Repost of TDP: What Went Wrong
The is Part II of my look at Changing World Technologies’ thermal depolymerization process. This essay came from a reader, and was originally posted on April 12, 2007.
But I also want to add some comments that regular reader “Optimist” added following the previous essay. First, those comments:
The 85% efficiency claim is based on a faulty mass balance. The faulty mass balance is the basis for an equally faulty energy balance. You can verify by comparing production data (bbl oil/ton of waste) to the mass balance (still) presented by CWT.
Contrary to what the breathless writers at Discover magazine believe, this technology is good only for recycling lipids (fats and oils) and the fat-soluble amino acids in protein. To understand why you need to follow the process flow diagram, which consists of three key steps:
1. Thermal Depolymerization (aka Dilute Acid Hydrolysis – yes, the process uses sulfuric acid).
2. Separation of water and fat/oil.
3. Decarboxylation of fatty acids to yield hycrocarbon (diesel) product.Anything soluble in water goes into the effluent in step 2. That includes (but is not limited to) all carbohydrate and the bulk of the protein hydrolysis product (amino acids).
CWT cleverly states that this makes the effluent a high quality fertilizer. Probably true. But that high quality fertilizer contains BTUs not available as fuel (the main product).
Another comment from Optimist:
To their credit, Discover magazine did raise another issue: product quality: Fuel quality was another challenge. Changing World Technologies‘ thick, tarry fuel resembles boiler-grade fuel oil. One prospective buyer insisted on what the company called “unacceptable pricing terms” for its relatively unproven product. In the end, CWT sold only 93,000 of the 391,000 gallons of fuel it produced and earned just 99 cents for each one. At the time, wholesale fuel oil distributors were raking in $2.50 to $3.30 per gallon. Even with the $1-per-gallon U.S. biofuels tax credit for every gallon sold, Changing World Technologies paid more for Butterball’s turkey offal than it earned back in revenue. (Accounting for all its operating costs, the company lost $5,003,000 in the first quarter of 2008, though operating at a loss is not uncommon or necessarily a very bad sign for a technology startup.) Emphasis added.
Don’t worry – I’m sure next year they’ll be printing money…
In light of this, I am not sure why they think it’s a good idea to do an IPO now.
Now for the essay from a reader who provided some very specific details on what went wrong. He included a presentation in which he referred to several slides, and I will pull those out and post them so the references are clear. I will also insert some comments in the text [like this].
—————————————
Robert,
I enjoy your blog quite a lot. Intelligent analysis is rare. Coupled with unbiased interpretation it is almost an unknown.
Saw your discussion of TDP/TCP. Pretty much spot on. As a chemical engineer I thought you’d be interested in some deeper insights of how the process works. This is all information that used to be available on the web, but most of it has been removed.
Start with the lecture (attached) by Terry Adams, CWT technical officer at MIT in April 2005 – best TDP technical article I know of [I have searched for an online version of this, but to no avail. Perhaps using the Wayback Machine one could locate an online archive of the original presentation]. The way I understand it, the process basically consists of two thermal treatment steps. The first step (slide #13) is a low temp/high pressure step that causes hydrolysis of all the biological material. A check of steam tables confirms that pressure is just high enough to maintain liquid water at the temperature given.
The first stage is followed by separation (slide #3).
As indicated in slide #14 they have a clever way of flashing off some of the water and then using the steam to heat the feedstock [This sort of heat recovery is standard practice in the petrochemical industry]. This is at the heart of their claims about high efficiency: the steam is condensed, so most of the water in the feedstock is discharged as liquid. Calling it distilled water, is of course salesmen talk that would make a used car salesman’s eye’s water.
But take a closer look: After separation only the “organic oil” goes to the second stage. After full hydrolysis (let’s just assume that for now) what monomers would be part of the organic oil? Fatty acids barely make it into this oil, due to the little known fact (see flow diagram on slide #11) that sulfuric acid is used to aid hydrolysis [If I had known that, I had forgotten about it. That does put quite a different spin on the whole process]. (DOE would call the first stage by another name: Dilute Acid Hydrolysis). Some fat-soluble amino acids. That’s it. (I bet you can figure out what cellulose fed to these two units would yield…) [It would interesting to see some yields on this. What I would really like to see is what they get if they threw corn in there. If their energy balances are really good - and even with all that has gone wrong they appear to be better than for corn ethanol - then I would like to see some experiments in that direction.]
Of course, CWT are master salesmen. The water-soluble amino acid and glycerol solution is not waste: it is a wonderful liquid fertilizer (slide #23). Talk about taking a lemon and making lemonade…
So, the “organic oil” goes to the second stage (high temperature/low pressure) where the fatty acids are decarboxylized (to yield oil) and some of the amino acids are deaminated and decarboxylized to yield who-knows-what (slide #15, point 2).
You raise the question of how on earth did CWT get their cost estimates so wrong. Well, a large factor in that would be overestimating yield (and per extension efficiency). CWT has long claimed that TDP has an energy efficiency of 85% (heading slide #12). Right there you smell a skunk. Now the dirty details.
The mass balance, slide #11 [posted earlier], shows that CWT probably did not take the CO2 that results from decarboxylation into account. This causes them to overestimate fuel production. You can easily do the calc’s I’m sure, but it is spelled out here. Apologies for the format, got mangled when they changed their format [That thread was a very good discussion on this issue; perhaps I will pull it out, reformat it, and post it at some point].
The energy balance, slide #12, does not include the energy present in the “liquid fertilizer”. What, all that glycerol and amino acids contain no energy? The water vapor also presents energy lost, even if it’s not much.
The mass and energy balances actually date from a previous publication (February and March 2004), also attached. One would expect that CWT would have discovered the error in the interceding year, and corrected it. I guess they were to busy ironing out the substantial start-up problems, such as the odor issue, you mentioned.
You may have notice a subtle shift between those two breathless Discover articles. Instead of producing 500 bbl from 210 tons of waste (first article), they now need 290 tons (20 tons of it pure pig fat), or a 28% reduction in oil yield. Instead of claiming 2.4 bbl/ton of waste, it is now 1.7 bbl/ton (validating an estimate of the maximum yield of ~2.0 bbl/to). Funny thing is Appel and his team still use the 2.4 figure in their financial analysis, even when it would help their argument to use the 1.7 real number. From the second Discover article: “‘We thought we would get $24 a ton for taking the waste,’ says Appel. ‘Instead we are paying $30 a ton.’ That alone raises his production costs about $22 a barrel.” How did they get to $22? ($24/ton + $30/ton)/2.4 bbl/ton = $22.50/bbl. Using the real number would yield: ($24/ton + $30/ton)/1.7 bbl/ton = $32/bbl. Also getting less yield would raise production cost in a number of ways, including the fact that they may be buying natural gas for heating…
So where does that leave TDP? No doubt it is not the silver bullet once claimed. None of the “anything” into oil that seduced Discover’s reporters. And costs are substantial. However, it seems like a good process for converting waste grease into liquid fuel. Much better than say biodiesel. Look at the feedstock (slide #6). How much cleaning (i.e. money and energy) would that stuff need to make it suitable as feedstock for a biodiesel plant? TDP uses sulfuric acid, whereas biodiesel uses methanol and a catalyst (usually NaOH). In terms of energy and money, I suspect TDP has the better input here. TDP yields a liquid fuel that is chemically almost identical to fossil diesel (without the sulfur and aromatics). TDP-40 can be blended with diesel in any ratio 1 to 100, without any issues. As Minnesota discovered last winter, biodiesel has some issues with cold weather. [Having worked in a Montana refinery, I can attest to the fact that winter properties for diesel are critical. I am aware that biodiesel has some problems with pour and cloud points in cold weather, limiting their usage to small blend fractions.]
The main threat to TDP, as I see it, is a process developed by Neste Oil, Finland, that I read about at GCC. Apparently this process allows an existing refinery to incorporate waste grease as a feedstock, without a radical change to the process (or a brand new SS plant). Even that process is not a slam-dunk, as I’ve seen reports of canceled projects.
So yes, you nailed it: these guys overpromised and underdelivered big time. But in terms of the big picture I give them some credit: at least we are not talking about food -> fuel (as with most of the biodiesel plants being built in Europe, proving that the food -> fuel madness is not endemic to North America). [Oh, I agree completely. It is not the process that I took issue with; in fact I do applaud their initiative. My concern was the completely willingness of so many to accept this as the solution to our energy problems. I see the same thing happening right now with cellulosic ethanol.] They probably help to advance the debate on waste -> energy quite a bit. And they do have a working plant, which is more than we can say about Washington’s next big thing, aka cellulosic ethanol. [I will probably write the same article on cellulosic ethanol in just a few years - overpromised and underdelivered. I see many parallels here.]
Repost of TDP: What Went Wrong
The is Part II of my look at Changing World Technologies’ thermal depolymerization process. This essay came from a reader, and was originally posted on April 12, 2007.
But I also want to add some comments that regular reader “Optimist” added following the previous essay. First, those comments:
The 85% efficiency claim is based on a faulty mass balance. The faulty mass balance is the basis for an equally faulty energy balance. You can verify by comparing production data (bbl oil/ton of waste) to the mass balance (still) presented by CWT.
