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 🙂

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.

Protesting on Climate Change

It is interesting these days to see the level of protest; so many people want to protest against doing something. In many cases, that is fair as what they are protesting about should not happen, but then the problem comes, what happens when they get the rhythm, and what sort of protests get results as opposed to the protestors just making a nuisance of themselves? Recently, there were widespread protests here against the inaction of governments on the issue of climate change and that is a fair enough target of protest but how should they go about it? Blocking major roads to prevent traffic from going home after work simply leads to the production of more greenhouse gas. Then there were people here who used superglue to attach themselves to windows. My view on that is they should have been identified so that any bills for damages could be sent, then they be left there. Since they glued their hands, they would need friends to even feed them and a couple of cold fronts were coming.

What I find interesting is that one of the proposed ways of attacking climate change is to plant trees and they even protest about that. They argue the trees grow, then get cut down and the CO2 is returned to the atmosphere so we are no further ahead. In my opinion, that is wrong. First, we buy time. The trees can stand for a reasonable length of time, and further, when we cut them down, we can use the wood to build houses, etc. Leaves fall and return some carbon to the soil. And, of course, when we cut them down, we can replant. But most important, from my point of view, is we can do this now. There is no king hit that will deal with climate change so we shall have to do a very large number of things and unfortunately we don’t actually know how to do many of them beneficially. There is nothing like getting started on what you can do, and that you know what the consequences of doing it are.

Another objection noted in our local paper was that, wait for it, had we started thirty years ago when we knew about the problem this might have worked, but now we need more trees than we can reasonably plant quickly. Well, maybe. It does take time to get the necessary seedlings. The argument seems to be, we can’t solve the entire crisis this way, so why bother? Yes, I know there is no king hit, but if you are going to solve this crisis with a number of different approaches, getting started now is better than not doing anything. As the callers for doing nothing argue, we only have the problem because we did nothing some time ago. Yes, it is true we have wasted a lot of time, but why will wasting more now be beneficial?

Another argument seems to be, the land is too valuable for food production to waste on planting trees. Well, if I look out the window from where I am writing this, I see a range of somewhat tortured hills that stand between 300 to 700 meters above the valley floor, and these hills proceed as hills and steep valleys for a considerable distance. They are largely devoid of big trees, despite the fact that this whole area was initially heavily forested. When the settlers came, the valley was cleared of forest for farmland (farming has now long gone, having been replaced by urban development) then the hillsides were denuded of forest for timber. Now there is light scrub in places, but the big trees are long gone, and this is typical of a lot of land here. Planting trees would stabilise a lot of such steep hillsides, which are often prone to severe erosion, especially with heavy rain, which is expected to become more common over time due to climate change, at least here. For such country where harvesting trees becomes unlikely, by planting a judicious mix of trees such a forest could be self-sustaining so once established and it would store carbon indefinitely.

There are additional benefits of forests. An article in he recent Physics World mentioned that forests decrease the effect of storms, the reason being that the rough land surface offers a frictional restraint on wind speed. The forest has to be reasonably large, and of course the beneficial effects tend to apply to places distant from the coast. The forests also offer a benefit to rainfall through evapotranspiration and it is notable that many areas that are now facing desertification in Africa once had reasonable rainfall and extensive forests. It should be emphasised that forests may also reduce total rainfall by reducing the effect of heavy tropical storms, however in general these do little to provide water in a useful form as the water runs off very quickly. Forests are also beneficial in that they hold up water from heavy rains and allow it to be absorbed by the soil, and hence be available later, and of course, reduce heavy erosion. Also, in areas prone to severe flooding, and we have seen many examples of flooded urban areas on television recently, by holding up the water and thus spreading its movement over more time, the effects of such floods are mitigated. To my mind, anything that achieves more than one benefit is far more worthwhile to pursue.

As for the argument that when the trees mature, they will be harvested and eventually the carbon will return to the atmosphere, I have two responses. First, at least some of it can be stored in buildings, where it will remain for quite some time. Second, you could burn it for fuel or convert it to biofuel, in which case the carbon will return quickly, several decades in the future, but it displaces fossil carbon you would have otherwise converted to CO2, so you are still ahead. Finally, you have bought time to develop new means of solving this problem. And, at the same time, you do generate a future resource, in some cases from land that is otherwise producing nothing except erosion. From my point of view, it probably does not matter whether we act because I shall be dead by the time the really worst of the consequences arrive. However, I would like my grandchildren’s children to have a reasonable chance at life, and that means that we must stop protesting against change because our society cannot continue this way. Change will come; the issue is, what sort of change? Let us control it and make it beneficial.

