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Mitigating Global Warming Through Chemistry: Recycling Carbon Dioxide into Useful Fuels and Hydrocarbon Products

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Mitigating Global Warming Through Chemistry: Recycling Carbon Dioxide into Useful Fuels and Hydrocarbon Products
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Climate change due to mankind’s carbon dioxide emissions is a highly topical and controversial issue. As such it is also frequently discussed in the Inselhalle, the venue of the Lindau Nobel Laureate Meetings. Usually, in such discussions a great deal of effort is put into answering questions like: does anthropogenic climate change actually exist or is it a mere myth? Can we measure climate change reliably? What exactly is its extent? Should we be worried about it? And if yes, how can we reduce carbon dioxide emissions?In his first Lindau Lecture, 1994 Chemistry Laureate George Olah takes a refreshingly different approach to the subject. He calls it the approach of a “simple chemist”. Olah’s line of thought is based on the statement that even if climate change should be as harmful as predicted by many, mankind still has undeniable needs. The ongoing growth of the world’s population will require more energy and more industrial raw materials rather than less. Since avoiding growth is not a viable option, other, scientific solutions have to be found, according to Olah.On this basis, he suggests not to reduce the carbon dioxide emissions, but to deal with them appropriately where they occur in their most concentrated form: at powerplants and factories. If the carbon dioxide emitted there could be collected and subjected to chemical processes, it could subsequently be converted to valuable raw chemicals, Olah explains. In detail he suggests to convert carbon dioxide to methanol by a catalytic processes, which had been investigated in his laboratory for quite some time. The yielded methanol could then be used for synthetic fuels, which could power vehicles even after earth’s fossil fuel reserves run out.That Olah’s suggestion is not an immediate solution to the energy and climate change problems at hand is due to the fact that the catalytic process he mentions requires energy to work. Mining for fossil fuels is still much more energy efficient. Olah’s ultimate vision for earth’s future thus involves strong investments in nuclear energy. According to him there is in fact no way around this form of energy generation. However, on the basis of an abundant energy supply, the “chemical recycling” of carbon dioxide to methanol would be feasible. Although Olah reminds the audience not to take his “solution” to climate change all too seriously, the collection of carbon dioxide at major pollution sites (the so called “carbon capture and sequestration” approach) has become a very active field of research and various storage and/or conversion strategies have been proposed. Time will have to tell whether Olah’s scientific optimism in the spirit of “Don’t regulate, innovate!” can provide a solution to some of mankind’s most pressing concerns. David Siegel
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Transkript: Englisch(automatisch erzeugt)
This is the first time we are with my wife in Lindau and we greatly enjoyed the hospitality
of the meeting and particularly meeting young colleagues. Now, I have still widespread interest and I'm going to talk about a topic which basically involves two very simple one-carbon containing molecules, carbon dioxide and
methane. And this work started a while ago but it picked up steam in the last number of years. Now, I just would like to add one thing to the very kind introduction. My professor Geezer Zeppelin was a student of Emile Fisher, so I'm in a way a scientific grandson of
Emile Fisher. And I hope he forgives me that I'm talking about this relatively unassuming simple chemistry we are involved. But why this is interesting, I guess Sherry Rowland
yesterday introduced the topic very well. We are living in a world where man's activity increasingly have a serious effect on the environment and we must somehow get an equilibrium. Now, I do care as much about the environment, clean air and water and so on as anybody
else. I have children and grandchildren and I want them and their grandchildren to have at least a good or better word than we have. On the other hand, I also realize that society has needs and I strongly believe that besides pinpointing the environmental
problems, which is absolutely necessary, it's like a medical diagnosis. Your physician first must find out what's wrong. But then besides some regulation within limits which I willingly accept, I think it's very important to try to find solution.
