Biofuels from Algae

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

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

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

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

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

Climate Change and the Oceans

It appears that people are finally seeing that climate change is real, although the depth of their realization leaves much to be desired. Thus German politicians are going to close down their nuclear reactors and presumably burn more carbon. Not exactly constructive. A number of US politicians simply deny it, as if to say that if you deny it often enough, it will go away. Here in New Zealand we have politicians who say, yes it is real, but what they are doing about it tends to be to encourage electric vehicles and bicycles, with a bit of tree planting. Good intentions, but perhaps the commitment is a little less than necessary, but still better than the heads in sand approach. So, consider the size of the problem: the Intergovernmental Panel on Climate Change has stated that to limit global warming to 1.5 degrees compared with pre-industrial levels could require the removal of 20 billion tonnes of CO2 from the atmosphere each year until 2100. That is a much bigger than average ask. However, planting trees is a start, and the good news is they keep working at it, year after year. So, what to do? In my opinion, there is no one big fix. The concept of beating climate change with a thousand cuts is more appropriate. Part of the problem is to persuade people to do something. They turn around and say, why me? Who pays?

As an example, it has been argued that in the US the application of biochar to soils could improve grain harvests by 4.87 – 6.4 %. The carbon tends to last for maybe hundreds of years, at least to some extent, so the argument goes that it will eventually pay for itself, but initially it is a cost. This works particularly well in acidic heavily weathered soils, where the yields are generally somewhat low because they do not hold nutrients well. This is also not exactly a single bullet solution, since with good uptake, it would sequester and offset about 0.5% of US emissions.

There was an article in a recent edition of Nature that summarised marine geoengineering. Rather pickily, they stated that none of the proposals have been rigorously tested scientifically nor published in peer-reviewed journals. Part of this gripe is fair: they complain that results have been published, but in places like websites that no longer work. That is a separate issue really, and provided the work is properly done, peer-reviewed journals, following editorial contractions to save space, may not be the best. But let us leave that for the moment. The oceans are an attractive place for one reason: they are not doing much else other than being a place for fish to live in. Land tends to be owned, and much is either required for environmental reserves or food production. Certainly, there is a lot of land that is little better than waste, often left over from previous forest harvesting, and there is no reason why this could not be planted. Another useful contribution, but what are the options for the sea?

The first approach noted by Nature is to try to reduce the albedo, by reflecting incoming sunlight. Two ways proposed for doing this would be to put films on the water, or to spray water upwards and let it form clouds. The latter should be reasonably harmless, leaving aside the problem of whether some places might be adversely affected, a problem that applies to any such proposal. The former could have a serious adverse effect on marine life. Squirting water into the air to form clouds would seem to reasonably easily tested, but it also leaves the question, who is going to do it because ultimately this concept involves a cost for which there is no return.

Two more processes noted in the article are the spreading of alkaline rock into the sea to absorb CO2, and the spreading of iron-rich fertiliser to promote the growth of microalgae. The problem for the first is what sort of rock? A billion tonne of burnt lime per year would do, but first it would have to have its CO2 pyrolysed off, so that would emit as much as it saved. We could try basalt, such as peridotite, but if we powdered that it would make more sense to apply it to land where previously we had applied lime because it does much the same job, but also absorbs carbon dioxide. The iron fertiliser case is more interesting. There have been experiments to do this. An example: a ship sailed around, spread the crushed rock, and found that yes, there was a microalgal bloom. However, they also concluded that the amount of carbon that was fixed by sinking to the bottom of the sea was insufficient to justify the exercise. That, however, omits two other thoughts. First, what happened to the algae? If it was eaten by fish (or mammals) that would increase the food supply, and an increase in animal biomass also fixes carbon. The second thought is that if it were harvested, it could well be used to make biofuels, which would reduce the requirement for oil consumption, so that is equally useful. Can it be harvested? That is a question that needs more research. As a general rule, if there is just one thing that needs doing, there is usually a way, if you can find it. The making of fuel is easy. I have done it. There is, of course, the problem of making money from it, and with the current cost of oil that is impossible. Also, scale-up is still a problem to be solved.