Contrary to what the breathless writers at Discover magazine believe, this technology is good only for recycling lipids (fats and oils) and the fat-soluble amino acids in protein. To understand why you need to follow the process flow diagram, which consists of three key steps:
1. Thermal Depolymerization (aka Dilute Acid Hydrolysis – yes, the process uses sulfuric acid).
2. Separation of water and fat/oil.
3. Decarboxylation of fatty acids to yield hycrocarbon (diesel) product.Anything soluble in water goes into the effluent in step 2. That includes (but is not limited to) all carbohydrate and the bulk of the protein hydrolysis product (amino acids).
CWT cleverly states that this makes the effluent a high quality fertilizer. Probably true. But that high quality fertilizer contains BTUs not available as fuel (the main product).
Another comment from Optimist:
To their credit, Discover magazine did raise another issue: product quality: Fuel quality was another challenge. Changing World Technologies‘ thick, tarry fuel resembles boiler-grade fuel oil. One prospective buyer insisted on what the company called “unacceptable pricing terms” for its relatively unproven product. In the end, CWT sold only 93,000 of the 391,000 gallons of fuel it produced and earned just 99 cents for each one. At the time, wholesale fuel oil distributors were raking in $2.50 to $3.30 per gallon. Even with the $1-per-gallon U.S. biofuels tax credit for every gallon sold, Changing World Technologies paid more for Butterball’s turkey offal than it earned back in revenue. (Accounting for all its operating costs, the company lost $5,003,000 in the first quarter of 2008, though operating at a loss is not uncommon or necessarily a very bad sign for a technology startup.) Emphasis added.
Don’t worry – I’m sure next year they’ll be printing money…
In light of this, I am not sure why they think it’s a good idea to do an IPO now.
Now for the essay from a reader who provided some very specific details on what went wrong. He included a presentation in which he referred to several slides, and I will pull those out and post them so the references are clear. I will also insert some comments in the text [like this].
—————————————
Robert,
I enjoy your blog quite a lot. Intelligent analysis is rare. Coupled with unbiased interpretation it is almost an unknown.
Saw your discussion of TDP/TCP. Pretty much spot on. As a chemical engineer I thought you’d be interested in some deeper insights of how the process works. This is all information that used to be available on the web, but most of it has been removed.
Start with the lecture (attached) by Terry Adams, CWT technical officer at MIT in April 2005 – best TDP technical article I know of [I have searched for an online version of this, but to no avail. Perhaps using the Wayback Machine one could locate an online archive of the original presentation]. The way I understand it, the process basically consists of two thermal treatment steps. The first step (slide #13) is a low temp/high pressure step that causes hydrolysis of all the biological material. A check of steam tables confirms that pressure is just high enough to maintain liquid water at the temperature given.
The first stage is followed by separation (slide #3).
As indicated in slide #14 they have a clever way of flashing off some of the water and then using the steam to heat the feedstock [This sort of heat recovery is standard practice in the petrochemical industry]. This is at the heart of their claims about high efficiency: the steam is condensed, so most of the water in the feedstock is discharged as liquid. Calling it distilled water, is of course salesmen talk that would make a used car salesman’s eye’s water.
But take a closer look: After separation only the “organic oil” goes to the second stage. After full hydrolysis (let’s just assume that for now) what monomers would be part of the organic oil? Fatty acids barely make it into this oil, due to the little known fact (see flow diagram on slide #11) that sulfuric acid is used to aid hydrolysis [If I had known that, I had forgotten about it. That does put quite a different spin on the whole process]. (DOE would call the first stage by another name: Dilute Acid Hydrolysis). Some fat-soluble amino acids. That’s it. (I bet you can figure out what cellulose fed to these two units would yield…) [It would interesting to see some yields on this. What I would really like to see is what they get if they threw corn in there. If their energy balances are really good - and even with all that has gone wrong they appear to be better than for corn ethanol - then I would like to see some experiments in that direction.]
Of course, CWT are master salesmen. The water-soluble amino acid and glycerol solution is not waste: it is a wonderful liquid fertilizer (slide #23). Talk about taking a lemon and making lemonade…
So, the “organic oil” goes to the second stage (high temperature/low pressure) where the fatty acids are decarboxylized (to yield oil) and some of the amino acids are deaminated and decarboxylized to yield who-knows-what (slide #15, point 2).
You raise the question of how on earth did CWT get their cost estimates so wrong. Well, a large factor in that would be overestimating yield (and per extension efficiency). CWT has long claimed that TDP has an energy efficiency of 85% (heading slide #12). Right there you smell a skunk. Now the dirty details.
The mass balance, slide #11 [posted earlier], shows that CWT probably did not take the CO2 that results from decarboxylation into account. This causes them to overestimate fuel production. You can easily do the calc’s I’m sure, but it is spelled out here. Apologies for the format, got mangled when they changed their format [That thread was a very good discussion on this issue; perhaps I will pull it out, reformat it, and post it at some point].
The energy balance, slide #12, does not include the energy present in the “liquid fertilizer”. What, all that glycerol and amino acids contain no energy? The water vapor also presents energy lost, even if it’s not much.
The mass and energy balances actually date from a previous publication (February and March 2004), also attached. One would expect that CWT would have discovered the error in the interceding year, and corrected it. I guess they were to busy ironing out the substantial start-up problems, such as the odor issue, you mentioned.
You may have notice a subtle shift between those two breathless Discover articles. Instead of producing 500 bbl from 210 tons of waste (first article), they now need 290 tons (20 tons of it pure pig fat), or a 28% reduction in oil yield. Instead of claiming 2.4 bbl/ton of waste, it is now 1.7 bbl/ton (validating an estimate of the maximum yield of ~2.0 bbl/to). Funny thing is Appel and his team still use the 2.4 figure in their financial analysis, even when it would help their argument to use the 1.7 real number. From the second Discover article: “‘We thought we would get $24 a ton for taking the waste,’ says Appel. ‘Instead we are paying $30 a ton.’ That alone raises his production costs about $22 a barrel.” How did they get to $22? ($24/ton + $30/ton)/2.4 bbl/ton = $22.50/bbl. Using the real number would yield: ($24/ton + $30/ton)/1.7 bbl/ton = $32/bbl. Also getting less yield would raise production cost in a number of ways, including the fact that they may be buying natural gas for heating…
So where does that leave TDP? No doubt it is not the silver bullet once claimed. None of the “anything” into oil that seduced Discover’s reporters. And costs are substantial. However, it seems like a good process for converting waste grease into liquid fuel. Much better than say biodiesel. Look at the feedstock (slide #6). How much cleaning (i.e. money and energy) would that stuff need to make it suitable as feedstock for a biodiesel plant? TDP uses sulfuric acid, whereas biodiesel uses methanol and a catalyst (usually NaOH). In terms of energy and money, I suspect TDP has the better input here. TDP yields a liquid fuel that is chemically almost identical to fossil diesel (without the sulfur and aromatics). TDP-40 can be blended with diesel in any ratio 1 to 100, without any issues. As Minnesota discovered last winter, biodiesel has some issues with cold weather. [Having worked in a Montana refinery, I can attest to the fact that winter properties for diesel are critical. I am aware that biodiesel has some problems with pour and cloud points in cold weather, limiting their usage to small blend fractions.]
The main threat to TDP, as I see it, is a process developed by Neste Oil, Finland, that I read about at GCC. Apparently this process allows an existing refinery to incorporate waste grease as a feedstock, without a radical change to the process (or a brand new SS plant). Even that process is not a slam-dunk, as I’ve seen reports of canceled projects.
So yes, you nailed it: these guys overpromised and underdelivered big time. But in terms of the big picture I give them some credit: at least we are not talking about food -> fuel (as with most of the biodiesel plants being built in Europe, proving that the food -> fuel madness is not endemic to North America). [Oh, I agree completely. It is not the process that I took issue with; in fact I do applaud their initiative. My concern was the completely willingness of so many to accept this as the solution to our energy problems. I see the same thing happening right now with cellulosic ethanol.] They probably help to advance the debate on waste -> energy quite a bit. And they do have a working plant, which is more than we can say about Washington’s next big thing, aka cellulosic ethanol. [I will probably write the same article on cellulosic ethanol in just a few years - overpromised and underdelivered. I see many parallels here.]
Repost of TDP: The Next Big Thing
Because of the upcoming IPO for Changing World Technologies (See this story at Seeking Alpha) the articles that I wrote on the company are getting quite a bit of traffic. I thought I would bump them to the top for a review of who they are, what they do, and where things went wrong for them. The following essay was originally published on April 9, 2007. If you want to immediately read the sequel to this post, it was TDP: What Went Wrong. That post was written by a reader, and is full of slides and some very keen insight. I will bump it up to the top in a couple of days.
————————–
If you are a layperson, it may not be clear to you just how much of the current infatuation with cellulosic ethanol is hype, and how much is based on realistic assessments. So, I thought I would take you down memory lane and revisit another technology that was going to reduce our dependence on foreign oil.
