Energy from the Sea. A Difficult Environmental Choice.

If you have many problems and you are forced to do something, it makes sense to choose any option that solves more than one problem. So now, thanks to a certain virus, changes to our economic system will be forced on us, so why not do something about carbon emissions at the same time? The enthusiast will tell us science offers us a number of options, so let’s get on with it. The enthusiast trots out what supports his view, but what about what he does not say? Look at the following.

An assessment from the US Energy Information Administration states the world will use 21,000 TWh of electricity in 2020. According to the International Energy Agency, the waves in the world’s oceans store about 80,000 TWh. Of course much of that is, well, out at sea, but they estimate about 4,000 TWh could be harvested. While that is less than 20% of what is needed, it is still a huge amount. They are a little coy on how this could be done, though. Wave power depends on wave height (the amplitude of the wave) and how fast the waves are moving (the phase velocity). One point is that waves usually move to the coast, and there are many parts of the world where there are usually waves of reasonable amplitude so an energy source is there.

Ocean currents also have power, and the oceans are really one giant heat engine. One estimate claimed that 0.1% of the power of the Gulf Stream running along the East Coast of the US would be equivalent to 150 nuclear power stations. Yes, but the obvious problem is the cross-sectional area of the Gulf Stream. Enormous amounts of energy may be present, but the water is moving fairly slowly, so a huge area has to be trapped to get that energy. 

It is simpler to extract energy from tides, if you can find appropriate places. If a partial dam can be put across a narrow river mouth that has broad low-lying ground behind it, quite significant flows can be generated for most of the day. Further, unlike solar and wind power, tides are very predictable. Tides vary in amplitude, with a record apparently going to the Bay of Fundy in Canada: 15 meters in height.

So why don’t we use these forms of energy? Waves and tides are guaranteed renewable and we do not have to do anything to generate them. A surprising fraction of the population lives close to the sea, so transmission costs for them would be straightforward. Similarly, tidal power works well even at low water speeds because compared with wind, water is much denser, and the equipment lasts longer. La Rance, in France, has been operational since 1966. They also do not take up valuable agricultural land. On the other hand, they disturb sea life. A number of fish appear to use the Earth’s magnetic field to navigate and nobody knows if EMF emissions have an effect on marine life. Turbine blades most certainly will. They also tend to be needed near cities, which means they disturb fishing boats and commercial ships.

There are basically two problems. One is engineering. The sea is not a very forgiving place, and when storms come, the water has serious power. The history of wave power is littered with washed up structures, smashed to pieces in storms. Apparently an underwater turbine was put in the Bay of Fundy, but it lasted less than a month. There is a second technical problem: how to make electricity? The usual way would be to move wire through a magnetic field, which is the usual form of a generator/dynamo. The issue here is salt water must be kept completely out, which is less than easy. Since waves go up and down, an alternative is to have some sort of float that mechanically transmits the energy to a generator on shore. That can be made to work on a small scale, but it is less desirable on a larger scale.The second problem is financial. Since history is littered with failed attempts, investors get wary, and perhaps rightly so. There may be huge energies present, but they are dispersed over huge areas, which means power densities are low, and the economics usually become unattractive. Further, while the environmentalists plead for something like this, inevitably it will be, “Somewhere else, please. Not in my line of sight.” So, my guess is this is not a practical solution now or anytime in the reasonable future other than for small specialized efforts.

After Lockdown, Now What?

A number of countries are emerging from lockdown and New Zealand is in the select group in which there are very few new cases, and indeed we have days in which no new cases are recorded. Now comes the damage. The Economist ran an article that summarized what happened in China following the release of lockdown. Rides on public transport are down by a third, restaurants have 40% fewer clients, and hotel stays are a third of normal. Bankruptcies may be up to 20%. People are still wary, either of the virus or their wallet.

It is one thing to open shops, but another thing to get people to go to them and buy stuff. If the disease is still around, while some will take the risk, many others will not, although on this front, in NZ shops initially had huge days. It is not totally bad for those shops that can last the distance because for many things provided people have the money, they will still buy the same amount, other than, perhaps luxury consumables. However, the question then is, will they still have money? Different countries will have different problems here. Apparently in Europe a fifth of the labor force are in special schemes where the state pays their wages, but that presumably, cannot go on indefinitely. In NZ, after a week following lockdown, the jury is still out. People are working, but are they becoming wary?

