Wednesday, December 19, 2012

Russian oil and the future of catalytic chemistry

Here I am, in Siberia, with Prof. Irina Kurzina (right in the photo) and Dr. Tamara Kharlamova (center) of the department of Chemistry of the University of Tomsk. Prof. Kurzina organized there a conference titled "Catalysis: from the laboratory to industry" and she has been so kind to invite me to give a presentation. This trip to Tomsk has been interesting for various reasons and I was impressed by the enthusiasm and the dedication of the young Russian scientists I met. Here is a version of my talk at the meeting; it is condensed and somewhat modified to cater for a larger audience than specialists in catalysis, but it maintains the substance of what I said. 

Tomsk - Nov 1, 2012
by Ugo Bardi

Ladies and gentlemen, first of all I'd like to tell you that it is a pleasure to be here in Tomsk to discuss heterogeneous catalysis. And I say this because I am one of you, even though I haven't been working in this field for some years. Let me show you this picture:

It was taken in 1994 and it is the earliest picture I have been able to find that shows me in a chemistry lab, studying heterogeneous catalysis. (what you see behind me is an apparatus for photoelectron spectroscopy). I had been studying that subject from 1980, when I was post-doc in Berkeley. As you can see, I look a bit younger in that picture. I looked even younger in 1980, but let's not harp on that! I just wanted to show you where I started my career as a researcher which, by now, has changed quite a bit.

Today, I am still very much interested in catalysis and surface science, but I tend to take a wider view of the field. I am not studying specific processes any more, but the whole subject of catalysis in its economic relevance. You know better than me that catalysis is strongly related to petroleum which, together with natural gas, provides the basic feedstock for most industrial catalytic reactions. It is with catalytic reactions that we create fuels from petroleum, and not just fuels, we create everything from plastics to fertilizers and everything else you can think in terms of chemicals.

Now, the point is, of course that once you realize how important is petroleum for so many things then you also wonder how long it will last. I am sure you have been asking yourselves this question, at least in the back of your minds. Occasionally, I was asking myself the same question when I was a young researcher studying catalytic chemistry but I must say I never placed much importance on it. It was only with time that I found that I couldn't ignore the question any more and so I started studying it as if it were another problem in physical chemistry. I am not sure I found good answers for this question, but at least I did find some answers. That's what I would like to discuss with you today.

I'll try to tell you about petroleum in general, but also about the specific subject of Russian petroleum. As a disclaimer, let me say that I am not a specialist in Russian oil. There are people who spent their lives studying oil production in Russia and they know everything about where oil is produced, resources, reserves, wells, fields, pipelines, refineries and all the rest. I can't claim to have that kind of knowledge but I'll try nevertheless to tell you a few things on this subject that I found interesting and that you may have missed.

So, the talk will start with a brief history of petroleum, then I'll tell you something about the problems caused by petroleum, climate change, then some perspectives about Russian oil production and finally on how catalytic chemistry can come to the rescue of a future world in which we'll have much less petroleum to burn that we have today. That means "CO2 activation", but let's go in order.

1. Introduction on petroleum

So, as fellow chemists you know that petroleum often arrives as an awful blackish goo that, as it is, is almost completely useless as fuel. It burns, yes, but very slowly and, in some cases it doesn't burn at all, at least if you try to ignite it at atmospheric pressure. It is catalysis, in particular what we call "catalytic cracking", that turns oil into fuels. But even before industrial cracking, people had learned how to distill oil to make a nice and clear fluid, called "kerosene" that could burn in lamps - that was in mid 19th century in the United States. Here is an advertisement for kerosene in Russia, there is no date in this image, but from the style it could be late 19th century.

Maybe you don't know that for some time Russia imported kerosene from the US. That sounds strange to us because we know that Russia has vast petroleum resources and you probably know that the Caucasus oil fields were exploited already in the 18th century. But the technology to transform crude oil into lamp fuel took some time to be developed here and so for some time Russia had to rely on the US for kerosene. Perhaps you also don't know that Dmitry Mendeleev - the one famous for the periodic table - traveled to Pennsylvania to study the American ways to process crude oil. Here is his publication, dated 1877.