The Hydrogen Economy

Now that climate change has finally struck home to at least some politicians, we have the problem, what to do next. An obvious point could be that while the politicians made grandiose promises about it thirty years ago, and then for economic reasons did nothing, they could at least have carried out research so they knew what their options are so that when they finally got around to doing something, they knew what to do. Right now, they don’t. One of the possibilities for transport is the use of hydrogen, but is that helpful? If so, where? The first point is you have to make your hydrogen. That is easy: you pass electricity through water. There is no shortage of water but you still have to generate your electricity. This raises the question, how, and at what cost? The good news is that generating hydrogen merely consumes energy so it can be turned down or off at peak load periods, but the difficulty now is the renewables everyone is so happy about offer erratic loads. As an example, Germany is turning off its nuclear power stations and finds it has to burn more coal, especially when the wind is not blowing. 

Assume we have the electricity and we have hydrogen, now what? The hydrogen could be burned directly in a compression motor, or used to power fuel cells. The latter is far more energy efficient, and we can probably manage about 70% overall efficiency. The reason the fuel cell is more desirable than the battery is simply that the battery cannot contain the desired energy density. The advantages of hydrogen include it is light and when burned (including in a fuel cell) all it makes is water. Water is a very powerful greenhouse gas, but the atmosphere has a way of promptly removing excess: rain.

However, hydrogen does have some disadvantages. A hydrogen-air mix is explosive over a rather wide mix ratio. Even outside this ratio, it has a clear flammability and an exceptionally fast flame speed, it leaks far faster than any other gas other than, possibly, helium, and it is odourless and colourless so you may not know it is there. But suppose you put that behind you, there are still clear problems. A small fuel cell car would need approximately 1 kg of hydrogen to drive 100 km. Now, suppose we need a range of 500 km. The storage of 5 kg of hydrogen would take up most of the boot space if you use a tank that is pressurised to 700 bar. (1 bar is atmospheric pressure.) That requires a lot of energy to compress the gas, and it adds a significant weight to the reinforced tank, which you most certainly do not want to rupture. The volume is important for a small car. You wish to go on holiday, then find your boot is occupied by a massive gas tank. However, this is trivial for very large machines, and a company in the US makes hydrogen powered forklifts. Here, a very heavy counterballancing weight is required so a monstrous steel tank is actually an asset. I previously wrote a blog post on hydrogen for vehicles, here.

There are different possible ways to store hydrogen. For those with a technical bent, the objective is to have something that absorbs hydrogen and binds it with an energy of between 15 – 20 kJ/mol. That is fairly weak. If you can mange that range you can store hydrogen at up to 100 bar with good reversibility. If you bind it in metal hydrides, you get a better density of storage at atmospheric pressure, but the difficulty is then to get the hydrogen back out. Most of the proposed metal organic absorbers bind it too weakly and you can’t get enough in. The metals that strongly absorb can be made to release it easier if the metal is present as nanoparticles, and to prevent these clumping, they can be embedded into carbon. There is an issue here, though, that the required volume is starting to become large for a given usage range because there are so many components that are not hydrogen.

There is another problem with hydrogen that most overlook: how do you deliver it to filling stations? Pressurizing won’t work because you can’t get enough into any container to be worth it. You could ship liquefied hydrogen, but it is only a liquid at or below -253 degrees Centigrade. It takes a lot of energy to cool that far, a lot to keep it that cold, and the part that most people will not realize is that at those very low temperatures for very light atoms, there are some effects of quantum mechanics that have to be taken into account. One problem is that hydrogen occurs as two isomers: ortho and para hydrogen. (Isomers are where there are at last two distinctly different forms with the same components, that may or may not readily interconvert.)  These arise because the hydrogen molecule comprises two protons bound by two electrons. The protons have what we call nuclear spin and as a consequence, have a magnetic moment. In ortho hydrogen, the spins are aligned; in para they are opposed. At room temperature, the hydrogen is 75% in the ortho form, but this is of higher energy than the para form. Accordingly, if you just cool hydrogen to the liquid form, you get the room temperature mix. This slowly converts to the para form, but it gives off heat as it does so. That means a tank of liquid hydrogen slowly builds up pressure. To be used as liquid hydrogen it is probably best to let it switch to the para form first, but that takes a lot more energy maintaining the low temperatures while the conversion is going on. Currently, liquefying hydrogen takes 12 kWh of power per kilogram of hydrogen, which is about 25% that of what you get from a fuel cell. In practice, you may need almost that much again to keep it cold, and since this power has to be electrical, we have an even greater demand for electricity.