The Hype: TDP Will Save the World
In May of 2003, Discover Magazine published Anything Into Oil. It was a look at a technology called thermal depolymerization (TDP), which could take any organic material and turn it into oil. This was a high profile write-up with a lot of hype, and the technology of Brian Appel and his company Changing World Technologies (CWT) was really going to change the world.
I remember the first time I read the article, and I thought to myself “Wow, this is really something special.” However, the hype of the technology didn’t quite match up with reality. Let’s take a look back at that original article, and see if we can draw some parallels with some of our current biofuels delusions.
The article starts off:
“This is a solution to three of the biggest problems facing mankind,” says Brian Appel, chairman and CEO of Changing World Technologies, the company that built this pilot plant and has just completed its first industrial-size installation in Missouri. “This process can deal with the world’s waste. It can supplement our dwindling supplies of oil. And it can slow down global warming.”
Pardon me, says a reporter, shivering in the frigid dawn, but that sounds too good to be true. “Everybody says that,” says Appel. He is a tall, affable entrepreneur who has assembled a team of scientists, former government leaders, and deep-pocketed investors to develop and sell what he calls the thermal depolymerization process, or TDP.
So far, so good. An entrepeneur (like Vinod Khosla), former government leaders (like Tom Daschle), and lots of deep-pocketed investors. The article opens with a little bit of hype, and follows with another liberal dose:
“The potential is unbelievable,” says Michael Roberts, a senior chemical engineer for the Gas Technology Institute, an energy research group. “You’re not only cleaning up waste; you’re talking about distributed generation of oil all over the world.”
“This is not an incremental change. This is a big, new step,” agrees Alf Andreassen, a venture capitalist with the Paladin Capital Group and a former Bell Laboratories director.
Yeah, but it’s got to be expensive, right? Not so:
Private investors, who have chipped in $40 million to develop the process, aren’t the only ones who are impressed. The federal government has granted more than $12 million to push the work along.
“We will be able to make oil for $8 to $12 a barrel,” says Paul Baskis, the inventor of the process. “We are going to be able to switch to a carbohydrate economy.”
The article goes on to explain that the technology originated back in the 1980’s:
Usually, the Btu content in the resulting oil or gas barely exceeds the amount needed to make the stuff. That’s the challenge that Baskis, a microbiologist and inventor who lives in Rantoul, Illinois, confronted in the late 1980s. He says he “had a flash” of insight about how to improve the basic ideas behind another inventor’s waste-reforming process.
“The prototype I saw produced a heavy, burned oil,” recalls Baskis. “I drew up an improvement and filed the first patents.” He spent the early 1990s wooing investors and, in 1996, met Appel, a former commodities trader. “I saw what this could be and took over the patents,” says Appel, who formed a partnership with the Gas Technology Institute and had a demonstration plant up and running by 1999.
And they were on the verge of printing money, planning to make oil for $15 a barrel (I thought it was $8-$12?):
And it will be profitable, promises Appel. “We’ve done so much testing in Philadelphia, we already know the costs,” he says. “This is our first-out plant, and we estimate we’ll make oil at $15 a barrel. In three to five years, we’ll drop that to $10, the same as a medium-size oil exploration and production company. And it will get cheaper from there.”
The Hype Begins to Unravel
Well, it’s been 3 to 5 years, and things have not worked out as planned. Costs were much, much higher than forecast. Unforeseen complications appeared. Small technical problems turned out to be big technical problems after the process was scaled up.
Let’s look at some of the issues. A Newsday article in 2004, while also full of hype, foretold of some potential problems:
Turning Garbage into Oil—and Cash
Appel and his financial backers have bet more than $66 million that the modern-day alchemy practiced by Changing World Technologies Inc. will revolutionize the way the world deals with its waste, reduce dependence on foreign oil, fight the spread of mad cow disease and even ease global warming.
Not bad for a 25-person company that Appel, who has no scientific training, runs from the top floor of a Hempstead Avenue china shop owned by his wife, Doreen.
No scientific training? Hmm. Where else have I seen amateurs jumping into an alternative fuel technology with both feet? Oh, yeah. Here and here. (I don’t mean to sound elitist, because amateurs have made valuable contributions in many fields. However, they are more likely to make mistakes/miscalculations than a professional).
The article continues with one more bit of hype that eventually turned out to be unfounded. More on this later:
Incredibly, the only “waste” that’s left behind is distilled water. There are no smokestacks bellowing chemical-laden smoke, and no pipes discharging fetid wastewater.
The article continues by indicating that despite the hype, there really isn’t that much that is known about the process:
Although Discover, Money and Scientific American magazines have all written wildly enthusiastic stories about the company recently — Money called it “The Next Big Thing” — competitors and independent researchers point out that Changing World Technologies has released very little information about the details of its patented process.
So the skeptics (AKA, naysayers) weigh in:
“You have to remember that people have been pressure-cooking different types of biomass for a long time now, and we really haven’t seen these kinds of breakthroughs,” said Ralph Overend, a leading authority in the bio-energy field and a research fellow at the National Renewable Energy Laboratory in Golden, Colo.
“People always stay skeptical until they can see the real data,” added Overend, editor of the academic journal Biomass & Bioenergy.
Appel said the company’s focus has been on building the Missouri plant, not on publishing scientific papers that he worries could tip off potential competitors.
And then there were those nagging cost issues:
Skeptics also wonder about the project’s profitability, and whether it can truly compete with traditional oil drillers and refiners.
Appel acknowledges that producing a barrel of oil through thermal conversion costs about 50 percent more than doing it by conventional refining.
Only 50% more?
And then he makes the mistake that so many others repeatedly make:
If the price of oil keeps rising, he said, so will profits.
This is the same mistake that proponents of tar sands, GTL, oil shale, cellulosic ethanol, and many others have run into. They believe that oil prices will rise, and yet their costs will magically remain where they were. In fact, what happens is that as oil prices rise, all the costs associated with these various projects rise. That’s why oil shale has been imminent for 100 years. That’s why ExxonMobil is scrapping GTL plans. And that’s why tar sands costs have skyrocketed. A poster at The Oil Drum has referred to this trend as The Law of Receding Horizons.
The Bloom Comes off the Rose
So, where does the technology stand today? How far off were those $8 or $15/bbl costs estimates? After all they had run the pilot plants. They had “done so much testing in Philadelphia“, they “already know the costs.” Turns out they didn’t:
Reports from 2005 summarized some economic setbacks which the Carthage plant encountered since its planning stages. It was thought that concern over mad cow disease would prevent the use of turkey waste and other animal products as cattle feed, and thus this waste would be free. As it turns out, turkey waste may still be used as feed in the United States, so that the facility must purchase that feed stock at a cost of $30 to $40 per ton, adding $15 to $20 per barrel to the cost of the oil. Final cost, as of January 2005, was $80/barrel ($1.90/gal).
$80 a barrel! That was an an order of magnitude higher than their earlier estimates. (Incidentally, if their process really worked as they claimed, they could just feed it corn and turn it into oil at a very high EROEI). Not only that, they obviously made more errors in their estimates than just presuming the feedstock would be free. Subtract that $20/bbl and you are still at $60 a barrel – 300% over their highest prior estimate of $15/bbl. Cellulosic ethanol hypesters, take note.
And there was more bad news:
Turkey-oil plant closed due to foul odors
SPRINGFIELD, Mo. – A foul-smelling plant that turns turkey byproducts into fuel oil was ordered closed by the governor Wednesday until the company finds a way to clear the air.
Renewable Environmental Solutions Inc. in the southwest Missouri community of Carthage had agreed in May to improve its odor-control systems after state and city officials sued, alleging the smell posed a public nuisance.
The company also was cited six times by state environmental officials this year, Gov. Matt Blunt said, but the smell continued.
Well, at least there were “no smokestacks bellowing chemical-laden smoke.”
The Lesson Here
CWT still exists as a company today. Like cellulosic ethanol, TDP is a technology that actually works. But the technology was hyped beyond reason. People did not apply enough skepticism before embracing the promise of the technology. It was really going to be “the next big thing.”
But costs and complications were grossly underestimated. They fell victim to The Law of Receding Horizons. They learned that the public doesn’t like smelly plants in their community. Discover ran an updated article in 2006 in which Appel admitted “We have made mistakes. We were too aggressive in our earlier projections.” The hype just ultimately did not match the reality. And while TDP may make some small contribution to our energy needs, it isn’t going to make any measurable dent in our fossil fuel usage.
But at least we have cellulosic ethanol, which I have heard really is “the next big thing.”
Why Gas Prices are Rising Again
Every time gas prices start to go up, my essay “Why Are Gas Prices Rising?” gets a lot of hits from Google searches by people looking for an explanation. Because the supply/demand dynamics have changed, that essay needs dusting off, especially in light of stories like this:
Fuel industry pundits have been left scratching their heads at the recent jump in gas prices, which have increased despite plummeting crude prices.
“The nationwide average retail price of self-serve regular gasoline seems to be defying gravity this month,” according to American Automobile Association (AAA) Director of Public Relations, Geoff Sundtrom, “as it continued to rise in the face of sharply lower prices for crude oil and wholesale gasoline.”