In New Zealand, the State offered wage assistance to companies that had their income reduced by 30% due to the lockdown, which was a lot, but a number of companies, including the airlines, shed a lot of staff because it was obvious they were not going to operate at anywhere near their previous level. Airlines create a rather unusual situation: pilots rightly earn a lot of money, so would they be prepared to share work with another pilot, each at half-pay? The company keeps pilots on its books for when things improve, and most importantly for the pilots, they keep their minimum required flying hours up to date. That approach won’t work for low-paid workers. But then airlines may not have much work anyway. Here, there has to be social distancing. The passengers may at last get reasonable leg room (Yay!) but either ticket prices increase sharply or the airline realizes there is no point in losing money with half-full planes through social distancing.  The simplest way to raise ticket prices is to cut out the “specials”, so designed to fill aircraft. If the expensive ones with a small markup still sell, the airline may remain viable. So what should the pilots do? The question then comes down to predicting the future.

Herein lies the problem: most people will have choices, and those who more correctly accommodate themselves to whatever happens prosper. Those who make unfortunate choices, or worse, bad choices, will suffer. Governments also have choices, and they tend to be influenced by the next election, which in our case is this year. Propping up zombie companies is bad for the economy, but mass unemployment is bad for votes. What will happen? The pandemic will uncover some scabs in our society. Here, half of our deaths came from badly run rest homes. My guess is the biggest economic price will be paid by the poor, or the small business owner who is joining the poor. Furthermore, governments may still not be able to stem the downturn. In New Zealand, the Government announced a big spend-up in infrastructure, and shortly afterwards the biggest construction and civil engineering company shed 10% of its staff.

What happens to globalization? What most people do not realize is how interconnected the world economy is. As an example, Boeing assembles aircraft, but the parts come from a wide-ranging source. For a Rolls Royce motor, it too will depend on parts from a wide range of sources. If any of these sources break down because of the pandemic, there will be a problem. Equally, with a great reduction in international flights, maybe Boeing will stop buying when it can’t sell. Widespread unemployment could cascade out. Meanwhile, selected industries will clamour to their governments for bail-outs. There will be a cry for protectionism, without realizing how much “local” industry depends on elsewhere.The odd thing is, we now have a rather unique chance to shape the future. Can we do it sensibly? And what, really, is sensible? And how do you prevent the spoils, such as they are, going to the already super rich?

What to do with Waste Plastics

One of the great environmental problems of our time is waste plastics, and there are apparently huge volumes floating around in the oceans of the world. These would generally get there by people throwing them away, so in principle this problem is solved if we can stop that irresponsible attitude. I can already hear the, “Good luck with that,” response. Serious fines for offenders would help, as would more frequent proper rubbish disposal bins. But this raises the question, what should we do with waste plastics?

The first answer is it is unlikely there is a single answer because there are such a variety of plastics. Some, like polyester or polyethylene, can be reasonably easily recycled for low specification uses, but the problem here is there is a limit to how many plastic buckets, etc, can be sold. Technically, quite a high level of recycling can be achieved. Quite a while ago, during the first oil crisis, a client asked me to devise a means of recycling mixed coloured polyethylene so I devised a process that recovered a powder that could be used to make almost anything that virgin polyethylene could make, except maybe clear: there was always a slight beige colour from residual dyes etc that could not be got out, at least in a one-cycle process. Polyethylene degrades – you will all have seen it go brittle from sunlight. This shortens the chains and oxidizes parts and I was proud of this process because it got rid of all the degradation and short-chain material.

A pilot plant was built, then the process was abandoned.  The reason was the oil prices tumbled, and there was no way the process could make money, particularly since big multinationals appeared to be dumping polyethylene into New Zealand. Some manufacturers loved this, and were able to export all sorts of plastic things, at least for a while. Part of the reason the process would have lost money, of course, was that despite getting the raw material rather cheaply, the yield at the end was lower because of the loss of the degradation products, but the killer was getting rid of the degradation products. They could be burnt for process heat, but that would need a specially designed burner, and there would still be the pigment remains to be disposed of. Good idea, but could not compete with the oil industry.