So, is there an answer? My feeling is still that hydrogen is not the most desirable material for a fuel cell, from the point of view of usage in transport. The reason it is pursued is that it is easiest to make a fuel cell work with hydrogen. There are alternatives. Two that come to mind are ammonia and methanol. Both can drive fuel cells, and ammonia reacts to give water and nitrogen while methanol reacts to give water and carbon dioxide. Currently, the ammonia cell may be more efficient, but ammonia is somewhat difficult to make, although there is evidence it can be made from hydrogen and nitrogen under mild conditions. The methanol fuel cell has a problem that too much of the methanol sneaks through the membrane that keeps the two sides of the cell separate, and carbon monoxide tends to poison electrodes. Methanol could be made by the reduction of carbon dioxide from the air with solar energy.

So where does that leave us? In my opinion, what we need more than anything else is progress on better performing methanol or ammonia fuel cells, or some better fuel cell. My preference for the fuel cell is simply an issue of weight and power density, and I do not see hydrogen as being useful for light vehicles. The very heavy machines are a different matter, and batteries will never adequately power them. The problem of energy production in the future is a real one, and I feel we need to do a lot more research to pick the better options. We should have been doing this over the last thirty years, but we didn’t. However, there is no point in moaning about time wasted; we are here, and we have to act with a lot more urgency. However, it is not right to use the easiest but not very good options; we need to get these problems right.

The Hydrogen Economy to solve Climate Change?

One of the interesting aspects of climate change is the number of proposals put forward to solve it that do not take into account adverse consequences. There is a strong association of wishful thinking with some of these. On the other side are the gloomy ones, and maybe I fall into that category. What brought that thought to the fore was I have seen further claims for hydrogen as a solution. Why? Well, there are wild claims that wind and solar will solve everything. One problem with these is they tend to deliver their energy in pulses: solar during the day, wind when it is blowing. The net result is that if these can deliver adequate power for all times, there is serious overproduction required at other times. The problem then is how to store this energy. One way is to pump water uphill, but that requires large storage. In a country like New Zealand, where much of the electricity is hydro generated, you would just turn off that generation and use the hydro to manage power demand. However, that assumes there is not a large increase in electricity demand. One proposed solution is to generate hydrogen by electrolysing water. This is a well-understood technology, with no problems, given the power. There are, however, significant economic ones.

This is claimed to solve another problem; a very significant amount of domestic heating is obtained from burning gas. Now, all we have to do is burn hydrogen. We could also use hydrogen in vehicles. My big problem, having worked with hydrogen before, is that it leaks, and is extremely flammable. According to Wikipedia, the flammability range of hydrogen in air is between 4% and 75%; to detonate, the limits are 18.3 – 59% (each by volume), and a leak can support combustion at flow rates as low as 4 micrograms/second. Mixtures can ignite with very low energy input, 1/10 of that needed to ignite gasoline/air, and any static electric spark can ignite it.

The leak problem is made worse by the fact that hydrogen can embrittle metals, and thus create a way for it to escape. It is lighter than air, so it tends to accumulate at the ceilings of buildings, and its very wide explosive range is a broad hazard. The idea that hydrogen could be piped into houses to provide heating is not something I would want to see. The problem is made worse in that you might be sensible and cautious and not take it up, but your neighbour might. The consequences of that can impinge on you. Recently, in Christchurch, a house blew up, and reduced itself to a collection of boards, roofing material, etc., with only the foundations remaining more or less where they started. Several neighbours houses were severely damaged, and made effectively unliveable, at least without major repairs. By some miracle, nobody was killed, although a number had injuries. What apparently happened was a registered gasfitter had done some work on the house’s gas system, there was a natural gas leak, and something ignited it. My guess is, he has some explaining to do, but my point is if this can happen to a registered tradesman, what will happen if there is widespread use of something that leaks with orders of magnitude more ease?

