydrogen. Hydrogen is the smallest atom so low weight is easy, except the vehicle will have a lot of weight and volume tied up with the gas pressurized storage. The question then is, how many fuel stations will have this very large hydrogen storage? If you are running a vehicle fleet or buses around the city, then your staff can refill as well, which gets them to and from work, but the vehicle will not be much use for holidays unless there are a lot of such stations.

Another possible use is in aircraft, but I don’t see that, except maybe small short-haul flights driven by electric motors with propellors. Hydrogen would burn well enough, but the secret of hydrocarbons for aircraft is they have a good energy density and they store the liquids in the wings. The tanks required to hold hydrogen would add so much weight to the wings they might fall off. If the main hull is used, where do the passengers and freight go? Another possibility is to power ships. Now you would have to use liquid hydrogen, which would require extremely powerful refrigeration. That is unlikely to be economic compared with nuclear propulsion that we have now.

The real problem is not so much how do you power a ship, or anything else for that matter, but rather what do you do with the current fleet? There are approximately 1.4 billion motor vehicles in the world and they run on oil. Let us say that in a hundred years everyone will use fuel cell-driven cars, say. What do we do in the meantime? Here, the cheapest new electric car costs about three times the cost of the cheapest petrol driven car. Trade vans and larger vehicles can come down to about 1.5 times the price, in part due to tax differences. But you may have noticed that government debt has become somewhat large of late, due to the printing of large amounts of money that governments have promptly spent. That sort of encouragement will probably be limited in the future, particularly as a consequence of shortages arising from sanctions. In terms of cost, I rather think that many people will be hanging on to their petrol-powered vehicles, even if the price of fuel increases, because the difference in the price of fuel is still a few tens of dollars a week tops, whereas discarding the vehicle and buying a new electric one involves tens of thousands of dollars, and with the current general price increases, most people will not have those spare dollars to throw away. Accordingly, in my opinion we should focus some attention on finding an alternative to fossil fuels to power our heritage fleet.

“Green” Electricity

Before thinking about how to replace fossil fuels for electricity, we need to look at how the power demand varies through the day. Not unexpectedly, this varies depending on where you live, but if you take various parts of the US as an example of industrialized usage, there is a baseline that involves minimal usage at about 0500 hrs, and that baseline varies by up to 30% seasonally. The difference between day and night can vary by up to 60%, the biggest variation is in hot summer and is due to the use of air conditioning. This means there is a huge difference between peak demand and minimum demand, which in turn means that difference has to be supplied by generation that can be turned on and off. The big thermal plants do not turn on and off easily. You can run the plant without producing electricity, but now you are simply burning fuel for no purpose.

The most responsive generators are the gas turbine and hydroelectricity. Hydro is an obvious “green” source for load smoothing; you simply shut the gate, save water, and stop generating, but most suitable hydro sites are already used. Wind power is also useful; you simply let wind pass if you do not want power, but it runs into trouble when you need power and there is no wind. Solar means you charge batteries during the day and used the power later, but in a previous post I showed it is impossible to make enough batteries to power our vehicle fleet, so how do we make an even greater supply of batteries? A further alternative is to run your base load near maximum usage, and use the surplus to make something like hydrogen when it is not needed. More on hydrogen in a later post.

The “inconvenient truth” for some is the only general major base load provider to replace coal and gas for electricity generation is nuclear. Unfortunately, nuclear has a bad press. Other downsides include, currently, it is too expensive. Most people think it is too dangerous and it is too likely to leak radiation. Actually, the smoke from coal combustion also is cancer inducing to lungs, while in the US there are around 13,000 premature deaths per year due to coal, and 23,000 annually in Europe. Coal is nowhere nearly as safe as people think. So far, nuclear power has a death rate of 0.07 deaths per terawatt-hour of electricity, or about 1 death per 14 years. That figure is enhanced substantially due to stupidity at Chernobyl. Fukushima has 1 death attributed to it, although there are claims that the stresses of it on those who had to move caused a further 2,200. Up to 2004 (18 years later) 78 died from Chernobyl. This is not good, but it is avoidable.

Current reserves of uranium total 5.3 million tonne, about a third of which are in Australia. However, only about 36,000 t of that is U235, which is what is fissile, and has to be enriched. The depleted uranium waste from the enrichment process goes into armour-piercing military rounds. What happens in most nuclear power stations is the enriched uranium rods generate heat, then have to be taken away to be reprocessed, which involves removing the plutonium for weapons. A long time ago, when I was at school, we had a visiting energy expert who told us that in the future the world would develop breeder reactors, and the enriched uranium would produce more fuel in the form of plutonium than it consumed in making electricity, The need to feed the military complex means that did not happen.