After all, if you are real, you go to your physician, you already know something is wrong. You expect the physician able to do something for you. So I tried to tell you a simple chemist approach, how we could probably work to find solution. Don't take it too
seriously. It's my approach. I'm not trying to convince you it's only or the best approach. But at least I tried to show you that chemistry and modern science, hopefully, can contribute on the way to find solution. Now, I will spend a few minutes just to introduce a background. And one of the problems, of course, is
on our present life that we are too many on planet earth and we need a lot of energy. And we are burning fossil fuels predominantly which nature gave us as a present, a most valuable presence in the form of petroleum oil and
natural gas, heavy tar sand shale and so on. Now, when we burn these, these are basically all hydrocarbons. When we burn them, carbon goes up as carbon dioxide and hydrogen goes up as water. Now, as you will see and of course you know, nature has its own way to recycle. However, we
are overloading nature and this causes a problem and we should try to do something about it. Now, these hydrocarbons, as you know, as the name says, are compounds of two elements, carbon and hydrogen, and they differ in the ratio of hydrogen to carbon. The highest ratio is in
methane which is basically the major component of natural gas. Petroleum oil has of course lower ratios because you can form chain, rings and so on and you go to heavies and you go eventually to coal, which has a significant deficiency of carbon. Now, we are using a hell of a lot
of energy and I don't want to overload you with data, but these are the energy we use and it's a lot and it goes up. Now, whether these predictions are in a limited or moderate way, as somebody said, it's difficult to make predictions, particularly for the future. But
let's take the optimistic approach. We still will use increasing amount of energy and this energy, where is it coming from? Now, these are some data for the US and I'm not trying to tell you the US is the best model, but we are probably the largest user of
energy. And as you see, we are using mostly oil, natural gas and coal, in other words, fossil fuels. Nuclear energy is very limited. As a matter of fact, this 8% probably is now down to 7%. We haven't built a single nuclear power plant in the US for
20 years and whereas hydro, geothermal, solar, all other energies of course are very useful and clean, but compared with the overall enormous energy need, this is a relatively small factor.
Now, it may be different in countries which has a lot of hydro energy and so on, but still work while hydro power and so on is limited. And I'm afraid, but I must tell you that I don't think that this will make a very big impact, not in my
life, but in the younger generation lifetime and their grandchildren's lifetime. Now, in other countries, of course, the situation is different. Look, for example, France. France is producing a very high amount of its energy from nuclear energy. They also have significant hydro energy, a total of
87% compared to the US, which produces very little. Canada, this was in 1990, so it was West Germany, but still not insignificant amount. And here is the US, the largest
consumer of energy at the very bottom. Now, why I am showing it to you is that whereas I also care about safety and I fully realize all the arguments against nuclear energy, but I must tell you, whether someone likes it or not, what
we know today, in the nearing 21st century, mankind will need to increasingly use atomic energy on a massive scale. And I'm not saying that we shouldn't make nuclear energy much safer. After all, we were able to create the bomb in
three years, putting in great resources and energy and so on. Nobody will convince me that we can't make atomic energy safer. Professor Rubi and his colleague at CERN are working on new reactor designs, which may be a way to do this. You don't need to use uranium, giving all the
problems of very radioactive, very long-time things. You could use thorium and so on. But, personally, I believe that there is no way for mankind, based on what we know now, that in a sensible way, use atomic energy and
use it as safely as we can. Now, the energy, what we are using, is really enormous. I'm just telling you a little bit. We are, as I said, burning a lot of oil and gas and coal. Now, of course, ever since I remember, I was always told that we are running out of oil and gas and so on. De facto, the reserves, if you look at
this table from 1960 to 1990, have grown significantly. They tripled. And natural gas has grown the reserves even more so. So, most people, including politicians and
people concerned about the environment, are telling you, why worry? We are practically swimming in oil and we have lots of gas. Now, the sad thing is, however, that this, per se, is very misleading. You must look at it as a per capita consumption. And when you look
at the per capita consumption and what we consume, then you realize that these impressive numbers mean relatively little. We are, what I mean, the world is consuming presently, I guess, in the order of 11 or 12 million
metric tons of oil per day. That's an enormous amount. I mean, multiply this by 365. You have an annual consumption, and then you see that the reserves which we have won't last for very long. What I mean, very long, say 40 years or 35 years, isn't a very long period.
And we may find new resources within limits, but certainly we are limited. And even coal is limited. Some people estimate that the world coal reserves will last maybe 200 years. On the other hand, some of the
coal is different from metal. I guess in Germany, coal production has drastically decreased because becoming coal miner is not one of the most choice occupation. Also, you see, we worry about nuclear power plant safety, except of Chernobyl, which I don't want to
comment because it's a special case. Fatalities concerning nuclear power plant accidents were minimal in the last 50 years. On the other hand, coal miners are dying each year in very significant number, both in mining accidents and through black lung disease. And
very, very little concern is expected of this. So what I'm simply trying to say is that we have an enormous need for energy, and of course the other problem is that our population is growing in an alarming rate. This figure, when the century
started, we were about 1.6 billion. We passed 6 billion last October. At least somebody told me that the United Nations preliminary report was issued last October, which will become officially
circulated in a broader way. And as was said yesterday, whatever we do, we are locked in on a course where in 20 years or so we will be 8 billion, and by 2040 we will be 10 or 11 billion, and let's hope we will level out. And
again, there are all kind of data showing where we came from and where we are going, but obviously we need to worry about the future in a very significant way. Now, as I said, when you burn fossil fuels, carbon goes up as carbon dioxide.
