Synthetic Fuel Concept to Steal CO2 From Air....[But Using Nuclear Power to Do It]
Nancy Ambrosiano
nwa@ lanl.gov
(505) 667-0471 (04-349)
http://www.lanl.gov/news/index.php/fuseaction/home.story/story_id/12554
LOS ALAMOS, N.M., February 12, 2008 - Green FreedomTM for carbon-neutral, sulfur-free fuel and chemical production
Los Alamos National Laboratory has developed a low-risk, transformational concept, called Green FreedomTM, for large-scale production of carbon-neutral, sulfur-free fuels and organic chemicals from air and water.
Currently, the principal market for the Green Freedom production concept is fuel for vehicles and aircraft.
At the heart of the technology is a new process for extracting carbon dioxide from the atmosphere and making it available for fuel production using a new form of electrochemical separation. By integrating this electrochemical process with existing technology, researchers have developed a new, practical approach to producing fuels and organic chemicals that permits continued use of existing industrial and transportation infrastructure. Fuel production is driven by carbon-neutral power.
"Our concept enhances U.S. energy and material security by reducing dependence on imported oil. Initial system and economic analyses indicate that the prices of Green Freedom commodities would be either comparable to the current market or competitive with those of other carbon-neutral, alternative technologies currently being considered," said F. Jeffrey Martin of the Laboratory's Decisions Applications Division, principal investigator on the project.
Martin will be presenting a talk on the subject at the Alternative Energy NOW conference in Lake Buena Vista, Florida, February 20, 2008.
In addition to the new electrochemical separation process, the Green Freedom system can use existing cooling towers, such as those of nuclear power plants, with carbon-capture equipment that eliminates the need for additional structures to process large volumes of air. The primary environmental impact of the production facility is limited to the footprint of the plant. It uses non-hazardous materials for its feed and operation and has a small waste stream volume. In addition, unlike large-scale biofuel concepts, the Green Freedom system does not add pressure to agricultural capacity or use large tracts of land or farming resources for production.
The concept's viability has been reviewed and verified by both industrial and semi-independent Los Alamos National Laboratory technical reviews. The next phase will demonstrate the new electrochemical process to prove the ability of the system to both capture carbon dioxide and pull it back out of solution. An industrial partnership consortium will be formed to commercialize the Green Freedom concept.
Los Alamos National Laboratory, a multidisciplinary research institution engaged in strategic science on behalf of national security, is operated by Los Alamos National Security, LLC, a team composed of Bechtel National, the University of California, The Babcock & Wilcox Company, and the Washington Division of URS for the Department of Energy's National Nuclear Security Administration.
Los Alamos enhances national security by ensuring the safety and reliability of the U.S. nuclear stockpile, developing technologies to reduce threats from weapons of mass destruction, and solving problems related to energy, environment, infrastructure, health, and global security concerns.
More:
http://www.dotyenergy.com/Investors/Others_Patents.htm
Nuclear Methanol and Gasoline. Martin and Kubic of Los Alamos National Laboratories have recently suggested that a novel approach to electrolytic rejuvenation of an aqueous solution of CO2-laden K2CO3 may permit lower-cost separation of CO2 from the atmosphere. They then propose that this CO2, along with hydrogen from water electrolyzed by nuclear energy, be converted to methanol and then to gasoline in a process they call "Green FreedomTM".
Their primary innovation is an improved method of separating CO2 from the atmosphere, though it is not clear from the available information that they have made a significant improvement here. Martin's process, like most others, would require enormous amounts of low-grade heat and low-cost high-quality water. It would certainly be much more expensive than using upgraded conventional technologies to separate CO2 from the exhaust of natural gas or coal-fired power plants (where the concentration of CO2 is three orders of magnitude higher than in the atmosphere), as we propose.
The next big problem is what they propose to do with the CO2. They clearly have not figured out how to make the RWGS reaction work efficiently (as we have); so they propose to make methanol from a syngas consisting of just CO2 and H2 (mostly from electrolyzed water) rather than using the more efficient processes that usually have a ratio of CO/CO2 greater than 3 and have always had this ratio greater than 1. It is true that methanol can be synthesized without CO in the syngas, but the process has not been commercialized because it hasn't worked as well. Mitsui will soon attempt to demonstrate CO2-to-methanol in a very small pilot plant in which at least some of the hydrogen will be generated by solar photolysis and some will probably come from solar PV. Almost no technical details are being made public, but the catalysts being used are the same that have been around for more than a decade.
