Reducing Electricity Usage in Your Refrigerator

When thinking about battling climate change, did you know that a major electricity consumer in your house is your refrigerator? The International Institute of Refrigeration (yes, there are institutes for just about everything) estimates that about 20% of all electricity used is expended on vapour compression refrigeration. The refrigerator works by compressing a vapour, often some sort of freon, or in industry, with ammonia, and when compressed it gives off heat. When you ship it somewhere else and expand it, the somewhere else gets colder. This is also the principle of the heat pump and various air conditioning units. Compress gas here to add heat from a heat exchanger; ship the gas there and expand it, where it cools a heat exchanger. The compression and expansion of gas moves heat from A to B, hence the name heat pump. Also, the refrigerant gases tend to be powerful greenhouse gases. One kilogram of R410a has the same greenhouse impact as two tonne of carbon dioxide. Refrigerants leak into the atmosphere from faulty equipment or when equipment is not properly disposed of.

It is possible to heat or cool without any gas through the Peltier effect. Basically, when electric current passes between two conductors, heating or cooling effects may be generated. There are commercial solid-state such cooling systems, but they suffer from high cost and poor efficiency, in part because the effect is restricted to the specific junction.

There is an alternative. Some solid state materials can cool when they are subjected to strain, which is generated from an external field, such as  the electric or magnetic fields, or simply pressure. So far most efforts have been focused on the magnetic field, and one material, Mn3SnC apparently gives significant cooling,  but the magnetic field has to be greater than 2 tesla. That means expensive and bulky magnets, and additionally the refrigerator, if it used them, would have to be a “no-go” area for credit cards, and possibly people with a pacemaker. Even aside from direct messing with the pacemaker, losing all those bitcoin just because you wanted a cool beer could lead to medical problems.

However, there has been an advance. Wu et al. (Acta Materiala 237: 118154) have taken the Mn3SnC and coated it with a piezoelectric layer of lead zirconate titanate. Don’t ask me how they come up with these things; I have no idea, but this is certainly interesting. They probably do it by looking through the literature to find materials already known to have certain properties. Thus a piezoelectric effect is where you generate an electric voltage by applying pressure. Such effects are reversible so if you can generate a voltage by applying pressure to something, you can generate pressure by applying a potential difference. Recall that pressure also can generate a cooling effect. Accordingly, by applying an electric field to this coated material a cooling effect was obtained equivalent to that of a 3 tesla magnetic field. When the electric field is removed, the temperature returns to where it was. How useful will this be? Hard to tell right now. The temperature drop when applying a field of 0.8 kV/cm was slightly under 0.6 of a degree Centigrade, which is not a huge change while the voltage is tolerably high. Interestingly, if you apply a magnetic field you also get a temperature change, but in the opposite direction – instead of cooling, it heats. Why that is is unclear.

As you might guess, there is still a significant distance to go before we get to a refrigerator. First, you have to get the cooling into some other fluid that can transport it to where you need it. To do that you have to take the heat out of the cooling fluid, but that will heat up your unit, so you need another fluid to take the heat to where it can be dissipated. We have very roughly the same cycle as our present system except we are not compressing anything but we have two fluids. Except I rather think we will be, because pumping a fluid involves increasing its pressure so it flows. The alternative is to put the material across the rear wall of the refrigerator thus to cool the interior and have the heat dissipated out the back. The problem now is the change of temperature is rather small for the voltage. This is not so much a problem with fluids transporting it, but if the solids transport it, the solids are always heated by the environment so your temperature drop is from the room temperature. Half a degree is not very helpful, although you could increase the electric field. Unfortunately, to get a big enough temperature change you might be into the spark jumping region. Lightning in the kitchen! Finally, do you want the back of your refrigerator to be carrying even a kilovolt electric field? My guess is this effect may remain a curiosity for some length of time.

Economic Consequences of the Ukraine War

My last post mentioned the USSR collapse. One of the longer term consequences has been this Ukraine war. Currently, there have been problems of shelling of the Zaporizhzhia nuclear plant, and this appears to have happened in that our TV news has shown some of the smashed concrete, etc. The net result is the plant has shut down. Each side accuses the other of doing the shelling, but it seems to me that it had to be the Ukrainians. Russia has troops there, and no military command is going to put up with his side shelling his own troops. However, that is far from the total bad news. So far, Ukraine has been terribly lucky, but such luck cannot last indefinitely. There are consequences outside the actual war itself. The following is a summary of some of what was listed in the August edition of Chemistry World.