Svente Arrhenius, the Swedish physical chemist, in 1898 published a paper, it's just 100 years ago, where he showed the correlation between CO2 concentration and temperature, and definitely showed that carbon dioxide has a warming effect.
Now, I don't want to argue details because obviously in nature there are many other ways for nature to dissipate some or even probably most of the excess carbon dioxide, but it's a scientific fact that global warming is affected
by CO2. We are arguing probably to what degree. Now, these are some data going back a millennium and the temperature increase or the variation was in the range of one and a half degrees centigrade. Sherry showed yesterday that I guess in the last
century the temperature increased as far as we know by something like 0.6 or 7 degrees centigrade. But it certainly is going up, and this is, I think, the graph he showed too, which shows that in parts per million, that's where we are now,
around 360, and if we go on like business as usual, then it will increase, and again, now you can make your guesses how much will be the annual increase, and then you can make all kinds of extrapolation. But I am not an atmospheric chemist. I am not an environmental
chemist. I don't know what kind of chemist I am. I may be a simple chemist who is worrying, however, like any of you about these problems. Carbon dioxide is a very minor component of air. It's quite, at least to me it was quite
educational, refresh my memory, that argon, a noble gas, is present in 30-fold excess of a carbon dioxide in the air we are breathing. Nonetheless, this relatively minor amount of carbon dioxide is absolutely essential for our terrestrial life, and when we are talking
about global warming to man's effect, small variation can be significant, particularly because climate, of course, is a chaotic system, and we disturb the chaotic system even in a minor way. It could have major consequences. It's not quite clear that this
would always be warming and not cooling, but it certainly, man has a substantial effect on climate. Now, I already said that mother nature, of course, in its miraculous way recycles, and we have no problem with hydrogen recycling circle to water. Of course,
nature also recycles carbon dioxide in a miraculous way. Any of you who read Primo Levi's book, The Periodic Table, this is a collection of essays, not necessarily chemistry, but the essay under the title of carbon has this wonderful description,
what's happened, with this single carbon molecule which was sitting there in limestone for ages. Somebody was digging it up, putting in a kiln, heating it, and then this CO2 was liberated, circling our beautiful planet Earth, till one day it got too close to a leaf and was captured,
and this is nature's wonderful way. For us, to capture this low concentration of CO2 from the air will be a formidable problem, even with modern membrane technology, but I sincerely believe that we can do things, particularly at the
source where we create high CO2 concentration, and these are in, say, fossil fuel burning power plants, in chemical plants, and so on. So what I'm trying now to tell you briefly is that I feel that chemistry could contribute to supplement mother nature recycler by chemically helping recycle
CO2, and many of you would feel that this is futuristic because, of course, whatever you do, you need hydrogen, and this is the major kick. When we have hydrogen, of course, we know how to reduce CO2, say, to methanol, and
I will tell you a little bit about methanol where we and others had a great degree of interest, because by very simple chemistry, you can not only use methanol and methanol- derived fuels as energy sources, which I will briefly say in connection with some work we were doing on fuel
cells, but you can also, in a very simple way, convert methanol to ethylene, and once you have ethylene, you can make all the hydrocarbon products we are used to and we all use in our style we get accustomed to in the 19th century. Now, anyhow,
think about it, we are just barely 200 years past the Industrial Revolution. In these 200 years, mankind did a lot. We also did use up a hell of a lot of resources, it's a problem. But in the 19th century, it was coal, which fueled the industrial operation
of the world. In the 20th century, we added oil and gas, and this is all fine, except in the 21st century, we will start to run short on them, and then we need to do something, and I visualize a very central role
of methanol, which can be made from recycling CO2 in different ways. Now, I had a lot of interest in C1 chemistry. Now, as you know, when you talk about one carbon chemistry, most people think about Fischer-Tropsch, and with all
regard to Fischer-Tropsch, which was proven, of course, during World War II, Germany really haven't lost the war entirely because of running out of fuel. Synthetic gasoline was made on a scale of 10,000 metric tons a day,
which is a fair amount. Of course, what I was telling you, the word consumption is such that if we would shift to Fischer-Tropsch, we would need to use an enormous amount of coal per day in the order of tens of millions of metric tons, and an investment which is astronomical.