There is a further irony. The objective behind using hydrogen is to help the greenhouse effect by reducing the amount of carbon dioxide we emit. Unfortunately, leaked hydrogen also magnifies the greenhouse effect. At first sight, this does not look right because greenhouse gases work because there is a change of dipole moment in the vibrational mode. This is needed because unless the transition involves a change of electric moment, it cannot absorb a photon. Hydrogen has only one vibrational mode and no electric moment, and no change of electric moment when it is stretched because of its symmetry, i.e.one end of H2 is exactly the same as the other end. There is a minor effect in that the molecule can be polarised for an instant in a collision with something else, but that is fairly harmless.

The problem lies in downstream consequences. One of the important greenhouse gases is methane, emitted by natural gas leaks, farm animals, other farm processes, anaerobic fermentation, etc. Methane is about 35 times more powerful than carbon dioxide as a greenhouse gas, and worse, it absorbs in otherwise transparent parts of the infrared spectrum. (The otherwise does not include other hydrocarbon gases.) However, methane is not as serious as it might be because it is short-lived. UV radiation in the upper atmosphere breaks water, directly or indirectly, into hydroxyl radicals and hydrogen radicals. The hydroxyl radicals rapidly degrade methane, and the hydrogen radicals react with oxygen in the air to make peroxyl radicals that also degrade methane. Molecular hydrogen reacts with both these sort of radicals, and thus indirectly preserves the methane.

There are, of course, other ways of using hydrogen, such as in chemical reactions, including upgrading biofuels, and it can be stored in chemical compounds. Hydrazine (N2H4) is an example of a liquid that could make a very useful fuel. (In the book, and film “The Martian”, the hero has hydrazine from the fuel tank of a rocket, so he catalytically converts it to hydrogen to burn to make water, and blows up his “dome”. It would have been so much easier to burn hydrazine, as it was, after all, from a rocket fuel tank.) Other options include storing hydrogen as hydrides, e.g. borohydrides, or as ammonia, which is cheaper to make than hydrazine, but it is also a gas, unlike hydrazine. The problem is usually how to deliver the hydrogen at a regular and controllable rate.

The use of hydrogen in a chemical manufacturing plant, or when handled with expertise, such as when used by NASA, is no problem. My concern would be for the average person doing repairs themselves to pipes conveying hydrogen, or worse still, plumbing incorrectly. As for having hydrogen as a fuel to be delivered at refuelling stations, I used this concept in my ebook “Puppeteer” to illustrate the potential danger if there are terrorists on the loose.

Biofuels from Algae

In the previous post, I described work that I had done on making biofuels from lignin related materials, but I have also looked at algae, and here hydrothermal processing makes a lot of sense, if for no other reason than algae is always gathered wet. There are two distinct classes: microalgae and macroalga. The reason for distinguishing these has nothing to do with size, but rather with composition. Microalgae have the rather unusual property of being comprised of up to 25% nucleic acid, and the bulk of the rest is lipid or protein, and the mix is adjustable. The reason is microalgae are primarily devoted to reproduction, and if the supply of nitrogen and phosphate is surplus to requirements, they absorb what they can and reproduce, mainly making more nucleic acid and protein. Their energy storage medium is the lipid fraction, so given nutrient-rich conditions, they contain very little free lipids. Lipids are glycerol that is esterified by three fatty acids, in microalgae primarily palmitic (C16) and stearic (C18), with some other interesting acids like the omega-three acids. In principle, microalga would be very nutritious, but the high levels of nucleic acid give them some unfortunate side effects. Maybe genetic engineering could reduce this amount. Macroalgae, on the other hand, are largely carbohydrate in composition. Their structural polysaccharides are of industrial interest, although they also contain a lot of cellulose. The lipid nature of microalgae makes them very interesting when thinking of diesel fuel, where straight-chain hydrocarbons are optimal.