The Donbas area is Ukraine’s heavy industry area, and this includes the chemical industry. Recently, Russian air strikes at Sieverierodonetsk hit a nitric acid plant, and we saw images of the nitrogen dioxide gas spewing into the atmosphere.

Apparently, in 2017 Ukrainian shelling was around a chemical plant that contained 7 tonne of chlorine. Had a shell hit a critical tank, that would have been rather awkward. Right now, in the eastern Donbas there is a pipeline almost 700 km long that pipes ammonia. There are approximately 1.5 million people in danger from that pipeline should it burst; exactly how many depends on where it is broken. There are also just under  200,000 t of hazardous waste stored in various places. The question now is, with all this mess generated, in addition to demolished buildings and infrastructure, who will pay what to clean it up? It may or may not be fine for Western countries to use their taxes to produce weapons to give to Ukraine, but cleaning up the mess requires the money to go to Ukraine, not armament-making corporations at home.

The separation of the Donbas has led to many mines being closed, and these have filled with water. This has allowed mercury and sulphuric acid to be leached and then enter the water table. During 2019, a survey of industrial waste was made, and Ukraine apparently stores over 5.4 billion t of industrial waste, about half of which is in the Donbas. Ukraine has presumably inherited a certain amount, together with some of the attitudes, from the old Soviet Union. From experience, their attitude to environmental protection was not their strong point. I recall  one very warm sunny morning going for a walk around Tashkent. I turned a corner and saw rather a lot of rusty buildings, and also, unbelievably, a cloud. How could water droplets form during such a warm dry climate? The answer was fairly clear when I got closer. One slight whiff, and I knew what it was: the building was emitting hydrogen chloride into the atmosphere and the hydrochloric acid droplets were the reason for the rust.

Meanwhile, some more glum news. We all know that the sanctions in response to the Ukraine war has led to a gas shortage. What most people will not realize is what this is doing to the chemical industry. The problem for the chemical industry is that unlike most other industries, other than the very sophisticated, the chemical industry is extremely entangled and interlinked. A given company may make a very large amount of chemical A, which is then sold as a raw material to a number of other companies, who in turn may do the same thing. There are many different factories dependent on the same raw chemical and the material in a given chemical available to the public may have gone through several different steps in several different factories.

An important raw mixture is synthesis gas, which is a mix of carbon monoxide and hydrogen. The hydrogen may be separated and used in steps to make a variety of chemicals, such as ammonia, the base chemical for just about all nitrogen fertilizer, as well as a number of other uses. The synthesis gas is made by heating a mixture of methane gas and water. Further, almost all chemical processing requires heat, and by far the bulk of the heat is produced by burning gas. In Europe, the German government is asking people to cut back on gas usage. Domestic heating can survive simply by lowering the temperature, although how far down one is prepared to go during winter is another question. However, the chemical industry is not so easily handled. Many factories use multiple streams, and it is a simple matter to shut down such a stream, but you cannot easily reduce the amounts going through a stream because the reactions are highly dependent on pressure, and the plant is in a delicate balance between amount processed and heat generated.  A production unit is really only designed to operate one way, and that is continuously with a specific production rate. If you close it down, it may take a week to get it started again, to get the temperature gradients right. One possibility is the complete shutdown of the BASF plant at Ludwigshafen, the biggest chemical complex in the world. The German chemical industry uses about 135 TWhr of gas, or about 15% of the total in the country. The price of such gas has risen by up to a factor of eight since Russia was sanctioned, and more price rises are likely. That means companies have to try to pass on costs, but if they face international competition, that may not be possible. This war has consequences far beyond Ukraine.

Burying Carbon Dioxide, or Burying Cash?

In the last post, I expressed my doubt about the supply of metals for electric batteries. There is an alternative to giving up things that produce CO2 and that is to trap and sequester CO2. The idea is that for power stations the flu gases have the CO2 removed and pumped underground. That raises the question, how realistic is this? Chemistry World has an article that casts doubt, in my mind, that this can work. First, the size of the problem. One company aims to install 70 such plants, each capable of sequestering 1 million t of CO2. If these are actually realized, we almost reach 0.2% of what is required. Oops. Basically, we need to remove at least 1 billion t/a to stand still. This problem is large. There is also the problem of how we do it.

