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New Route to Hydrocarbon Biofuels

A simple catalytic process converts plant sugars into gasoline, diesel, and jet fuel.

By Prachi Patel

Monday, September 22, 2008

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Researchers at the University of Wisconsin-Madison have developed a simple, two-step chemical process to convert plant sugars into hydrocarbon fuels. The compounds created during the process could also be used to make other industrial chemicals and plastics.

Green gasoline: Researchers at the University of Wisconsin-Madison are using catalysts to speedily convert plant sugar solutions into a mixture of organic compounds that float like oil. Passing the organic compounds over various catalysts transforms them into hydrocarbons found in gasoline, diesel, and jet fuel.
Credit: Ben Barnhart

Several companies are making hydrocarbon biofuels--which can be cheaper to produce than ethanol and have higher energy density--using microbes. Startups such as LS9 and Amyris are trying to genetically engineer the metabolic systems of microbes so that they ferment sugars into useful hydrocarbons.

The Wisconsin researchers, led by chemical- and biological-engineering professor James Dumesic, employ chemical reactions instead of microbial fermentation. They use catalysts at high temperatures to convert glucose into hydrocarbon biofuels. The process works thousands of times faster than microbes do because of the higher temperatures, so it requires smaller, cheaper reactors, Dumesic says. The catalysts and reformer systems that they use are similar to those used in oil refineries, which would also make the process simpler.

The catalytic process, presented online in Science, requires two main steps, which can be integrated and run sequentially with the output from one reactor going to the other. Both the catalyst mechanism and the continuous process design make the new approach promising, says John Regalbuto, director of the catalysis and biocatalysis program at the National Science Foundation, which funds Dumesic's work. Moreover, the catalysts can be recycled, whereas the microbes die and have to be replenished, he says. Compared to using enzymes or microbes, he says, "my sense is that at this stage of the game, catalysts have more potential."

In the first reactor, a sugar-water solution is passed over a platinum-rhenium catalyst at about 500 K. This strips five out of six oxygen atoms from the sugar, creating a mixture of various hydrocarbon compounds, such as alcohols and organic acids. The compounds form an oil-like layer that floats on top of the solution.

The oil is transferred to the second reactor, where it is passed over various solid catalysts, resulting in a range of hydrocarbon molecules that make up gasoline, diesel, and jet fuel. For instance, a copper and magnesium-based catalyst produces the hydrocarbons found in diesel and jet fuel. Gasoline contains hydrocarbons in which carbon atoms are connected in branched and ring-shaped structures, while carbon atoms in diesel and jet fuel form long, linear chains. The alcohols and organic acids in the oil from the first step could also be used to make plastics and industrial chemicals, Dumesic says.

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The researchers' final goal is to use sugars derived from cellulosic biomass such as agricultural waste and switchgrass instead of using food sources such as corn and sugarcane. That would be the key to making environmentally beneficial hydrocarbon fuels from plants that are economically competitive with petroleum fuels. However, enzymes used to extract glucose and other sugars from cellulose are currently too expensive to make the process competitive for creating cellulosic biofuels.

Whether or not biogasoline competes with its petroleum counterpart, it might still make more sense than making ethanol, Regalbuto says. One of the most expensive parts of producing ethanol is the energy-intensive distillation step, in which ethanol has to be separated from water. Hydrocarbons such as gasoline and diesel, meanwhile, float to the top, so they are easier and less expensive to separate. Plus, he says, "you're getting a fuel that's 30 percent more energy dense [than ethanol]. So it's cheaper to make, and it gives you 30 percent more gas mileage."

Comments

  • if real!
    Finally! Finally, a real step (a step, mind you) towards real fuel production!
    I am sooo sick of these endless annoucements of biofuel work which are nothing but laboratory hobby farms. To make a REAL impact, to really replace any petroleum, this would have to be done on an industrial scale, which this system might well do.
      Now if cellulose can be likewise cracked, there is a chance of meaningfull fuel production. If not, then it is just more political hay, and a waste. I hope this does prove out.
    Rate this comment: 12345

    kitk
    09/22/2008
    Posts:66
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    • Real doesn't matter
      Biofuels will not break our dependence on fossil fuels, they'll just delay the inevitable, possibly to the point where us foolish humans completely deforest our planet and manage to make it unsustainable for human life. The US has roughly the same amount of farmland in production now as in the year 1900 but with three times the population. You do the math.

      It's time for research grants to go to more sensible sustainable alternatives. Solar powered public transportation. Tidal, geothermal, solar, wind . . .

