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Carbon Monoxide Catalyst Could Solve Energy and Global Warming Problems

6.30.09   Chris Neil, Energy Economist

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    A catalyst that converts carbon monoxide into carbon and oxygen could solve the world's need for energy, particularly energy that doesn't emit greenhouse gases. In the gasification process, water and a carbon-rich fuel react to produce hydrogen and carbon monoxide. If a catalyst could be developed that would convert carbon monoxide back into carbon and oxygen, the carbon could be used over and over again rather than being used once and producing emissions of the greenhouse gas, carbon dioxide (CO2).

    The Obama administration recently announced the start of the Advanced Research Projects Agency -- Energy. This agency is patterned after the Defense Advanced Research Projects Agency (DARPA) that brought us such innovations as the internet. ARPA-E's assignment is not run of the mill R&D but "technological advances in high-risk areas that industry is not likely to pursue independently." ARPA-E is looking to make major leaps forward in technology by undertaking high-risk concepts with potentially high payoff.

    ARPA-E issued a funding notice on April 27, 2009 to provide an initial $150 million in stimulus bill funding for research projects, with another $250 million coming later. ARPA-E estimates that most awards will be in the range of $2 million to $5 million. Applicants were asked to submit only an 8-page "concept paper" to outline the technical concept by June 10, 2009. Applicants that make the first cut will be asked to submit final applications.

    A project that is fits ARPA-E's high-risk, high-reward criteria is a catalyst that converts carbon monoxide to carbon and oxygen. Carbon dioxide (CO2) is the primary green house gas. One problem with CO2 is that it is a stable compound. Once CO2 is generated, it is difficult to convert it back into carbon and oxygen. There may be ways to convert CO2 back into carbon and oxygen, but that doesn't seem like a very promising avenue of research, not even for ARPA-E.

    A more promising compound is carbon monoxide (CO). Carbon monoxide does not appear to be as stable as CO2. Catalysts have been developed to convert carbon monoxide into CO2 -- that is one of the functions of the catalytic converter on cars. Rather than converting carbon monoxide into CO2, the question is whether a catalyst can be developed that will convert carbon monoxide into carbon and oxygen. The ability to convert carbon monoxide into CO2 using a catalyst gives promise to the possibility of converting carbon monoxide into carbon and oxygen using a catalyst.

    Carbon monoxide is also promising because it is one of the products of gasification of carbon fuels and water. In a gasifier, water and carbon are converted into hydrogen and carbon monoxide. The resultant mixture of hydrogen and carbon monoxide is called syngas. The chemical reaction is shown in Equation 1 below. The carbon can come from coal, natural gas, oil, wood, municipal waste, crop wastes, or other sources abundant in carbon.



    The proposal here is to split the carbon monoxide back into carbon and oxygen. This process is shown in Equation 2. The carbon would be re-used in the reaction. Hydrogen (H2) is produced and is sent to the power plant for power generation or used for transportation. The oxygen (O) shown in Equation 2 would quickly convert to the more stable O2 form and could also be used for power generation.



    It may be necessary to take the syngas out of the gasifier and separate the hydrogen and carbon monoxide. The catalytic reaction converting carbon monoxide back into carbon and oxygen would take place in a vessel separate from the gasifier. The carbon would be fed back into the gasifier to continue the process.

    An ideal catalyst would be able to work within the gasifier, however. The carbon monoxide would be converted almost instantly and continuously back into carbon and oxygen. This also means that water would be continuously converted into hydrogen and carbon monoxide in the gasifier. Another possible advantage of working in the gasifier is that the elevated temperature and pressure of the gasifier might make it easier to accomplish the catalytic reaction converting carbon monoxide back to carbon and oxygen. Trying to accomplish this catalytic reaction at room temperature may be impossible, but doing it in a gasifier at a temperature of several hundred degrees may be an entirely different story.

    Reusing carbon through the catalytic reaction means that the fuel for this type of power plant is water. Hydrogen is split out of water using carbon. If the carbon can be re-used, then water becomes the primary fuel.

    Some may doubt that water is a realistic fuel for power plants. Water is already being used for fuel in power plants. Water is a significant part of the fuel used in the syngas of existing IGCC plants, as shown in the IGCC reaction in Equation 1. Water would be almost the entire fuel for IGCC plants that have carbon capture and sequestration. Carbon from coal is not the fuel for IGCC plants that have carbon capture and sequestration. The entire carbon stream is stripped out and never enters the power generation module. Hydrogen is the only fuel that would enter the power generation module (assuming 100% carbon capture). The purpose of the carbon (coal) in an IGCC plant that has carbon capture and sequestration is to hydrogen out of water (again, assuming 100% carbon capture). GE says that water would contribute about 85% of the total hydrogen in a coal-fired IGCC plant and the other 15% would come from the hydrogen in coal. The IGCC manufacturers maintain the fiction that coal is the fuel because power-plant people are more comfortable with coal-fired power plants than with water-fueled power plants. The manufacturers even report heat rates (fuel burn rates) for coal usage, even though coal would never enter the power generation module. It just turns out that the amount of carbon required to split hydrogen out of water in a once through process is about the same amount as would be required if the carbon were burned directly. Coal-fired IGCC power plants with carbon capture and storage are called "clean coal" plants. Clean coal plants are fueled with water.