Microalgae have been heavily researched, and are usually grown in various tubes by those carrying out research on making biofuels. Occasionally they have been grown in ponds, which in my opinion is much more preferable, if for no other reason than it is cheaper. The ideal way to grow them seems to be to feed them plenty of nutrients, which leads them to reproduce but produce little in the way of hydrocarbons (but see below) then starve them. They cannot shut down their photosystems, so they continue to take on carbon dioxide and reduce the carbon all the way to lipids. The unimaginative thing to do then is to extract the microalgae and make “biodiesel”, a process that involves extracting the lipids, usually with a solvent such as a volatile hydrocarbon, distilling off the solvent, then reacting that with methanolic potassium hydroxide to make the methyl esters plus glycerol, and if you do this right, an aqueous phase separates out and you can recover your esters and blend them with diesel. The reason I say “unimaginative” is that when you get around to doing this, you find there are problems, and you get ferocious emulsions. These can be avoided by drying the algae, but now the eventual fuel is starting to get expensive, especially since the microalgae are very difficult to harvest in the first place. To move around in the water, they have to have a density that is essentially the same as water, so centrifuging is difficult, and since they are by nature somewhat slimy, they clog filters. There are ways of harvesting them, but that starts to get more expensive. The reason why hydrothermal processing makes so much sense is it is not necessary to dry them; the process works well if they are merely concentrated.

The venture I was involved in helping had the excellent idea of using microalgae that grow in sewage treatment plants, where besides producing the products from the algae, the pollution was also cleaned up, at least it is if the microalgae are not simply sent out into the environment. (We also can recover phosphate, which may be important in the future.). There are problems here, in that because it is so nutrient-rich the fraction of extractable lipids is close to zero. However, if hydrothermal liquefaction is used, the yield of hydrocarbons goes up to the vicinity of over 20%, of which about half are aromatic, and thus suitable for high-octane petrol. Presumably, the lipids were in the form of lipoprotein, or maybe only partially substituted glycerol, which would produce emulsifying agents. Also made are some nitrogen-rich chemicals that are about an order of magnitude more valuable than diesel. The hydrocarbons are C15 and C17 alpha unsaturated hydrocarbons, which could be used directly as a high-cetane diesel (if one hydrogenated the one double bond, you would have a linear saturated hydrocarbon with presumably a cetane rating of 100), and some aromatic hydrocarbons that would give an octane rating well over a hundred. The lipid fraction can be increased by growing them under nutrient-deprived conditions. They cannot reproduce, so they make lipids, and swell, until eventually they die. Once swollen, they are easier to handle as well. And if nothing else, there will be no shortage of sewage in the future.

Macroalgae will process a little like land plants. They are a lot easier to handle and harvest, but there is a problem in obtaining them in bulk: by and large, they only grow in a narrow band around the coast, and only on some rocks, and then only under good marine conditions. If the wave action is too strong, often there are few present. However, they can live in the open ocean. An example is the Sargasso Sea, and it appears that there are about twenty million tonne of them in the Atlantic where the Amazonian nutrients get out to sea. However, in the 1970s the US navy showed they could be grown on rafts in the open ocean with a little nutrient support. It may well also be that free-floating macroalgae can be grown, although of course the algae will move with the currents.

The reason for picking on algae is partly that some are the fastest-growing plants on the planet. They will take more carbon dioxide from the atmosphere more quickly than any other plant, the sunlight absorbed by the plant is converted to chemical energy, not heat, and finally, the use of the oceans is not competing with any other use, and in fact may assist fish growth.

Biofuels as Alternative Fuel Sources

In the previous post I suggested that municipal refuse could be converted to liquid fuels of similar nature to modern hydrocarbon fuels from oil. There are some who think transport can be readily electrified, but three other considerations suggest not. The first is that, as noted by Physics World, a publication by the Institute of Physics, there is a very good chance that a car sold today will still be being used twenty years out. The second is that electric vehicles also have considerable greenhouse emissions. The actual running of the car is free of emissions, but you still have to make the car, which has significant emissions and may exceed that of the standard car; you have to generate the electricity, and the majority of the world’s electricity is generated from fossil fuels, and much from coal; and finally you have to make the batteries, and this is also a serious emitter. There are also parts of the vehicle fleet that will not easily electrify, such as the big road trailers that go into remote Australia, heavy construction equipment, simply because the extra mass to store the batteries would be horrendous, and recharge is not simple in remote places. Shipping will continue to use oil, as will aircraft, and as noted in a previous post, so will much of the vehicle fleet because it is not possible to make satisfactory batteries for replacement vehicles because with current technology there is insufficient cobalt. So what else can replace fossil fuel?

One such possibility is biofuels. The case for biofuels is that in principle their combustion is carbon neutral: their carbon may return to the air, but it came from the air. The energy source is essentially solar, and that is not going to run out soon. The problem then is that biomass is a strange mix of different chemicals. Worse, we eat biomass, and we must not remove our food supply.