The simplest way is to pass the flu gases through amine solvents, with monoethanolamine the most common absorbent used. Leaving aside the problem of getting enough amine, which requires a major expansion of the chemical manufacturing industry, what happens is the amine absorbs CO2 and makes the amine carbonate, and the CO2 is recovered by heating the carbonate and regenerating the amine. However, the regeneration will never be perfect and there are losses. Leaving aside finding the raw materials actually synthesizing the amine takes about 0.8 MWh of energy, the inevitable losses mean we need up to 240 MWh every year to run a million tonne plant. We then need heat to decompose the amine carbonate, and that requires about 1 MWh per tonne of CO2 absorbed. Finally, we need a little less than 0.12 MWh per tonne of CO2 to compress it, transport it and inject it into the ground. If we wanted to inject 1 billion t of CO2, we need to generate something like 840 TWh of electricity. That is a lot of electricity.

We can do a little better with things called metal organic frameworks (MOFs).These can be made with a high surface energy to absorb CO2 and since they do not form strong chemical bonds the CO2 can be recovered at temperatures in the vicinity of  80 – 100 degrees C, which opens the possibility of using waste heat from power stations. That lowers the energy cost quite a bit. Without the waste heat the energy requirement is still significant, about half that of the amines. The comes the sting – the waste heat approach still leaves about 60% of what was absorbed, so it is not clear the waste heat has saved much. The addition of an extra step is also very expensive.

The CO2 content of effluent gases is between 4 – 15%; for ordinary air it is 0.04%, which makes it very much more difficult to capture. One proposal is to capture CO2 by bubbling air through a solution of potassium hydroxide, and then evaporating off the water and heating the potassium carbonate to decomposition temperature, which happens to be about 1200 degrees C. One might have thought that calcium oxide might be easier, which pyrolyses about 600 degrees C, but what do I know? This pyrolysis takes about 2.4 MWh per tonne of CO2, and if implemented, this pyrolysis route that absorbs CO2 from the air would require about 1.53 TWh of electricity per year for sequestering 1 million t of CO2.

When you need terawatt hours of electricity to run a plant capable of sequestering one million tonne of CO2, and you need to sequester a billion t, it becomes clear that this is going to take an awful lot of energy. That costs a lot money. In the UK, electricity costs between £35 – 65 per MWh, and we have been talking in terms of a million times that per plant. Who pays? Note this scheme has NO income stream; it sells nothing, so we have to assume it will be charged to the taxpayer. Lucky taxpayer!

One small-scale effort in Iceland offers a suggested route. It is not clear how they capture the CO2, but then they dissolve it in water and inject that into basalt, where the carbonic acid reacts with the olivine-type structures to make carbonates, where it is fixed indefinitely. That suggests that provided the concentration of CO2 is high enough, using pressure to dissolve it in water might be sufficient. That would dramatically lower the costs. Of course, the alternative is to crush the basalt and spread it in farmland, instead of lime. My preferred option to remove CO2 from the air is to grow plants. They work for free at the low concentrations. Further, if we select seaweed, we get the added benefit of improving the ecology for marine life. But that requires us to do something with the plants, or the seaweed. Which means more thinking and research. The benefit, though, is the scheme could at least earn revenue. The alternatives are to bankrupt the world or find some other way of solving this problem.

Banana-skin Science

Every now and again we find something that looks weird, but just maybe there is something in it. And while reading it, one wonders, how on Earth did they come up with this? The paper in question was Silva et. al. 2022. Chemical Science 13: 1774. What they did was to take dried biomass powder and exposed it to a flash of 14.5 ms duration from a high-power xenon flash lamp. That type of chemistry was first developed to study the very short-lived intermediates generated in photochemistry, when light excites the molecule to a high energy state, where it can decay through unusual rearrangements. This type of study has been going on since the 1960s and equipment has steadily been improving and being made more powerful. However, it is most unusual to find it used for something that ordinary heat would do far more cheaply. Anyway, 1 kg of such dried powder generated about 100 litres of hydrogen and 330 g of biochar. So, what else was weird? The biomass was dried banana skin! Ecuador, sit up and take notice. But before you do, note that flash xenon lamps are not going to be an exceptionally economical way of providing heat. That is the point; this very expensive source of light was actually merely providing heat.

