R-Squared Energy Blog

Pure Energy

I Never Cease to be Amazed

Thanks to a reader for sending me this story:

Company trying to turn waste into biofuel

Salem businessmen to turn dairy dung into butanol for vehicles

Diesel Brewing would burn dairy waste and turn it into butanol.

Butanol is mainly used as a solvent, but company officials want to use it as a renewable fuel.

If Diesel Brewing succeeds, it likely would be the first company in the world to make butanol with what’s called a gasification process, said Andy Aden, a senior research engineer with the biomass center at the National Renewable Energy Lab in Golden, Colo.

Once the process is proved feasible, Raines and his team hope to build commercial-scale plants that use 100 tons of waste per day — and produce a couple million gallons of butanol per year.

Why does this amaze me? Chemical companies like Celanese (my former employer), Dow, BASF, Eastman – oil companies like BP and Shell – and numerous other companies around the world produce butanol. They have big research budgets, and they would love to find an economical direct gasification route to butanol. These companies have looked at probably thousands of catalysts, and people have spent their careers working on this problem. The challenge is that syngas (produced from gasification) doesn’t like to form butanol. You can form a little bit directly, but CO (carbon monoxide) likes to do lots of things besides form a C4 alcohol like butanol.

Methanol is not a problem. You can also produce ethanol, which is what Range Fuels is planning on doing (although you almost always have methanol to deal with as well). But the selectivity falls off sharply as you go to higher alcohols. By the time you get to butanol, you are lucky if 5% of the product is butanol. More typical is 1-2%. See this NREL report for more details:

Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass

So why does any of this amaze me? This is all known technology. It has been looked at for 50 years by multiple big companies spending untold millions of dollars. The economics simply don’t work, because of the very low yields. But a small company in Oregon still got someone to give them money to work on it:

The only way Diesel Brewing could get its start was through Oregon’s business energy tax credit program — one of the most robust in the nation.

The tax credit is worth 50 percent of their $1.4 million in capital costs, Stapleton said.

And then they also suggest that they will be profitable:

Raines doesn’t expect to make a profit until the 100-ton-per-day plant is running.

I spent several years working on butanol, and am quite familiar with the chemistry. How butanol is typically made involves a gasification step, but then you react the syngas with propylene and hydrogenate the product. This produces normal and iso-butanol, with very high selectivity and conversion. I believe it is highly unlikely that anyone is going to economically produce butanol by gasification of biomass. The chemistry just doesn’t work. Methanol or mixed alcohols? Those economics look better, and might eventually have staying power.

Don’t get me wrong, butanol is a fine fuel, and I have a special fondness for it. I would like to see it work out. But my observation is that people grossly underestimate the difficulty of economically producing butanol from biomass.

Now, I have to get back to work on my Unified Field Theory. I know that I am not a physicist, and a solution eluded Albert Einstein. But if I can just get a large enough grant, I think I can pull it off…

May 14, 2009 Posted by | biobutanol, butanol | 32 Comments

Answering Questions – Part II

OK, I think this finishes off the questions. Thanks to all who asked a question. I think this has been a productive exercise, and I hope you find my answers useful. I may do this again at some point, but for now, I am back to posting and then lurking.

The Questions

Jeff Sutherland asked: It seems to me that electricity is going to be the key energy source in the future….Biofuels, like ethanol, if produced with electrical equipment seems like a good method to store energy….What do you see as the best option for a transportable form of energy in the future? Answer

garsky asked: A couple of posts ago you mentioned some things you were doing to prepare for a worst-case scenario. How about some details? Especially the part about your savings. Answer

Rob asked: Have you given up hope? Based on your more recent posts, it certainly looks like it. Answer

ape man asked: Take a look at this Bloomberg story. Does the story indicate that there are too many tankers, or that OPEC is not following through with its promised production increase? Answer

Doug asked: What would be an optimal location to live in ten or twenty years from now? Answer

Armchair261 asked: There’s always a lot of press about gasoline prices and inventory levels. How are these inventories affected by demand for other products, like diesel, propane, or fuel oil? Are refiners having trouble meeting demand for those products too, and is this siphoning some crude away from gasoline production? Answer

Chris said: Dr. Ramey has created a new and more efficient method of production which increases the yield of butanol and decreases the number of and volume of byproducts….not all species of high oil yielding algae are perfect but there are plenty to choose from.

Questions:

1. Don’t you think that at least one of these species could efficiently produce oil if the electrical energy input was reduced?

2. What was the reasoning behind the #3 point saying that closed bioreators are “totally absurd”?

3. Since you have ruled out the two most efficient and promising fuel alternatives, what do you propose we replace gasoline and diesel with? Answer

anonymous asked: What is the motivation to maintain high gasoline inventories? Answer

mink asked: 1) How do you see the way forward for “peakoilers”? Here and on the oil drum you are interested in getting reliable information and predictions out to the public. But the number of people interested is small.

2) There will come a time when peak-oil will hit public awareness, and it will be an ugly sight. Panic is very possible, and this panic may be very destructive. How do we prevent this? Answer

optimist wrote: Here’s my request: write a posting describing how one might tell if a given technology is promising or not. I think this would be immensely helpful to non-technical readers. Answer

The Answers

Answer

First, I agree that electricity is going to be key. We have the ability to produce much more electricity than we do now, but I don’t think we have the ability to significantly increase our output of liquid fuels. However, I would not produce biofuels from electricity. It would be too inefficient to go that route. For instance, if I had biomass, I wouldn’t convert it into electricity, I would gasify it and convert it into a liquid fuel. The heat produced from the process could be used to produce electricity, but the energy efficiency of the biomass is going to be much higher if you go straight to liquid fuels (if that’s what you intend the final product to be).

As far as the best option, I think electric transport will be the core of our transport system long-term, but we will always have a need for liquid fuels. I think biofuels can fill part of this gap. But we have to get away from this belief that we are going to displace most of our current oil usage with biofuels. That kind of thinking is very dangerous, because it could divert too many resources and waste precious time that could be used on more sustainable long-term solutions. Right now, the government is banking far too much on biofuels as THE solution, when they should be spreading the bets a lot more than they are doing.

Return to Top

Answer

My strategy is very long-term, and I do not advise anyone else to do what I do. It has worked for me, but it may not work for you. Going all the way back to the early 90’s, I put a lot of thought into a very long-term strategy. I didn’t want to time the market, so I tried to identify sectors that I thought would fare best over a 20-year period. Health care/biotech was one of the sectors that I could see outperforming, especially as the Baby Boomers grew older. People are going to spend money on health care. I still believe that, so I have a fair amount of money in that sector (and have had for many years).

In the late 90’s and early part of this decade, I partially abandoned my long-term strategy and jumped on the tech bandwagon like many others. I got burned like many others. Why did I get burned? Primarily, because I didn’t really understand the things I was investing in, and I was lured by the prospect of the incredible returns that tech stocks were delivering. I joined the flock with the other sheep and got sheared. So, I reevaluated, and decided: Stick to the areas that I really know, and focus on those. I brainstormed on what I thought the future held, and I concluded that higher oil prices looked very likely. But the U.S. is very dependent upon oil, so it appeared to me that the economy in the U.S. is very vulnerable to higher oil prices.

So, these assumptions were the basis of my strategy. I left my position in the chemical industry for a position in the oil industry. I figured that as oil supplies tightened up and the price rose, and people continued to need energy, the people providing that energy would have the greatest job security. To hedge against the dollar, I put about 20% of my portfolio into international funds (this is more than most financial advisors would recommend). I also made a bet that energy stocks were undervalued. More recently, with my position in the UK, I have further insulated myself against the falling dollar because my compensation is now tied to the British Pound.

Following the tech stock fiasco, my strategy since 2001 has paid off. My overall portfolio – which includes the money I have added into it – has increased at an average annual return of 36% for 6 years. If I exclude the savings, the returns alone have averaged 26% for 6 years. I am now in the process of using some of that capital to acquire land in various locations, which will provide further diversification.

Return to Top

Answer

Absolutely not. In fact, I am more hopeful than I have been in some time. I believe I am realistic, in that we are going to have to reduce our energy usage. But I am cautiously optimistic that if things get really tough, we can change in ways that don’t seem likely at the moment. We don’t give ourselves enough credit for our adaptability. If oil did peak soon and the price went a great deal higher, a lot of people would find areas of fat that they could cut out. This sort of behavioral shift would give us added time to formulate a better strategy than counting on biofuels to provide the net equivalent of 40 or 50 million barrels per day of oil.