The final two proposals were to cultivate macroalgae and to upwell deep water and cool the top. The latter does nothing for the carbon problem, so I shall not think too hard about that, but it is almost essential for the former. In the 1970s the US Navy carried out experiments on growing macroalgae on rafts in deep water, and they only grew when deep water was brought to the surface to act as a fertiliser. These algae can also be used as fuel, or the carbon absorbed somewhere else, and some algae are the fastest growing plants on Earth. It is quite fascinating to watch through a microscope and see continual cell division. This may be easier than some think. Apparently floating Sargassum is filling up some sections of the Atlantic and off the coast of Mexico.

So the question then is, should any of this be done? The macroalgae probably have the lowest probability of undesired side effects, since it is merely farming on water that is otherwise unused. However, to absorb enough carbon dioxide to make a serious difference an awful lot of algae would have to be grown. However, the major oceans have plenty of area.

Fuel for Legacy Vehicles in a “Carbon-free” Environment

Electric vehicles will not solve our emissions problem: there are over a billion petroleum driven vehicles, and they will not go away any time soon. Additionally, people have a current investment, and while billionaires might throw away their vehicles, most ordinary people will not change unless they can sell what they have, which in turn means someone else is using it. This suggests the combustion motor is not yet finished, and the CO2emissions will continue for a long time yet. That gives us a rather awkward problem, and as noted in the previous posts on global warming, there is no quick fix. One of the more obvious contributions could be biofuels. Yes, you still burn carbon, but the carbon came from the atmosphere. There will also be processing energy, but often that can come from the byproducts of the process. At this point I should add a caveat: I have spent quite a bit of my professional life researching this route so perhaps I have a degree of bias.

The first point is that it will be wrong to take grain and make alcohol for fuel, other than as a way of getting rid of spare or spoiled grain. The world will also have a food shortage, especially if the sea levels start rising, because much of the most productive land is low-lying. If we want to grow biomass, we need an area of land roughly equivalent to the area used for food production, and that land is not there. There are wastelands, but they tend to be non-productive. However, that does not mean we cannot grow biomass for fuel; it merely states there is nowhere nearly enough. Again, there is no single fix.

What you get depends critically on how you do it, and what your biomass is. Of the various processes, I prefer hydrothermal processing, which involves heating the biomass in water up to supercritical temperatures with some additional conditions. In effect, this greatly accelerates the processes that formed oil naturally. Corresponding pyrolysis will break down plastics, and in general high quality fuel is obtainable. The organic fraction of municipal refuse could also be used to make fuel, and in my ebook “Biofuel” I calculated that refuse could produce roughly seven litres per week per person. Not huge, but still a contribution, and it helps solve the landfill problem. However, the best options that I can think of include macroalgae and microalgae. Macroalgae would have to be cultivated, but in the 1970s the US navy carried out an exercise that grew macroalgae on “submerged rafts” in the open Pacific, with nutrients from the sea floor brought up from wind and wave action. Currently there is work being carried out growing microalgae in tanks, etc, in various parts of the world. In principle, microalgae could be grown in the open ocean, if we knew how to harvest it.

I was involved in one project that used microalgae grown in sewage treatment plants. Here there should have been a double benefit – sewage has to be treated so the ponds are already there, and the process cleans up the nitrogen and phosphate that would otherwise be dumped into the sea, thus polluting it. The process could also use sewage sludge, and the phosphate, in principle, was recoverable. A downside was that the system would need more area than the average treatment plant because the residence time is somewhat longer than the current time, which seems designed to remove the worst of the oxygen demand then chuck everything out to sea, or wherever. This process went nowhere; the venture needed to refinance and unfortunately they left it too late, namely shortly after the Lehman collapse.

From the technical point of view, this hydrothermal technology is rather immature. What you get can critically depend on exactly how you do it. You end up with a thick brown fluid, from which you can obtain a number of products. Your petrol fraction is generally light aromatics, with a research octane number (RON) of about 140, and the diesel fraction can have a cetane number approaching 100 (because the main components are straight chain C15 or C17 saturated hydrocarbons. Cetane is the C16 equivalent.) These are superb fuels, however while current motors would run very well on them, they are not optimal.