There are three ways of doing pyrolysis. In the previous post I pointed out that if you took cellulose and eliminated all the oxygen in the form of water, you were left with carbon. If you eliminate the oxygen as carbon monoxide you are left with hydrogen. If you eliminate it as carbon dioxide you get hydrogen and hydrocarbon. In practice what you get depends on how you do it. Slow pyrolysis at moderate heat mainly makes charcoal and water, with some gas. It may come as a surprise to some but ordinary charcoal is not carbon; it is about 1/3 oxygen, some minor bits and pieces such as nitrogen, phosphorus, potassium, and sulphur, and the rest carbon.

If you do very fast pyrolysis, called ablative pyrolysis, you can get almost all liquids and gas. I once saw this done in a lab in Colorado where a tautly held (like a hacksaw blade) electrically heated hot wire cut through wood like butter, the wire continually moving so the uncondensed liquids (which most would call smoke) and gas were swept out. There was essentially no sign of “burnt wood”, and no black. The basic idea of ablative pyrolysis is you fire wood dust or small chips at a plate at an appropriate angle to the path so the wood sweeps across it and the gas is swept away by the gas stream (which can be recycled gas) propelling the wood. Now the paper I referenced above claimed much faster pyrolysis, but got much more charcoal. The question is, why? The simple answer, in my opinion, is nothing was sweeping the product away so it hung around and got charred.

The products varied depending on the power from the lamp, which depended on the applied voltage. At what I assume was maximum voltage the major products were (apart from carbon) hydrogen and carbon monoxide. 100 litres of hydrogen, and a bit more carbon monoxide were formed, which is a good synthesis gas mix. There were also 10 litres of methane, and about 40 litres of carbon dioxide that would have to be scrubbed out. The biomass had to be reduced to 20 μm size and placed on a surface as a layer 50 μm thick. My personal view is that is near impossible to scale this up to useful sizes. It uses light as an energy source, which is difficult to generate so almost certainly the process is a net energy consumer. In short, this so-called “breakthrough” could have been carried out to give better yields of whatever was required far more cheaply by people a hundred years ago.

Perhaps the idea of using light, however, is not so retrograde. The trick would be to devise apparatus that with pyrolyse wood ablatively (or not if you want charcoal) using light focused by large mirrors. The source, the sun, is free until it hits the mirrors. Most of us will have ignited paper with a magnifying glass. Keep the oxygen out and just maybe you have something that will make chemical intermediates that you can call “green”.

The Case for Hydrogen in Transport

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

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

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

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

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

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

Solar Energy in India

There is currently a big urge to move to solar energy, and apparently India has decided that solar energy would greatly assist its plans to deal with climate change. However, according to a paper by Ghosh et Environmental Research Letters, there is a minor problem: air pollution. It appears that while India is ranked fifth in the world for solar energy capacity, parts of it, and these tend to be the parts where you need the power, suffer from growing levels of particulate air pollution. There are two problems. First, the particles in the air block sunlight, thus reducing the power that strikes the panels. Second, the particles land on the panels and block the light until someone cleans the detritus off the panels.

I am not sure I understand why, but the impact on horizontal panels ranged from 10% to 16%, but the impact was much greater on panels that track the position of the sun (which is desirable to get the most power) as they suffered a 52% loss of power from pollution. Apparently if it were not for such pollution it was calculated (not sure on what basis – existing panels or proposed panels) to be able to generate somewhere between an additional six to sixteen TWh of solar electricity per year. That is a lot of power.

But if you are reducing the output of your panels by fifty percent, that means also you are doubling the real cost of the electricity from those panels prior to entering the grid because you are getting half the power from the same fixed cost installation. The loss of capacity translates into hundreds of millions of dollars annually. China has the same problem, with some regions twice as badly off as the Indian regions, although care must be taken with that comment because they are not necessarily measured the same way. In all cases, averaging down over area is carried out, but then different people may select different types of area.

So, what can be done about this? The most obvious approach is to alter the sources of the pollution, but this could be a problem. In India, the sources tend to be the use of kerosine to provide lighting and the use of dirty fuel for cooking and heating in rural villages.

The answer is to electrify them, but now the problem is there are 600,000 such villages. Problems in a country like India or China tend to be very large, although the good news is the number of people available to work on them is also very large. Unfortunately, these villages are not very wealthy. If you want to replace home cooking with electricity, and domestic heating with electricity, someone has to pay for electric ranges. One estimate is 80 million of them. Big business for the maker of electric cookers, but who pays for them when the rural people are fairly close to the poverty line. They cook with fuel like biomass that gets smoky because that is cheap or free. Their cookers may even be home-made, but even if not so, they would have to be discarded as they could not be used for electric cooking.