Return to Top

Answer

Note that this story dates back to August, well before the OPEC announcement that they would supply more crude. So I wouldn’t read anything into it regarding whether OPEC is following through on their promised increase. In fact, reports so far indicate that Saudi has in fact advised Asian refiners that they will be bumping up deliveries there.

Now, as far as why tanker demand was down in September, I can’t say for sure. Spring and fall are typical turnaround seasons, in which refinery utilization goes down and crude demand follows. So what would be of interest would be to compare the tanker demand rate with the typical September rate, and also to look at the condition of oil inventories in the area. That might clarify the situation.

Return to Top

Answer

I think it will be safe within the walls of my compound. 🙂

Seriously, if you strongly believe in a worst-case scenario, there are certain attributes that I would look for. I want to see a high ratio of farmland to surrounding population. I want to be relatively close to decent medical facilities. I would like to be close to transportation via rail or water. I want the place to have a reliable water supply. Those are just a few of the things that would be on my check-list, and there are some places that fit the bill. I think areas on both coasts of the U.S. will fare well. Needless to say, I think Scotland – which will still produce a lot of oil and gas for a long time – will fare well. I absolutely would not want to live (among others) in Houston, L.A., Phoenix, or Las Vegas (although one could argue that the latter two are well-placed for reliable solar energy).

Return to Top

Answer

Refiners are always looking at margins on diesel and gasoline. When margins for diesel are higher than for gasoline, they will shift production toward diesel (which will also affect things like the propane balance). A typical refinery can shift between diesel and gasoline to a limited extent – perhaps 5%. If production is shifted toward diesel, then that should eventually improve the gasoline margins as supply is taken off the market, and as this happens they will shift some production back. And they literally look at this and adjust multiple times per week.

The one big caveat is that commitments to existing customers take precedence. So, if margins for diesel look better, but you would have to short an existing gasoline customer to take advantage, you are stuck. You can’t declare force majeure for something like that. Maintaining relationships with your customers sometimes means that you have to give up short-term profits.

Are refiners having trouble meeting demand? Yes. Refinery utilization has been down since Hurricane Katrina, and the only thing that has kept this from resulting in $4 gasoline are strong imports. If the imports dried up, refiners would attempt to maximize gasoline, and this may precipitate a distillate shortage. And we don’t import much in the way of distillates, because demand is high elsewhere in the world (unlike gasoline, which is produced in excess, allowing some to be exported).

Return to Top

Answer

First of all, I certainly don’t want to denigrate Ramey’s patent. It is a good contribution. However, it is clear to me that many people do not understand the real problem with bio-butanol. It is not a problem of conversion rate or reaction speed. Those are the areas that Ramey addressed, and while those things are nice to have, there is a knock-out factor that has not been addressed. That is, if you read Ramey’s patent (which I have done many times), he is still talking about butanol concentrations in the range of 2.5%. That is the problem, not whether the conversion is 25% or 35%.

Butanol is very toxic to the bugs, so it is very difficult to increase the concentration of butanol in the solution. What is needed is a breakthrough that would allow the bugs to thrive at the solubility limit of butanol, which is about 8%. In that case, excess butanol production would phase out, and this would be much less energy intensive than a distillation. But you can’t afford to distill off a 2.5% solution of butanol. The energy inputs into the process will be far greater than the energy content of the butanol. I know this from experience. I have done a lot of work on butanol distillations. At a 3% concentration of butanol, we don’t even attempt to separate it out. Even using relatively cheap (at that time) natural gas, it didn’t make economic sense to extract that butanol. Those levels of butanol are sent to wastewater treatment for disposal.

Believe me, I have a soft spot for butanol. I want to see it work. But right now there are serious issues. That’s not to say that it isn’t worth pursuing. In fact, I am working on it myself. But I have to be realistic.

Now, your specific questions:

1. Don’t you think that at least one of these species could efficiently produce oil if the electrical energy input was reduced?

The collection is the problem. If you go back to first principles of solar insolation, in the absolute best case a square meter of water can produce about a gallon per year of biodiesel. Once you add up the costs and energy inputs to harvest that meter and process the oil, it becomes an exercise in economic futility. Will it ever be economical? I won’t say never. I will say that it is nowhere close.

2. What was the reasoning behind the #3 point saying that closed bioreators are “totally absurd”?

I didn’t write that. It was written by Dr. John Benemann, who was involved in the algal biodiesel work and coauthored the closeout report of the project. He has 30 years of experience in the field, and like me, he likes to reel in hype when it gets out of hand. That’s what he was doing. His reasoning is that the cost of closed bioreactors is far too high – by a couple of orders of magnitude – to justify the amount of biodiesel that you could produce from the process.

3. Since you have ruled out the two most efficient and promising fuel alternatives, what do you propose we replace gasoline and diesel with?

It’s going to take conservation, efficiency, inputs from biofuels, electric transportation, public transportation, etc. There is nothing out there, and nothing on the horizon, that can actually replace our current usage of gasoline and diesel. We have to come to grips with this as soon as possible, and start spreading our bets a bit more. Right now, everyone is counting too heavily on biofuels to deliver.

Return to Top

Answer

Ideally you only keep inventories where they need to be to make sure that you are always able to supply product to your customers. If you keep inventories too high, you obviously have money tied up that’s not doing anything for you. So let’s say you were maintaining high inventories in 2005. Suddenly, Hurricane Katrina comes along, prices go through the roof, shortages start to crop up, but you are in fat city because you had high inventories. So, it’s a balancing act.

One thing you will see if you look back, is that after Katrina refiners started to keep their crude inventories much higher than before. They saw the effects of a supply disruption, so they played it cautious for a while. Over time, I think we will start to forget, and inventories will creep back into the normal ranges.

Gasoline inventories are a different matter. I think refiners would like to put more product on the market, especially back when margins were so high, but they just couldn’t make enough to satisfy demand and refill the tanks.

One other time that refiners are motivated to keep gasoline inventories high is when they are headed into a turnaround. You need to have very full gasoline tanks when you shut down, so you can supply your customers while you are down.

Return to Top

Answer

This was one of the more difficult questions to answer. You are correct that the number of interested people is small, but that number is growing. I am seeing more references in the media (some of which are merely to denounce those “crackpot Peak Oilers”). It has been very important to me, and to many others who are concerned about future oil supplies, that we maintain credibility as we discuss this. Those who cherry pick data to support preconceived notions, or who merely ignore inconvenient data do a great disservice to us all. (See Stuart Staniford addressing that here).

Arguments must be sound, and criticisms must be addressed. Where matters are open to interpretation, you must make a convincing case for why your interpretation is correct. With a few exceptions, I think that convincing large numbers of people with factual arguments has largely been a dismal failure. To convince the masses, you have to start convincing the media. The more this pops up in the media, the more the rest of the media will pay attention. But if the media is being presented half-baked arguments, it does tremendous damage.

Panic is only going to happen if things change rapidly. Anger is going to be a common emotion as oil prices spiral higher and higher, and people feel that their hard-earned money is flowing into the coffers of OPEC and the oil companies. The thing I have always believed in is educating people, which is the reason I do this. The best we can do is continue to chip away with sound arguments, and hope that the message starts to sink in. If people understand why things are happening, then we should be in better shape with respect to formulating solutions. If we simply blame the usual suspects (it’s those gouging oil companies!), then we may sit around and point fingers as we drive off a cliff.

Return to Top

Answer

If it was that easy, people wouldn’t keep offering me large sums of money to vet technologies for them. Seriously, there seems to be a great big vacuum in this area. I get questions from intelligent people who can look at an energy idea with a major flaw, but they can’t see it.

There is no magic formula. I think it requires experience, and you have to take them on a case by case basis. If someone brought me a potential breakthrough in biotechnology, I would be in the same boat as a lot of people are when they try to interpret the latest hyped energy breakthrough. Even though biotech is an interest/hobby of mine, it may be difficult for me to spot a fatal flaw. A molecular biologist may take one look, and say “You see that step where they say ‘insert gene A into position B?’ Well, the status of the technology is nowhere close to being able to do that.”