Oil prices closed out at $34.78 per barrel last Friday, according to AAA, the lowest they’ve been since April 5, 2005, when the nationwide average retail gasoline price was $1.76 per gallon compared to Monday’s nationwide average of $1.842. Average nationwide prices jumped slightly to $1.848 on Wednesday. The statewide average is slightly higher at $1.851 per gallon. By this Friday, prices had risen to $46.47, according to The Associated Press.
First things first. Checking the EIA data, their numbers/trends don’t match up. Per the EIA, in April 2005 retail gas prices were $2.28 a gallon (Source) when West Texas Intermediate was trading at $52.98. In early 2009, retail gas prices (per the EIA) are at $1.84 with WTI hovering around $40. AAA is obviously using their own metrics, but a scan of the various EIA gas prices show a pretty consistent trend: Gas and oil prices both sharply down from 2005.
But, it shouldn’t surprise anyone that gas prices would be headed back up – even if oil prices are stagnant. Gasoline had over-corrected to the downside in relation to oil prices. In fact, crack spreads – a measure of the difference between the price of oil and the price of the products – did go negative in late 2008. That is unsustainable, and an indication that gas prices must correct to the upside (or refiners will start to cut production since they are losing money on every barrel). So why are gas prices rising? Because they fell too far. (Nobody ever seems to ask why gas prices fell so much in relation to crude oil; they only get excited when the opposite occurs).
There is another key factor to consider when comparing the behavior of gasoline and oil prices. I have seen them move in opposite directions on numerous occasions. Here is an example of when they might do that. Let’s presume that we have a glut of oil, but a refining bottleneck. In such a case, you would see little demand for oil, keeping the price low. But if refiners are having trouble keeping the gasoline market supplied, then gasoline prices will rise in relation to oil prices. This has taken place multiple times over the past few years, and can usually be understood if you watch the crude and finished product inventories reported each week in This Week in Petroleum.
Other factors that impact the price of gasoline include the strength of gasoline imports (primarily from Europe), and refinery utilization (both of which are reported weekly at the EIA). If gasoline demand is strong, and something happens to reduce the utilization number (e.g., hurricane), prices spike. If demand starts to slacken, you will see refiners start to dial back their utilization.
What Manpower Shortage?
Much has been made of the manpower shortage in the oil industry. I have been interviewed about it, I have written about it, and I saw it first hand when I was working for ConocoPhillips in Aberdeen, Scotland. Recruiting people was very difficult, and contractors – especially process engineers – were commanding unbelievable salaries. I got so many calls from headhunters – including the companies mentioned in the story below – that I literally hated to pick up the phone for fear I was going to get tied up for 15 minutes.
Well, that was then. Since oil prices have fallen, ConocoPhillips has announced they are laying off 4% of the workforce, Schlumberger is laying off 5% of their North American workforce, and now contractors in the North Sea are rolling back salaries by 10%:
North Sea contractors facing a 10% pay cut
More than 1,000 North Sea contractors will see their pay cut by an average of 10% as oil companies feel the impact of lower crude prices.
The wage reductions affect only one oil service business, Wood Group Engineering (North Sea), but its rivals could follow suit as their oil company clients seek to reduce costs.
I worked with Production Services Network (PSN) when I was there, and the story mentioned them as well:
Among the other large North Sea oil service firms are PSN and AMEC.
Bob Keiller, chief executive of Aberdeen-based PSN, said: “We are looking at all ways to help our customers reduce costs.”
One of the reasons that I decided to join the oil industry in the first place was that I felt like it was a safe harbor in a world that would be facing big energy challenges in the near future. In fact, the energy sector has been mentioned as a place to find ‘recession-proof jobs.’ Some are about to discover that even so-called recession-proof jobs can be impacted by a recession.
Note: For the gardeners who read this blog, I just started a gardening journal this morning. It is basically just a journal of my gardening experiences in North Texas. I find it easier to do this via a blog than to keep a notebook. Anyway, feel free to stop by and share any tips you might have. The URL is My Gardening Blog, and I will update it quite often as gardening season gears up.
Amazing Ethanol Lawsuit Against Oil Companies
I did a double-take when I saw this headline:
Ethanol Lawsuit Proceeds against Oil Companies
It turns out that oil companies – forced to use ethanol in gasoline despite many protests – are now being sued because ethanol blends can corrode fiberglass tanks in boats.
NAPLES, Fla. — A Florida lawsuit against six oil companies that alleges negligence for failing to warn boat owners of potential harm from ethanol-blended gasoline, survived a motion to dismiss from the defendants, NaplesNews.com reported.
Plaintiff attorney Jeffrey Ostrow of Fort Lauderdale said the next step is pursuing certification to become a class-action lawsuit. The intent is to represent all Florida boat owners who have used ethanol-blended fuel and whose boats have been damaged by the fuel, Ostrow said. He filed the lawsuit in August 2008 on behalf of three plaintiffs.
The defendants include Chevron, Exxon, BP, Shell Oil, ConocoPhillips and Tower Energy Corp., a California-based independent petroleum wholesaler, the report stated.
Our judicial system never ceases to amaze me. Why not instead go after the lawmakers who thought it would be a good idea to rapidly increase the amount of ethanol in the fuel system without thoughtfully considering the impacts?
At issue is a state law adopted in spring 2008, which states all gasoline sold in Florida must contain 10 percent ethanol, called E10, by the end of 2010 as part of conservation measures. Two exemptions were included allowing ethanol-free gas to be sold for airplanes and boats. About half a dozen other states require ethanol additives in gasoline.
I guess it’s like Willie Sutton’s alleged answer about why he robbed banks: “Because that’s where the money is.” So, why sue oil companies for complying with this mandate that was forced on them? Because that’s where the money is.
All BTUs Are Not Created Equally
I sometimes have to pause and remind people that I am not anti-ethanol. As I have said numerous times, I am opposed to recycling fossil fuel into ethanol, and paying massive subsidies to do it. This is what we do with corn ethanol. That is a false solution to our fossil fuel dependence. If we could produce corn ethanol as we can sugarcane ethanol – with minimal fossil fuel inputs – that would address the vast majority of my ethanol objections. I think I made that clear over two years ago with my support for E3 Biofuels attempt to produce corn ethanol in a more sustainable fashion.
But ethanol has one particularly compelling argument: Ethanol has a high octane rating (103), which means it does not easily pre-ignite. This means higher engine efficiencies could be obtained than can be achieved with gasoline.
It is known that ethanol added to gasoline normally causes the fuel efficiency to drop. Ethanol contains about 2/3rds of the BTUs (heating value) as the same volume of gasoline, and gasoline/ethanol blends normally shows the drop in fuel efficiency one would expect. However, because of ethanol’s resistance to preignition, it should be theoretically possible to design an engine with a much higher compression ratio, which could then extract more useful work from the ethanol. Diesel engines are designed with high compression ratios, which is the key to their engine efficiencies of around 45%, versus 25-30% for a gasoline engine.
Let’s take a simple example, to show how ethanol’s BTU deficit could be made up with an increase in engine efficiency. Gasoline contains about 115,000 BTUs/gallon. If the engine efficiency is 25%, then 28,750 BTUs/gallon ultimately power the vehicle. The rest are expelled as heat. Ethanol contains about 75,000 BTUs/gallon. One could in theory achieve the same fuel efficiency with ethanol as with gasoline if an engine was designed with an efficiency that resulted in the same 28,750 BTUs/gallon powering the vehicle (assuming same weight, frictional losses, etc.) That means that if the efficiency of the ethanol-powered car was 28,750/75,000 – or 38.33%, then 1 gallon of ethanol could provide the same power to the vehicle as 1 gallon of gasoline. And of course if the efficiency of the ethanol vehicle could be increased further, it is possible to use 1 gallon of ethanol to travel farther than one could travel on 1 gallon of gasoline – despite the BTU deficit.
This has been true in theory, and some small scale engines have been created. The Saab Biopower, which debuted a couple of years ago, showed that the BTU-deficit could be partially compensated for. The Saab engine was designed with a higher compression ratio, so that on E-85 it showed a 12.5% drop in fuel efficiency instead of the typical 20-30% drop that one typically sees on E-85. The Saab also achieved a reported 20% extra power and 15% extra torque from this engine.
But I was recently made aware that Swedish automaker Scania has been producing ultra-high compression ratio engines designed for ethanol usage, and they reach engine efficiencies as high as 43%:
Scania’s Ethanol Diesel-Engine, Runs On Biodiesel Too
That means that if all else was equal (no significant weight penalty from the high-compression engine), a gallon of ethanol could enable a vehicle to travel farther than it could on a gallon of gasoline.
In reality, the comparison is not quite apples and oranges, as these Scania engines are used in heavy, commercial applications. I wrote to the company a couple of months ago and asked them some questions about any possible plans to produce a smaller engine for passenger vehicles, but they never responded.
But the point of the essay was to show that all BTUs aren’t the same for liquid fuels, and that a modified compression ratio has the potential to give the counter-intuitive result that a fuel with few BTUs per gallon can actually provide better fuel efficiency in some cases.
