Hydrogen: The Next Generation
 Cleaning up production of a future fuel
 Jessica Gorman
 From Science News, Vol. 162, No. 15,
 Oct. 12, 2002, p. 235  
 
http://www.phschool.com/science/science_news/articles/hydrogen_next_generation.html
 

 Today's world might run on fossil fuel, but many people predict that
 hydrogen will fuel the future—in cars, houses, and countless handheld
 electronic devices. Hydrogen-powered fuel cells (SN: 9/7/02, p. 155:
 http://www.sciencenews.org/20020907/bob10.asp) can generate electricity
 much more efficiently than fossil fuel can and without spewing polluting
 byproducts such as nitrous oxides, which contribute to smog, and
 carbon dioxide, the most prevalent gas behind global warming.

 "All you do is generate water," says engineer Bruce E. Logan of the
 Pennsylvania State University in State College. "Who can argue with
 water coming out of tailpipes?"

 Yet there's a big cloud hanging over this sunny image of the
 fossil-fuel-free future: The main source of hydrogen at the moment is
 the hydrocarbon molecules in fossil fuel. That has to change, says Logan.
 Not only does the use of fossil fuel for making hydrogen create pollution,
 but fossil fuel eventually will run out.

 "Right now, we can produce hydrogen," says Logan.
 "Can we do it with a sustainable method? No."

 That's why Logan and others are trying to find alternative sources of
 hydrogen. Among these are renewable fuels, such as crops, agricultural
 detritus, and factory wastewater. Some researchers are even turning to dirt
 containing hydrogen-generating microbes. The success of the search could
 well determine whether hydrogen's promise as the clean fuel of the future
 will be fully realized.

 Hydrogen world

 The first and simplest element on the periodic table, hydrogen is colorless,
 odorless, and tasteless. It's the most common element in the galaxy, but
 frustratingly difficult to make on Earth without using fossil fuel.

 Nature is rich in hydrogen. It turns up throughout animal and plant tissue and
 fossil fuel, but breaking the element free is generally difficult. Water, for
 example, can split into hydrogen and oxygen when electricity passes through it.
 Unfortunately, on large scales, this seemingly straightforward process isn't
 yet economical. "And we are far, far, far away from it," says chemical engineer
 Jens Rostrup-Nielsen at Haldor Topsoe in Lyngby, Denmark.

 "Of course, the ideal would be to split water, but you need energy to
 split water, and where do you get the energy from?" says Rostrup-Nielsen.
 "Today, no doubt, the most economic way of producing hydrogen is from
 fossil fuels."

 Producers generate some 45 million metric tons of hydrogen globally
 each year from fossil fuel. Almost half of this hydrogen goes to
 making ammonia, NH3, a major component of fertilizer and a familiar
 ingredient in household cleaners. Refineries use the second largest chunk
 of hydrogen for chemical processes such as removing sulfur from gasoline
 and converting heavy hydrocarbons into gasoline and diesel fuel.
 Food producers use a small percentage, adding hydrogen to some
 edible oils in a process called hydrogenation.

 To make hydrogen, Haldor Topsoe and other companies usually employ a
 method called steam reforming. Vaporized fossil fuels, primarily natural gas,
 mix with steam at high pressures and temperatures with assistance from a
 nickel-based catalyst. The reforming technique yields hydrogen, but it also
 gives off carbon monoxide and carbon dioxide, the primary greenhouse gas.

 Such hydrogen generation from fossil fuel is the first step toward a
 new hydrogen economy, says Rostrup-Nielsen.

 Logan explains that although this approach still generates the pollution
 people are trying to avoid, those gases are released in a potentially more
 manageable way—in the reforming plant rather than in millions of
 mobile car engines.

 Nonetheless, shedding the habit of fossil fuel entirely is the only way a
 wholesale shift to hydrogen will work in the long term, Logan says.

 One approach to this goal is to apply steam-reforming methods to
 alternative renewable materials, says Esteban Chornet, who works at the
 National Renewable Energy Laboratory in Golden, Colo. Such materials
 might be derived from crops. Other scientists are experimenting with
 ponds of algae that use sunlight-driven reactions to make hydrogen
 (SN: 2/26/00, p. 134: http://www.sciencenews.org/20000226/fob6.asp).
 Yet others are considering innovative ways of electrolyzing water
 for large-scale hydrogen generation.