Another possible process is pyrolysis. This came to my attention when I recently saw a paper in the latest copy of “Energy and Fuels” put out by the American Chemical Society. Polyethylene gives a mix of oil, gas and carbonaceous solid, but you can get almost 80% in the form of oil that could be directly used as a diesel fuel after distillation. There appear to be a fraction that boils too high for the diesel range, and gets waxy, but those who have recalled a recent post by me will see that it would do well in the heavier marine heavy fuel oil. The resultant oil has a mix of linear alkanes and terminal alkenes, and the fragmentation is such that the double bond prefers the smaller fragment. There is also some miscellaneous stuff resulting from the oxidative degradation. Polypropylene, however, showed a lot more oxygen, with a range of alcohols, esters and also acids in addition to highly branched hydrocarbons, however, almost 20% was the single compound 2,4-dimethyl-1-heptene. It would manage with the light ends as petrol, and the heavier ends contributing to diesel. 

Polystyrene gave what corresponds more to a heavy oil, although 40% was actually styrene, which could be used to make more polystyrene. Importantly, the cetane rating for the oil from polyethylene was 73; for polypropylene, 61. Polystyrene oil was unsuitable for diesel, but if hydrogenated, the lower boiling cut would make a high octane petrol. The average pump diesel fuel has a cetane rating of about 50, and the higher the rating, the faster the engines can go, so pyrolysis of waste polyethylene and waste polypropylene will make an excellent diesel fuel, with the heavy ends going towards shipping.  However, the heavy ends of polystyrene would have to be dumped because they contain fluorinated material, presumably a consequence of additives, and you certainly do not want an exhaust stream rich in hydrogen fluoride. And here is the curse that plagues anything involving recycling: too many companies put in additives that will be impossible to remove, and which either prevent proper recycling or will have consequences that are at best highly unpleasant, while they offer no option for dealing with them.

How do we separate these plastics out? Fragment them, and stir in water. Polyethylene and polypropylene are the two plastics that float. Foam, of course, has to be omitted. So, will this end up being done? My guess is, not in the immediate future. In terms of economics, it cannot beat the entrenched oil industry, unless governments decide that cleaning up the environment is worth the effort.

Government bails them out, but then what?

In New Zealand, I am far from certain that anyone knows what to do when our lockdown ends. The economist thinks that the money supply will fix all things and reserve bank has done what it has not done before: embarked on quantitative easing, Many other governments have done the same and the world will be awash with money. Is this a solution? It is supposed to compensate for the lockdown Two questions: is the lockdown worth it, and is the money supply the answer? To the first question, here the answer appears to be so, if you value lives. After two weeks of lockdown, the number of new cases per day were clearly falling, and by Good Friday the number of new cases had dropped to almost a third of their peak. They continue to drop and the day before this post, there were only 20 new cases. However, if we look at the price, our Treasury Department has predicted the best case is something like 10% unemployment, and if the lockdown lasts significantly longer than the four weeks, unemployment may hit 26%.

To the second question, the jury is out. Around the world, Governments think yes. The US Congress has prepared a gigantic fiscal stimulus of $2 trillion, which is roughly 10% of GDP. Some European countries have made credit guarantees worth as much as 15% of GDP to stop a cascade of defaults. New Zealand is rather fortunate because its national debt was only about 28% of GDP prior to the virus. Some predict the stimulus may reach 22% of GDP, but it has room to move before reaching the heights of some other countries. However, it is far from clear that it will successfully prevent a raft of defaults.

First, defaults always happen. In the OECD about 8% of businesses go bust each year, while 10% of the workforce lose their jobs. Of course, since economies have been expanding there was an equal or greater creation of business and jobs before this virus. That won’t happen post virus. Take restaurants as an example. Restaurants closing down may well re-open under new management, without the old debt, and not so many workers. That may not happen post-virus because people under financial strain or fear that unemployment might be imminent will not eat out, and the tourists, who have to eat out, will not be here. Therein lies the problem. If people fear there will be a slump, there will be; such fear is self-fulfilling. 