I think it just pays to be a skeptic first. There is nothing wrong with being a skeptic, even though many people confuse skepticism with negativity. I always tell people that I am a skeptic, but also a problem-solver. I am not shooting these ideas down for fun; I want some of them to work. But you have to sort the wheat from the chaff.

Return to Top

October 12, 2007 Posted by | algal biodiesel, biobutanol, biofuels, ethanol, gas inventories, oil production, oil refineries, Peak Oil, refining margins, Saudi Arabia | 11 Comments

Answering Questions – Part II

OK, I think this finishes off the questions. Thanks to all who asked a question. I think this has been a productive exercise, and I hope you find my answers useful. I may do this again at some point, but for now, I am back to posting and then lurking.

The Questions

Jeff Sutherland asked: It seems to me that electricity is going to be the key energy source in the future….Biofuels, like ethanol, if produced with electrical equipment seems like a good method to store energy….What do you see as the best option for a transportable form of energy in the future? Answer

garsky asked: A couple of posts ago you mentioned some things you were doing to prepare for a worst-case scenario. How about some details? Especially the part about your savings. Answer

Rob asked: Have you given up hope? Based on your more recent posts, it certainly looks like it. Answer

ape man asked: Take a look at this Bloomberg story. Does the story indicate that there are too many tankers, or that OPEC is not following through with its promised production increase? Answer

Doug asked: What would be an optimal location to live in ten or twenty years from now? Answer

Armchair261 asked: There’s always a lot of press about gasoline prices and inventory levels. How are these inventories affected by demand for other products, like diesel, propane, or fuel oil? Are refiners having trouble meeting demand for those products too, and is this siphoning some crude away from gasoline production? Answer

Chris said: Dr. Ramey has created a new and more efficient method of production which increases the yield of butanol and decreases the number of and volume of byproducts….not all species of high oil yielding algae are perfect but there are plenty to choose from.

Questions:

1. Don’t you think that at least one of these species could efficiently produce oil if the electrical energy input was reduced?

2. What was the reasoning behind the #3 point saying that closed bioreators are “totally absurd”?

3. Since you have ruled out the two most efficient and promising fuel alternatives, what do you propose we replace gasoline and diesel with? Answer

anonymous asked: What is the motivation to maintain high gasoline inventories? Answer

mink asked: 1) How do you see the way forward for “peakoilers”? Here and on the oil drum you are interested in getting reliable information and predictions out to the public. But the number of people interested is small.

2) There will come a time when peak-oil will hit public awareness, and it will be an ugly sight. Panic is very possible, and this panic may be very destructive. How do we prevent this? Answer

optimist wrote: Here’s my request: write a posting describing how one might tell if a given technology is promising or not. I think this would be immensely helpful to non-technical readers. Answer

The Answers

Answer

First, I agree that electricity is going to be key. We have the ability to produce much more electricity than we do now, but I don’t think we have the ability to significantly increase our output of liquid fuels. However, I would not produce biofuels from electricity. It would be too inefficient to go that route. For instance, if I had biomass, I wouldn’t convert it into electricity, I would gasify it and convert it into a liquid fuel. The heat produced from the process could be used to produce electricity, but the energy efficiency of the biomass is going to be much higher if you go straight to liquid fuels (if that’s what you intend the final product to be).

As far as the best option, I think electric transport will be the core of our transport system long-term, but we will always have a need for liquid fuels. I think biofuels can fill part of this gap. But we have to get away from this belief that we are going to displace most of our current oil usage with biofuels. That kind of thinking is very dangerous, because it could divert too many resources and waste precious time that could be used on more sustainable long-term solutions. Right now, the government is banking far too much on biofuels as THE solution, when they should be spreading the bets a lot more than they are doing.

Return to Top

Answer

My strategy is very long-term, and I do not advise anyone else to do what I do. It has worked for me, but it may not work for you. Going all the way back to the early 90’s, I put a lot of thought into a very long-term strategy. I didn’t want to time the market, so I tried to identify sectors that I thought would fare best over a 20-year period. Health care/biotech was one of the sectors that I could see outperforming, especially as the Baby Boomers grew older. People are going to spend money on health care. I still believe that, so I have a fair amount of money in that sector (and have had for many years).

In the late 90’s and early part of this decade, I partially abandoned my long-term strategy and jumped on the tech bandwagon like many others. I got burned like many others. Why did I get burned? Primarily, because I didn’t really understand the things I was investing in, and I was lured by the prospect of the incredible returns that tech stocks were delivering. I joined the flock with the other sheep and got sheared. So, I reevaluated, and decided: Stick to the areas that I really know, and focus on those. I brainstormed on what I thought the future held, and I concluded that higher oil prices looked very likely. But the U.S. is very dependent upon oil, so it appeared to me that the economy in the U.S. is very vulnerable to higher oil prices.

So, these assumptions were the basis of my strategy. I left my position in the chemical industry for a position in the oil industry. I figured that as oil supplies tightened up and the price rose, and people continued to need energy, the people providing that energy would have the greatest job security. To hedge against the dollar, I put about 20% of my portfolio into international funds (this is more than most financial advisors would recommend). I also made a bet that energy stocks were undervalued. More recently, with my position in the UK, I have further insulated myself against the falling dollar because my compensation is now tied to the British Pound.

Following the tech stock fiasco, my strategy since 2001 has paid off. My overall portfolio – which includes the money I have added into it – has increased at an average annual return of 36% for 6 years. If I exclude the savings, the returns alone have averaged 26% for 6 years. I am now in the process of using some of that capital to acquire land in various locations, which will provide further diversification.

Return to Top

Answer

Absolutely not. In fact, I am more hopeful than I have been in some time. I believe I am realistic, in that we are going to have to reduce our energy usage. But I am cautiously optimistic that if things get really tough, we can change in ways that don’t seem likely at the moment. We don’t give ourselves enough credit for our adaptability. If oil did peak soon and the price went a great deal higher, a lot of people would find areas of fat that they could cut out. This sort of behavioral shift would give us added time to formulate a better strategy than counting on biofuels to provide the net equivalent of 40 or 50 million barrels per day of oil.

Return to Top

Answer

Note that this story dates back to August, well before the OPEC announcement that they would supply more crude. So I wouldn’t read anything into it regarding whether OPEC is following through on their promised increase. In fact, reports so far indicate that Saudi has in fact advised Asian refiners that they will be bumping up deliveries there.

Now, as far as why tanker demand was down in September, I can’t say for sure. Spring and fall are typical turnaround seasons, in which refinery utilization goes down and crude demand follows. So what would be of interest would be to compare the tanker demand rate with the typical September rate, and also to look at the condition of oil inventories in the area. That might clarify the situation.

Return to Top

Answer

I think it will be safe within the walls of my compound. 🙂

Seriously, if you strongly believe in a worst-case scenario, there are certain attributes that I would look for. I want to see a high ratio of farmland to surrounding population. I want to be relatively close to decent medical facilities. I would like to be close to transportation via rail or water. I want the place to have a reliable water supply. Those are just a few of the things that would be on my check-list, and there are some places that fit the bill. I think areas on both coasts of the U.S. will fare well. Needless to say, I think Scotland – which will still produce a lot of oil and gas for a long time – will fare well. I absolutely would not want to live (among others) in Houston, L.A., Phoenix, or Las Vegas (although one could argue that the latter two are well-placed for reliable solar energy).

Return to Top

Answer

Refiners are always looking at margins on diesel and gasoline. When margins for diesel are higher than for gasoline, they will shift production toward diesel (which will also affect things like the propane balance). A typical refinery can shift between diesel and gasoline to a limited extent – perhaps 5%. If production is shifted toward diesel, then that should eventually improve the gasoline margins as supply is taken off the market, and as this happens they will shift some production back. And they literally look at this and adjust multiple times per week.

The one big caveat is that commitments to existing customers take precedence. So, if margins for diesel look better, but you would have to short an existing gasoline customer to take advantage, you are stuck. You can’t declare force majeure for something like that. Maintaining relationships with your customers sometimes means that you have to give up short-term profits.