What is possible is a new generation of reactor, based on the fuel being dissolved in molten salt. The reactor is now at thermal equilibrium so it is impossible to have a melt-down – there is nothing to melt. The one catch is the issue of corrosion. That can undoubtedly be dealt with, but we have yet to learn the real long-term issues. China is currently testing one demonstration plant, and it is designed to simply provide the boiling pressurized water to run an existing power plant. The idea is simply the coal-firing is removed, this heat source is plugged in and everything else continues working. As the U238 gets converted to plutonium, it also fissions and generates heat to make electricity. What the surplus neutrons in the reactor do is also to burn “hot” isotopes, so the waste disposal problems are far less. Finally, once going, it can also take thorium as a fuel, and there is far more thorium in the world. Simple fission could keep us going for centuries.

Arguably, nuclear is not “green”. My argument is we either use it or not, but it alone has any chance of providing the levels of electricity we need and replace fossil fuel burning.

Ultimately, fusion power would solve all our energy problems. There is only one problem with it: we do not know how to make it work. There is also one general problem. To change our ways, we shall have to spend a very large amount of money, and basically replace about two thirds of our existing electricity generating infrastructure. The alternative is to do nothing and then rebuild all our major coastal cities when the ice sheets collapse. That is also expensive. We have a choice, but unfortunately our politicians seem to want to do nothing and leave the problem for our grandchildren.

The IPCC Orders Action

The Intergovernmental Panel on Climate Change has produced Part 3 of a report, and with only about 2900 pages, that has one stark message: we need aggressive action to curb greenhouse gas emission AND we need aggressive action to absorb CO2 from the atmosphere, and the action must start now, not some indefinite time in the future. As I recall, this problem was highlighted thirty years ago, and in that thirty years, emissions have increased. There was not even a hint of a reduction. To give some idea of how seriously some take this matter, Germany closed down its nuclear power plants, and now it threatens not to use Russian gas, but instead burn lignite. We cannot do much worse than that can we?

Maybe we can, and maybe we are. According to an article by Lawrence et al. (Front. For. Glob. Change https://doi.org/10.3389/ffgc.2022.756115 (2022) tropical rain forests not only secrete carbon and take it out of circulation, saving around 0.5 of a degree C, but they also physically cool the planet by a further 0.5 degrees C. What the trees do is to emit much humidity from their leaves, with the result that they cool themselves (similar to sweating) and this humidity creates clouds, which reflect sunlight back to space. This is the sort of a geo-engineering proposal often made, but the trees do it for free. So, what are we doing? Why, cutting down the rain forests. Apparently a third has been removed, and another third has been heavily logged so it is not as functional as it should be. We are supposed to be trying to hold the temperatures to an increase of no more than 1.5 degrees C, we are nearly there already, so do we really need another degree of heating added in for no good reason?

According to the IPCC, carbon emissions will have to decline rapidly after 2025, halve by 2030, and hit “net zero” by the early 2050s. Given current efforts, a warming of 3 degrees is forecast. Emissions from existing and planned projects already exceed the allowable carbon budget. But even going to zero emissions will not suffice in the short term. Nations also need to extract carbon dioxide from the atmosphere.

So, what can we do? First, consider the problem. For our electricity, which has a little under 750 GW global capacity, wind power provides a little over 6%; solar provides a little over 2%, hydropower about 16%, nuclear about 10%. For fuels, earth consumes about 3.8 trillion cubic meters of natural gas, 35.4 billion barrels of oil, and 8.5 billion t of coal a year. Why we have a problem should be clear. Currently, about 2/3 of our electricity comes from burning fossil fuel. Worse, you don’t build a coal-fired power station today and turn it off tomorrow. Wind turbines need solid support. Making a tonne of cement produces roughly 800 kg of CO2, making a tonne of steel releases 1.85 t of CO2; combined they sum to about 16% of the world’s CO2 production. Wind power might be “green” but look at the CO2 emitted making and installing the equipment. Solar is free, but the demand for electricity is when solar is weak or non-existent, so massive storage is required, and that gets expensive, both in terms of money and in CO2 emissions for making the batteries. The point is, all new infrastructure is going to involve a lot of CO2 emissions before any energy is generated.

