Transport System Fuel. Some passing Comments

In the previous series of posts, I have discussed the question of how we should power our transport systems that currently rely on fossil fuels, and since this will be a brief post, because I have been at a conference for most of this week, I thought it would be useful to have a summary. There are two basic objectives: ensure that there are economic transport options, and reduce the damage we have caused to the environment. The latter one is important in that we must not simply move the problem.

At this stage we can envisage two types of power: heat/combustion and electrical. The combustion source of power is what we have developed from oil, and many of the motors, especially the spark ignition motors, have been designed to optimise the amount of the oil that can be so used. The compression of most spark ignition engines is considerably lower than it could be if the octane rating was higher. These motors will be with us for some time; a car bought now will probably still be on the road in twenty years so what do we do? We shall probably continue with oil, but biofuels do offer an alternative. Some people say biofuels themselves have a net CO2 output in their manufacture. Maybe, but it is not necessary; the main reason would be that the emphasis is put onto producing the appropriate liquids because they are worth more than process heat. Process heating can be provided from a number of other sources. The advantages of biofuels are they power existing vehicles, they can be CO2 neutral, or fairly close to it, we can design the system so it produces aircraft fuel and there is really no alternative for air transport, and there are no recycling problems following usage. The major disadvantages are that the necessary technology has not really been scaled up so a lot of work is required, it will always be more expensive than oil until oil supplies run down so there is a poor economic reason to do this unless missions are taxed, and the use of the land for biofuels will put pressure on food production. The answers are straightforward: do the development work, use the tax system to change the economic bias, and use biomass from the oceans.

There are alternatives, mainly gases, but again, most of them involve carbon. These could be made by reducing CO2, presumably through using photolysis of water (thus a sort of synthetic photosynthesis) or through electricity and to get the scale we really need a very significant source of electricity. Nuclear power, or better still, fusion energy would work, but nuclear power has a relative disappointing reputation, and fusion power is still a dream. Hydrazine would make a truly interesting fuel, although its toxicity would not endear it to many. Hydrogen can work well for buses, etc, that have direct city routes.

Electricity can be delivered by direct lines (the preferred option for trains, trams, etc.), but otherwise it must be by batteries or fuel cells. The two are conceptually very similar. Both depend on a chemical reaction that can be very loosely described as “burning” something but generating electricity instead of heat. In the fuel cell, the material being “burnt” is added from somewhere else, and the oxidising agent, which may be air, must also be added. In the battery, nothing is added, and when what is there is used, it is regenerated by charging.

Something like lithium is almost certainly restricted to batteries because it is highly reactive. Lithium fires are very difficult to put out. The lithium ion battery is the only one that has been developed to a reasonable level, and part of the reason for that is that the original market was for mobile phones and laptops. There are potential shortages of materials for lithium ion batteries, but they would never cut in for those original uses. However, as shown in my previous post, recycling of lithium ion batteries will be very difficult to solve the problem for motor vehicle batteries. One alternative for batteries is sodium, obtainable from salt, and no chance of shortage.

The fuel cell offers some different options. A lot has been made of hydrogen as the fuel of the future, and some buses use it in California. It can be used in a combustion motor, but the efficiencies are much better for fuel cells. The technology is here, and hydrogen-powered fuel cell cars can be purchased, and these can manage 500 km on  single charge, and can totally refuel in about 5 minutes. The problem again is, hydrogen refuelling is harder to find. Methanol would be easier to distribute, but methanol fuel cells as of yet cannot sustain a high power take-off. Ammonia fuel cells are claimed to work almost as well as hydrogen and would be the cheapest to operate. Another possibility I advocated in one of my SF novels is the aluminium/chlorine cell, as aluminium is cheap, although chlorine is a little more dangerous.