We can consider ethanol as an example. It has an RON somewhere in the vicinity of 120 – 130. People say ethanol is not much of a fuel because its energy content is significantly lower than hydrocarbons, and that is correct, but energy is not the whole story because efficiency also counts. The average petrol motor is rather inefficient and most of the energy comes out as heat. The work you can get out depends on the change of pressure times volume, so the efficiency can be significantly improved by increasing the compression ratio. However, if the compression is too great, you get pre-ignition. The modern motor is designed to run well with an octane number of about 91, with some a bit higher. That is because they are designed to use the most of the distillate from crude oil. Another advantage of ethanol is you can blend in some water with it, which absorbs heat and dramatically increases the pressure. So ethanol and oxygenates can be used.

So the story with biofuels is very similar to the problems with electric vehicles; the best options badly need more research and development. At present, it looks as if they will not get it in time. Once you have your process, it usually takes at least ten years to get a demonstration plant operating. Not a good thought, is it?

Liquid Fuels from Algae

In the previous post, I discussed biofuels in general. Now I shall get more specific, with one particular source that I have worked on. That is attempting to make liquid fuels from macro and microalgae. I was recently sent the following link:

https://www.fool.com/investing/2017/06/25/exxonmobil-to-climate-change-activists-chew-on-thi.aspx

In this, it was reported that ExxonMobil partnering Synthetic Genomics Inc. have a $600 million collaboration to develop biofuels from microalgae. I think this was sent to make me green with envy, because I was steering the research efforts of a company in New Zealand trying to do the same, except that they had only about $4 million. I rather fancy we had found the way to go with this, albeit with a lot more work to do, but the company foundered when it had to refinance. It could have done this in June 2008, but it put it off until 2009. I think it was in August that Lehmans did a nosedive, and the financial genii of Wall Street managed to find the optimal way to dislocate the world economies without themselves going to jail or, for that matter, becoming poor; it was the lesser souls that paid the price.

The background: microalgae are unique among plants in that they devote most of their photochemical energy into either making protein and lipids, which in more common language are oily fats. If for some reason, such as a shortage of nitrogen, they will swell up and just make lipids, and about 75 – 80% of their mass are comprised of these, and when nitrogen starved, they can reach about 70% lipids before they die of starvation. When nitrogen is plentiful, they try to reproduce as fast as they can, and that is rapid. Algae are the fastest growing plants on the planet. One problem with microalgae: they are very small, and hence difficult to harvest.

So what is ExxonMobil doing? According to this article they have trawled the world looking for samples of microalgae that give high yields of oil. They have tried gene-editing techniques to grow a strain that will double oil production without affecting growth rate, and they grow these in special tubes. To be relevant, they need a lot of tubes. According to the article, if they try open tanks, they need an area about the size of Colorado to supply America’s oil demand, and a corresponding lot of water. So, what is wrong here? In my opinion, just about everything.

First, you want to increase the oil yield? Take the microalgae from the rapidly growing stage and grow them in nitrogen-starved conditions. No need for special genetics. Second, if you are going to grow your microalgae in open tanks (to let in the necessary carbon dioxide and reduce containment costs) you also let in airborne algae. Eventually, they will take over because evolution has made them more competitive than your engineered strain. Third, no need to consider producing all of America’s liquid fuels all at once; electricity will take up some, and in any case, there is no single fix. We need what we can get. Fourth, if you want area, where is the greatest area with sufficient water? Anyone vote for the ocean? It is also possible that microalgae may not be the only option, because if you use the sea, you could try macroalgae, some of which such as Macrocystis pyrifera grow almost as fast, although they do not make significant levels of lipids.

We do not know how ExxonMobil intended to process their algae. What many people advocate is to extract out the lipids and convert them to biodiesel by reacting them with something like sodium methoxide. To stop horrible emulsions while extracting, the microalgae need to be dried, and that uses energy. My approach was to use simple high pressure processing in water, hence no need to dry the algae, from which both a high-octane petrol fraction and a high-cetane diesel fraction could be obtained. Conversion efficiencies are good, but there are many other byproducts, and some of the residue is very tarry.

After asking where the best supply of microalgae could be found, we came up with sewage treatment ponds. No capital requirement for building the ponds, and the microalgae are already there. In the nutrient rich water, they grow like mad, and take up the nutrients that would otherwise be considered pollutants like sponges. The lipid level by simple extraction is depressingly low, but the levels that are bound elsewhere in the algae are higher. There is then the question of costs. The big cost is in harvesting the microalgae, which is why macroalgae would be a better bet in the oceans.