The first problem that gives biofuels a bad name is the urge to take the low hanging fruit, especially for tax benefits. Palm oil for biodiesel has made a terrible mess of the Indonesian rain forests, and for what benefit (apart from clipping the tax ticket?) Corn for ethanol similarly makes little sense exceptfor the case where the corn would otherwise go to waste. The problem in part is that corn also utilises so little of the sunlight; most of the plant is simply wasted, and often burned. Seed oils do make sense for specialist uses, such as drying oils in paint, or in cosmetics, or as a feedstock to make other specialist chemicals, but something like “biodiesel” from palm oil makes the overall situation worse, not better. It will never replace the carbon fixed in the rain forest.

Forestry is another interesting case. We are much better off to use the logs for timber in construction: it is worth more, and at the same time it fixes carbon in the buildings. However, if you have ever seen forestry, you will know there is an awful lot of biomass just left to rot: the branches, twigs, stumps, roots, leaves/needles, etc. That is essentially free to use. There are big problems in that it packs extremely badly, so transport costs for any distance are too great.

From a technical point of view, the processes to use woody biomass would come down to the same ones for municipal wastes as noted in the previous post, except that gasification is unlikely to be suitable. A significant plant was put up in the US to gasify biomass and use the gas for a modified Fischer-Tropsch process, but it failed. There were probably several reasons for this, but one is immediately obvious: if we rely on market forces we cannot compete with oil. There are two reasons for that. The first is that the oil is “free” originally, and since liquids can be pumped, it is easily handled, while the second is there is a huge infrastructure to process oil. The cost per unit mass of product becomes lower, usually the ratio of the throughput rates to the power of 0.6. The reason for this is simple. Costs of processing plant are proportional (all other things being equal) to the area of the container, which is proportional to r squared, while the production rate is proportional to volume, which is proportional to rcubed. The huge oil processing plants are extremely efficient, and no much smaller biomass processing unit can have any hope of matching it. The reason for the 0.6 as opposed to 0.66666 is that there are also some extra savings. Control equipment, gauges, etc tend to cost much the same because they are the same, and pumps, etc, tend to be excessively costly when small. The six-tenths rule is, of course, only a rough approximation, but it is a guide.

My approach to this, when I started, was to consider biomass hydrothermal liquefaction. The concept here was that if we merely heated the biomass up with water and simple catalysts under pressure to approaching the critical point, we could end up with liquids. These would have to be refined, but that could be done in a large central plant, while the initial processing could be done in smaller units that could be, with effort, portable. One of the surprises from this was that a certain fraction was already effectively a very high-grade fuel, at least for petrol craft or jet engines without further refining. Exactly what you got depended on catalysts, and a case could also be made to add certain other chemicals to enhance certain products. A lot more work would be needed to get such technology operational, but needing more work is not a reason to discard the concept if saving the world is at stake.

So why did I stop doing this work? Basically, because I felt the desire to change my working environment, and because the funding for this work was drying up. Regarding my working environment, there is a funny story there – well, sort of funny, but it did not feel that way then. The journal Naturedid a quick survey of science in New Zealand. I worked in a Government laboratory, and I had the rather dubious honour of having Head Office describe me in Natureas “an eccentric”. Why? Because I was trying to promote an industry based on a by-product of a synthetic fuels plant constructed at Motunui that would make a key starting material for high-temperature plastics. I suppose some of my antics were unusual, for example there was a program on national television of the dangers of flammable foam plastics, so I went there and pointed out they did not haveto be flammable. I had a piece of foam I had made in the lab that afternoon in the palm of my hand and I fired a gas torch at it so the foam was in my hand, yet yellow-hot on the outside. I held it there for quite some time, until everyone got bored. Anyway, when your employer decides you are eccentric, it felt like time to quit and start up by myself. There were two consequences of this. Before I left, the technical staff made me a brass “eggcup” with a large glass egg in it. One of my prized possessions. The second was I got a letter of apology from Head Office, in which it was explained they did not mean I was eccentric, but rather my ideas were. Not a great improvement, as seen by me. I suppose there was a further example of eccentric behaviour. The laboratory was set up with the purpose of promoting the New Zealand economy by finding new industrial opportunities. I suppose it was somewhat eccentric to actually be following “the Prime Directive”.