There are claimed to be other benefits for reducing such pollution. Thus reducing air pollution would reduce cloudiness, which means even better solar energy production. It is also claimed that precipitation is inhibited from polluted clouds, so it is concluded that with more precipitation that would wash more pollution from the air. I am not sure I follow that reasoning, because they have already concluded that they will have fewer clouds.

If they removed these sources of air pollution, they calculated that an extra three TWh per year could be generated from flat surface panels, or eight TWh per year could be generated from tracking panels. The immediate goal is apparently to have 100 GW solar installed. It will be interesting to see if this can be achieved. One problem is that while the economics look good in terms of money saved from increased solar energy, the infrastructure costs associated with it were neglected. My guess is the current air pollution will be around for a while. It also shows the weaknesses of many solar energy projects, such as setting up huge farms in the Sahara. How do you stop fine sand coating panels? An army of panel polishers?

Plastics and Rubbish

In the current “atmosphere” of climate change, politicians are taking more notice of the environment, to which as a sceptic I notice they are not prepared to do a lot about it. Part of the problem is following the “swing to the right” in the 1980s, politicians have taken notice of Reagan’s assertion that the government is the problem, so they have all settled down to not doing very much, and they have shown some skill at doing very little. “Leave it to the market” has a complication: the market is there to facilitate trade in which all the participants wish to offer something that customers want and they make a profit while doing it. The environment is not a customer in the usual sense and it does not pay, so “the market” has no direct interest in it.

There is no one answer to any of these problems. There is no silver bullet. What we have to do is chip away at these problems, and one that indicates the nature of the problem is plastics. In New Zealand the government has decided that plastic bags are bad for the environment, so the single use bags are no longer used in supermarkets. One can argue whether that is good for the environment, but it is clear that the wilful throwing away of plastics and their subsequent degradation is bad for it. And while the disposable bag has been banned here, rubbish still has a lot of plastics in it, and that will continue to degrade. If it were buried deep in some mine it probably would not matter, but it is not. So why don’t we recycle them?

Then first reason is there are so many variations of them and they do not dissolve in each other. You can emulsify a mix, but the material has poor strength because there is very little binding at the interface of the tiny droplets. That is because they have smooth surfaces, like the interface between oil and water. If the object is big enough this does not matter so much, thus you can make reasonable fence posts out of recycled plastics, but there really is a limit to the market for fence posts.

The reason they do not dissolve in each other comes from thermodynamics. For something to happen, such as polymer A dissolving in polymer B, the change (indicated by the symbol Δ) in what is called the free energy ΔG has to be negative. (The reason it is negative is convention; the reason it is called “free” has nothing to do with price – it is not free in that sense.) To account for the process, we use an equation

            ΔG = ΔH -T ΔS

ΔH reflects the change of energy between each molecule in its own material and in solution of the other material. As a general rule, molecules favour having their own kind nearby, especially if they are longer because the longer they are the interactions per atom are constant for other molecules of the same material, but other molecules do not pack as well. Thinking of oil and water, the big problem for solution is that water, the solvent, has hydrogen bonds that make water molecules stick together. The longer the polymer, per molecule that enhances the effect. Think of one polymer molecule has to dislodge a very large number of solvent molecules. ΔS is the entropy and it increases as the degree of randomness increases. Solution is more random per molecule, so whether something dissolves is a battle between whether the randomness per molecule can overcome the attractions between the same kind. The longer the polymer, the less randomness is introduced and the greater any difference in energy between same and dissolved. So the longer the polymers, the less likely they are to dissolve in each other which, as an aside, is why you get so much variety in minerals. Long chain silicates that can alter their associate ions like to phase separate.

So we cannot recycle, and they are useless? Well, no. At the very least we can use them for energy. My preference is to turn them, and all the organic material in municipal refuse, into hydrocarbons. During the 1970s oil crises the engineering was completed to build a demonstration plant for the city of Worcester in Massachusetts. It never went ahead because as the cartel broke ranks and oil prices dropped, converting wastes to hydrocarbon fuels made no economic sense. However, if we want to reduce the use of fossil fuels, it makes a lot of sense to the environment, IF we are prepared to pay the extra price. Every litre of fuel from waste we make is a litre of refined crude we do not have to use, and we will have to keep our vehicle fleet going for quite some time. The basic problem is we have to develop the technology because the engineering data for that previous attempt is presumably lost, and in any case, that was for a demonstration plant, which is always built on the basis that more engineering questions remain. As an aside, water at about 360 degrees Centigrade has lost its hydrogen bonding preference and the temperature increase means oil dissolves in water.