Another (and bigger) problem is that they plan to power their plant using a huge nuclear reactor - four times larger than most that have been built. Their processes are not sufficiently efficient to be competitive if renewable energy is utilized. Nuclear power has never been cheap, and it is steadily becoming more expensive. It has competed thus far only because of enormous subsidies (in the research, development, fuel processing, security, waste storage, etc.), and these are increasingly harder to support politically. The Union of Concerned Scientists and most other environmental organizations do not support ramping up nuclear energy - primarily for safety reasons.
Their nuclear-generated methanol cannot compete with fossil-derived methanol. The price of methanol has spiked severely on a few occasions in recent history, largely due to some process plant problems in Chile and natural gas price spikes in the U.S. However, methanol plants are being built fast enough in China, Qatar, Iran, Russia, and elsewhere to insure that the price of methanol (per unit energy) should average well below the cost of all other transportation fuels for many years.
The latest research indicates that electrical energy will cost $40/GJ from new nuclear plants that would be ordered next year in the US - or three times as much as wind energy. (See our comments on nuclear fission.) If we assume 55% conversion efficiency and add (very conservatively) about 25% for a few other cost components, the "nuclear methanol" from their process will cost $2/kg. The mean price of methanol this year is likely to end up at $0.5/kg. No one will pay four times as much for "nuclear methanol" as for methanol from natural gas or coal. Their "nuclear gasoline" would cost at least $13/gal.
Since methanol has not been accepted as a fuel extender/oxygenate in the U.S. and most industrialized nations, they propose to convert the methanol to gasoline using conventional processes. These processes have achieved 85% efficiency in production of gasoline. Undoubtedly, the processes can be improved, and methanol-to-gasoline processes are likely to play a larger role in the future as enormous amounts of renewable methanol become available from WindFuels.
Finally, it is important to return to a sub-theme in the first point - the fundamental market reason for abandoning the CO2-to-methanol route that has been advocated by Nobel Laureate George Olah for many years. Mid-alcohols and light olefins have been 20% more expensive per unit energy than methanol over most of the past five years and that trend is likely to continue - partly because of an undeniable trend in agricultural commodities. If expensive energy is to be used to make carbon-neutral products, the products should be mostly those with the highest value per unit energy - mid-alcohols and light olefins. We have shown that these more valuable products can be made at significantly higher efficiency than others have yet achieved in the production of methanol.
Nuclear Diesel. Severinsky is to be commended for the valiant efforts in his pending patents (U.S. published application 2006/0211777, etc.), as his work is mostly sound - to the extent that it can really be evaluated. Basically, he has attempted to patent the general process of making carbon-neutral fuels (diesel and gasoline) using the RWGS reaction and the FTS reaction. He thinks the best source of the hydrogen would be nuclear reactors electrolyzing water, but he realizes other renewable energy and other processes could also be used.
The problem of course is that the above general concepts have been discussed since the mid-1970's. Severinsky collects a lot of relevant technical information and presents a variety of different plant designs in very general and confusing language. He makes claims about efficiencies that he thinks are possible, but provides no clear explanations of how or why his ideas are better than what has been done before. While most of the details on the various components he describes are sound, his system designs (which is what he is attempting to claim) are completely unintelligible (even to an expert who has spent years trying to understand such things).
One test is to ask: "Is there anything in his patent of value that was not really present in the prior literature?". Another is to ask: "Is it likely that anyone on a technical team designing and developing an RFTS plant would ever take a second glance at his patent when trying to scope out the design, understand the plant, or optimize some process?" The answer to both is a resounding no.
It is not surprising that the initial PCT written opinion (9/2007) stated that none of his claims contained an inventive step. Of course, he will likely revise them and eventually get some very narrow claims allowed. Patent attorneys and inventors without sufficient relevant experience often propose very broad claims in the initial submission because they think their claims will be worth less if narrowed by additional specifics. However, a narrower claim is not worth less if there is not a better way of accomplishing its objective. The real problem with starting with overly broad claims is that the specification may not have been written in such a way as to support valuable claims that could be granted - and significant amendments in the specification after formal submission are seldom allowed. Most likely, his claims will end up including restrictions that are suboptimal and will never be practiced, such as: the use of an electrolyzer operating very near the thermo-neutral potential, the use of a heat pump for transfer of energy from the FTS reactor to the RWGS reactor, the use of specific phase-change liquids for heat transfer, FTS conditions suitable only for production of diesel with specific catalysts, and the use of a fission reactor. The Written Opinion of the International Searching Authority makes it clear that Severinsky's pending patent is of no concern to us.