On top of it, Fischer-Tropsch is a very energy wasteful process. You burn coal or natural gas partially to make thin gas, use up half of the energy in this process, and then you put it together in a very disadvantageous way. Now, there are other ways. Of course, photosynthesis per se is
C1 chemistry by nature, and what I'm telling you is that we could consider seriously how we convert CO2 chemically to methanol and through methanol hydrocarbon products, but you can also do C1 chemistry on methane.
Sherry Roland mentioned that methane is also a greenhouse gas. We have a lot of methane in the atmosphere, and we still have a lot of natural gas. If we wouldn't burn all of it, it would last us for a long while to make our products, and I tell you a little bit about what we were doing on
methane. Now, a lot of people are working on partial oxidation of methane. It would be a very advantageous goal to take methane and oxidize it selectively to metal alcohol. Unfortunately, it's not enough because oxidation won't stop at metal alcohol, but we have found a chemical way
which I think is quite interesting. Some of you know that in studying carbocations, I have found ways to generate five-coordinate ions, and this opened up a way to the electrophilic chemistry of single bond, like CH bond. So, whereas halogenation of
methane generally under usual radical conditions gives a mixture of all four halomethanes, if you do electrophilic halogenation over well selected, and we are using now solid super acid, you can produce metal halide in high selectivity. Now, what you do
with metal halides, the world market for metal halide is very limited, but one simple way you can do, you can hydrolyze it. Now, we are teaching SN2 reactions for students for ages, but nobody, I guess, in the last 70 years considered to make methanol by hydrolyzing metal halides.
It's very surprising, but if you can make metal halide efficiently from methane, then simple catalytic hydrolysis gives you metal halide, and now if you run this with the bromine cycle, then you can re-oxidize very readily HBr to bromine.
To re-oxidize HCl in deacon type of chemistry is very tough, but HBr is oxidized back exceedingly readily. So, what we are doing, we can use in this cycle bromine really only as a catalyst, which is continuously re-oxidizing the system, and this gives metal alcohol in very high
selectivity. Now, what you do with metal alcohol? One thing you can do with metal alcohol, you can condense it to ethylene and through it hydrocarbon product. Many of you know that the Nobel company developed a zeolite-based process using HCSM-5 catalyst.
We developed about the same time a non-zeolite type of approach. I believe that we understand the mechanism. The zeolite is a policeman directing traffic. It won't let form high molecular weight product.
But we have found that, for example, tungsten oxide and alumina converts very efficiently methanol or dimethyl ether, which is of course the first dehydration step, through what I call an oxonium ylide. First, the acid side forms an oxonium salt, the equivalent of a merman salt,
but you can have the catalyst coordinating with dimethyl ether forming the equivalent, and the base side then deprotonates it, forming this very reactive surface-bound oxonium ylide, which immediately, because you are running this in excess methanol or dimethyl ether,
is metallated. So that's the key step. That's the key step where you convert one carbon entity into a cooked carbon entity, which then beta eliminates to ethylene. And you can run this not only on methanol, you can run it on metal halides. The mechanism
is exactly the same. You first form a dimethylhalonium ion or an equivalent complex, which then deprotonates to the halonium ylide, and this halonium ylide being exceedingly reactive in the presence of excess metallating agent undergoes the usual C1-C2 reaction.
You can do this on the sulfur cycle. You can convert methane to metal mercaptan or dimethyl sulfide, and then do the same type of acid-base catalyzed conversion to ethylene. E.J. Corey, in
his nice work on this corresponding sulfonium metallide, which is a wonderful synthetic tool. There's a footnote in the paper which said that you should do this reaction below 20 degrees C, otherwise you get decomposition. I say that's a wonder
of chemistry. For one chemist, an unwanted side reaction or decomposition, for another chemist, it's the most useful reaction, because what we have, this sulfonium ylide under our condition gives ethylene, and if you keep it in the reactor, propylene again with high cell activity.
Now, the last topic I would briefly mention is that we got involved with my colleague, Professor Surya Prakash, and friends from Caltech and Caltech Jet Proportion Laboratory eight or nine years ago in some work on fuel cells.