The alternative is to burn it and make electricity. I am less keen on this, even though we can purchase plants to do that right now. The reason is simple. The combustion will release more gases into the atmosphere. The CO2 is irrelevant as both do that, but the liquefaction approach sends nitrogen containing material out as water soluble material which could, if the liquids were treated appropriately, be used as a fertilizer, whereas in combustion they go out the chimney as nitric oxide or even worse, as cyanides. But it is still better to do something with it than simply fill up local valleys.

One final point. I saw an item where some environmentalist was condemning a UK thermal plant that used biomass arguing it put out MORE CO2 per MW of power than coal. That may be the case because you can make coal burn hotter and the second law of thermodynamics means you can extract more energy in the form of work. (Mind you, I have my doubts since the electricity is generated from steam.) However, the criticism shows the inability to understand calculus. What is important is not the emissions right now, but those integrated over time. The biomass got its carbon from the atmosphere say forty years ago, and if you wish to sustain this exercise you plant trees that recover that CO2 over the next forty years. Burn coal and you are burning carbon that has been locked away from the last few million years.

Thorium as a Nuclear Fuel

Apparently, China is constructing a molten salt nuclear reactor to be powered by thorium, and it should be undergoing trials about now. Being the first of its kind, it is, naturally, a small reactor that will produce 2 megawatt of thermal energy. This is not much, but it is important when scaling up technology not to make too great of leaps because if something in the engineering has to be corrected it is a lot easier if the unit is smaller. Further, while smaller is cheaper, it is also more likely to create fluctuations, especially with temperature, and when smaller they are far easier to control. The problem with a very large reactor is if something is going wrong it takes a long time to find out, but then it also becomes increasingly difficult to do anything about it.

Thorium is a weakly radioactive metal that has little current use. It occurs naturally as thorium-232 and that cannot undergo fission. However, in a reactor it absorbs neutrons and forms thorium-233, which has a half-life of 22 minutes and β-decays to protactinium-233. That has a half-life of 27 days, and then β-decays to uranium-233, which can undergo fission. Uranium-233 has a half-life of 160,000 years so weapons could be made and stored.  

Unfortunately, 1.6 tonne of thorium exposed to neutrons and if appropriate chemical processing were available, is sufficient to make 8 kg of uranium-233, and that is enough to produce a weapon. So thorium itself is not necessarily a form of fuel that is free of weapons production. However, to separate Uranium-233 in a form to make a bomb, major chemical plant is needed, and the separation needs to be done remotely because apparently contamination with Uranium-232 is possible, and its decay products include a powerful gamma emitter. However, to make bomb material, the process has to be aimed directly at that. The reason is, the first step is to separate the protactinium-233 from the thorium, and because of the short half-life, only a small amount of the thorium gets converted. Because a power station will be operating more or less continuously, it should not be practical to use it to make fissile material for bombs.

The idea of a molten salt reactor is that the fissile material is dissolved in a liquid salt in the reactor core. The liquid salt also takes away the heat which, when the salt is cycles through heat exchangers, converts water to steam, and electricity is obtained in the same way as any other thermal station. Indeed, China says it intends to continue using its coal-fired generators by taking away the furnaces and replacing them with a molten salt reactor. Much of the infrastructure would remain. Further, compared with the usual nuclear power stations, the molten salt reactors operate at a higher temperature, which means electricity can be generated more efficiently.

One advantage of a molten salt reactor is it operates at lower pressures, which greatly reduces the potential for explosions. Further, because the fuel is dissolved in the salt you cannot get a meltdown. That does not mean there cannot be problems, but they should be much easier to manage. The great advantage of the molten salt reactor is it burns its reaction products, and an advantage of a thorium reactor is that most of the fission products have shorter half-lives, and since each fission produces about 2.5 neutrons, a molten salt reactor further burns larger isotopes that might be a problem, such as those of neptunium or plutonium formed from further neutron capture. Accordingly, the waste products do not comprise such a potential problem.