Transport is a particularly difficult problem. I think it is a common problem, but where I live the cities expanded significantly after WW 2, and they expanded with the automobile in mind. The net result is it is most people get around by car. Most people have access to a car, and that is petrol driven. The electric vehicle that might replace the petrol-driven car costs (here, at least) over twice that of the petrol driven car and you cannot really convert them. The reason is the electric vehicle needs a huge mass of batteries to have a useful driving range. Further, as I pointed out in a previous post, we cannot have everyone driving electric cars because we do not have the cobalt to make the batteries, and we still need ships and aircraft, which use a rather small fraction of the oil cut. We have to do something with the rest of the fuel cut. You may have noticed that large electricity production above and how so much comes from fossil fuels. Transport uses about 25% of the total energy production. That means to convert transport to electricity, we need to expand electricity generation by about another 250 GW. That is easy to write down, but just think of all the CO2 emitted by making the concrete and steel to build the power stations. Our current wind power would have to expand by a factor of 5.5 and we have to hope there are no still days. Of course, you may legitimately argue that if we charged batteries at night that would even the base load and you do not need all the additional installation. That is true, except green electricity generation  usually is not optimal for base loads.

My view is it cannot be done the way the enthusiasts want it done. We shall never get everybody to cooperate sufficiently to achieve the necessary reductions because society simply cannot afford it. We need a different approach, and in some  later posts, I shall try to offer some suggestions.

Molecular Oxygen in a Comet

There is a pressure, these days, on scientists to be productive. That is fair enough – you don’t want them slacking off in a corner, but a problem arises when this leads to the publication of papers: there are so many of them that nobody can keep up with even a small fraction of them. Worse, many of them do not seem to say much. Up to a point, this has an odd benefit: if you leave a lot unclear, all your associates can publish away and cite you, which has this effect of making you seem more important because funders like to count citations. In short, with obvious exceptions, the less you advance the science, the more important you seem at second level funding. I am going to pick, maybe unfairly, on one paper from Nature Astronomy (https://www.nature.com/articles/s41550-022-01614-1) as an illustration.

One of the most unexpected findings in the coma of comet 67P/Churyumov-Gerasimenko was “a large amount” of molecular oxygen. Something to breathe! Potential space pilots should not get excited; “a large amount” is only large with respect to what they expected, which was none. At the time, this was a surprise to astronomers because molecular oxygen is rather reactive and it is difficult to see why it would be present. Now there is a “breakthrough”: it has been concluded there is not that much oxygen in the comet at all, but this oxygen came from a separate small reservoir. The “clue” came from the molecular oxygen being associated with molecular water when emitted from a warm site. As it got cooler, any oxygen was associated with carbon dioxide or carbon monoxide. Now, you may well wonder what sort of clue that is? My question is, given there is oxygen there, what would you expect? The comet is half water, so when the surface gets warm, it sublimes. When cooler, only gases at that lower temperature get emitted. What is the puzzle?

However, the authors of the paper came to a different conclusion. They decided that there had to be a deep reservoir of oxygen within the comet, and a second reservoir close to the surface that is made of porous frozen water. According to them, oxygen in the core works its way to the surface and gets trapped in the second reservoir. Note that this is an additional proposition to the obvious one that oxygen was trapped in ice near the surface. We knew there was gas trapped in ice that was released with heat, so why postulate multiple reservoirs, other than to get a paper published?

So, where did this oxygen come from? There are two possibilities. The first is it was accreted with the gas from the disk when the comet formed. This is somewhat difficult to accept. Ordinary chemistry suggests that if oxygen molecules were present in the interstellar dust cloud it should react with hydrogen and form water. Maybe that conclusion is somehow wrong, but we can find out. We can estimate the probability by observing the numerous dust clouds from which stars accrete. As far as I am aware, nobody has ever found rich amounts of molecular oxygen in them. The usual practice when you are proposing something unusual is you find some sort of supporting evidence. Seemingly, not this time.

The second possibility is that we know how molecular oxygen could be formed at the surface. High energy photons and solar wind smash water molecules in ice to form hydrogen and hydroxyl radicals. The hydrogen escapes to space but the hydroxyl radicals unite to form hydrogen peroxide or other peroxides or superoxides, which can work their way into the ice. There are a number of other solids that catalyse the degradation of peroxides and superoxides back to oxygen, which would be trapped in the ice, but released when the ice sublimed. So, from the chemist’s point of view there is a fairly ordinary explanation why oxygen might be formed and gather near the surface. From my point of view, Occam’s Razor should apply: you use the simplest explanation unless there is good evidence. I do not see any evidence about the interior of the comet.

Does it matter? From my point of view when someone with some sort of authority/standing says something like this, there is the danger that the next paper will say “X established that . . “  and it becomes almost a gospel. This is especially so when the assertion cannot be easily challenged with evidence as you cannot get inside that comet. Which gives the perverse realization that you need strong evidence to challenge an assertion, but maybe no evidence at all to assert it in the first place. Weird?