My conclusions:

(a)  We need a lot more research because most options are not sufficiently well developed,

(b)  None will out-compete oil for price. For domestic transport, taxes on oil are already there, so the competitors need this tax to not apply

(c)  We need biofuels, if for no other reason that maintaining existing vehicles and air transport

(d)  Such biofuel must come at least partly from the ocean,

(e)  We need an alternative to the lithium ion battery,

(f)  We badly need more research on different fuel cells, especially something like the ammonia cell.

Yes, I gree that is a little superficial, but I have been at a conference, and gave two presentations. I need to come back down a little 🙂

Book Discount

From November 21 – 28, Athene’s Prophecy will be discounted to 99c/99p on Amazon. Science fiction with some science you can try your hand at. The story is based around Gaius Claudius Scaevola, given the cognomen by Tiberius, who is asked by Pallas Athene to do three things before he will be transported to another planet, where he must get help to save humanity from total destruction. The scientific problem is to prove the Earth goes around the Sun with what was known and was available in the first century. Can you do it? Try your luck. I suspect you will fail, and to stop cheating, the answer is in the following ebook. Meanwhile, the story.  Scaevola is in Egypt for the anti-Jewish riots, then to Syria as Tribunis laticlavius in the Fulminata, then he has the problem of stopping a rebellion when Caligulae orders a statue of himself in the temple of Jerusalem. You will get a different picture of Caligulae than what you normally see, supported by a transcription of a report of the critical meeting regarding the statue by Philo of Alexandria. (Fortunately, copyright has expired.). First of a series. http://www.amazon.com/dp/B00GYL4HGW

Recycling Lithium Ion Batteries

One of the biggest contributors to greenhouse warming is transport, and the solution that seems to be advocated is to switch to electric vehicles as they do not release CO2, and the usual option is to use the lithium ion battery A problem that I highlighted in a previous blog is we don’t have enough cobalt, and we run out of a lot of other things if we do not recycle. A recent review in Nature (https://doi.org/10.1038/s41586-019-1682-5)   covered recycling and the following depends on that review. The number of vehicles in the world is estimated to reach 2 billion by 2035 and if all are powered by lithium ion batteries the total pack wastes would be 500 million tonnes, and occupy a billion cubic meters. Since the batteries last about nine years, we eventually get drowned in dead batteries, unless we recycle. Also, dead lithium ion batteries are a fire hazard. 

There are two initial approaches, assuming we get the batteries cleanly out of the vehicle. One is to crush the whole and burn off the graphite, plastics, electrolyte, etc, which gives an alloy of Co, Cu, Fe and Ni, together with a slag that contains aluminium and manganese oxides, and some lithium carbonate. This loses over half the mass of the batteries and contributes to more greenhouse warming, which was what we were trying to avoid. Much of the lithium is often lost this way to, and finally, we generate a certain amount of hydrogen fluoride, a very toxic gas. The problem then is to find a use for an alloy of unknown composition. Alternatively, the alloy can be treated with chlorine, or acid, to dissolve it and get the salts of the elements.

The alternative is to disassemble the batteries, and some remaining electricity can be salvaged. It is imperative to avoid short-circuiting the pack, to prevent thermal runaway, which produces hydrofluoric acid and carcinogenic materials, while fire is a continual hazard. A further complication is that total discharge is not desirable because copper can dissolve into the electrolyte, contaminating the materials that could be recycled. There is a further problem that bedevils recycling and arises from free market economics: different manufacturers offer different batteries with different physical configurations, cell types and even different chemistries. Some cells have planar electrodes, others are tightly coiled and there are about five basic types of chemistries used. All have lithium, but additionally: cobalt oxide, iron phosphorus oxide, manganese oxide, nickel/cobalt.aluminium oxide, then there are a variety of cell manufacturers that use oxides of lithium/manganese/cobalt in various mixes. 

Disassembling starts with removing and the wiring, bus bars, and miscellaneous external electronics without short-circuiting the battery, and this gets you to the modules. These may have sealants that are difficult to remove, and then you may find the cells inside stuck together with adhesive, the components may be soldered, and we cannot guarantee zero charge. Then if you get to the cell, clean separation of the cathode, anode, and electrolyte may be difficult, we might encounter nanoparticles which provide a real health risk, the electrolyte may generate hydrogen fluoride and the actual chemistry of the cell may be unclear. The metals in principle available for recycling are cobalt, nickel, lithium, manganese and aluminium, and there is also graphite.