The reason we don’t directly engage and make lots of such reactors is there is a lot of development work required. A typical molten salt mix might include lithium fluoride, beryllium fluoride, the thorium tetrafluoride and some uranium tetrafluoride to act as a starter. Now, suppose the thorium or uranium splits and produces, say, a strontium atom and a xenon atom. At this point there are two fluorine atoms as surplus, and fluorine is an extraordinarily corrosive gas. As it happens, xenon is not totally unreactive and it will react with fluorine, but so will the interior of the reactor. Whatever happens in there, it is critical that pumps, etc keep working. Such problems can be solved, but it does take operating time to be sure such problems are solved. Let’s hope they are successful.

The Fusion Energy Dream

One of the most attractive options for our energy future is nuclear fusion, where we can turn hydrogen into helium. Nuclear fusion works, even on Earth, as we can see when a hydrogen bomb goes off. The available energy is huge. Nuclear fusion will solve our energy crisis, we have been told, and it will be available in forty years. That is what we were told about 60 years ago, and you will usually hear the same forty year prediction now!

Nuclear fusion, you will be told, is what powers the sun, however we won’t be doing what the sun does any time soon. You may guess there is a problem in that the sun is not a spectacular hydrogen bomb. What the sun does is to squeeze hydrogen atoms together to make the lightest isotope of helium, i.e. 2He. This is extremely unstable, and the electric forces will push the protons apart in an extremely short time, like a billionth of a billionth of a second might be the longest it can last, and probably not that long. However, if it can acquire an electron, or eject a positron, before it decays it turns into deuterium, which is a proton and a neutron. (The sun also uses a carbon-oxygen cycle to convert hydrogen to helium.) The difficult thing that a star does, and what we will not do anytime soon, is to make neutrons (as opposed to freeing them).

The deuterium can then fuse to make helium, usually first with another proton to make 3He, and then maybe with another to make 4He. Each fusion makes a huge amount of energy, and the star works because the immense pressure at the centre allows the occasional making of deuterium in any small volume. You may be surprised by the use of the word “occasional”; the reason the sun gives off so much energy is simply that it is so big. Occasional is good. The huge amount of energy released relieves some of the pressure caused by the gravity, and this allows the star to live a very long time. At the end of a sufficiently large star’s life, the gravity allows the material to compress sufficiently that carbon and oxygen atoms fuse, and this gives of so much energy that the increase in pressure causes  the reaction  to go out of control and you have a supernova. A bang is not good.

The Lawrence Livermore National Laboratory has been working on fusion, and has claimed a breakthrough. Their process involves firing 192 laser beams onto a hollow target about 1 cm high and a diameter of a few millimeters, which is apparently called a hohlraum. This has an inner lining of gold, and contains helium gas, while at the centre is a tiny capsule filled with deuterium/tritium, the hydrogen atoms with one or two neutrons in addition to the required proton. The lasers heat the hohlraum so that the gold coating gives off a flux of Xrays. The Xrays heat the capsule causing material on the outside to fly off at speeds of hundreds of kilometers per second. Conservation of momentum leads to the implosion of the capsule, which gives, hopefully, high enough temperatures and pressures to fuse the hydrogen isotopes.

So what could go wrong? The problem is the symmetry of the pressure. Suppose you had a spherical-shaped bag of gel that was mainly water, and, say, the size of a football and you wanted to squeeze all the water out to get a sphere that only contained the gelling solid. The difficulty is that the pressure of a fluid inside a container is equal in all directions (leaving aside the effects of gravity). If you squeeze harder in one place than another, the pressure relays the extra force per unit area to one where the external pressure is weaker, and your ball expands in that direction. You are fighting jelly! Obviously, the physics of such fluids gets very complicated. Everyone knows what is required, but nobody knows how to fill the requirement. When something is unequal in different places, the effects are predictably undesirable, but stopping them from being unequal is not so easy.