Sea Fuels. Behrens has proposed in US Pat 7,302,903 (12/2007) that wind energy could be used to produce hydrocarbons from seawater in floating vessels. One of the showstoppers with his concept is that it utilizes CO2 that has already been sequestered in the ocean, so it is no better for the climate than fossil fuels. Another showstopper is that it would add the cost of a ship the size of an aircraft carrier to the cost of the small RFTS plant that it would support. And there are numerous other technical problems too, but there is no point in continuing here. However, Behrens' patent does provide an interesting example of how severely the scope of the claims must be limited in this subject area when substantive technical innovation is not supported in the patent's specification.
CO2 Electrolysis. Stoots et al in US Pub 2008002338 disclose a method of producing a CO+H2 syngas by electrolyzing a steam/CO2 mixture at high temperatures. One of the showstopper problems with their invention is that is requires a ceramic electrolyte, and the best option that anyone has come up with over the past two decades of related work in high-temperature steam electrolysis is zirconia.
Few companies have more experience with zirconia at high temperatures and high stresses than Doty Scientific. We know all too well how fragile and expensive zirconia is. Reliance on zirconia ensures that neither steam electrolysis nor steam/CO2electrolysis will ever work in the real world. Even if they could make it work with acceptable lifetime (irrespective of the cost of the electrolytes), it does not appear that they could offer any efficiency advantage in an RFTS plant.
Junk Science. Seymour's work in US Patent 7,238,728 (7/2007) and elsewhere is a classic example of the kind of stuff that gives patenting a bad name. Most patents simply prove to be uncompetitive in the real world; but some, like this one, are poorly conceived or vague ideas by individuals with just enough technical expertise to convince an unqualified patent attorney that they have a good idea. (They sometimes are even able to convince investors.)
Seymour seems to understand that syngas (CO and H2) can be converted to liquid hydrocarbons in an FTS reactor and that the combination of partial combustion and pyrolysis of biomass can produce syngas. He apparently also understands that the mixture ratio may need adjustment, and that electrolysis of water produces hydrogen and oxygen which should be able to be used in the process. So he proposes to: (A) send some of the H2 and O2 along with some waste CO2 into a turbine; (B) generate heat to assist in the pyrolysis; (C) reduce some of the CO2 to CO; (D) separate the CO from the turbine products; (E) feed a proper syngas mixture into the FTS reactor; and (F) collect the reaction products.
There is no way such a process could ever be made to work at efficiencies even a quarter of what we'll achieve. For starters, one cannot have turbine exit conditions that permit the combination of (A) efficient utilization of its remaining enthalpy in pyrolysis, (B) high CO fraction in the turbine exhaust, and (C) efficient separation of the turbine products (CO, CO2, and H2O). It also seems silly to deliberately design an inefficient turbine (as needed to get the desired pyrolysis heat), especially when burning electrolysis hydrogen; and there are a host of other detail issues that the inventor has not begun to think about.
The patent examiners don't worry about patents like this as long as they don't obviously violate the second law of thermodynamics. They might suggest some claim language that is clearly of no value and quickly have the patent allowed to get it off their desk. This one issued only 11 months after it was submitted. It is completely worthless and of no concern to us.
Conventional FTS. Andre Steynberg and colleagues disclose in pending US patent 2007/0142481 an improvement on a two-stage FTS reactor arrangement. In this design, the syngas first partially reacts in a 3-phase LT-FTS reactor, and its tail gas (some products and un-reacted syngas) then go to a 2-phase HT-FTS reactor for further reaction. This approach appears optimum for their desired balance of mostly lubricants, high-quality waxes, linear alkyl-benzenes, gasoline, diesel, and some light olefins and oxygenates from coal-syngas. This is a beautifully written reference by the world's best team in fossil-based FTS, but there is little here that can be applied to renewable, carbon-neutral products. Two other nice reference patents on fossil FTS are US Pat # 7,001,927 by Zhang and US Pat # 7,115,670 by Hensman and Newton.
NYTimes
http://www.nytimes.com/2008/02/19/science/19carb.html
February 19, 2008
Scientists Would Turn Greenhouse Gas Into Gasoline
By KENNETH CHANG
If two scientists at Los Alamos National Laboratory are correct, people will still be drivinggasoline-powered cars 50 years from now, churning out heat-trapping carbon dioxide into the atmosphere - and yet that carbon dioxide will not contribute to global warming.
The scientists, F. Jeffrey Martin and William L. Kubic Jr., are proposing a concept, which they have patriotically named Green Freedom, for removing carbon dioxide from the air and turning it back into gasoline.
The idea is simple. Air would be blown over a liquid solution of potassium carbonate, which would absorb the carbon dioxide. The carbon dioxide would then be extracted and subjected to chemical reactions that would turn it into fuel: methanol, gasoline or jet fuel.