Suppose we try to automate? Automation requires a precisely structured environment, in which the robot makes a pre-programmed repetitive action. In principle, machine sorting would be possible if the batteries had some sort of label that would specify precisely what it was. Reading and directing to a suitable processing stream would be simple, but as yet there are no such labels, which, perforce, must be readable at end of life. It would help recycling if there were some standardised designs, but good luck trying to get that in a market economy. If you opt for manual disssembling, this is very laboour intensive and not a particularly healthy occupation.

If the various parts were separated, metal recovery can be carried out chemically, usually by treating the parts with sulphuric acid and hydrogen peroxide. The next part is to try to separate them, and how you go about that depends on what you think the mixture is. Essentially, you wish to precipitate one material and leave the others, or maybe precipitate two. Perhaps easier is to try to reform the most complex cathode by taking a mix of Ni, Mn, and Co that has been recovered as hydroxides, analysing it and making up what is deficient with new material, then heat treating to make the desired cathode material. This assumes you have physically separated the anodes and cathodes previously.

If the cathodes and anodes have been recovered, in principle they can be directly recycled to make new anodes and cathodes, however the old chemistry is retained. Cathode strips are soaked in N-methylpyrrolidine (NMP) then ultrasonicated to make the powder to be used to reformulate a cathode. Here, it is important that only one type is used, and it means new improved versions are not made. This works best when the state of the battery before recycling was good. Direct recycling is less likely to work for batteries that are old and of unknown provenance. NMP is a rather expensive solvent and somewhat toxic. Direct recycling is the most complicated process.

The real problem is costs. As we reduce the cobalt content, we reduce the value of the metals. Direct recycling may seem good, but if it results in an inferior product, who will buy it? Every step in a process incurs costs, and also produces is own waste stream, including a high level of greenhouse gases. If we accept the Nature review, 2% of the world’s cars would eventually represent a stream of waste that would encircle the planet so we have to do something, but the value of the metals in a lithium ion battery is less than 10% of the cost of the battery, and with all the toxic components, the environmental cost of such electric vehicles is far greater than people think. All the steps generate their own waste streams that have to be dealt with, and most steps would generate their own greenhouse gases. The problem with recycling is that since it usually makes products of inferior quality because of the cost of separating out all the “foreign” material, economics means that in a market economy, only a modest fraction actually gets recycled.

Galactic Collisions

As some may know, the Milky Way galaxy and the Andromeda galaxy are closing together and will “collide” in something like 4 – 5 billion years. If you are a good distance away, say in a Magellenic Cloud, this would look really spectacular, but what about if you were on a planet like Earth, right in the middle of it, so to speak? Probably not a lot of difference from what we see. There could be a lot more stars in the sky (and there should be if you use a good telescope) and there may be enhanced light from a dust cloud, but basically, a galaxy is a lot of empty space. As an example, light takes 8 minutes and twenty seconds to get from the sun to Earth. Light from the nearest star takes 4.23 years to get here. Stars are well-spaced.

As we understand it, stars orbit the galactic centre. The orbital velocity of our sun is about 828,000 km/hr, a velocity that makes our rockets look like snails, but it takes something like 230,000,000 years to make an orbit, and we are only about half-way out. As I said, galaxies are rather large. So when the galaxies merge, there will be stars going in a lot of different directions until things settle down. There is a NASA simulation in which, over billions of years, the two pass through each other, throwing “stuff” out into interstellar space, then they turn around and repeat the process, except this time the centres merge, and a lot more “stuff” is thrown out into space. The meaning of “stuff” here is clusters of stars. Hundreds of millions of stars get thrown out into space, many of which turn around and come back, eventually to join the new galaxy. 