Are refiners having trouble meeting demand? Yes. Refinery utilization has been down since Hurricane Katrina, and the only thing that has kept this from resulting in $4 gasoline are strong imports. If the imports dried up, refiners would attempt to maximize gasoline, and this may precipitate a distillate shortage. And we don’t import much in the way of distillates, because demand is high elsewhere in the world (unlike gasoline, which is produced in excess, allowing some to be exported).

Return to Top

Answer

First of all, I certainly don’t want to denigrate Ramey’s patent. It is a good contribution. However, it is clear to me that many people do not understand the real problem with bio-butanol. It is not a problem of conversion rate or reaction speed. Those are the areas that Ramey addressed, and while those things are nice to have, there is a knock-out factor that has not been addressed. That is, if you read Ramey’s patent (which I have done many times), he is still talking about butanol concentrations in the range of 2.5%. That is the problem, not whether the conversion is 25% or 35%.

Butanol is very toxic to the bugs, so it is very difficult to increase the concentration of butanol in the solution. What is needed is a breakthrough that would allow the bugs to thrive at the solubility limit of butanol, which is about 8%. In that case, excess butanol production would phase out, and this would be much less energy intensive than a distillation. But you can’t afford to distill off a 2.5% solution of butanol. The energy inputs into the process will be far greater than the energy content of the butanol. I know this from experience. I have done a lot of work on butanol distillations. At a 3% concentration of butanol, we don’t even attempt to separate it out. Even using relatively cheap (at that time) natural gas, it didn’t make economic sense to extract that butanol. Those levels of butanol are sent to wastewater treatment for disposal.

Believe me, I have a soft spot for butanol. I want to see it work. But right now there are serious issues. That’s not to say that it isn’t worth pursuing. In fact, I am working on it myself. But I have to be realistic.

Now, your specific questions:

1. Don’t you think that at least one of these species could efficiently produce oil if the electrical energy input was reduced?

The collection is the problem. If you go back to first principles of solar insolation, in the absolute best case a square meter of water can produce about a gallon per year of biodiesel. Once you add up the costs and energy inputs to harvest that meter and process the oil, it becomes an exercise in economic futility. Will it ever be economical? I won’t say never. I will say that it is nowhere close.

2. What was the reasoning behind the #3 point saying that closed bioreators are “totally absurd”?

I didn’t write that. It was written by Dr. John Benemann, who was involved in the algal biodiesel work and coauthored the closeout report of the project. He has 30 years of experience in the field, and like me, he likes to reel in hype when it gets out of hand. That’s what he was doing. His reasoning is that the cost of closed bioreactors is far too high – by a couple of orders of magnitude – to justify the amount of biodiesel that you could produce from the process.

3. Since you have ruled out the two most efficient and promising fuel alternatives, what do you propose we replace gasoline and diesel with?

It’s going to take conservation, efficiency, inputs from biofuels, electric transportation, public transportation, etc. There is nothing out there, and nothing on the horizon, that can actually replace our current usage of gasoline and diesel. We have to come to grips with this as soon as possible, and start spreading our bets a bit more. Right now, everyone is counting too heavily on biofuels to deliver.

Return to Top

Answer

Ideally you only keep inventories where they need to be to make sure that you are always able to supply product to your customers. If you keep inventories too high, you obviously have money tied up that’s not doing anything for you. So let’s say you were maintaining high inventories in 2005. Suddenly, Hurricane Katrina comes along, prices go through the roof, shortages start to crop up, but you are in fat city because you had high inventories. So, it’s a balancing act.

One thing you will see if you look back, is that after Katrina refiners started to keep their crude inventories much higher than before. They saw the effects of a supply disruption, so they played it cautious for a while. Over time, I think we will start to forget, and inventories will creep back into the normal ranges.

Gasoline inventories are a different matter. I think refiners would like to put more product on the market, especially back when margins were so high, but they just couldn’t make enough to satisfy demand and refill the tanks.

One other time that refiners are motivated to keep gasoline inventories high is when they are headed into a turnaround. You need to have very full gasoline tanks when you shut down, so you can supply your customers while you are down.

Return to Top

Answer

This was one of the more difficult questions to answer. You are correct that the number of interested people is small, but that number is growing. I am seeing more references in the media (some of which are merely to denounce those “crackpot Peak Oilers”). It has been very important to me, and to many others who are concerned about future oil supplies, that we maintain credibility as we discuss this. Those who cherry pick data to support preconceived notions, or who merely ignore inconvenient data do a great disservice to us all. (See Stuart Staniford addressing that here).

Arguments must be sound, and criticisms must be addressed. Where matters are open to interpretation, you must make a convincing case for why your interpretation is correct. With a few exceptions, I think that convincing large numbers of people with factual arguments has largely been a dismal failure. To convince the masses, you have to start convincing the media. The more this pops up in the media, the more the rest of the media will pay attention. But if the media is being presented half-baked arguments, it does tremendous damage.

Panic is only going to happen if things change rapidly. Anger is going to be a common emotion as oil prices spiral higher and higher, and people feel that their hard-earned money is flowing into the coffers of OPEC and the oil companies. The thing I have always believed in is educating people, which is the reason I do this. The best we can do is continue to chip away with sound arguments, and hope that the message starts to sink in. If people understand why things are happening, then we should be in better shape with respect to formulating solutions. If we simply blame the usual suspects (it’s those gouging oil companies!), then we may sit around and point fingers as we drive off a cliff.

Return to Top

Answer

If it was that easy, people wouldn’t keep offering me large sums of money to vet technologies for them. Seriously, there seems to be a great big vacuum in this area. I get questions from intelligent people who can look at an energy idea with a major flaw, but they can’t see it.

There is no magic formula. I think it requires experience, and you have to take them on a case by case basis. If someone brought me a potential breakthrough in biotechnology, I would be in the same boat as a lot of people are when they try to interpret the latest hyped energy breakthrough. Even though biotech is an interest/hobby of mine, it may be difficult for me to spot a fatal flaw. A molecular biologist may take one look, and say “You see that step where they say ‘insert gene A into position B?’ Well, the status of the technology is nowhere close to being able to do that.”

I think it just pays to be a skeptic first. There is nothing wrong with being a skeptic, even though many people confuse skepticism with negativity. I always tell people that I am a skeptic, but also a problem-solver. I am not shooting these ideas down for fun; I want some of them to work. But you have to sort the wheat from the chaff.

Return to Top

October 12, 2007 Posted by | algal biodiesel, biobutanol, biofuels, ethanol, gas inventories, oil production, oil refineries, Peak Oil, refining margins, Saudi Arabia | Comments Off on Answering Questions – Part II

The Problem With Biobutanol

The Essay I Didn’t Want to Finish

Note: I will insert references a bit later. I have to dig them up.

This is an essay that I have been promising for some time. I have had to start it from scratch a couple of times, and I am starting it from scratch again now. I tend to get a lot of e-mail about biobutanol, especially after people read the essay that I wrote on the subject last year:

Biobutanol

However, I did write in that essay:

I need to spend some time going over the patents and linked reports more closely to see if anything suggests a problem that has been glossed over.

When I first started this essay, I was going to review the literature and outline what I felt needed to happen to make biobutanol a reality. Furthermore, since butanol is about 8% soluble in water, I was going to write that a real holy grail would be to find a microorganism that can tolerate 8% butanol, or one that produces a higher alcohol – one that is completely insoluble in water. That would allow the alcohol that was produced to phase from the water, and eliminate the energy intensive distillation that is typically required. That’s what I was going to write. However, reality butted in.

My Initial Thoughts

Just for completeness, here is what I had originally written:

There has been much press lately about the potential of butanol as an alternative fuel. As I have mentioned before, I spent many years as an engineer in butanol units in Texas and in Germany, and I have received a patent for a butanol process that I invented while working in Germany.

Butanol production via petrochemicals is a very straight-forward process. Once the petro-process was invented, it put the bio-process (ABE) out of business. My guess is that due to the nature of biological processes, the product from the ABE process contains copious amounts of water [I was right]. In contrast, the petrochemical process generally contains product with only 5-10% water. Therefore, the energy requirements for purification are much lower for the petrochemical process.

If butanol could be produced without having to purify it via an energy-intensive distillation, the energy return would be much higher and the costs should be lower. If butanol was completely insoluble in water, for instance, it would float to the top as it was produced and it could just be skimmed off. However, butanol is about 8% soluble in water, which means it won’t start phasing until that concentration is reached. And for a biological process, 8% butanol would most likely poison the microorganisms that were producing it.