The first progress was apparently to make the laser pulses more energetic at the beginning. The net result was to get up to 17 kJ of fusion energy per pulse, an improvement on their original 10 kJ. The latest success produced 1.3 MJ, which was equivalent to 10 quadrillion watts of fusion power for a 100 trillionth of a second. An energy generation of 1.3 MJ from such a small vessel may seem a genuine achievement, and it is, but there is further to go. The problem is that the energy input to the lasers was 1.9 MJ per pulse. It should be realised that that energy is not lost. It is still there so the actual output of a pulse would be 3.2 MJ of energy. The problem is that the output includes the kinetic energy of the neutrons etc produced, and it is always as heat whereas the input energy was from electricity, and we have not included the losses of power when converting electricity to laser output. Converting that heat to electricity will lose quite a bit, depending on how it is done. If you use the heat to boil water the losses are usually around 65%. In my novels I suggest using the magnetohydrodynamic effect that gets electricity out of the high velocity of the particles in the plasma. This has been made to work on plasmas made by burning fossil fuels, which doubles the efficiency of the usual approach, but controlling plasmas from nuclear fusion would be far more difficult. Again, very easy to do in theory; very much less so in practice. However, the challenge is there. If we can get sustained ignition, as opposed to such a short pulse, the amount of energy available is huge.

Sustained fusion means the energy emitted from the reaction is sufficient to keep it going with fresh material injected as opposed to having to set up containers in containers at the dead centre of a multiple laser pulse. Now, the plasma at over 100,000,000 degrees Centigrade should be sufficient to keep the fusion going. Of course that will involve even more problems: how to contain a plasma at that temperature; how to get the fuel into the reaction without melting then feed tubes or dissipating the hydrogen; how to get the energy out in a usable form; how to cool the plasma sufficiently? Many questions; few answers.

A New Way of Mining?

One of the bigger problems our economies face is obtaining metals. Apparently the price of metals used in lithium-ion batteries is soaring because supply cannot expand sufficiently, and there appears to be no way current methodology can keep up.

 Ores are obtained by physically removing them from the subsurface, and this tends to mean that huge volumes of overburden have to be removed. Global mining is estimated to produce 100 billion t of overburden per year, and that usually has to be carted somewhere else and dumped.  This often leads to major disasters, such as mine tailing causing dams, and then collapsing, thus Brazil has had at least two such collapses that led to something like 140 million cubic meters of rubble moving and at least 256 deaths. The better ores are now worked out and we are resorting to poorer ores, most of which contain less than 1% is what you actually want. The rest, gangue, is often environmentally toxic and is quite difficult to dispose of safely. The whole process is energy intensive. Mining contributes about 10% of the energy-related greenhouse gas emissions. Yet if we take copper alone, it is estimated that by 2050 demand will increase by up to 350%. The ores we know about are becoming progressively lower grade and they are found at greater depths.

We have heard of the limits to growth. Well, mining is becoming increasingly looking like becoming unsustainable, but there is always the possibility of new technology to get the benefit from increasingly more difficult sources. One such possible technique involves first inserting acid or lixiviant into the rock to dissolve the target metal in the form of an ion then use a targeted electric field to transport the metal-rich solution to the surface. This is a variant of a technique used to obtain metals from fly ash, sludge, etc.

The objective is to place an electrode either within or surrounding the ore, then the acid is introduced from an external reservoir. There is an alternative reservoir with a second electrode with opposite charge to that of the metal-bearing ion. The metal usually bears a positive charge in the textbooks, so you would have your reservoir electrode negatively charged, but it is important to keep track of your chemistry. For example, if iron were dissolved in hydrochloric acid, the main ion would be FeCl4-, i.e. an anion.

Because transport occurs through electromigration, there is no need for permeability enhancement techniques, such as fracking. About 75% of copper ore reserves are as copper sulphide that lie beneath the water table. The proposed technique was demonstrated on a laboratory scale with a mix of chalcopyrite (CuFeS2) and quartz, each powdered. A solution of ferric chloride was added, and a direct current of 7 V was applied to electrodes at opposite ends of a 0.57 m path, over which there was a potential drop of about 5V, giving a maximal voltage gradient of 1.75 V/cm. The ferric chloride liberated copper as the cupric cation. The laboratory test extracted 57 weight per cent of the available copper from a 4 cm-wide sample over 94 days, although 80% was recovered in the first 50 days. The electric current decreased over the first ten days from 110 mA to 10 mA, suggestive of pore blocking. Computer simulations suggest that in the field, about 70% of the metal in a sample accessed by the electrodes could be recovered over a three year period. The process would have the odd hazard, thus a 5 meter spacing between electrodes employed, in the simulation, a 500 V difference. If the ore is several hundred meters down, this could require quite a voltage. Is this practical? I do not know, but it seems to me that at the moment the amount of dissolved material, the large voltages, the small areas and the time taken will count against it. On the other hand, the price of metals are starting to rise dramatically. I doubt this will be a final solution, but it may be part of one.