Because of the distance between stars the chances of stars colliding comes pretty close to zero, however, it is possible that a star might pass by close enough to perturb planetary orbits. It would have to come quite close to affect Earth, as, for example, if it came as close as Saturn, it would only make a minor perturbation to Earth’s orbit. On the other hand, if that close it could easily rain down a storm of comets, etc, from further out, and seriously disrupt the Kuiper Belt, which could lead to extinction-type collisions. As for the giant planets, it would depend on where they were in their orbit. If a star came that close, it could be travelling at such a speed that if Saturn were on the other side of the star it could know little of the passage.

One interesting point is that such a galactic merger has already happened for the Milky Way. In the Milky Way, the sun and the majority of stars are all in orderly near-circular orbits around the centre, but in the outer zones of the galaxy there is what is called a halo, in which many of the stellar orbits are orbiting in the opposite direction. A study was made of the stars in the halo directly out from the sun, where it was found that there are a number of the stars that have strong similarities in composition, suggesting they formed in the same environment, and this was not expected. (Apparently how active star formation is alters their composition slightly. These stars are roughly similar to those in the Large Magellenic Cloud.)  This suggests they formed from different gas clouds, and the ages of these different stars run from 13 to 10 billion years ago. Further, it turned out that the majority of the stars in this part of the halo appeared to have come from a single source, and it was proposed that this part of the halo of our galaxy largely comprises stars from a smaller galaxy, about the size of the Large Magellenic Cloud that collided with the Milky Way about ten billion years ago. There were no comments on other parts of the halo, presumably because parts on the other side of the galactic centre are difficult to see.

It is likely, in my opinion, that such stars are not restricted to the halo. One example might be Kapteyn’s star. This is a red dwarf about eleven light years away and receding. It, too, is going “the wrong way”, and is about eleven billion years old. It is reputed to have two planets in the so-called habitable zone (reputed because they have not been confirmed) and is of interest in that since the star is going the wrong way, presumably as a consequence of a galactic merger, this shows the probability running into another system sufficiently closely to disrupt the planetary system is of reasonably low probability.

Where to Find Life? Not Europa

Now that we have found so many exoplanets, we might start to wonder whether they have life. It so happens I am going to give a presentation on this at a conference in about three weeks time, hence the temptation to focus attention on the topic. My argument is that whether a place could support life is irrelevant; the question is, could it get started? For the present, I am not considering panspermia, i.e. it came from somewhere else on the grounds that if it did, the necessities to reproduce still had to be present and if they were, life would probably evolve anyway. 

I consider the ability to reproduce to be critical because, from the chemistry point of view, it is the hardest to get right. One critical problem is reproduction itself is not enough; it is no use using all resources to make something that reproduces a brown sludge. It has to guess right, and the only way to do that is to make lots of guesses. The only way to do that is to tear to bits that which is a wrong guess and try again and re-use the bits. But then, when you get something useful that might eventually work, you have to keep the good bits. So reproduction and evolution have opposite requirements, but they have to go through the same entity. Reproduction requires the faithful transmission of information; evolution requires the information to change on transmission, but eventually not by much. Keep what is necessary, reject that which is bad. But how?

Information transfer requires a choice of entities to be attached to some polymer, and which can form specific links with either the same entity only (positive reproduction) or through a specific complementary entity (to make a negative copy). To be specific they have to have a strongly preferred attachment, but to separate them later, the attachment has to be able to be converted to near zero energy. This can be done with hydrogen bonds, because solvent water can make up the energy during separation. One hydrogen bond is insufficient; there are too many other things that could get in the road. Adenine forms two hydrogen bonds with uracil, guanine three with cytosine, and most importantly, guanine and uracil both have N-H bonds while adenine and cytosine have none; the wrong pairing either leads to a steric clash that pushes them apart or ends up with only one hydrogen bond that is not strong enough. Accordingly we have the condition for reliable information transfer. Further good news is these bases form themselves from ammonium cyanide, urea and cyanoacetylene, all of which are expected on an earth-like planet from my concept of planetary formation.