There will be changes, and some may be guided by the virus problem. Some businesses will cut costs by specializing in home delivery, and they should be doing that now because first in that performs well probably wins. For manufacturing, the relief of the lockdown may well retain heavy restrictions, such as expecting people to devise a way for working so they remain two meters away from others. That requires significant investment to do this. Will it be worth it? It seriously raises costs, so will people buy the more expensive products? But will this happen? The basic problem for small business is that it is almost a waste of time planning until the government makes its future laws and regulations clear, and once stated, sticks to them. I have run a small business since 1986, and the one thing that has always made things difficult is a change of rules. You get to know how to operate in one set of rules, but when those change the small business has too many things for too few people to do, and a successful small business is light on management. The owner tends to do everything, and I found new regulations to be a complete pest.

Meanwhile, the governments of the world have some interesting choices. Historically, when governments intervene, they seldom let things go back to where they were. If governments get used to regulating, will they let go? If you prefer to leave it to market forces, will that lead to greater wealth for all? As I heard one man say on the radio today, those with money will be looking to buy up assets, i.e. company shares that have become somewhat undervalued. Unfortunately, while that makes some richer, it does nothing for the general public.All of which raises the question, what should they do? That depends on what is required to get out of the slump. The obvious answer is to start additional businesses to replace what has failed, but how do you do that? One of the things that is critically required is money, but while that is necessary, it is not sufficient.  Throwing money at such things is usually a waste. A business needs three basics: technology (more broadly, how to make whatever you are selling), the ability to sell whatever you are making, and management, which is essentially getting the best us of your money, staff, and other assets. Only a very moderate number of people are skilled in even one of those, very few can handle two, and nobody can cover all three well. This is why so many small businesses fail. And that raises the possibility that what governments need to do is to somehow bring the required people together. And that is something with which governments have no experience.

Business Under Stress

In my last post, I outlined some of the problems as I see them on getting out of this virus problem. A clear example of the problems to be faced comes from what happened here within an hour of my posting. It turned out that the German conglomerate Bauer had bought up all the major magazines in New Zealand. It was one week into the lockdown when it said it was closing down the lot. Normally in tough economic times, weaker businesses can be expected to go under due to competition, but in this case, it was the strongest, the ones that had been going for up to eighty years, that go to the wall. Why? The stated reason was that due to lockdown, advertising revenue had dropped. Well, yes, but the lockdown will not last forever. It could have tried to last it out, and if everybody complies with the lockdown, the virus is supposed to die out in about four weeks. Bauer was seemingly buying up competition to its Australian magazines, and it needed the money. (Why it didn’t try to sell the NZ magazines is unclear.) It also probably thought the smaller New Zealand market would buy the Australian equivalent.

However, there were additional factors here that may apply more generally. The first is that in economic terms, if the owner is going to close down because that is inevitable, it is best to do it as soon as possible because all money spent in the intervening period between problem arising and submitting to it is money lost forever. A second factor is that the big conglomerate has no emotional link to its business; all it cares about is whether it is a sufficientlyprofitable business. Can it make more money by switching its resources elsewhere? In this case there is also a considerable cultural loss. Unfortunately, that is intangible, and only applies to the customers. The conglomerate seldom cares, and in this case since it is homed at the other side of the world, there is no benefit to it. Only dollars flowing in matter.

Looking at the consequences, a large number of journalists, proof-readers, etc. are unemployed, and at least for a limited amount of time, there is no further possible work for any of them. Nobody is likely to take over any of the magazines right now because of the lack of advertising revenue, although the lockdown period is likely to be over by the time all the legal complexities would be completed. There are downside consequences. The printer has just lost a very large amount of work, and maybe they cannot continue. Stores that sell magazines will not have any, and many of these stores would have magazines to attract people in who might not otherwise come, but when they do, they often buy other things. Also, a high fraction of the magazine sales would be on subscription. Subscribers have no comeback if the conglomerate does not refund unused money, but that would sour the field for anyone trying to resurrect such magazines.

Another problem for exports comes from the fact that many fruit such as kiwifruit and pip fruit are due to be harvested about now. With lockdown, pickers are in short supply, and the requirement for them to keep two meters apart can be a problem. If the fruit are not picked, the farmer loses valuable income, and that income only comes once a year. Owners of tourism ventures will be pulling out their hair because movement is forbidden, and when the lockdown is over, who will come?