This process could transform carbon dioxide from an unwanted, climate-changing pollutant into a vast resource for renewable fuels. The closed cycle - equal amounts of carbon dioxide emitted and removed - would mean that cars, trucks and airplanes using the synthetic fuels would no longer be contributing to global warming.
Although they have not yet built a synthetic fuel factory, or even a small prototype, the scientists say it is all based on existing technology.
"Everything in the concept has been built, is operating or has a close cousin that is operating," Dr. Martin said.
The Los Alamos proposal does not violate any laws of physics, and other scientists, like George A. Olah, a Nobel Prize-winning chemist at the University of Southern California, and Klaus Lackner, a professor of geophysics at Columbia University, have independently suggested similar ideas. Dr. Martin said he and Dr. Kubic had worked out their concept in more detail than previous proposals.
There is, however, a major caveat that explains why no one has built a carbon-dioxide-to-gasoline factory: it requires a great deal of energy.
To deal with that problem, the Los Alamos scientists say they have developed a number of innovations, including a new electrochemical process for detaching the carbon dioxide after it has been absorbed into the potassium carbonate solution. The process has been tested in Dr. Kubic's garage, in a simple apparatus that looks like mutant Tupperware.
Even with those improvements, providing the energy to produce gasoline on a commercial scale - say, 750,000 gallons a day - would require a dedicated power plant, preferably a nuclear one, the scientists say.
According to their analysis, their concept, which would cost about $5 billion to build, could produce gasoline at an operating cost of $1.40 a gallon and would turn economically viable when the price at the pump hits $4.60 a gallon, taking into account construction costs and other expenses in getting the gas to the consumer. With some additional technological advances, the break-even price would drop to $3.40 a gallon, they said.
A nuclear reactor is not required technologically. The same chemical processes could also be powered by solar panels, for instance, but the economics become far less favorable.
Dr. Martin and Dr. Kubic will present their Green Freedom concept on Wednesday at the Alternative Energy Now conference in Lake Buena Vista, Fla. They plan a simple demonstration within a year and a larger prototype within a couple of years after that.
A commercial nuclear-powered gasoline factory would have to jump some high hurdles before it could be built, and thousands of them would be needed to fully replace petroleum, but this part of the global warming problem has no easy solutions.
In the efforts to reduce humanity's emissions of carbon dioxide, now nearing 30 billion metric tons a year, most of the attention so far has focused on large stationary sources, like power plants where, conceptually at least, one could imagine a shift from fuels that emit carbon dioxide - coal and natural gas - to those that do not - nuclear, solar and wind. Another strategy, known as carbon capture and storage, would continue the use of fossil fuels but trap the carbon dioxide and then pipe it underground where it would not affect the climate.
But to stabilize carbon dioxide levels in the atmosphere would require drastic cuts in emissions, and similar solutions do not exist for small, mobile sources of carbon dioxide. Nuclear and solar-powered cars do not seem plausible anytime soon.
Three solutions have been offered: hydrogen-powered fuel cells, electric cars and biofuels. Biofuels like ethanol are gasoline substitutes produced from plants like corn, sugar cane or switch grass, and the underlying idea is the same as Green Freedom. Plants absorb carbon dioxide as they grow, balancing out the carbon dioxide emitted when they are burned. But growing crops for fuel takes up wide swaths of land.
Hydrogen-powered cars emit no carbon dioxide, but producing hydrogen, by splitting water or some other chemical reaction, requires copious energy, and if that energy comes from coal-fired power plants, then the problem has not been solved. Hydrogen is also harder to store and move than gasoline and would require an overhaul of the world's energy infrastructure.
Electric cars also push the carbon dioxide problem to the power plant. And electric cars have typically been limited to a range of tens of miles as opposed to the hundreds of miles that can be driven on a tank of gas.
Gasoline, it turns out, is an almost ideal fuel (except that it produces 19.4 pounds of carbon dioxide per gallon). It is easily transported, and it generates more energy per volume than most alternatives. If it can be made out of carbon dioxide in the air, the Los Alamos concept may mean there is little reason to switch, after all. The concept can also be adapted for jet fuel; for jetliners, neither hydrogen nor batteries seem plausible alternatives.
"This is the only one that I have seen that addresses all of the concerns that are out there right now," Dr. Martin said.
Other scientists said the Los Alamos proposal perhaps looked promising but could not evaluate it fully because the details had not been published.
"It's definitely worth pursuing," said Martin I. Hoffert, a professor of physics at New York University. "It's not that new an idea. It has a couple of pieces to it that are interesting."