 Logan thinks that converting biological waste, such as the sugar and starch
 in candy- or soda-factory wastewater, is a good way to go. Chemical engineer
 James A. Dumesic of the University of Wisconsin‚ Madison is
 focusing on the byproducts of his state's corn, cheese, and
 paper production to make hydrogen.

 Not only do these biomass-conversion schemes turn trash into a
 valuable product, but the researchers say there's another plus:
 Any carbon dioxide released in the processes could be
 soaked right back up by the planting of new crops to
 provide the needed biomass.

 A biomass strategy of hydrogen generation could be a
 useful intermediate step between the current fossil fuel method
 and the dream of efficient water splitting, says Rostrup-Nielsen.
 Still, any realistic contender for hydrogen generation must first
 knock out the reforming of fossil fuel as the cheapest and
 most efficient process, says Chornet.

 That's not going to be easy.

 Waste to fuel

 About 5 years ago, Logan was taking a walk in his town, State College,
 thinking about new research projects for his environmental engineering lab.
 He realized that working on an alternative method of hydrogen generation
 appealed to him. The work not only involves the kind of science he knows a
 lot about, he says, but it could help solve the world's energy conundrum.

 "Right now, it's dirt cheap to reform a fossil fuel into hydrogen," says Logan.
 Pursuing an even cheaper, more environmentally friendly method, he's
 actually turned to dirt—that is, the soil microbes that can
 generate hydrogen from sugars and starches.

 "These hydrogen-producing bacteria are everywhere," Logan says.
 "You go outside, grab a bucket of soil, and they're there."
 Using bacteria to ferment biological waste is not a new idea,
 but in the June 1 Environmental Science and Technology, Logan and
 his coworkers from Penn State and the KwangJu Institute of Science
 and Technology in Korea reported that it's easier and more efficient
 to produce hydrogen in this way than other scientists had predicted.

 The researchers found they could easily segregate hydrogen-generating
 bacteria from those that consume hydrogen. When they heated some
 ordinary soil—taken from a local tomato plot—for 2 hours at a temperature
 just above water's boiling point, the hydrogen-consuming microbes died off.
 However, bacteria that generate hydrogen survived because they can form
 heat-resistant spores. "You don't need some specialized bacterium or
 genetically engineered bacterium in some science professor's lab," Logan says.

 The researchers then mixed the tomato-plot dirt in an enclosed reactor
 with sugar water to represent wastewater from a food-production plant.
 It looked like "dirty river water," says Logan, but the concoction
 generated gas that was about 60 percent hydrogen.

 Logan and his coworkers also found that similar fermentation experiments
 done by other research groups probably had unwittingly hindered hydrogen
 generation. Those researchers had collected hydrogen from their reactors
 only intermittently rather than continuously as Logan's group had done.
 Letting the gas build up seems to suppress hydrogen production, says Logan.
 Culling it continuously from a reactor yields 43 percent more hydrogen.

 Although Logan and his coworkers haven't yet completed studies on actual
 wastewaters from food manufacturers, Logan says his team's preliminary
 results indicate that common sugar- or starch-bearing wastewaters can be
 used to generate hydrogen in this rather simple way. What's more, he says,
 this kind of biological method—which relies on bacteria and sugar- or
 starch-rich crops—has an advantage over, say, algae-based production,
 because it doesn't require large ponds for collecting the sunlight that
 drives the hydrogen-generating chemistry.

 Technical challenges remain, of course. For example, the researchers need
 to improve the hydrogen yield of their process, and they need to scale it up
 for commercial use. Moreover, says Chornet, in any biological process,
 researchers still must determine whether the input has components that will
 be toxic to the bacteria or limit their efficiency.

 Dumesic and his colleagues use a metal catalyst rather than microorganisms.
 The Wisconsin researchers were working on a project unrelated to
 hydrogen generation when they realized that oxygenated hydrocarbons
 could release hydrogen at more modest temperatures than those required in
 the steam reforming of fossil fuel. In the Aug. 29 Nature, the team reports
 that a platinum catalyst on an aluminum oxide base can be used to make
 hydrogen from glucose. The reaction also produces carbon dioxide and methane,
 and the latter might be burned to generate more energy, Dumesic suggests.

 The method is much like the steam reforming process, but it occurs in
 liquid water at high pressures and moderate temperatures around 250°C,
 instead of in much hotter vapor.

 Although Dumesic and his coworkers used ordinary sugar and other
 laboratory supplies in their experiments, they hope eventually to turn to
 agricultural waste materials, such as cheese whey and corn stover. Other
 Wisconsin industries, including paper manufacturing, also create waste likely
 to be useful, Dumesic says.