However, longer-chain alcohols – pentanol, hexanol, hetpanol, etc. – are essentially insoluble in water. These alcohols would phase out and float to the top as they were produced. Separation would be a snap.

The major problem with butanol is that it doesn’t start to phase out of water until the concentration reaches about 8%. If there was a yeast-based process for butanol that could tolerate concentrations higher than this, you would have the makings of a very cost effective process. Do the fermentation, and then just skim off concentrated butanol. This would be much more energy efficient than a distillation.

What I Learned

While butanol is absolutely a superior fuel to ethanol, the production of butanol from microorganisms is a problem. As I was dreaming about pushing concentration to the point that they start to phase out, a little research showed the current status quo. Here was the first reality check:

Significant improvements in acetone-butanol (AB) fermentation by Clostridium acetobutylicum must be achieved before it can become an economically viable industrial process (8, 12). Key factors which contribute to the elevated costs of fermentative production of acetone and butanol are the low product titers and low product selectivity. Butanol inhibits cell growth even at relatively low concentrations, and its final titers are limited to ca. 13 g/liter. This and the low product selectivity (i.e., the production of more than one product) result in increased costs for product separation. In addition, continuous cultures have been of limited applicability because solventogenic clostridia degenerate under continuous-culture conditions; that is, they stop producing solvents.

13 grams per liter is about 1.3% butanol. While we can expect improvements in the technology, the yield needs to go up by almost an order of magnitude to keep the distillation energy (and costs) reasonable. While one may be able to push the conversion to a high level with extreme dilution, such an approach is simply unworkable from an economical or energy return viewpoint. I won’t address the paper in-depth – I leave that up to others for now – but you can see that this was the approach taken in the paper that is basically responsible for the current biobutanol craze in which 2.5 gallons of butanol per bushel of corn was claimed:

Effects of Butyrate Uptake and Long-term Stability of a Fibrous Bed Bioreactor on Continuous ABE Fermentation by Clostridium acetobutylicum

Here is a graphic that shows the extent of the problem:

Note that the concentration of butanol achieved 1.3% for one specific strain. Typical butanol concentrations were just over 1.0%. The total concentration of acetone, butanol, and ethanol amounted to 1.8%. For reference, the petrochemical process produces a product that is somewhere between 85% and 95% butanol. Now you can see why the biochemical process was dropped when the petrochemical process came along. If your objective is merely to produce butanol for some specific application, then the fermentation process can do that – with enormous energy inputs. If your objective is to make fuel with an EROEI of > 1.0, it is nowhere close to being able to achieve that.

Higher Alcohols

How about my desire to find microorganisms that could make higher chain alcohols that could be phase-separated?

As a follow-up to earlier studies on the emission of long-chain alcohols from broth cultures of Gram-negative enteric bacteria, E. coli was examined for the production of 1-octanol, 1-decanol, and 1-dodecanol. Ten strains of E. coli cultured in tryptic soy broth were assayed for volatile metabolites using solid-phase microextraction. Long-chain alcohols were produced by all strains with 1-decanol predominating with production ranging from 23.6 ng mL(-1) to 148 ng mL(-1). The production of long-chain alcohols followed the onset of the exponential growth phase of the broth culture. Doubling the concentration of glucose (5 g L(-1)) in the broth had no effect on the concentration of long-chain alcohols produced.

I would have to check on each one to be sure, but my guess is that even though the higher chain alcohols are essentially insoluble, 148 ng/mL (0.0148%) is not going to phase out. I was hoping to find that something in the range of 0.5-1.0% could be produced. However, 1% would require the process to become about 70 times as productive. So, it looks like we will colonize Mars before higher chain alcohols will be produced commercially from microorganisms. (Gasification may still have a shot at doing it economically).

Conclusion

Sad to say, but I believe biobutanol is dead. While research will (and should) continue, the process is currently at least 10 years from any sort of commercially feasibility. And I would point out that “never” falls under the umbrella of “at least 10 years.”

June 12, 2007 Posted by | alcohols, biobutanol, biofuels | 103 Comments

The Problem With Biobutanol

The Essay I Didn’t Want to Finish

This is an essay that I have been promising for some time. I have had to start it from scratch a couple of times, and I am starting it from scratch again now. I tend to get a lot of e-mail about biobutanol, especially after people read the essay that I wrote on the subject last year:

Biobutanol

While I wrote about the potential for biobutanol in that essay, I also noted:

I need to spend some time going over the patents and linked reports more closely to see if anything suggests a problem that has been glossed over.

When I first started this essay, I was going to review the literature and outline what I felt needed to happen to make biobutanol a reality. Furthermore, since butanol is about 8% soluble in water, I was going to write that a real holy grail would be to find a microorganism that can tolerate 8% butanol, or one that produces a higher alcohol – one that is completely insoluble in water. That would allow the alcohol that was produced to phase from the water, and eliminate the energy intensive distillation that is typically required. That’s what I was going to write. However, reality intervened.

My Initial Thoughts

Just for completeness, here is what I had originally written:

There has been much press lately about the potential of butanol as an alternative fuel. As I have mentioned before, I spent many years as an engineer in butanol units in Texas and in Germany, and I have received a patent for a butanol process that I invented while working in Germany.

Butanol production via petrochemicals is a very straight-forward process. Once the petro-process was invented, it put the bio-process (ABE) out of business. My guess is that due to the nature of biological processes, the product from the ABE process contains copious amounts of water [I was right]. In contrast, the petrochemical process generally contains product with only 5-10% water. Therefore, the energy requirements for purification are much lower for the petrochemical process.

If butanol could be produced without having to purify it via an energy-intensive distillation, the energy return would be much higher and the costs should be lower. If butanol was completely insoluble in water, for instance, it would float to the top as it was produced and it could just be skimmed off. However, butanol is about 8% soluble in water, which means it won’t start phasing until that concentration is reached. And for a biological process, 8% butanol would most likely poison the microorganisms that were producing it.

However, longer-chain alcohols – pentanol, hexanol, hetpanol, etc. – are essentially insoluble in water. These alcohols would phase out and float to the top as they were produced. Separation would be a snap.

The major problem with butanol is that it doesn’t start to phase out of water until the concentration reaches about 8%. If there was a yeast-based process for butanol that could tolerate concentrations higher than this, you would have the makings of a very cost effective process. Do the fermentation, and then just skim off concentrated butanol. This would be much more energy efficient than a distillation.

What I Learned

While butanol is absolutely a superior fuel to ethanol, the production of butanol from microorganisms is a problem. As I was dreaming about pushing concentration to the point that the butanol starts to phase out, a little research showed the current status quo. Here was the first reality check:

Significant improvements in acetone-butanol (AB) fermentation by Clostridium acetobutylicum must be achieved before it can become an economically viable industrial process (8, 12). Key factors which contribute to the elevated costs of fermentative production of acetone and butanol are the low product titers and low product selectivity. Butanol inhibits cell growth even at relatively low concentrations, and its final titers are limited to ca. 13 g/liter. This and the low product selectivity (i.e., the production of more than one product) result in increased costs for product separation. In addition, continuous cultures have been of limited applicability because solventogenic clostridia degenerate under continuous-culture conditions; that is, they stop producing solvents. (1)

13 grams per liter is about 1.3% butanol. While we can expect improvements in the technology, the yield needs to go up by almost an order of magnitude to keep the distillation energy (and costs) reasonable. It has been demonstrated that you push the conversion to a high level with extreme dilution, but such an approach is simply unworkable from an economical or energy return viewpoint. I won’t address the paper in-depth – I leave that up to others for now – but you can see the dilution approach taken in the paper that is basically responsible for the current biobutanol craze in which 2.5 gallons of butanol per bushel of corn was claimed:

Effects of Butyrate Uptake and Long-term Stability of a Fibrous Bed Bioreactor on Continuous ABE Fermentation by Clostridium acetobutylicum (They have taken this link down; the journal probably complained about them providing the paper for free).