Of course, Russian chemists quickly learned how to make kerosene and then how to process petroleum using modern methods. Today, the Russian oil industry is probably the largest in the world, but where does Russia stand in terms of future perspectives? To answer this question we must examine oil production in general.

2. Patterns of oil production

As I said, Russia started a little slower and a little later than America with petroleum but, with time, Russian production grew rapidly until it overtook the American production in the 1970s. Let's see a comparison of US and Russia (actually the former Soviet Union) in terms of oil production. This is an image made in 1997 by the French oil expert Jean Laherrere. (Link)

This is a rather old set of data, many things have changed since 1997. But I wanted to show to you this specific image to evidence how things appeared during the collapse of the Soviet Union.

You see how the Soviet production started growing rapidly later than in the US  but that eventually it overcame the US production with the 1970s (the graph doesn't show Alaska's production, but the change is not large). Note how both curves show the same pattern: first they grow exponentially, then they peak and decline. There is a difference, though: the US consumption continued to grow with imports from the Middle East and other regions. Instead, the Soviet Union was relatively isolated as an economic system and consumption declined together with production. That was a feature of the collapse of the Soviet Union.

You may be interested to know that there are two schools of thought on what caused oil production to decline in the Soviet Union. One says that oil production collapsed because of the collapse of the political system, the other that the Soviet political system collapsed because of the collapse in oil production. My opinion is that you can't think of answer this question with an "either-or". The right answer is "both". You need a functioning political and economic system to produce oil and you need oil as a source of energy in order to maintain a functioning political and economic system. So, eventually, the decline of both things came together. But why exactly?

As we saw, there seems to be a similar pattern in the two cases, USA and USSR. The first to note the existence of this pattern was an American geologist, Marion King Hubbert. In 1956, Hubbert foresaw what would have been the shape of the oil production curve in the United States. This figure is rather famous:

Hubbert saw this model as empirical, but whenever you have a pattern, a regularity in a phenomenon, then there has to be some deep reason for it to occur. That is, the fact that two very different economic and political systems such as USA and USSR showed the same pattern is telling us that something at the basis of the economy creates this pattern. That is, it was not political choices of the American government or of the Soviet government that generated this pattern. It is a general phenomenon of some kind that appears everywhere you have a large producing region.

Let me give you another example of this pattern; some data about the oil field of Samotlor, in West Siberia. It is not so far from where we are, in Tomsk. Well, "not so far" has to be taken in relative terms. Somewhat less than a thousand km, which, I figure, is not so much by Russian standards!

Samotlor is  "supergiant" - one of the largest oil fields in the world. You see how production reached a maximum level of more than a billion barrels of oil per year. That's a huge value; at that time Samotlor, alone, produced a significant fraction of the world's oil production. But then, production went down.

The case of Samotlor is interesting also because it illustrates how a mature field can be revitalized, at least in part. In the late 1990s, the two companies that manage the field, TNK and BP, decided to invest in Samotlor to revamp production. That meant "squeezing" more oil from the old field by various methods; it can be done and it worked because the decline was halted. But it was impossible to bring back the field to the levels of its heyday. Production has remained nearly constant up to now but there is no doubt that it will have to decline again. So, you see, there are strong factors that lead the curve to assume that shape and the fact that people don't want production to decline doesn't mean that decline can be stopped. Not easily at least.

So, what is that creates this pattern? Well, there is a theory that explains it, but I can't go in the details, here. Let me just say that the economy must, in the end, obey to physical laws and physical laws say that it takes energy to extract oil. The less oil you have left, the more energy it takes to extract it. That translates into higher costs and, in the end, nobody extracts oil at a loss. So, oil is extracted rapidly when it is easy to extract, but with time production tends to decline. These considerations can be set in mathematical form and the result is the "bell shaped" curve that you saw.

In a way, oil extraction is a big chemical reaction where oil and oxygen are the reactants and human beings are the catalyst. It is impressive that these models work so well in some historical cases - not all cases, of course: the world's economy is a complicated system. But the fact that it is a complicated system doesn't mean that it doesn't obey the laws of physics. When there are no more reactants, the reaction must end.