Renewable Diesel Primer
Given the recent news that biodiesel has caused buses in Minnesota to malfunction in cold weather, I thought this would be a good time to review the differences between diesel, biodiesel, and green diesel. In order to explain the key issues, I am going to excerpt from the chapter on renewable diesel that I wrote for Biofuels, Solar and Wind as Renewable Energy Systems: Benefits and Risks.
First, what happened in Minnesota?
Biodiesel fuel woes close Bloomington schools
All schools in the Bloomington School District will be closed today after state-required biodiesel fuel clogged in school buses Thursday morning and left dozens of students stranded in frigid weather, the district said late Thursday.
Rick Kaufman, the district’s spokesman, said elements in the biodiesel fuel that turn into a gel-like substance at temperatures below 10 degrees clogged about a dozen district buses Thursday morning. Some buses weren’t able to operate at all and others experienced problems while picking up students, he said.
And in case you think this was an isolated incident:
The decision to close school today came after district officials consulted with several neighboring districts that were experiencing similar problems. Bloomington staffers tried to get a waiver to bypass the state requirement and use pure diesel fuel, but they weren’t able to do so in enough time, Kaufman said. They also decided against scheduling a two-hour delay because the temperatures weren’t expected to rise enough that the problem would be eliminated.
What is Biodiesel?
Biodiesel is defined as the mono-alkyl ester product derived from lipid1 feedstock like SVO or animal fats (Knothe 2001). The chemical structure is distinctly different from petroleum diesel, and biodiesel has somewhat different physical and chemical properties from petroleum diesel.
Biodiesel is normally produced by reacting triglycerides (long-chain fatty acids contained in the lipids) with an alcohol in a base-catalyzed reaction (Sheehan 1998) as shown in Figure 1. Methanol, ethanol, or even longer chain alcohols may be used as the alcohol, although lower-cost and faster-reacting methanol2 is typically preferred. The primary products of the reaction are the alkyl ester (e.g., methyl ester if methanol is used) and glycerol. The key advantage over straight vegetable oil (SVO) is that the viscosity is greatly reduced, albeit at the cost of additional processing and a glycerol byproduct.
The key thing to note here is that biodiesel contains oxygen atoms (the ‘O’ in the biodiesel structure above), but petroleum diesel and green diesel do not. This leads to different physical properties for biodiesel.
Biodiesel Characteristics
Biodiesel is reportedly nontoxic and biodegradable (Sheehan et al. 1998). An EPA study published in 2002 showed that the impact of biodiesel on exhaust emissions was mostly favorable (EPA 2002). Compared to petroleum diesel, a pure blend of biodiesel was estimated to increase the emission of NOx by 10%, but reduce emissions of carbon monoxide and particulate matter by almost 50%. Hydrocarbon emissions from biodiesel were reduced by almost 70% relative to petroleum diesel. However, other researchers have reached different conclusions. While confirming the NOx reduction observed in the EPA studies, Altin et al. determined that both biodiesel and SVO increase CO emissions over petroleum diesel (Altin et al. 2001). They also determined that the energy content of biodiesel and SVO was about 10% lower than for petroleum diesel. This means that a larger volume of biodiesel consumption is required per distance traveled, increasing the total emissions over what a comparison of the exhaust concentrations would imply.
The natural cetane3 number for biodiesel in the 2002 EPA study was found to be higher than for petroleum diesel (55 vs. 44). Altin et al. again reported a different result, finding that in most cases the natural cetane numbers were lower for biodiesel than for petroleum diesel. These discrepancies in cetane results have been attributed to the differences in the quality of the oil feedstock, and to whether the biodiesel had been distilled (Van Gerpen 1996).
A major attraction of biodiesel is that it is easy to produce. An individual with a minimal amount of equipment or expertise can learn to produce biodiesel. With the exception of SVO, production of renewable diesel by hobbyists is limited to biodiesel because a much larger capital expenditure is required for other renewable diesel technologies.
Biodiesel does have characteristics that make it problematic in cold weather conditions. The cloud and pour points4 of biodiesel can be 20° C or higher than for petroleum diesel (Kinast 2003). This is a severe disadvantage for the usage of biodiesel in cold climates, and limits the blending percentage with petroleum diesel in cold weather.
Green Diesel
Definition
Another form of renewable diesel is ‘green diesel.’ Green diesel is chemically the same as petroleum diesel, but it is made from recently living biomass. Unlike biodiesel, which is an ester and has different chemical properties from petroleum diesel, green diesel is composed of long-chain hydrocarbons, and can be mixed with petroleum diesel in any proportion for use as transportation fuel. Green diesel technology is frequently referred to as second-generation renewable diesel technology.
There are two methods of making green diesel. One is to hydroprocess vegetable oil or animal fats. Hydroprocessing may occur in the same facilities used to process petroleum. The second method of making green diesel involves partially combusting a biomass source to produce carbon monoxide and hydrogen – syngas – and then utilizing the Fischer-Tropsch reaction to produce complex hydrocarbons. This process is commonly called the biomass-to-liquids, or BTL process.
Hydroprocessing
Hydroprocessing is the process of reacting a feed stock with hydrogen under elevated temperature and pressure in order to change the chemical properties of the feed stock. The technology has long been used in the petroleum industry to ‘crack’, or convert very large organic molecules into smaller organic molecules, ranging from those suitable for liquid petroleum gas (LPG) applications through those suitable for use as distillate fuels.
In recent years, hydroprocessing technology has been used to convert lipid feed stocks into distillate fuels. The resulting products are a distillate fuel with properties very similar to petroleum diesel, and propane (Hodge 2006). The primary advantages over first-generation biodiesel technology are: 1). The cold weather properties are superior; 2). The propane byproduct is preferable over glycerol byproduct; 3). The heating content is greater; 4). The cetane number is greater; and 5). Capital costs and operating costs are lower (Arena et al. 2006).
A number of companies have announced renewable diesel projects based on hydroprocessing technology. In May 2007 Neste Oil Corporation in Finland inaugurated a plant that will produce 170,000 t/a of renewable diesel fuel from a mix of vegetable oil and animal fat (Neste 2007). Italy’s Eni has announced plans for a facility in Leghorn, Italy that will hydrotreat vegetable oil for supplying European markets. Brazil’s Petrobras is currently producing renewable diesel via their patented hydrocracking technology (NREL 2006). And in April 2007 ConocoPhillips, after testing their hydrocracking technology to make renewable diesel from rapeseed oil in Whitegate, Ireland, announced a partnership with Tyson Foods to convert waste animal fat into diesel (ConocoPhillips 2007).
Like biodiesel production, which normally utilizes fossil fuel-derived methanol, hydroprocessing requires fossil fuel-derived hydrogen5. No definitive life cycle analyses have been performed for diesel produced via hydroprocessing. Therefore, the energy return and overall environmental impact have yet to be quantified.
Biomass-to-Liquids
When an organic material is burned (e.g., natural gas, coal, biomass), it can be completely oxidized (gasified) to carbon dioxide and water, or it can be partially oxidized to carbon monoxide and hydrogen. The latter partial oxidation (POX), or gasification reaction, is accomplished by restricting the amount of oxygen during the combustion. The resulting mixture of carbon monoxide and hydrogen is called synthesis gas (syngas) and can be used as the starting material for a wide variety of organic compounds, including transportation fuels.
Syngas may be used to produce long-chain hydrocarbons via the Fischer-Tropsch (FT) reaction. The FT reaction, invented by German chemists Franz Fischer and Hans Tropsch in the 1920s, was used by Germany during World War II to produce synthetic fuels for their war effort. The FT reaction has received a great deal of interest lately because of the potential for converting natural gas, coal, or biomass into liquid transportation fuels. These processes are respectively referred to as gas-to-liquids (GTL), coal-to-liquids (CTL), and biomass-to-liquids (BTL), and the resulting fuels are ‘synthetic fuels’ or ‘XTL fuels’. Of the XTL processes, BTL produces the only renewable fuel, as it utilizes recently anthropogenic (atmospheric) carbon.
Renewable diesel produced via BTL technology has one substantial advantage over biodiesel and hydrocracking technologies: Any source of biomass may be converted via BTL. Biodiesel and hydrocracking processes are limited to lipids. This restricts their application to a feedstock that is very small in the context of the world’s available biomass. BTL is the only renewable diesel technology with the potential for converting a wide range of waste biomass.
Like GTL and CTL, development of BTL is presently hampered by high capital costs. According to the Energy Information Administration’s Annual Energy Outlook 2006, capital costs per daily barrel of production are $15,000-20,000 for a petroleum refinery, $20,000-$30,000 for an ethanol plant, $30,000 for GTL, $60,000 for CTL, and $120,000-$140,000 for BTL (EIA 2006).
While a great deal of research, development, and commercial experience has gone into FT technology in recent years6, biomass gasification biomass gasification technology is a relatively young field, which may partially explain the high capital costs. Nevertheless, the technology is progressing. Germany’s Choren is building a plant in Freiberg, Germany to produce 15,000 tons/yr of their SunDiesel® product starting in 2008 (Ledford 2006).