The overall consequences of stories such as these is that only too many people are going to be short of money. That makes investment in new businesses very difficult to raise. There will be many rich people with lots of spare cash, and the ability to raise a lot more through banks, but that may not be available to start new businesses, as what that sort of money tends to do is to buy up existing assets that happen to be very cheap. The virus has brought a lot of problems, but such problems may also be opportunities. The difficulty is to see them, and act on them. Thus it is obvious that New Zealand has an opportunity for a new magazine, or maybe a continuation of the more successful of the old ones. Will that happen? Watch this space.Finally, in these testing times, Easter is upon us, and I wish you all a pleasant Easter.

Lockdown! Now What?

By now, everyone should be aware there is a virus out there, and it has been generally agreed that action was needed to protect citizens. So far there is no vaccine, and in some cases the treatment required to preserve life is restricted. In New Zealand, thanks to various travellers bringing it here, we are starting to feel the effects. It is easy to flash around figures but with a population of about 5 million, one estimate is that if nothing were done, about 70% of the population would get it, and about 80,000 would die. The reason is, if all those got it about the same time, say over a two-month period, there are insufficient ventilators, etc. for them. If they got it one at a time, most of those 80,000 would not die.  Our hospitals did not have 20,000 ventilators sitting around waiting for this event. So what we have done (as have many other countries) is we have initiated a lockdown, the idea being that by breaking the possible chains of transmission the virus will die out. The associated problem is, so will many businesses that cannot earn during this period. So the question is, what will emerge from this, or perhaps a more reasonable question is, what is more probable to arise from this?

The average estimate here is that unemployment will rise to about 9%, and many small businesses will go under. Life will be particularly difficult for restaurants, etc. because many of them tend to operate on slim margins, and they are more designed to offer the owners a life-style rather than direct them to be a developing business owner. Our airline will shrink down to 10% of what it was because international travel will almost disappear. One slight bright sign for them lies in the domestic market: their major competitor has already decided to call it quits here. Such competitors restricted themselves to the major intercity services and left the minor spots alone. The price for those tickets will now rise, but with the far lower ticket sales there would have been blood on the floor had such cheaper flights continued for that many aircraft. There will be a great reduction in the number of tourists for some time, because even if our lockdown works, what happens if other countries have not gone as hard? Do we want to succeed, at great cost, then let in fresh infection?

One of the other things that has happened is we have discovered the “just in time” purchasing ethic has a cost. One slightly ironic fact is there was a claim we were running low on hospital gowns, and the biggest manufacturer anywhere of hospital gowns is in Wuhan, except it closed because of the virus. Apparently, a couple of small manufacturers are switching to make some of this necessary equipment, including ventilators, but that will not continue because they cannot compete on price with China, and in any case, the hospitals will not need more when this dies down.

On the issue of more general manufacturing, I heard one small manufacturer say that in response to the difficulties some are having in getting certain things, he has ordered a major robotic machine. The capital cost is higher, but the wage bill is much lower, and if the equipment is sufficiently flexible, the major expenditure, apart from raw materials and capital cost, will be in paying designers. This suggests this pandemic may well be the straw that broke the back of the current way of making goods. Strategic niche manufacturing, manufacturing close to raw materials, and the use of brains may be the key factors in future prosperity.That raises the question of what happens to current workers. If half the small businesses go to the wall, there will be a lot of workers who have few resources and only limited skills. There will also be a number of highly skilled people who are unemployed. Think of the airlines. Where do pilots and cabin crew of the big jets find jobs? Nobody else will want them because all the other airlines are in the same boat, and it has nothing to do with management or mistakes. It is going to require a lot of imagination and investment to get out of this, and both may be in rather short supply. Also, new businesses need customers, and who is going to have spare money when this wrings out?

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.

The Year of Elements, and a Crisis

This is the International Year of the Periodic Table, and since it is almost over, one can debate how useful it was. I wonder how many readers were aware of this, and how many really understand what the periodic table means. Basically, it is a means of ordering elements with respect to their atomic number in a way that allows you to make predictions of properties. Atomic number counts how many protons and electrons a neutral atom has. The number of electrons and the way they are arranged determines the atom’s chemical properties, and thanks to quantum mechanics, these properties repeat according to a given pattern. So, if it were that obvious, why did it take so long to discover it?