The next problem is to form two polymer strands that can separate in water. First, to link them something must have two links. For evolution to work, these have to be strong, but breakable under the right conditions. To separate, they need to have a solubilizing agent, which means an ionic bond. In turn, this means three functional valence electrons. Phosphate alone can do this. The next task is to link the phosphate to the bases that carries the information code. That something must also determine a fixed shape for the strands, and for this nature chose ribose. If we link adenine, ribose and phosphate at the 5 position of ribose we get adenosine monophosphate (AMP); if we do he same for uracil we get uridine monophosphate (UMP). If we put dilute solutions of AMP and UMP into vesicles (made by a long chain hydrocarbon-based surfactant) and let them lie on a flat rock in the sun and splash them from time to time with water, we end with what is effectively random “RNA” strands with over eighty units in a few hours. At this point, useful information is unlikely, but we are on the way.

Why ribose? Because the only laboratory synthesis of AMP from only the three constituents involves shining ultraviolet light on the mixture, and to me, this shows why ribose was chosen, even though ribose is one of the least likely sugars to be formed. As I see it, the reason is we have to form a phosphate ester specifically on the 5-hydroxyl. That means there has to be something unique about the 5-hydroxyl of ribose compared with all other sugar hydroxyl groups. To form such an ester, a hydroxyl has to hit the phosphate with an energy equivalent to the vibrations it would have at about 200 degrees C. Also, if any water is around at that temperature, it would immediately destroy the ester, so black smokers are out. The point about a furanose is it is a flexible molecule and when it receives energy (indirectly) from the UV light it will vibrate vigorously, and UV light has energy to spare for this task. Those vibrations will, from geometry, focus on the 5-hydroxyl. Ribose is the only sugar that has a reasonable amount of furanose; the rest are all in the rigid pyranose form. Now, an interesting point about ribose is that while it is usually only present in microscopic amounts in a non-specific sugar synthesis, it is much more common if the sugar synthesis occurs in the presence of soluble silica/silicic acid. That suggests life actually started at geothermal vents.

Now, back to evolution. RNA has a rather unique property amongst polymers in that the strands, when they get to a certain length and can be bent into a certain configuration and presumably held there with magnesium ions, they can catalyse the hydrolysis of other strands. It does that seemingly by first attacking the O2 of ribose, which breaks the polymer by hydrolysing the adjacent phosphate ester. The next interesting point is that if the RNA can form a double helix, the O2 is more protected. DNA is, of course, much better protected because it has no O2. So the RNA can build itself, and it can reorganise itself.

If the above is correct, then it places strong restrictions on where life can form. There will be no life in under-ice oceans on Europa (if they exist) for several reasons. First, Europa seemingly has no (or extremely small amounts of) nitrogen or carbon. In the very thin atmosphere of Europa (lower pressures than most vacuum pumps can get on Earth) the major gas is the hydroxyl radical, which is made by sunlight acting on ice. It is extremely reactive, which is why there is not much of it. There is 100,000 times less sodium it the atmosphere. Nitrogen was undetected. The next reason is the formation of the nucleic acid appears to require sunlight, and the ice will stop that. The next reason is that there is no geothermal activity that will make the surfactants, and no agitation to convert them to the vesicles needed to contain the condensation products, the ice effectively preventing that. There is no sign of hydrocarbon residues on the surface. Next, phosphates are essentially insoluble in water and would sink to the bottom of an ocean. (The phosphate for life in oceans on Earth tends to come from water washed down from erosion.) Finally, there is no obvious way to make ribose if there is no silicic acid to orient the formation of the sugar.

All of which suggests that life essentially requires an earth-like planet. To get the silicic acid you need geothermal activity, and that may mean you need felsic continents. Can you get silica deposits from volcanism/geothermal activity when the land is solely basalt? I don’t know, but if you cannot, this proposed mechanism makes it somewhat unlikely there was ever life on Mars because there would be no way to form nucleic acids.