Straight Vegetable Oil
Unmodified vegetable-derived triglycerides, commonly known as vegetable oil, may also be used to fuel a diesel engine. Rudolf Diesel demonstrated the use of peanut oil as fuel for one of his diesel engines at the Paris Exposition in 1900 (Altin et al. 2001). Modern diesel engines are also capable of running on straight (unmodified) vegetable oil (SVO) or waste grease, with some loss of power over petroleum diesel (West 2004). Numerous engine performance and emission tests have been conducted with SVO derived from many different sources, either as a standalone fuel or as a mixture with petroleum diesel (Fort and Blumberg 1982, Schlick et al. 1988, Hemmerlein et al. 1991, Goering et al. 1982).
The advantage of SVO as fuel is that a minimal amount of processing is required, which lowers the production costs of the fuel. The energy return for SVO, defined as energy output over the energy required to produce the fuel, will also be higher due to the avoidance of energy intensive downstream processing steps.
There are several disadvantages of using SVO as fuel. The first is that researchers have found that engine performance suffers, and that hydrocarbon and carbon monoxide emissions increase relative to petroleum diesel. Particulate emissions were also observed to be higher with SVO. However, the same studies found that nitrogen oxide (NOx) emissions were lower for SVO (Altin et al. 2001). On long-term tests, carbon deposits have been found in the combustion chamber, and sticky gum deposits have occurred in the fuel lines (Fort and Blumberg 1982). SVO also has a very high viscosity relative to most diesel fuels. This reduces its ability to flow, especially in cold weather. This characteristic may be compensated for by heating up the SVO, or by blending it with larger volumes of lower viscosity diesel fuels.
Conclusions
In order to understand the potential problems with biodiesel under cold weather conditions, it is important to understand that biodiesel is chemically different from petroleum or green diesel – and thus should not be expected to have the same chemical properties. Biodiesel is an ester, while petroleum and green diesel are hydrocarbons. The only reason it is called ‘diesel’ is that it can fuel a diesel engine. Likewise vegetable oil, butanol, and even ethanol blends could be called ‘diesels’, as each of these can be used to fuel a diesel engine.
Finally, it should also be noted that petroleum diesel is not immune from cold weather gelling. It is just that these problems don’t begin to occur until the temperatures are much lower than those at which biodiesel begins to gel. If extremely cold weather conditions are likely, then petroleum diesel is blended differently. More kerosene is put into the mixture, which is a lighter diesel (and has a shorter carbon chain length and is just a little heavier than gasoline) and is referred to as #1 diesel.
Footnotes
1. Lipids are oils obtained from recently living biomass. Examples are soybean oil, rapeseed oil, palm oil, and animal fats. Petroleum is obtained from ancient biomass and will be specifically referred to as ‘crude oil’ or the corresponding product ‘petroleum diesel.’
2. Methanol is usually produced from natural gas, although some is commercially produced from light petroleum products or from coal. Methanol therefore represents a significant – but often overlooked – fossil fuel input into the biodiesel process.
3. The cetane number is a measure of the ignition quality of diesel fuel based on ignition delay in a compression ignition engine. The ignition delay is the time between the start of the injection and the ignition. Higher cetane numbers mean shorter ignition delays and better ignition quality.
4. The cloud point is the temperature at which the fuel becomes cloudy due to the precipitation of wax. The pour point is the lowest temperature at which the fuel will still freely flow.
5. Hydrogen is produced almost exclusively from natural gas.
6. Companies actively involved in developing Fischer-Tropsch technology include Shell, operating a GTL facility in Bintulu, Malaysia since 1993; Sasol, with CTL and GTL experience in South Africa; and ConocoPhillips and Syntroleum, both with GTL demonstration plants in Oklahoma.
References
Altin, R., Cetinkaya S., & Yucesu, H.S. (2001). The potential of using vegetable oil fuels as fuel for Diesel engines. Energy Convers. Manage. 42, 529–538.
Arena, B.; Holmgren, J.; Marinangeli, R.; Marker, T.; McCall, M.; Petri, J.; Czernik, S.; Elliot, D.; & Shonnard, D. (2006, September). Opportunities for Biorenewables in Petroleum Refineries (Paper presented at the Rio Oil & Gas Expo and Conference, Instituto Braserileiro de Petroleo e Gas).
ConocoPhillips. (2007). ConocoPhillips and Tyson Foods Announce Strategic Alliance To Produce Next Generation Renewable Diesel Fuel. Retrieved July 21, 2007 from the ConocoPhillips corporate web site: http://www.conocophillips.com/newsroom/news_releases/2007+News+Releases/041607.htm
EIA, Energy Information Administration. (2006). Annual Energy Outlook 2006. DOE/EIA-0383, 57-58.
EPA, U.S. Environmental Protection Agency. (2002). A Comprehensive Analysis of Biodiesel Impacts on Exhaust Emissions. EPA420-P-02-001.
Fort, E. F. & Blumberg, P. N. (1982). Performance and durability of a turbocharged diesel fueled with cottonseed oil blends. (Paper presented at the International Conference on Plant and Vegetable Oils as Fuel, ASAE).
Goering C.E., Schwab, A. Dougherty, M. Pryde, M. & Heakin, A. (1981). Fuel properties of eleven vegetable oils. (Paper presented at the American Society of Agricultural Engineers meeting, Chicago, IL, USA).
Hodge, C. (2006). Chemistry and Emissions of NExBTL. (Presented at the University of California, Davis). Retrieved July 21, 2007 from http://bioenergy.ucdavis.edu/materials/NExBTL%20Enviro%20Benefits%20of%20paraffins.pdf
Hemmerlein M., Korte V., & Richter HS. (1991). Performance, exhaust emission and durability of modern diesel engines running on rapeseed oil. SAE Paper 910848.
Kinast, J. NREL, National Renewable Energy Laboratory. (2003). Production of Biodiesels from Multiple Feed-stocks and Properties of Biodiesels and Biodiesel/Diesel Blends. NREL/SR-510-31460.
Knothe, G. (2001). Historical perspectives on vegetable oil-based diesel fuels. INFORM 12 (11), 1103–7.
Ledford, H. (2006). Liquid fuel synthesis: Making it up as you go along. Nature 444, 677 – 678.
Neste Oil Corporation. (2007). Neste Oil inaugurates new diesel line and biodiesel plant at Porvoo. Retrieved July 21, 2007 from http://www.nesteoil.com/default.asp?path=1,41,540,1259,1260,7439,8400
NREL, National Renewable Energy Laboratory. (2006). Biodiesel and Other Renewable Diesel Fuels, NREL/FS-510-40419 Sheehan, J. NREL, National Renewable Energy Laboratory. (1998). An Overview of Biodiesel and Petroleum Diesel Life Cycles, NREL/TP-580-24772.
Schlick M. L., Hanna, M. A., & Schinstock, J. L. (1988). Soybean and sunflower oil performance in diesel engine. ASAE 31 (5).
Van Gerpen, J. (1996). Cetane Number Testing of Biodiesel. (Paper presented at the Third Liquid Fuel Conference: Liquid Fuel and Industrial Products from Renewable Resources, St. Joseph, MI).
West, T. (2004). The Vegetable-Oil Alternative. [Electronic version]. Car and Driver. Retrieved June 28, 2007 from http://www.caranddriver.com/article.asp?section_id=4&article_id=7818
Book Chapter Outline
While I have posted extended excerpts from my book chapter, I covered quite a bit more material in there. Here is the full chapter outline:
Renewable Diesel by Robert Rapier
1. The Diesel Engine
2. Ecological Limits
3. Straight Vegetable Oil (SVO)
4. Biodiesel
4.1.1. Definition/Production Process
4.1.2. Fuel Characteristics
4.1.3. Energy Return
4.1.4. Glycerin Byproduct
5. Green Diesel
5.1.1. Definition/Production
5.1.1.1. Hydroprocessing
5.1.1.2. BTL – Gasification/Fischer-Tropsch
6. Feedstocks
6.1.1. Soybean Oil
6.1.2. Palm Oil
6.1.3. Rapeseed Oil
6.1.4. Jatropha
6.1.5. Algae
6.1.6. Animal Fats
6.1.7. Waste Biomass
7. Conclusions
8. Conversion Factors and Calculations
8.1. Conversion Factors
8.2. Calculations
9. References
Renewable Diesel Primer
Given the recent news that biodiesel has caused buses in Minnesota to malfunction in cold weather, I thought this would be a good time to review the differences between diesel, biodiesel, and green diesel. In order to explain the key issues, I am going to excerpt from the chapter on renewable diesel that I wrote for Biofuels, Solar and Wind as Renewable Energy Systems: Benefits and Risks.
First, what happened in Minnesota?
Biodiesel fuel woes close Bloomington schools
All schools in the Bloomington School District will be closed today after state-required biodiesel fuel clogged in school buses Thursday morning and left dozens of students stranded in frigid weather, the district said late Thursday.
Rick Kaufman, the district’s spokesman, said elements in the biodiesel fuel that turn into a gel-like substance at temperatures below 10 degrees clogged about a dozen district buses Thursday morning. Some buses weren’t able to operate at all and others experienced problems while picking up students, he said.