There are two basic reasons. The first is it took a long time to discover what were elements. John Dalton, who put the concept of atoms on a sound footing, made a list that contained twenty-one, and some of those, like potash, were not elements, although they did contain atoms that were different from the others, and he inferred there was a new element present. The problem is, some elements are difficult to isolate from the molecules they are in so Dalton, unable to break them down, but seeing from their effect on flames knew they were different, labelled them as elements. The second problem is although the electron configurations appear to have common features, and there are repeats in behaviour, they are not exact repeats and sometimes some quite small differences in electron behaviour makes very significant differences to chemical properties. The most obvious example is the very common elements carbon and silicon. Both form dioxides of formula XO2. Carbon dioxide is a gas; you see silicon dioxide as quartz. (Extreme high-pressure forces CO2 to form a quartz structure, though, so the similarity does emerge when forced.) Both are extremely stable, and silicon does not readily form a monoxide, while carbon monoxide has an anomalous electronic structure. At the other end of the “family”, lead does not behave particularly like carbon or silicon, and while it forms a dioxide, this is not at all colourless like the others. The main oxide of lead is the monoxide, and this instability is used to make the anode work in lead acid batteries.

The reason I have gone on like this is to explain that while elements have periodic properties, these are only indicative of the potential, and in detail each element is unique in many ways. If you number them on the way down the column, there may be significant changes depending on whether the number is odd or even that are superimposed on a general change. As an example: copper, silver, gold. Thus copper and gold are coloured; silver is not. The properties of silicon are wildly different from those of carbon; there is an equally dramatic change in properties from germanium to tin. What this means is that it is very difficult to find a substitute material for an element that is used for a very specific property. Further, the amounts of given elements on the planet depend partly on how the planet accreted, thus we do not have much helium or neon, despite these being extremely common elements in the Universe as a whole, and partly on the fact that nucleosynthesis gives variable yields for different elements. The heavier elements in a periodic column are generally formed in lower amounts, while elements with a greater number of stable isotopes, or particularly stable isotopes, tend to be made in greater amounts. On the other hand, their general availability tends to depend on what routes there are for their isolation during geochemical processing. Some elements such as lead form a very insoluble sulphide and that separates from the rock during geothermal processing, but others are much more resistant and remain distributed throughout the rock in highly dilute forms, so even though they are there, they are not available in concentrated forms. The problem arises when we need some of these more difficult to obtain elements, yet they have specific uses. Thus a typical mobile phone contains more than thirty different elements

The Royal Society of Chemistry has found that at least six elements used in mobile phones are going out be mined out in at least 100 years. These have other uses as well. Gallium is used in microchips, but also in LEDs and solar panels. Arsenic is also used in microchips, but also used in wood preservation and, believe it or not, poultry feed. Silver is used in microelectrical components, but also in photochromic lenses, antibacterial clothing, mirrors, and other uses. Indium is used on touchscreens and microchips, but also in solar panels and specialist ball bearings. Yttrium is used for screen colours and backlighting, but also used for white LED lights, camera lenses, and anticancer drugs, e.g. against liver cancer. Finally, there is tantalum, used for surgical implants, turbine blades, hearing aids, pacemakers, and nosescaps for supersonic aircraft. Thus mobile phones will put a lot of stress on other manufacturing. To add to the problems, cell phones tend to have a life averaging two years. (There is the odd dinosaur like me who keeps using them until technology makes it difficult to keep doing it. I am on my third mobile phone.)A couple of other facts. 23% of UK households have an unused mobile phone. While in the UK, 52% of 16 – 24 year olds have TEN or more electronic devices in their home. The RSC estimates that in the UK there are as many as 40 million old and unused such devices in people’s homes. I have no doubt that many other countries, including the US, have the same problem. So, is the obvious answer we should promote recycling? There are recycling schemes around the world, but it is not clear what is being done with what is collected. Recovering the above elements from such a mixture is anything but easy. I suspect that the recyclers go for the gold and one or two other materials, and then discard the rest. I hope I am wrong, but from the chemical point of view, getting such small mounts of so many different elements from such a mix is anything but easy. Different elements tend to be in different parts of the phone, so the phones can be dismantled and the parts chemically processed separately but this is labour intensive. They can be melted down and separated chemically, but that is a very complicated process. No matter how you do it, the recovered elements will be very expensive. My guess is most are still not recovered. All we can hope is they are discarded somewhere where they will lie inertly until they can be used economically.