Here is a graphic that shows the extent of the problem (2):

Note that the maximum concentration of butanol achieved was 1.3% for one specific strain. Typical butanol concentrations were just over 1.0%. The total concentration of acetone, butanol, and ethanol amounted to 1.8%. For reference, the petrochemical process produces a product that is somewhere between 85% and 95% butanol. Now you can see why the biochemical process was dropped when the petrochemical process came along. If your objective is merely to produce butanol for some specific application, then the fermentation process can do that – with enormous energy inputs. If your objective is to make fuel with an EROEI of > 1.0, it is nowhere close to being able to achieve that.

Finally, a number of people have written or commented that the work of David Ramey, who runs http://www.butanol.com, changes all of that. First of all, I certainly don’t want to denigrate Ramey’s work. It is a good contribution. However, it is clear to me that many people do not understand that what Ramey did gets us no closer to cracking the dilution problem. The big hurdle is not a problem of conversion rate or reaction speed. Those are the areas that Ramey addressed, and while those things are nice to have, there is a show-stopper that has not been addressed. That is, if you read Ramey’s patent (which I have done many times), he is still talking about butanol concentrations in the range of 2.5%. That is the problem, not whether the conversion is 25% or 35%.

Butanol is highly toxic to the “bugs”, so it is very difficult to increase the concentration of butanol in the solution. What is needed is a breakthrough that would allow the bugs to thrive at the solubility limit of butanol, which is about 8%. (This would be similar to humans thriving in an atmosphere with 5% oxygen). In that case, excess butanol production would phase out of solution, and separation would be much less energy intensive than a distillation. But you can’t afford to distill off a 2.5% solution of butanol. The energy inputs into the process will be far greater than the energy content of the butanol. I know this from experience. I spent several years as the process engineer in a butanol plant. At a 3% concentration of butanol, we didn’t even attempt to separate it out. Even using relatively cheap (at that time) natural gas, it didn’t make economic sense to extract that butanol. Those levels of butanol were sent to wastewater treatment for disposal.

Believe me, I have a soft spot for butanol. I want to see it work. But right now there are serious issues. That’s not to say that it isn’t worth pursuing. In fact, I am working on it myself. But I have to be realistic.

Higher Alcohols

How about my desire to find microorganisms that could make higher chain alcohols that could be phase-separated?

As a follow-up to earlier studies on the emission of long-chain alcohols from broth cultures of Gram-negative enteric bacteria, E. coli was examined for the production of 1-octanol, 1-decanol, and 1-dodecanol. Ten strains of E. coli cultured in tryptic soy broth were assayed for volatile metabolites using solid-phase microextraction. Long-chain alcohols were produced by all strains with 1-decanol predominating with production ranging from 23.6 ng mL(-1) to 148 ng mL(-1). The production of long-chain alcohols followed the onset of the exponential growth phase of the broth culture. Doubling the concentration of glucose (5 g L(-1)) in the broth had no effect on the concentration of long-chain alcohols produced. (3)

I would have to check on each one to be sure, but my guess is that even though the higher chain alcohols are essentially insoluble, 148 ng/mL (0.0148%) is not going to phase out. (And even if it did phase out, at those low concentrations the reactor would need to be the size of a football stadium to make useful quantities). I was hoping to find that something in the range of 0.5-1.0% could be produced. However, 1% would require the process to become about 70 times as productive. So, it looks like we will colonize Mars before higher chain alcohols will be produced commercially from microorganisms. (Gasification may still have a shot at doing it economically).

Conclusion

Sad to say, but biobutanol is not remotely at the level the hype implies. While research will (and should) continue, the process is currently at least 10 years from any sort of commercial feasibility. And I would point out that “never” falls under the umbrella of “at least 10 years.”

I would note that one “solution” to the poor EROEI problem would be to use heat from coal or nuclear energy to drive the distillation. You may start with 1 BTU and end up with 0.2 BTUs of butanol, and you will emit a lot of CO2, but it may be economically viable.

References

1. Bermejo, Lourdes L., et al.; Expression of Clostridium acetobutylicum ATCC 824 Genes in Escherichia coli for Acetone. Appl Environ Microbiol. 1998 March; 64(3): 1079–1085. Production and Acetate Detoxification.

2. Ladisch, Michael, et al. Research Challenges and Opportunities for Cellulose Conversion Technology in a Dry Mill Pathway; Midwest Consortium for Biobased Products & Bioenergy.

3. Hamilton-Kemp T, et al.; Production of the long-chain alcohols octanol, decanol, and dodecanol by Escherichia coli. Curr Microbiol. 2005 Aug;51(2):82-6. Epub 2005 Jun 27.

June 12, 2007 Posted by | alcohols, biobutanol, biofuels | Comments Off on The Problem With Biobutanol

The Problem With Biobutanol

The Essay I Didn’t Want to Finish

This is an essay that I have been promising for some time. I have had to start it from scratch a couple of times, and I am starting it from scratch again now. I tend to get a lot of e-mail about biobutanol, especially after people read the essay that I wrote on the subject last year:

Biobutanol

While I wrote about the potential for biobutanol in that essay, I also noted:

I need to spend some time going over the patents and linked reports more closely to see if anything suggests a problem that has been glossed over.

When I first started this essay, I was going to review the literature and outline what I felt needed to happen to make biobutanol a reality. Furthermore, since butanol is about 8% soluble in water, I was going to write that a real holy grail would be to find a microorganism that can tolerate 8% butanol, or one that produces a higher alcohol – one that is completely insoluble in water. That would allow the alcohol that was produced to phase from the water, and eliminate the energy intensive distillation that is typically required. That’s what I was going to write. However, reality intervened.

My Initial Thoughts

Just for completeness, here is what I had originally written:

There has been much press lately about the potential of butanol as an alternative fuel. As I have mentioned before, I spent many years as an engineer in butanol units in Texas and in Germany, and I have received a patent for a butanol process that I invented while working in Germany.

Butanol production via petrochemicals is a very straight-forward process. Once the petro-process was invented, it put the bio-process (ABE) out of business. My guess is that due to the nature of biological processes, the product from the ABE process contains copious amounts of water [I was right]. In contrast, the petrochemical process generally contains product with only 5-10% water. Therefore, the energy requirements for purification are much lower for the petrochemical process.

If butanol could be produced without having to purify it via an energy-intensive distillation, the energy return would be much higher and the costs should be lower. If butanol was completely insoluble in water, for instance, it would float to the top as it was produced and it could just be skimmed off. However, butanol is about 8% soluble in water, which means it won’t start phasing until that concentration is reached. And for a biological process, 8% butanol would most likely poison the microorganisms that were producing it.

However, longer-chain alcohols – pentanol, hexanol, hetpanol, etc. – are essentially insoluble in water. These alcohols would phase out and float to the top as they were produced. Separation would be a snap.

The major problem with butanol is that it doesn’t start to phase out of water until the concentration reaches about 8%. If there was a yeast-based process for butanol that could tolerate concentrations higher than this, you would have the makings of a very cost effective process. Do the fermentation, and then just skim off concentrated butanol. This would be much more energy efficient than a distillation.

What I Learned

While butanol is absolutely a superior fuel to ethanol, the production of butanol from microorganisms is a problem. As I was dreaming about pushing concentration to the point that the butanol starts to phase out, a little research showed the current status quo. Here was the first reality check:

Significant improvements in acetone-butanol (AB) fermentation by Clostridium acetobutylicum must be achieved before it can become an economically viable industrial process (8, 12). Key factors which contribute to the elevated costs of fermentative production of acetone and butanol are the low product titers and low product selectivity. Butanol inhibits cell growth even at relatively low concentrations, and its final titers are limited to ca. 13 g/liter. This and the low product selectivity (i.e., the production of more than one product) result in increased costs for product separation. In addition, continuous cultures have been of limited applicability because solventogenic clostridia degenerate under continuous-culture conditions; that is, they stop producing solvents. (1)

13 grams per liter is about 1.3% butanol. While we can expect improvements in the technology, the yield needs to go up by almost an order of magnitude to keep the distillation energy (and costs) reasonable. It has been demonstrated that you push the conversion to a high level with extreme dilution, but such an approach is simply unworkable from an economical or energy return viewpoint. I won’t address the paper in-depth – I leave that up to others for now – but you can see the dilution approach taken in the paper that is basically responsible for the current biobutanol craze in which 2.5 gallons of butanol per bushel of corn was claimed:

Effects of Butyrate Uptake and Long-term Stability of a Fibrous Bed Bioreactor on Continuous ABE Fermentation by Clostridium acetobutylicum (They have taken this link down; the journal probably complained about them providing the paper for free).