      Continuing burning hydrocarbons of any sort to power things is old and backward thinking. We need new solutions.
      Rate this comment: 12345

      bj
      09/22/2008
      Posts:38
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      • Re: Real doesn't matter
        In the first paragraph of the article it states "The compounds created during the process could also be used to make other industrial chemicals and plastics".

        Imagen a day that new technologies make solar cells, and batteries that store it so cost competitive that fossil fuel use to power transportation becomes obsolete. We will still need oil for making rubber, plastics, solvents, lubricants, and other industrial chemicals. Solar energy alone will not be enough. Advances in bio fuel technology aught to be applauded, even if bio fuels out pace solar for energy in transportation markets. It is still a win for carbon cycle conscious groups.
         
        We can all dream and work for the day that solar replaces most our energy needs and still appreciate advances in competing technologies.
        Rate this comment: 12345

        shomas
        09/29/2008
        Posts:43
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    • Re: if real!
      Unfortunately, the key word in the last sentence of the next-to-last paragrapph is, "However." ("However, enzymes used to extract glucose and other sugars from cellulose are currently too expensive to make the process competitive for creating cellulosic biofuels.")  So, now ... is there going to be National Science Foundation grant money available for bringing down the price of the enzymes? It seems with this kind of basic research there's always a "catch" like a carrot hanging out there on the end of the stick.
      Rate this comment: 12345

      ntnjim
      09/22/2008
      Posts:1
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      • Re: if real!
        More power to the lab hobbists!  It just might work. Help keep the grants flowing-- more cash in the feeding dish.

        Meanwhile, why not let Chlorella vulgaris do all of the synthesis and produce lipids which can be extracted as algal oil. Then we can use this veggie oil for cooking, skin lotion, soap, lubricants and biodiesel.  See: http://algaloildiesel.wetpaint.com.

        Oh yes, I've figured out how to open the single cell C.V. with minimal energy; but hey, I'm only a hobbist with a lowley BS degree in ag engineering, not even biochemistry -- what do I know? -- and I don't have a lab or even a work bench, just a laptop.  I did it without any grants in my feeding dish.
        Rate this comment: 12345

        jimmiller541...
        09/23/2008
        Posts:6
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      • Re: if real!
        Actually the first hint that this was yet another example of Technology Review hype comes in the 5th paragraph with the words "sugar and water solution."  Getting to the sugar water is the hard part. 
        Rate this comment: 12345

        leonardcrook
        09/25/2008
        Posts:1
  • The same old process...
    Heat, beat, and treat, baby!
    Rate this comment: 12345

    designgrizzl...
    09/22/2008
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  • Biofuels roadmap...
    Nice one Bucky! Always wonderful to hear positive news from the Dumesic research team.  Of course there are no silver bullets- and I'm not going to bet against biology's power in creating liquid fuel alternatives. Who knows how the cost vs speed factors will play out in the near term.  But clearly we have an opening here with chemical engineering that could help lower cost and push forward this era of biofuels and feedstocks.

    Well done...

    Garry Golden
    UW Madison '98
    Editor, TheEnergyRoadmap(.com)
    Rate this comment: 12345

    Garry Golden
    09/22/2008
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  • hydrocarbon fuels are wasteful
    Sugarcane to ethanol only captures 0.13% of the energy of the sunlight.

    Concentrated Solar Power captures 30% of the same energy as electricity.

    That's a factor of 230.

    The electricity can be used a factor of 4 more efficiently than ethanol at producing mechanical work.

    Make that 230 a factor of 923.

    Wasting 3 orders of magnitude is bad engineering.
    Rate this comment: 12345

    killian
    09/23/2008
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    • Re: hydrocarbon fuels are wasteful
      Wasting 3 orders of magnitude is bad engineering.
      >>>>>

      Not necessarily. Efficiency may defer to power to weight ratio, upfront capital costs, etc. and still be ‘good engineering’.

      Also, with respect to concentrated solar power, while it may convert sunlight energy at ~30%, the sunlight is free, and without the CSP, 100% of it would be ‘wasted’.

      All that really matters in terms of its viability is the price at which the fuel can be produced.
      Rate this comment: 12345

      ic
      09/24/2008
      Posts:1
    • Re: hydrocarbon fuels are wasteful
      But there are certain advantages to hydrocarbons, like storage (don't need expensive batteries), and weight (don't need heavy batteries).  Planes and ships will probably be burning hydrocarbons for many decades to come even if we go to all-electric ground vehicles and all non-hydrocarbon power generation.
      Rate this comment: 12345

      fbm1183
      09/28/2008
      Posts:1
    • Re: hydrocarbon fuels are wasteful
      Very good points. Although it would be good to add a few.