An Imminent Water Crisis?

We have all heard the line “Water water everywhere, nor any drop to drink.” Well, soon we may have to rethink “everywhere”. There was a tolerably scary future hinted at by a recent letter in Nature (de Graaf, et al574: 90). It points out that groundwater is critically important for food production and currently pumping exceeds recharge from rainfall and rivers in many parts of the world. Further, when groundwater levels drop, discharges to streams declines or even stops completely, which reduces river flow, with potentially devastating effects on aquatic life. These authors claim that about 70% of pumped groundwater is used to sustain irrigation and hence food production. There are other problems, such as ground subsidence. If you take away matter from below you, then what you have between you and where you took it must eventually lower, but with land it does not have to do so evenly. Coastal flooding in some US cities is not really exacerbated by climate change to anywhere near the extent it is by the ground lowering due to groundwater removal. 

If the streams to rivers are not recharged, there is a slow desiccation of the nearby land. The billions of tonnes of water locked in soils and bedrock and various aquifers is the biggest single source of fresh water on the planet. Life essentially depends on this resource yet we are unthinkingly depleting it. Most people know that people in dry lands will experience worse conditions due to rising temperatures. What most don’t realise is the inability to properly recharge the aquifers they depend on will lead to even worse problems, not the least through the requirement for more water as temperatures increase.

The paper also provided maps that outline the size of the crisis, but in my opinion also shows a problem inherent in such studies: there was a map that showed the head decline that might lead to a crisis, which really indicates how much groundwater there is. Included is two-thirds of the South Island of New Zealand. Now for parts of Canterbury that may well be the case, but it also includes the West Coast of the South Island. The geology there may well indicate there is not much groundwater, and in fairness I have never heard of anyone drilling wells there, but there is not exactly a water shortage there because the Alps get roughly ten meters of rain a year. The problem for farming in that region is not a shortage of water but rather too much. It is true that farming in Canterbury is probably over-drawing on aquifers, but that is in part because the farmers took to dairying in an area unsuitable for that activity. Prior to the dairy rush, the area was quite prosperous at farming, but without irrigation. Farmers tended to grow grain in the warm dry summers, and would also run sheep. Now wool is not really wanted, so the farmers switched.

Of course, just because I can find a problem in one place does not mean the paper does not raise a valid point. I suspect that when producing a world map like that the authors go to whatever resources they can find and may not check associated issues. So, what are the real problems? In a recent article in Physics World it was stated that within thirty years almost 80% of lands that irrigate through groundwater will reach their limits as wells run dry. It also states that for the other 20% of areas that rely on pumped groundwater, surface flow of streams and rivers has already fallen. This includes cities that depend on pumped water for a water supply. The effects are already being felt in the mid-west of the US.

This raises the question of what can we do about this problem? The most obvious answer is to use less. Most people domestically use far more than necessary, and those who rely on stored rainwater will show how to use less. At the city level, do we really need the number of home pools? On a lesser scale, how many houses really do not waste water? Irrigation needs to be managed in such a way as to lose less by evaporation (i.e. something other than sprinklers.) We need farming methods that are better suited to the local climate, except that also has the problem that we then lose production volumes, and it is far from clear we can afford that.

For coastal cities, desalination offers an answer, but it costs $US1 per 1 – 2 tonne so it is not cheap, and in terms of electrical energy, if we use reverse osmosis, roughly 5 kWh is required, which means we have to significantly increase electrical production. Reverse osmosis works by using pressure to force water through a membrane that will not permit salts to pass, so in principle it could be turned off during peak loads, which might make it useful for a base loading source like nuclear power, but this is not so useful for places distant from the coast. There is another problem with desalination. The seawater should be sterile and the membranes have to be regularly cleaned, which leads to the release of biocides, salts, chelating agents, etc into the sea, which in turn is not particularly good for the local environment.We could pipe water from somewhere else, except we may be running out of “somewhere elses”, and anyway, that place may well be what is feeding the groundwater aquifer. The unfortunate end-result is we may have to give up using so much. We have a problem, Houston!