Here is a graphic that shows the extent of the problem (2):

Note that the maximum concentration of butanol achieved was 1.3% for one specific strain. Typical butanol concentrations were just over 1.0%. The total concentration of acetone, butanol, and ethanol amounted to 1.8%. For reference, the petrochemical process produces a product that is somewhere between 85% and 95% butanol. Now you can see why the biochemical process was dropped when the petrochemical process came along. If your objective is merely to produce butanol for some specific application, then the fermentation process can do that – with enormous energy inputs. If your objective is to make fuel with an EROEI of > 1.0, it is nowhere close to being able to achieve that.

Finally, a number of people have written or commented that the work of David Ramey, who runs http://www.butanol.com, changes all of that. First of all, I certainly don’t want to denigrate Ramey’s work. It is a good contribution. However, it is clear to me that many people do not understand that what Ramey did gets us no closer to cracking the dilution problem. The big hurdle is not a problem of conversion rate or reaction speed. Those are the areas that Ramey addressed, and while those things are nice to have, there is a show-stopper that has not been addressed. That is, if you read Ramey’s patent (which I have done many times), he is still talking about butanol concentrations in the range of 2.5%. That is the problem, not whether the conversion is 25% or 35%.

Butanol is highly toxic to the “bugs”, so it is very difficult to increase the concentration of butanol in the solution. What is needed is a breakthrough that would allow the bugs to thrive at the solubility limit of butanol, which is about 8%. (This would be similar to humans thriving in an atmosphere with 5% oxygen). In that case, excess butanol production would phase out of solution, and separation would be much less energy intensive than a distillation. But you can’t afford to distill off a 2.5% solution of butanol. The energy inputs into the process will be far greater than the energy content of the butanol. I know this from experience. I spent several years as the process engineer in a butanol plant. At a 3% concentration of butanol, we didn’t even attempt to separate it out. Even using relatively cheap (at that time) natural gas, it didn’t make economic sense to extract that butanol. Those levels of butanol were sent to wastewater treatment for disposal.

Believe me, I have a soft spot for butanol. I want to see it work. But right now there are serious issues. That’s not to say that it isn’t worth pursuing. In fact, I am working on it myself. But I have to be realistic.

Higher Alcohols

How about my desire to find microorganisms that could make higher chain alcohols that could be phase-separated?

As a follow-up to earlier studies on the emission of long-chain alcohols from broth cultures of Gram-negative enteric bacteria, E. coli was examined for the production of 1-octanol, 1-decanol, and 1-dodecanol. Ten strains of E. coli cultured in tryptic soy broth were assayed for volatile metabolites using solid-phase microextraction. Long-chain alcohols were produced by all strains with 1-decanol predominating with production ranging from 23.6 ng mL(-1) to 148 ng mL(-1). The production of long-chain alcohols followed the onset of the exponential growth phase of the broth culture. Doubling the concentration of glucose (5 g L(-1)) in the broth had no effect on the concentration of long-chain alcohols produced. (3)

I would have to check on each one to be sure, but my guess is that even though the higher chain alcohols are essentially insoluble, 148 ng/mL (0.0148%) is not going to phase out. (And even if it did phase out, at those low concentrations the reactor would need to be the size of a football stadium to make useful quantities). I was hoping to find that something in the range of 0.5-1.0% could be produced. However, 1% would require the process to become about 70 times as productive. So, it looks like we will colonize Mars before higher chain alcohols will be produced commercially from microorganisms. (Gasification may still have a shot at doing it economically).

Conclusion

Sad to say, but biobutanol is not remotely at the level the hype implies. While research will (and should) continue, the process is currently at least 10 years from any sort of commercial feasibility. And I would point out that “never” falls under the umbrella of “at least 10 years.”

I would note that one “solution” to the poor EROEI problem would be to use heat from coal or nuclear energy to drive the distillation. You may start with 1 BTU and end up with 0.2 BTUs of butanol, and you will emit a lot of CO2, but it may be economically viable.

References

1. Bermejo, Lourdes L., et al.; Expression of Clostridium acetobutylicum ATCC 824 Genes in Escherichia coli for Acetone. Appl Environ Microbiol. 1998 March; 64(3): 1079–1085. Production and Acetate Detoxification.

2. Ladisch, Michael, et al. Research Challenges and Opportunities for Cellulose Conversion Technology in a Dry Mill Pathway; Midwest Consortium for Biobased Products & Bioenergy.

3. Hamilton-Kemp T, et al.; Production of the long-chain alcohols octanol, decanol, and dodecanol by Escherichia coli. Curr Microbiol. 2005 Aug;51(2):82-6. Epub 2005 Jun 27.

June 12, 2007 Posted by | alcohols, biobutanol, biofuels | 63 Comments

Bio-Butanol

Butanol Production Process

In my previous job, I worked for a major chemical company for seven years. For six of those years, I worked on various processes to produce butanol. This included roles in R&D, process, and production, and I received a patent while working in Germany for devising a novel process for making butanol. Butanol is an alcohol like ethanol, but whereas ethanol has 2 carbon atoms, butanol has 4.

The most common industrial process to produce butanol involves a few steps. First, synthesis gas is produced. Synthesis gas is a very important raw material. It is composed of hydrogen and carbon monoxide, and is produced by burning a feed at a high temperature while limiting the oxygen available for the reaction. The feed material for producing synthesis gas can be natural gas, fuel oil, coal, or even biomass. Once synthesis gas is produced, it can be used to make a wide variety of chemicals, including diesel (via the Fischer-Tropsch reaction), methanol, ethanol, propanol, or butanol.

If the desired end product is butanol, the synthesis gas is reacted under pressure with propylene to first produce butyraldehyde, and then this is reacted with hydrogen under pressure to produce butanol. The crude product contains butanol, isobutanol, and water, and must be distilled to obtain specification butanol, which has a wide variety of end uses.

The energy return on investment (EROI) for producing butanol in this way is certainly less than 1. I have never bothered to calculate it, but there are a number of energy intensive steps involved in butanol production. However, given the end uses for butanol, the EROI was never a major concern. Sure, saving energy during the production of butanol was always a priority, but since it typically is not used as a fuel, there was no requirement that the EROI be greater than 1 in order to have a viable process.

Bio-Butanol versus Bio-Ethanol

I have made clear in several of my essays on ethanol that my primary objection to using ethanol as fuel is the poor EROI. Ethanol production consumes large quantities of natural gas via fertilizer for corn and then distillation of the ethanol. (If coal is used instead of natural gas, you may have an economic process, but certainly not a green one). The reason so much distillation energy is required is that ethanol is completely soluble in water. The end product of the fermentation results in something like an 8% ethanol/92% water solution. It takes a lot of energy to heat water up, so the distillation of ethanol into a pure form uses up a lot of energy and contributes to the poor EROI.

Butanol, on the other hand, has a more limited solubility in water. According to the Material Safety Data Sheet (MSDS) for butanol, it is only 7.7% soluble in water. What does this mean? There is a much less energy intensive method of separating butanol from water, and that is by letting it phase out (just like oil and water). Therefore, you would expect the EROI for producing butanol from corn would be much better than for producing ethanol from corn.

Until this weekend, I didn’t realize that anyone was producing butanol from corn or biomass. During my graduate school studies, we produced butyric acid as a very smelly byproduct of our biomass process, and this can be converted into butanol. But one of the editors over at Omninerd pointed me to a site this weekend that demonstrates the viability of producing butanol from biomass. I encourage you to check out the claims at http://www.butanol.com, which are based on the work of a chemical engineering professor at Ohio State.

The entire site is worth a read. Here are a few excerpts:

How does butanol compare with ethanol as an alternative fuel?

Butanol has many superior properties as an alternative fuel when compared to ethanol. These include:

· Higher energy content (110,000 Btu’s per gallon for butanol vs. 84,000 Btu per gallon for ethanol). Gasoline contains about 115,000 Btu’s per gallon.

· Butanol is six times less “evaporative” than ethanol and 13.5 times less evaporative than gasoline, making it safer to use as an oxygenate in Arizona, California and other states, thereby eliminating the need for very special blends during the summer and winter months.