3. Oil: the present situation

So much for the so called "Hubbert model". It is an interesting model, but you have to remember that models are always approximations of reality. This is valid in chemistry just as well as in oil production. So, let's go see some data about the real world, here, for instance this one (taken from Wikipedia):

You see that there is a certain tendency for the production "reaction" to follow the Hubbert model, that is to flare up and then subsidize. But reality is more complex and there is always the possibility of restarting growth after an extended period of decline. You could say that the reactants are not well mixed and so the reaction goes on irregularly. You see that production in the countries of the former Soviet Union picked up speed again after reaching a minimum, around 1998 and now it has reached levels not far from those of the peak at the time of the old Soviet Union. That's because the system is not so simple as the models would want it to be and it reacts, among other things, to prices, to political events, wars, crisis and the like.

So, what can we expect for the future? Well, let me show you some recent data for the Russian oil production

You see that production growth has been slowing down during the past few years. Now, it doesn't seem to be able to grow any more; in this, it mirrors the general global trends: the world oil production is flat, or very slowly growing.

So, what's happening? Well, it is not because of lack of efforts; that is, the slowdown of growth is not a planned effect. From the data I have, it is clear that the Russian oil industry is making a tremendous effort to keep production at the present levels. They are investing money and resources, actively searching new areas, new fields, and using new technologies to get more oil from old fields. The problem is that many old oil fields, especially in West Siberia, are "mature" and slowing down - as we saw for the case of Samotlor. There is still plenty of oil to be extracted in the Russian republics, but it takes more and more effort to do so.

So, what's going to happen? Surely, we are not going to see a decline in production as long as the industry can keep up the effort of developing the available reserves. And that depends on several factors, including the international financial situation. I would say that, in the short term, we don't have to worry about Russian production declining; probably not even in the medium term. But, eventually, as I said, the reaction must run out of reactants. Whether that will take the form of a collapse or a slow decline, I cannot say, but I can say that  we must prepare for a world where, in the long run, there will be less petroleum available and it will be more expensive. The same is true for natural gas, even though Russian gas reserves are very abundant according to the data we have.

Note also that the high cost of extraction is not the only problem. As more effort is made to extract from expensive resources, we see that we produce more CO2 for the same amounts of energy generated. And this has an impact on climate. Even here in Russia. Let me just show to you the fires in East Siberia of this year - one of the consequences of climate change.

Probably, Russia will not be hit so hard by global warming as other countries, but it will still be a problem. Some people say that Russia will benefit from a warmer climate but I am not sure about that; especially if you consider these summer fires. Climate is a tricky subject that causes big changes everywhere. In some places, the changes may be for good, but I wouldn't bet on that for Russia. So we have to prepare not only for a world with less petroleum, but for a world in which we will not want (or we will not be able) to use the remaining resources.

4. Catalytic activation of CO2 as feedstock

So, if you have been following me up to now, I am sure that you have been asking yourselves how we are going to survive without petroleum. Of course, that will be for the future, we still have resources for quite a while; but we must be careful to avoid squandering them. In other words, we have to prepare for a future when there will be less oil (and also less natural gas). Where will we be able to find the resources we need?

Of course, you are all chemists and you know where oil comes from - that was a discovery of the Russian chemist Mikahil Lomonosov, back in 18th century. We know that crude oil, just like coal and natural gas, is a product of photosynthesis. It is the reaction of water with CO2 that produces organic molecules. This reaction has been going on for hundreds of millions of years on our planet and some of the products have been buried underground and slowly transformed into what we call "fossil" hydrocarbons and coal.

Now, the point is, of course, if we can replicate this reaction in the lab. And the answer is "yes", of course we can. We can make long chain hydrocarbons in the lab. This is well known and we call it the "Fischer-Tropsch" reaction. It works in the presence of catalysts based, usually, on iron and cobalt.

But in order to run this reaction we need carbon monoxide and H2, which are normally produced by reaction of water with coal, it is the so called "water shift" reaction. But that doesn't help us so much since coal is also a fossil fuel, it is polluting, it generates global warming, and it is not infinite. So, how can we run this reaction without recurring to coal?