 The researchers still need to show that their catalyst works with bone fide
 sugar-containing fluids, not just model solutions in the laboratory, cautions
 Chornet. Moreover, they must prove that the catalyst doesn't deactivate
 with extended, real-world use.

 The process also needs several improvements if it is to become
 commercially viable. For one thing, the glucose quickly decomposes in
 solution into other products before reacting on the catalyst to produce
 hydrogen efficiently. Another problem: Platinum-based catalysts don't come 
cheap.

 To solve these problems, Dumesic and his coworkers are improving the
 reactor design and identifying more-active metal catalysts.

 "Now, I think the challenge is to find better catalysts that are
 even more active or are based on cheaper components," Dumesic says.

 The new frontier

 Demand for hydrogen in the next decade—both for traditional uses, such as
 making ammonia, and for running fuel cells—is expected to accelerate, says
 Rostrup-Nielsen. In fact, many car manufacturers already have produced
 prototype vehicles powered by hydrogen fuel cells. At least in the near
 future, this thirst for hydrogen will be quenched primarily through
 the use of fossil fuels.

 Nontechnical issues also have a bearing on whether and how soon a
 hydrogen economy weaned from fossil fuel comes on line. For example,
 new regulations and cost-cutting legislation, such as tax credits,
 could help make alternative methods of hydrogen generation
 more financially attractive to industry.

 But when will an appropriate technique be ready for use? If more funding
 were put into the research, it could come sooner, Logan says. Nonetheless,
 he predicts, "in the next 10 years or so, I think we'll have figured out
 much more efficient and better ways to do this."

 References:

 Cortright, R.D., R.R. Davda, and J.A. Dumesic. 2002. Hydrogen from
 catalytic reforming of biomass-derived hydrocarbons in liquid water.
 Nature 418(Aug. 29):964-967. Abstract available at
 http://dx.doi.org/10.1038/nature01009 

 Logan, B.E., et al. 2002. Biological hydrogen production measured in
 batch anaerobic respirometers. Environmental Science and Technology
 36(June 1):2530-2535.

 Further Readings:

 Chornet, E., and S. Czernik. 2002. Harnessing hydrogen.
 Nature 418(Aug. 29):928-929. 

 Weiss, P. 2002. Pocket sockets. Science News 162 (Sept. 7):155-156.
 Available at http://www.sciencenews.org/20020907/bob10.asp 

 Wu, C. 2000. Power plants: Algae churn out hydrogen.
 Science News 157 (Feb. 26):134. Available to subscribers at
 http://www.sciencenews.org/20000226/fob6.asp 

 Sources:

 Esteban Chornet
 National Renewable Energy Laboratory
 Golden, CO 80401

 James A. Dumesic
 University of Wisconsin, Madison
 Department of Chemical Engineering
 1415 Engineering Drive
 Madison, WI 53706

 Bruce E. Logan
 Pennsylvania State University
 Civil and Environmental Engineering
 University Park, PA 16802

 Jens Rostrup-Nielson
 Haldor Topsoe A/S
 Nymoellevej 55
 DK 2800 Lyngby
 Denmark
 --- 

 Making Fuels from Biomass
 Jens R. Rostrup-Nielsen
 Science, Vol 308, Issue 5727, 1421-1422 ,
 3 June 2005 
 http://www.sciencemag.org 

 In an effort to replace fossil hydrocarbon fuels,
 chemists have looked for ways to convert biomass to
 useful fuels. In his Perspective, Rostrup-Nielsen
 discusses recent work on converting carbohydrates
 such as sugars and cellulose to ethanol and hydrogen,
 both of which can serve as alternatives to hydrocarbon fuels.
 However, ethanol requires an expensive distillation step,
 and hydrogen would require a new infrastructure.
 He highlights the report by Huber et al., who have
 found a way to convert carbohydrates directly to
 hydrocarbons. The latter would not require a new
 infrastructure nor expensive distillation. 
 --- 

 Production of Liquid Alkanes by
 Aqueous-Phase Processing of
 Biomass-Derived Carbohydrates 
 George W. Huber, Juben N. Chheda,
 Christopher J. Barrett, James A. Dumesic  
 Science, Vol 308, Issue 5727, 1446-1450 ,
 3 June 2005
 http://www.sciencemag.org 
 --- 

 Bug Power
 04 Jun 2005 
 http://www.mail-archive.com/biofuel@sustainablelists.org/msg51113.html

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