· Butanol can be shipped through existing fuel pipelines where ethanol must be transported via rail, barge or truck

· Butanol can be used as a replacement for gasoline gallon for gallon e.g. 100%, or any other percentage. Ethanol can only be used as an additive to gasoline up to about 85% and then only after significant modifications to the engine. Worldwide 10% ethanol blends predominate.

They claim the process is competitive with ethanol on a per gallon basis. Given that butanol has substantially more BTUs than ethanol, the price per BTU would be much lower than for ethanol:

Our preliminary cost estimates suggest that we can produce butanol from corn for about $1.20 per gallon, not including a credit for the hydrogen produced. This compares with ethanol production costs of about $1.28 per gallon. Taking into account the higher Btu content of butanol, this translates to 105,000 Btu per dollar for butanol and 84,000 Btu per dollar for ethanol with corn at $2.50 per bushel. As a further point of reference, butanol produced from petroleum costs about $1.35 per gallon to manufacture.

The economics of the EEI process will be even more attractive when waste material is used as feedstock instead of corn and the price to produce a gallon is $0.85. In such cases the need and cost to grow and prepare the corn for fermentation, by far among the major cost items, are eliminated.

A couple of other claims are worth noting. They say that they can produce 2.5 gallons of butanol for every bushel of corn. On a BTU basis, that is 30% more BTUs than can be produced if ethanol is the end product. Second, they also claim that butanol can be used in biodiesel applications, and can be blended with diesel. If true, that would give butanol a significant advantage over many other alternative fuel options. Finally, they note that the process produces a significant amount of hydrogen as a byproduct.

What’s the Catch?

I need to spend some time going over the patents and linked reports more closely to see if anything suggests a problem that has been glossed over. I can think of one possible issue off the top of my head. One of the knocks on methanol is the toxicity. Ethanol is considered non-toxic for the most part. If trace quantities of ethanol entered the groundwater, it would not be as alarming as methanol getting into our water supplies. Butanol is less toxic than methanol, but more toxic than ethanol, and it is somewhat soluble in water. Therefore, the one thing that should be addressed is the potential for butanol to find its way into our water supplies.

Other than that, this looks worth pursuing. Butanol has a number of clear-cut advantages over ethanol, and it should have a superior EROI. The authors of the site indicate that they need to complete testing on a demonstration plant and a pilot plant. I look forward to the results of their testing.

May 1, 2006 Posted by | biobutanol, butanol | 117 Comments

Bio-Butanol

Butanol Production Process

In my previous job, I worked for a major chemical company for seven years. For six of those years, I worked on various processes to produce butanol. This included roles in R&D, process, and production, and I received a patent while working in Germany for devising a novel process for making butanol. Butanol is an alcohol like ethanol, but whereas ethanol has 2 carbon atoms, butanol has 4.

The most common industrial process to produce butanol involves a few steps. First, synthesis gas is produced. Synthesis gas is a very important raw material. It is composed of hydrogen and carbon monoxide, and is produced by burning a feed at a high temperature while limiting the oxygen available for the reaction. The feed material for producing synthesis gas can be natural gas, fuel oil, coal, or even biomass. Once synthesis gas is produced, it can be used to make a wide variety of chemicals, including diesel (via the Fischer-Tropsch reaction), methanol, ethanol, propanol, or butanol.

If the desired end product is butanol, the synthesis gas is reacted under pressure with propylene to first produce butyraldehyde, and then this is reacted with hydrogen under pressure to produce butanol. The crude product contains butanol, isobutanol, and water, and must be distilled to obtain specification butanol, which has a wide variety of end uses.

The energy return on investment (EROI) for producing butanol in this way is certainly less than 1. I have never bothered to calculate it, but there are a number of energy intensive steps involved in butanol production. However, given the end uses for butanol, the EROI was never a major concern. Sure, saving energy during the production of butanol was always a priority, but since it typically is not used as a fuel, there was no requirement that the EROI be greater than 1 in order to have a viable process.

Bio-Butanol versus Bio-Ethanol

I have made clear in several of my essays on ethanol that my primary objection to using ethanol as fuel is the poor EROI. Ethanol production consumes large quantities of natural gas via fertilizer for corn and then distillation of the ethanol. (If coal is used instead of natural gas, you may have an economic process, but certainly not a green one). The reason so much distillation energy is required is that ethanol is completely soluble in water. The end product of the fermentation results in something like an 8% ethanol/92% water solution. It takes a lot of energy to heat water up, so the distillation of ethanol into a pure form uses up a lot of energy and contributes to the poor EROI.

Butanol, on the other hand, has a more limited solubility in water. According to the Material Safety Data Sheet (MSDS) for butanol, it is only 7.7% soluble in water. What does this mean? There is a much less energy intensive method of separating butanol from water, and that is by letting it phase out (just like oil and water). Therefore, you would expect the EROI for producing butanol from corn would be much better than for producing ethanol from corn.

Until this weekend, I didn’t realize that anyone was producing butanol from corn or biomass. During my graduate school studies, we produced butyric acid as a very smelly byproduct of our biomass process, and this can be converted into butanol. But one of the editors over at Omninerd pointed me to a site this weekend that demonstrates the viability of producing butanol from biomass. I encourage you to check out the claims at http://www.butanol.com, which are based on the work of a chemical engineering professor at Ohio State.

The entire site is worth a read. Here are a few excerpts:

How does butanol compare with ethanol as an alternative fuel?

Butanol has many superior properties as an alternative fuel when compared to ethanol. These include:

· Higher energy content (110,000 Btu’s per gallon for butanol vs. 84,000 Btu per gallon for ethanol). Gasoline contains about 115,000 Btu’s per gallon.

· Butanol is six times less “evaporative” than ethanol and 13.5 times less evaporative than gasoline, making it safer to use as an oxygenate in Arizona, California and other states, thereby eliminating the need for very special blends during the summer and winter months.

· Butanol can be shipped through existing fuel pipelines where ethanol must be transported via rail, barge or truck

· Butanol can be used as a replacement for gasoline gallon for gallon e.g. 100%, or any other percentage. Ethanol can only be used as an additive to gasoline up to about 85% and then only after significant modifications to the engine. Worldwide 10% ethanol blends predominate.

They claim the process is competitive with ethanol on a per gallon basis. Given that butanol has substantially more BTUs than ethanol, the price per BTU would be much lower than for ethanol:

Our preliminary cost estimates suggest that we can produce butanol from corn for about $1.20 per gallon, not including a credit for the hydrogen produced. This compares with ethanol production costs of about $1.28 per gallon. Taking into account the higher Btu content of butanol, this translates to 105,000 Btu per dollar for butanol and 84,000 Btu per dollar for ethanol with corn at $2.50 per bushel. As a further point of reference, butanol produced from petroleum costs about $1.35 per gallon to manufacture.

The economics of the EEI process will be even more attractive when waste material is used as feedstock instead of corn and the price to produce a gallon is $0.85. In such cases the need and cost to grow and prepare the corn for fermentation, by far among the major cost items, are eliminated.

A couple of other claims are worth noting. They say that they can produce 2.5 gallons of butanol for every bushel of corn. On a BTU basis, that is 30% more BTUs than can be produced if ethanol is the end product. Second, they also claim that butanol can be used in biodiesel applications, and can be blended with diesel. If true, that would give butanol a significant advantage over many other alternative fuel options. Finally, they note that the process produces a significant amount of hydrogen as a byproduct.

What’s the Catch?

I need to spend some time going over the patents and linked reports more closely to see if anything suggests a problem that has been glossed over. I can think of one possible issue off the top of my head. One of the knocks on methanol is the toxicity. Ethanol is considered non-toxic for the most part. If trace quantities of ethanol entered the groundwater, it would not be as alarming as methanol getting into our water supplies. Butanol is less toxic than methanol, but more toxic than ethanol, and it is somewhat soluble in water. Therefore, the one thing that should be addressed is the potential for butanol to find its way into our water supplies.

Other than that, this looks worth pursuing. Butanol has a number of clear-cut advantages over ethanol, and it should have a superior EROI. The authors of the site indicate that they need to complete testing on a demonstration plant and a pilot plant. I look forward to the results of their testing.

May 1, 2006 Posted by | biobutanol, butanol | 57 Comments