Now, JPL built, and it's still building, all the fuel cells for the U.S. space program. The shuttle and so on are all flying with their fuel cells. And it's wonderful, except that for practical applications there are major problems. Now, fuel cells are simple devices. I won't
stretch it, and I will be very simple about it, which convert chemical energy directly into electric energy. Fuel cells are known for 150 years. They were discovered, I guess, accidentally, where people were electrolyzing water over platinum electrodes and observed the reverse reaction.
Now, all of the fuel cells which were developed so far and used basically are hydrogen and oxygen fuel cells. Now, there is recently a lot of interest. Mercedes-Benz, in cooperation with the Ford Motor Company, is involved with a
small company in Vancouver, Canada, developing fuel cells for cars, and others are involved, and some of these are using liquid fuels. Now, our approach, however, is fundamentally different. These people who are developing these fuel cells, say for cars,
are using liquid fuels, but they are first putting the liquid fuel through a catalytic converter, which is like a small Fischer-Tropsch unit. It produces syngas, CO and hydrogen. They separate hydrogen and oxidize CO to CO2 and exhaust it. We are not using any catalytic converter
whatsoever. We have developed jointly a direct liquid fuel cell which uses a liquid fuel like methanol directly, and it burns methanol in the fuel cell directly over a platinum-ruthenium catalyst
with good efficiency. The key to this is, of course, membranes. We originally used DuPont's nephium membrane, but there is too much crossover from the anode cathode side. My colleagues were really quite ingenious to develop new, improved
membranes which cut down this crossover to practically zero. These are very simple devices where you really are just feeding a liquid fuel like methanol with water in the fuel cell oxidizing it and you produce electricity.
Now, what's new in our approach recently is the fact that we started to think in terms that as the fuel cell was discovered by reversing really the electrolysis of water, how about if we could
reverse the process with our methanol fuel cell? In other words, is there a possibility to use CO2 in water with electricity and drive it back? And indeed, this shows quite good progress. Now, of course, we are not producing energy. I want to emphasize this
that you still need to put in energy and we have what you could call a reversible storage device. Nonetheless, I think that this has real potential for the future because eventually if atomic energy or any other source of energy will be available
on a large scale at reasonable prices of course, we can produce all the hydrocarbon product to provide gasoline for your cars and all the synthetics and materials and so on. And there is a wide variety of chemical products you can do.
Now, we have developed a number of alternate fuels. I won't go into this and I already told you that we have and others have processes where you can produce ethylene or propylene very efficiently. So I think in my summary I can just summarize what I tried to tell you
that we start out with the problem that we have a growing population and a growing need for energy and men, of course, need a lot of things not just food and shelter and so on and this is going to be a very big problem and I told you
my personal view that besides using all other alternate sources to save and do all these things which I all agree with but we will have no alternate choice but also use atomic energy wisely and much safer as we're doing today.
And then this problem of energy is coupled, of course, with an environmental problem. One way to mitigate carbon dioxide-based warming is to emit less carbon dioxide. The cleanest fuel, of course, is atomic energy.
So people who really worry about this should promote atomic energy. But you can't put atomic reactors in your cars. At least we don't know it. Shielding problems would be enormous. So we still will need products like hydrocarbons to give transportation to us materials
for synthesis and so on. And I strongly believe that we will be able to produce this for future generations by converting CO2 in very simple chemistry which we already know today. And I am a great believer in the efficient use of fuel cells both to produce electricity.
After all, two-thirds of the world has no electricity yet. There is a crying need for efficient sources of energy. And these are clean, simple, there are no moving parts in this and they can be installed I guess quite efficiently.
So I took you on a little tour of a simple-minded chemist how some of the basic chemistry we were involved over the years and I never thought about it that some of these chemistry will have any bearing whatsoever in practicality. But as it turns out, some of these simple molecules like carbon dioxide and methane
became household name. President Clinton and obviously your politicians are talking a lot about carbon dioxide. There was a conference in Kyoto last December where I think 160 nations got together to try to do something about global warming.
They had typical solutions of politicians. They tried to tell the developing countries like India and China that you can't burn coal and so on because it's dirty. But of course they said, but you westerners are doing this for 200 years and you build up a high standard of living.
And my simple point is I don't think we have a privilege to have a better life than anybody else. So instead of trying to regulate and say no, I think we in the western world have an obligation to try to work to develop new technology through new chemistry which can help
the world as an entity. I thank you very much for your attention.