And in case you think this was an isolated incident:
The decision to close school today came after district officials consulted with several neighboring districts that were experiencing similar problems. Bloomington staffers tried to get a waiver to bypass the state requirement and use pure diesel fuel, but they weren’t able to do so in enough time, Kaufman said. They also decided against scheduling a two-hour delay because the temperatures weren’t expected to rise enough that the problem would be eliminated.
What is Biodiesel?
Biodiesel is defined as the mono-alkyl ester product derived from lipid1 feedstock like SVO or animal fats (Knothe 2001). The chemical structure is distinctly different from petroleum diesel, and biodiesel has somewhat different physical and chemical properties from petroleum diesel.
Biodiesel is normally produced by reacting triglycerides (long-chain fatty acids contained in the lipids) with an alcohol in a base-catalyzed reaction (Sheehan 1998) as shown in Figure 1. Methanol, ethanol, or even longer chain alcohols may be used as the alcohol, although lower-cost and faster-reacting methanol2 is typically preferred. The primary products of the reaction are the alkyl ester (e.g., methyl ester if methanol is used) and glycerol. The key advantage over straight vegetable oil (SVO) is that the viscosity is greatly reduced, albeit at the cost of additional processing and a glycerol byproduct.
The key thing to note here is that biodiesel contains oxygen atoms (the ‘O’ in the biodiesel structure above), but petroleum diesel and green diesel do not. This leads to different physical properties for biodiesel.
Biodiesel Characteristics
Biodiesel is reportedly nontoxic and biodegradable (Sheehan et al. 1998). An EPA study published in 2002 showed that the impact of biodiesel on exhaust emissions was mostly favorable (EPA 2002). Compared to petroleum diesel, a pure blend of biodiesel was estimated to increase the emission of NOx by 10%, but reduce emissions of carbon monoxide and particulate matter by almost 50%. Hydrocarbon emissions from biodiesel were reduced by almost 70% relative to petroleum diesel. However, other researchers have reached different conclusions. While confirming the NOx reduction observed in the EPA studies, Altin et al. determined that both biodiesel and SVO increase CO emissions over petroleum diesel (Altin et al. 2001). They also determined that the energy content of biodiesel and SVO was about 10% lower than for petroleum diesel. This means that a larger volume of biodiesel consumption is required per distance traveled, increasing the total emissions over what a comparison of the exhaust concentrations would imply.
The natural cetane3 number for biodiesel in the 2002 EPA study was found to be higher than for petroleum diesel (55 vs. 44). Altin et al. again reported a different result, finding that in most cases the natural cetane numbers were lower for biodiesel than for petroleum diesel. These discrepancies in cetane results have been attributed to the differences in the quality of the oil feedstock, and to whether the biodiesel had been distilled (Van Gerpen 1996).
A major attraction of biodiesel is that it is easy to produce. An individual with a minimal amount of equipment or expertise can learn to produce biodiesel. With the exception of SVO, production of renewable diesel by hobbyists is limited to biodiesel because a much larger capital expenditure is required for other renewable diesel technologies.
Biodiesel does have characteristics that make it problematic in cold weather conditions. The cloud and pour points4 of biodiesel can be 20° C or higher than for petroleum diesel (Kinast 2003). This is a severe disadvantage for the usage of biodiesel in cold climates, and limits the blending percentage with petroleum diesel in cold weather.
Green Diesel
Definition
Another form of renewable diesel is ‘green diesel.’ Green diesel is chemically the same as petroleum diesel, but it is made from recently living biomass. Unlike biodiesel, which is an ester and has different chemical properties from petroleum diesel, green diesel is composed of long-chain hydrocarbons, and can be mixed with petroleum diesel in any proportion for use as transportation fuel. Green diesel technology is frequently referred to as second-generation renewable diesel technology.
There are two methods of making green diesel. One is to hydroprocess vegetable oil or animal fats. Hydroprocessing may occur in the same facilities used to process petroleum. The second method of making green diesel involves partially combusting a biomass source to produce carbon monoxide and hydrogen – syngas – and then utilizing the Fischer-Tropsch reaction to produce complex hydrocarbons. This process is commonly called the biomass-to-liquids, or BTL process.
Hydroprocessing
Hydroprocessing is the process of reacting a feed stock with hydrogen under elevated temperature and pressure in order to change the chemical properties of the feed stock. The technology has long been used in the petroleum industry to ‘crack’, or convert very large organic molecules into smaller organic molecules, ranging from those suitable for liquid petroleum gas (LPG) applications through those suitable for use as distillate fuels.
In recent years, hydroprocessing technology has been used to convert lipid feed stocks into distillate fuels. The resulting products are a distillate fuel with properties very similar to petroleum diesel, and propane (Hodge 2006). The primary advantages over first-generation biodiesel technology are: 1). The cold weather properties are superior; 2). The propane byproduct is preferable over glycerol byproduct; 3). The heating content is greater; 4). The cetane number is greater; and 5). Capital costs and operating costs are lower (Arena et al. 2006).
A number of companies have announced renewable diesel projects based on hydroprocessing technology. In May 2007 Neste Oil Corporation in Finland inaugurated a plant that will produce 170,000 t/a of renewable diesel fuel from a mix of vegetable oil and animal fat (Neste 2007). Italy’s Eni has announced plans for a facility in Leghorn, Italy that will hydrotreat vegetable oil for supplying European markets. Brazil’s Petrobras is currently producing renewable diesel via their patented hydrocracking technology (NREL 2006). And in April 2007 ConocoPhillips, after testing their hydrocracking technology to make renewable diesel from rapeseed oil in Whitegate, Ireland, announced a partnership with Tyson Foods to convert waste animal fat into diesel (ConocoPhillips 2007).
Like biodiesel production, which normally utilizes fossil fuel-derived methanol, hydroprocessing requires fossil fuel-derived hydrogen5. No definitive life cycle analyses have been performed for diesel produced via hydroprocessing. Therefore, the energy return and overall environmental impact have yet to be quantified.
Biomass-to-Liquids
When an organic material is burned (e.g., natural gas, coal, biomass), it can be completely oxidized (gasified) to carbon dioxide and water, or it can be partially oxidized to carbon monoxide and hydrogen. The latter partial oxidation (POX), or gasification reaction, is accomplished by restricting the amount of oxygen during the combustion. The resulting mixture of carbon monoxide and hydrogen is called synthesis gas (syngas) and can be used as the starting material for a wide variety of organic compounds, including transportation fuels.
Syngas may be used to produce long-chain hydrocarbons via the Fischer-Tropsch (FT) reaction. The FT reaction, invented by German chemists Franz Fischer and Hans Tropsch in the 1920s, was used by Germany during World War II to produce synthetic fuels for their war effort. The FT reaction has received a great deal of interest lately because of the potential for converting natural gas, coal, or biomass into liquid transportation fuels. These processes are respectively referred to as gas-to-liquids (GTL), coal-to-liquids (CTL), and biomass-to-liquids (BTL), and the resulting fuels are ‘synthetic fuels’ or ‘XTL fuels’. Of the XTL processes, BTL produces the only renewable fuel, as it utilizes recently anthropogenic (atmospheric) carbon.
Renewable diesel produced via BTL technology has one substantial advantage over biodiesel and hydrocracking technologies: Any source of biomass may be converted via BTL. Biodiesel and hydrocracking processes are limited to lipids. This restricts their application to a feedstock that is very small in the context of the world’s available biomass. BTL is the only renewable diesel technology with the potential for converting a wide range of waste biomass.
Like GTL and CTL, development of BTL is presently hampered by high capital costs. According to the Energy Information Administration’s Annual Energy Outlook 2006, capital costs per daily barrel of production are $15,000-20,000 for a petroleum refinery, $20,000-$30,000 for an ethanol plant, $30,000 for GTL, $60,000 for CTL, and $120,000-$140,000 for BTL (EIA 2006).
While a great deal of research, development, and commercial experience has gone into FT technology in recent years6, biomass gasification biomass gasification technology is a relatively young field, which may partially explain the high capital costs. Nevertheless, the technology is progressing. Germany’s Choren is building a plant in Freiberg, Germany to produce 15,000 tons/yr of their SunDiesel® product starting in 2008 (Ledford 2006).
Straight Vegetable Oil
Unmodified vegetable-derived triglycerides, commonly known as vegetable oil, may also be used to fuel a diesel engine. Rudolf Diesel demonstrated the use of peanut oil as fuel for one of his diesel engines at the Paris Exposition in 1900 (Altin et al. 2001). Modern diesel engines are also capable of running on straight (unmodified) vegetable oil (SVO) or waste grease, with some loss of power over petroleum diesel (West 2004). Numerous engine performance and emission tests have been conducted with SVO derived from many different sources, either as a standalone fuel or as a mixture with petroleum diesel (Fort and Blumberg 1982, Schlick et al. 1988, Hemmerlein et al. 1991, Goering et al. 1982).
The advantage of SVO as fuel is that a minimal amount of processing is required, which lowers the production costs of the fuel. The energy return for SVO, defined as energy output over the energy required to produce the fuel, will also be higher due to the avoidance of energy intensive downstream processing steps.