      1. There are losses in the initial storage of electricity from solar that supply power outside peek supply.
      2. There are looses in the transmission of power.
      3. There are more looses in the storage and release of power for use in a motor vehicle.
      4. Hydrocarbons are more energy dense, meaning you need more weight in batteries to transport a vehicle the same distance hence wasting more energy to carrying this additional weight.
      5. If factored, sugar cane (sugar + Cellulose) to ethanol will be return more then 0.13% of the energy of the sunlight.

      Even with these losses, solar is probably still more efficient, but the numbers are nowhere close to 3 orders of magnitude.

      It is also noteworthy to mention hydrocarbon fuels are very competitive, when compared to electrical power for heating the cabin of a vehicle (something to consider in cold climates).
      Rate this comment: 12345

      shomas
      09/30/2008
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      • Re: hydrocarbon fuels are wasteful
        Yes, there are small efficiency losses on delivering solar power to the motor that my analysis did not include. On the other side, I didn't include the energy used in tilling, transportation, and so on. Careful analysis would include both. I was taking the order of magnitude approach to make a point.

        Let me try to put some numbers on the points you raise:
        1. First, aren't we talking about 80-90% efficiency of heat storage for later generation (e.g. Ausra)? Hardly a big loss compared to the crop pathways. However, there is no need to store energy to charge EV batteries, because the batteries are their own storage; if solar is their energy source, then we should charge during the day rather than at night. EVs are flexible enough to take energy when it is produced -- an excellent match to renewables.
        2. About 92% efficient.
        3. About 85% efficient.
        4. To be accurate include mass on both sides of the balance, not just the mass of the battery pack. On the gasoline vehicle side of the balance you have the mass of the gasoline, tank, engine, radiator, water, oil, oil filter, air filter, transmission, catalytic converter, and muffler. On the battery electric vehicle you have the mass of the motor, inverter, battery pack, and onboard charger (cabin heating comes from the same heat pump used for AC, so it is not extra mass). When I do the numbers, it comes out to 100-150 kg extra EV mass, or around 10%. Some real-world lithium-ion EVs are less massive than their ICE competition.
        5. In the production of ethanol from sugarcane, the cellulose is used to provide the heat to drive the process. If you converted the cellulose to ethanol too, you would need to use natural gas or something to provide heat.

        The big factor I left over (that you also missed) is that CSP doesn't typically occupy 100% of the land surface (there needs to be maintenance access for example), and tracking systems need room to move.

        shomas wrote, "Even with these losses, solar is probably still more efficient, but the numbers are nowhere close to 3 orders of magnitude."

        Let's do the math instead of saying things like "nowhere close". You get about one 1 GWh/ha/yr from CSP (e.g. Stirling Energy Systems' SunCatchers). This factors in the land-use inefficiency I left out the first time. Use the 92%, and 85% as above to get to the battery output and you're at 773 MWh/ha/yr. The motor to wheels for an EV is around 200 Wh/mi, so one hectare gives you 3,867,000 EV mi/ha/yr.

        Since there is no data on the sugar to hydrocarbons transformation in the article, let's use switchgrass to ethanol, for which data was just published in Science by Campbell et al. They estimated 16,600 mi/ha/yr (mid-size sedan).

        The ratio is 235, or 2.4 orders of magnitude.
        Rate this comment: 12345

        killian
        05/09/2009
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  • solar distillation
    Seems to me that solar distillation of ethanol would improve the numbers.  It's a good fuel for the short term using existing automotive technology.  Maybe hydrogen hybrids are the future.
    Rate this comment: 12345

    kd4ml
    09/23/2008
    Posts:1
  • cellulosic biomass
    There was an article published quite recently in AIChE J. by Zhang et al. from the Chinese Academy of Sciences titled "Complete Dissolution and Hydrolysis of Wood in Hot Water". At subcritical temperatures, but very high pressures, and with a little Na2CO3, they were able to completely dissolve wood.

    Most of the products are sugars. This might be a natural feedstock from Dumesic's catalytic process, enabling conversion of woody biomass to hydrocarbon fuels.

    Now, the question is economics. The jury is still out on that!
    Rate this comment: 12345

    ChuckInReno
    09/25/2008
    Posts:19
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