Hydrogen is something that we can get from the electrolysis of water. Water is abundant and splitting it doesn't produce greenhouse gases, at least if you use electric power generated by renewable or nuclear energy. But where can we get carbon monoxide without using fossil hydrocarbons? Well, it is possible, it is something called "CO2 activation".  Carbon dioxide is a stable gas, so we need energy to transform it into a "feedstock" that can react with hydrogen and produce carbon monoxide or useful products.

The main method for CO2 activation is something similar to photosynthesis, that is it is based on photochemistry. Activation is obtained by the promotion of an electron to a high energy state in a semiconductor. This electron then reacts with CO2; transforming it in an active compound that can react with hydrogen. Typically, TiO2 is the semiconductor used. Here, you see the electrochemical potentials that can be used in order to obtain the reaction, and the products you can obtain.

The reaction of photoelectrochemical activation of CO2 is still at the research stage but it is a promising idea. You see that there is plenty of interest in this concept and this year there has been the first conference on CO2 activation in Essen, in Germany

It is a hugely interesting field and very new: you notice that because it is the "first" conference on CO2 activation - there are not many subjects in chemistry that haven't been object of extensive studies and where you can have a "first" wordwide conference, today. So, a very interesting area. Unfortunately I could not attend this first conference for various reason, but I plan to be present at the next edition; in 2013. I think the concept of using CO2 as feedstock for the chemical industry is the real frontier of heterogeneous catalysis and I invite you to consider it for your future work.

6. Energy and CO2 activation

So, we saw that we need to start working in the direction of obtaining the chemicals we need from the activation of CO2. Right now, it is a route more expensive and more complex than the traditional ways of obtaining chemicals from fossil hydrocarbons, but in the future it is likely to became the chosen route. In the long run, it will be the only one.

Of course, we must be careful in what we are doing. Maybe you have read in some paper that people are claiming that they can "make gasoline out of air". It is referred to a particular path of reaction that starts with CO2 activation and leads to liquid fuels. In a certain way, it is true, but it is also clear that there is a fundamental difference. When you make gasoline out of petroleum, you use the energy embedded in petroleum (or maybe in natural gas) to power the whole process. But when you make gasoline out of CO2 you must provide the necessary energy. CO2 is a very stable chemical compound and to activate it you need to go uphill, thermodynamically, there is no way to avoid that. And you cannot use fossil hydrocarbons to obtain that energy: it would make no sense to burn hydrocarbons to make hydrocarbons.

So, if we want to substitute petroleum with CO2 as a feedstock, we must be careful that we need energy to power the whole process and this energy cannot come from fossil fuels; otherwise the whole thing would be self-defeating. Nuclear plants or renewable energy, possibly both things, but it is essential that we develop and install new forms of energy in the future.

This is the crucial point and the big challenge we face. Either we succeed in developing and using these new methods, or we'll have big, big troubles. And, as you saw, catalysis is a fundamental factor in these new perspectives. It is fascinating field to work in. It has always been one and now it is even more so!

7. Conclusion

I told you at the beginning that it was a pleasure for me to be here but now I would  like to tell you exactly why. You see, the first time I visited Russia was in 1993, almost 20 years ago. It was the time of the collapse of the Soviet Union. Many of you are too young to remember those times, but I am sure you understand what I am talking about. Those were sad times; especially sad for scientific research: there was no money, not even for the salaries of researchers. You had this feeling that so much work was being lost: competence, culture, history; all that was disappearing.  But today, visiting the university of Tomsk and seeing so many of you so enthusiastic, so committed, and doing so well; I can tell you that it is a great pleasure for me. Really, it is something that I won't forget so soon.

So, after having visited Russia many times during the past 20 years, I have only one regret: that I couldn't give this talk in Russian. But I can, at least, thank you for your attention in Russian: Спасибо за внимание!


Ugo Bardi is a member of the Club of Rome, faculty member of the University of Florence, and the author of "Extracted" (Chelsea Green 2014), "The Seneca Effect" (Springer 2017), and Before the Collapse (Springer 2019)