There are several disadvantages of using SVO as fuel. The first is that researchers have found that engine performance suffers, and that hydrocarbon and carbon monoxide emissions increase relative to petroleum diesel. Particulate emissions were also observed to be higher with SVO. However, the same studies found that nitrogen oxide (NOx) emissions were lower for SVO (Altin et al. 2001). On long-term tests, carbon deposits have been found in the combustion chamber, and sticky gum deposits have occurred in the fuel lines (Fort and Blumberg 1982). SVO also has a very high viscosity relative to most diesel fuels. This reduces its ability to flow, especially in cold weather. This characteristic may be compensated for by heating up the SVO, or by blending it with larger volumes of lower viscosity diesel fuels.
Conclusions
In order to understand the potential problems with biodiesel under cold weather conditions, it is important to understand that biodiesel is chemically different from petroleum or green diesel – and thus should not be expected to have the same chemical properties. Biodiesel is an ester, while petroleum and green diesel are hydrocarbons. The only reason it is called ‘diesel’ is that it can fuel a diesel engine. Likewise vegetable oil, butanol, and even ethanol blends could be called ‘diesels’, as each of these can be used to fuel a diesel engine.
Finally, it should also be noted that petroleum diesel is not immune from cold weather gelling. It is just that these problems don’t begin to occur until the temperatures are much lower than those at which biodiesel begins to gel. If extremely cold weather conditions are likely, then petroleum diesel is blended differently. More kerosene is put into the mixture, which is a lighter diesel (and has a shorter carbon chain length and is just a little heavier than gasoline) and is referred to as #1 diesel.
Footnotes
1. Lipids are oils obtained from recently living biomass. Examples are soybean oil, rapeseed oil, palm oil, and animal fats. Petroleum is obtained from ancient biomass and will be specifically referred to as ‘crude oil’ or the corresponding product ‘petroleum diesel.’
2. Methanol is usually produced from natural gas, although some is commercially produced from light petroleum products or from coal. Methanol therefore represents a significant – but often overlooked – fossil fuel input into the biodiesel process.
3. The cetane number is a measure of the ignition quality of diesel fuel based on ignition delay in a compression ignition engine. The ignition delay is the time between the start of the injection and the ignition. Higher cetane numbers mean shorter ignition delays and better ignition quality.
4. The cloud point is the temperature at which the fuel becomes cloudy due to the precipitation of wax. The pour point is the lowest temperature at which the fuel will still freely flow.
5. Hydrogen is produced almost exclusively from natural gas.
6. Companies actively involved in developing Fischer-Tropsch technology include Shell, operating a GTL facility in Bintulu, Malaysia since 1993; Sasol, with CTL and GTL experience in South Africa; and ConocoPhillips and Syntroleum, both with GTL demonstration plants in Oklahoma.
References
Altin, R., Cetinkaya S., & Yucesu, H.S. (2001). The potential of using vegetable oil fuels as fuel for Diesel engines. Energy Convers. Manage. 42, 529–538.
Arena, B.; Holmgren, J.; Marinangeli, R.; Marker, T.; McCall, M.; Petri, J.; Czernik, S.; Elliot, D.; & Shonnard, D. (2006, September). Opportunities for Biorenewables in Petroleum Refineries (Paper presented at the Rio Oil & Gas Expo and Conference, Instituto Braserileiro de Petroleo e Gas).
ConocoPhillips. (2007). ConocoPhillips and Tyson Foods Announce Strategic Alliance To Produce Next Generation Renewable Diesel Fuel. Retrieved July 21, 2007 from the ConocoPhillips corporate web site: http://www.conocophillips.com/newsroom/news_releases/2007+News+Releases/041607.htm
EIA, Energy Information Administration. (2006). Annual Energy Outlook 2006. DOE/EIA-0383, 57-58.
EPA, U.S. Environmental Protection Agency. (2002). A Comprehensive Analysis of Biodiesel Impacts on Exhaust Emissions. EPA420-P-02-001.
Fort, E. F. & Blumberg, P. N. (1982). Performance and durability of a turbocharged diesel fueled with cottonseed oil blends. (Paper presented at the International Conference on Plant and Vegetable Oils as Fuel, ASAE).
Goering C.E., Schwab, A. Dougherty, M. Pryde, M. & Heakin, A. (1981). Fuel properties of eleven vegetable oils. (Paper presented at the American Society of Agricultural Engineers meeting, Chicago, IL, USA).
Hodge, C. (2006). Chemistry and Emissions of NExBTL. (Presented at the University of California, Davis). Retrieved July 21, 2007 from http://bioenergy.ucdavis.edu/materials/NExBTL%20Enviro%20Benefits%20of%20paraffins.pdf
Hemmerlein M., Korte V., & Richter HS. (1991). Performance, exhaust emission and durability of modern diesel engines running on rapeseed oil. SAE Paper 910848.
Kinast, J. NREL, National Renewable Energy Laboratory. (2003). Production of Biodiesels from Multiple Feed-stocks and Properties of Biodiesels and Biodiesel/Diesel Blends. NREL/SR-510-31460.
Knothe, G. (2001). Historical perspectives on vegetable oil-based diesel fuels. INFORM 12 (11), 1103–7.
Ledford, H. (2006). Liquid fuel synthesis: Making it up as you go along. Nature 444, 677 – 678.
Neste Oil Corporation. (2007). Neste Oil inaugurates new diesel line and biodiesel plant at Porvoo. Retrieved July 21, 2007 from http://www.nesteoil.com/default.asp?path=1,41,540,1259,1260,7439,8400
NREL, National Renewable Energy Laboratory. (2006). Biodiesel and Other Renewable Diesel Fuels, NREL/FS-510-40419 Sheehan, J. NREL, National Renewable Energy Laboratory. (1998). An Overview of Biodiesel and Petroleum Diesel Life Cycles, NREL/TP-580-24772.
Schlick M. L., Hanna, M. A., & Schinstock, J. L. (1988). Soybean and sunflower oil performance in diesel engine. ASAE 31 (5).
Van Gerpen, J. (1996). Cetane Number Testing of Biodiesel. (Paper presented at the Third Liquid Fuel Conference: Liquid Fuel and Industrial Products from Renewable Resources, St. Joseph, MI).
West, T. (2004). The Vegetable-Oil Alternative. [Electronic version]. Car and Driver. Retrieved June 28, 2007 from http://www.caranddriver.com/article.asp?section_id=4&article_id=7818
Book Chapter Outline
While I have posted extended excerpts from my book chapter, I covered quite a bit more material in there. Here is the full chapter outline:
Renewable Diesel by Robert Rapier
1. The Diesel Engine
2. Ecological Limits
3. Straight Vegetable Oil (SVO)
4. Biodiesel
4.1.1. Definition/Production Process
4.1.2. Fuel Characteristics
4.1.3. Energy Return
4.1.4. Glycerin Byproduct
5. Green Diesel
5.1.1. Definition/Production
5.1.1.1. Hydroprocessing
5.1.1.2. BTL – Gasification/Fischer-Tropsch
6. Feedstocks
6.1.1. Soybean Oil
6.1.2. Palm Oil
6.1.3. Rapeseed Oil
6.1.4. Jatropha
6.1.5. Algae
6.1.6. Animal Fats
6.1.7. Waste Biomass
7. Conclusions
8. Conversion Factors and Calculations
8.1. Conversion Factors
8.2. Calculations
9. References
Chavez Back Pedals
Now this is pretty funny:
Chávez Lets West Make Oil Bids as Prices Plunge
CARACAS, Venezuela — President Hugo Chávez, buffeted by falling oil prices that threaten to damage his efforts to establish a Socialist-inspired state, is quietly courting Western oil companies once again.
Until recently, Mr. Chávez had pushed foreign oil companies here into a corner by nationalizing their oil fields, raiding their offices with tax authorities and imposing a series of royalties increases.
But faced with the plunge in prices and a decline in domestic production, senior officials have begun soliciting bids from some of the largest Western oil companies in recent weeks — including Chevron, Royal Dutch/Shell and Total of France — promising them access to some of the world’s largest petroleum reserves, according to energy executives and industry consultants here.
Let’s see. Invite oil companies in, steal their investments when oil prices go up, kick them out, invite them in again when oil prices fall. That sounds fair. Every oil company with a few billion dollars burning a hole in their pocket is probably lining up – presuming they don’t mind losing 100% of their investment based on Chavez’s whims.
In all seriousness, I have said on numerous occasions that the oil industry in Venezuela couldn’t survive with Chavez siphoning all the profits and using them to fund his social programs. The oil industry is capital intensive. You neglect those capital requirements at the peril of future production. Someone commented on a previous essay that it was arrogant to assume that Venezuela couldn’t expand oil production without outside help. As I pointed out, heavy oil production is technically challenging. Chavez’s move here is an admission that things haven’t worked out for him as planned, and that in fact they do need outside help; help that Chavez has thoroughly alienated.
As the article points it, the biggest irony is that Chavez has celebrated the demise of capitalism in Venezuela, even though it was capitalism that enabled him to carry out his social programs. So, he is going to give capitalism another chance – but we have seen what happens when prices go up. His motto is “You take the risk, I will reap the reward.”
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