The value of the high pressure processing (an accelerated treatment that mimics how nature made our crude oil in the first place) is now apparent: while the bulk of the material is not necessarily a fuel, the value of the “byproducts” of your fuel process vastly exceeds the value of the fuel. It is far easier to make money while still working on the smaller scale. (The chemical industry is very scale dependent. The cost of making something is such that if you construct a similar processing plant that doubles production, the unit cost of the larger plant is about 60% that of the smaller plant.)

So the approach I favour involves taking mainly algal biomass, including some microalgae from the ocean (and containing that might be a problem) and aiming initially to make most of your money from the chemical outputs. One of the ones I like a lot is a suite of compounds with low antibacterial activity, which should be good for feeding chickens and such, which in turn would remove the breeding ground for antibiotic resistant superbugs. There are plenty of opportunities, but unfortunately, a lot of effort and money required it make it work.

For more information on biofuels, my ebook, Biofuels An Overview is available at Smashwords through July for $0.99. Coupon code NY22C

Geoengineering: to do or not do?

For those interested in science, and in global warming, a recent issue of Nature (vol 516, pp 20 – 21) showed some of the problems relating to geoengineering, which involves taking action to change the climate. Strictly speaking, we are already doing it. By burning fossil fuels we are warming the planet through the additional carbon dioxide in the atmosphere. The question is, can we reverse this warming in a controlled fashion? The argument behind geoengineering is simple: we can either try it or not try it. If we do, we have the potential to create massive new problems; if we do not, sea levels will eventually rise somewhere between 20 – 50 meters, drowning all our coastal cities, destroying a surprising amount of some of the most productive farmland, and altering rainfall distributions quite dramatically. Then, of course, there are more violent storms. So, what are the options?
One is to try to increase the amount of light reflected to space, which can be achieved by forming more clouds. One way to do this is to spray salt water into the air. This has the advantage of being easy to do, and easy to stop doing. It is harder to know the consequences, but we should be able to predict to some extent because volcanic eruptions will do something similar to what is being proposed. Climate scientists, however, complain that this may reduce rainfall in some regions and possibly worsen ozone depletion. Of course they also warn that rainfall will be reduced anyway. Meanwhile, a computer simulation produced results that indicated changes in rainfall consequent to geoengineering “could affect 25 – 65% of the world’s population”. Charming! No comment that the changes could be beneficial. No comment either about the fact that any given model has consistently failed to predict details of weather.
However, from my point of view, the most bizarre outcome came from the proposal to seed the oceans to grow microalgae, which grow very rapidly and take up carbon dioxide in doing so. When the algae die, they should sink to the ocean floor and trap carbon. Trouble was, in some of the few experiments, it seems they did not, possibly because the algae did not die, or possibly because the experimenters did not count it properly. One other outcome might be that they get eaten by fish, thus improving the world’s food supply, and another might be that they give off dimethyl sulphide (and use up quite a bit of solar energy in doing so) which goes to the atmosphere, gets oxidized by absorbing more light, and then forms clouds, which reflects light. Ideal?
As a potential means of fighting climate change, I admit to liking this idea, nevertheless there is a problem, but not what you might think. Or maybe you would. Yep, it is financial embarrassment. Entrepreneurs decided to seed the oceans this way to generate large volumes of carbon credits, which could be sold to those who wanted to burn more coal, a sure way of reducing greenhouse gases! Yeah, right! Anyway, that was headed off by an international treaty, in which this activity was stopped by labeling it “ocean pollution”, and no further experiments have taken place. Talk about useless politicians!
The problem is as I see it that the politicians cannot seem to recognize that a technical problem needs a technical solution. The economists cannot solve this, as shown by that response to an emissions trading scheme noted above. The problem is, changing the prices of forms of energy cannot in themselves generate energy. Conservation may be encouraged, and that is good, but ultimately our lifestyle requires a very high fraction of what we currently use. Worse, there is no point in denying the fact that the planet is warming, and the only solution is to cool it. Cutting emissions is definitely desirable, but it is not enough to retain our previous climate because the gases currently there produce net warming, and this extra warming would continue for at least a hundred years if no further gases were emitted during that time. If we do not want to do something, who pays the price for what happens?