    The existing IGCC approach can be thought of as once-through carbon usage for converting water into hydrogen and carbon monoxide (syngas). The proposal here is to develop a catalyst so that the carbon can be used over and over again rather than only once. Rather than bring millions of tons of coal and producing millions of tons of CO2, it would certainly seem better to try to re-use the carbon. A catalyst would enable the carbon to be re-used.

    The only fuel for this system would be water. But this does not mean that the generation costs would be "too cheap to meter," as once was expected of nuclear power. Like nuclear, there would be substantial capital costs. Gasifiers are expensive. The combined cycle power module is also expensive. The plant may also need a module to separate hydrogen and carbon monoxide and a module for the catalytic reaction to convert carbon monoxide back into carbon and oxygen (unless the ideal catalyst could be developed and the catalytic reaction took place in the gasifier).

    Gasifier capital costs are probably the second most important factor in determining the economic viability of this approach, after developing a catalyst. If a gasifier costs less than about $1,000 per kilowatt of installed capacity, then this process would likely be highly economic. Gasifiers could be widely added to existing plants and used in new power plants. If gasifiers cost $2,000 to $3,000 per kilowatt of installed capacity, however, then this approach will likely be adopted only slowly and with significant government prodding.

    Reduced capital costs for the gasifiers might be possible if gasifier modules were built overseas and shipped to the U.S., which is an approach that has been used to reduce capital costs for many power plant components. These gasifiers would be limited in size due to shipping restrictions. Power plants with barge access might have advantages over plants that had only rail or highway access due to the ability to obtain larger gasifiers with less expensive transportation costs. Multiple gasifiers may be required for larger power plants. Multiple modular gasifiers would be beneficial, however, in that they would increase reliability as one gasifier going down would not take the entire plant down. Multiple gasifiers could also increase capacity factor by incorporating a spare gasifier. Then an individual gasifier module could be taken out for maintenance and the remaining gasifier modules would keep the power plant running at full capacity.

    The carbon monoxide catalyst is likely to be expensive. The initial catalyst charge would add to the initial capital costs of the plant. Some catalyst replacement over time will probably be needed, which would add to operations and maintenance (O&M) costs.

    There would probably be some fuel costs associated with this type of power plant. The regeneration of the carbon might not be perfect. Some carbon dioxide is created in the gasifier and some of the carbon might slip past the catalyst and be burned in the power generation module. As a rough guess, a plant like this might use 10% to 20% as much fuel as a regular coal-fired or IGCC power plant (which implies 80% to 90% carbon sequestration).

    Thus, new carbon monoxide catalytic regenerative power plants are likely to have electric generation costs of the same order of magnitude as today's new power plants given their capital, O&M and fuel costs. The carbon monoxide catalytic regenerative power plant would implicitly sequester carbon, however, while existing plants would not or would do so only with much additional cost. Thus, re-cycling carbon monoxide back to carbon would be an inexpensive approach to reduce greenhouse gas emissions and address global climate change.

    While IGCC plants are normally thought of as coal-fired plants, natural gas becomes a viable fuel for base load operation if catalytic regenerative power plants would use only 10% to 20% as much fuel as a conventional power plant. This means that a large fleet of gasification power plants could be quickly created by adding gasifiers to the existing natural gas-fired combined cycle plants. Adding gasifiers to existing plants would also be much less expensive and involve fewer permitting issues than building new power plants from scratch. Roughly 200,000 MW of natural gas-fired combined cycle power plants were built during the boom period of the late 1990s and early 2000s, which amounts to about 20% of the total installed generation capacity in the U.S. This large fleet of under-utilized natural gas-fired combined cycle plants could be converted to carbon monoxide regenerative plants by adding gasifiers (and, if necessary, carbon monoxide separation and regeneration modules). The fuel cost savings would pay for a substation portion of the gasifier capital costs.

    Converting a portion of the fleet of existing natural gas-fired combined cycle plants to catalytic regenerative power plants and operating them in base load duty would displace coal-fired generation and reduce large amounts of CO2 emissions. Over time (say 15 to 20 years), this type of conversion might be able to reduce electricity-related CO2 emissions by over 80%. This is the type of game-changing strategy that ARPA-E is targeting.

    While the focus of this analysis has been on power generation (because of the author's background in the power industry), catalytic regeneration could also have a significant impact on transportation. The first way to impact transportation would be to have electric and plug-in hybrid vehicles that would be charged over-night by catalytic regeneration power plants. The second way would be to use catalytic regenerative gasifiers to provide hydrogen for hydrogen-powered vehicles. Corner service stations or fleet operation centers could have a natural-gas-fired gasifier that would provide hydrogen. The hydrogen could initially fuel internal combustion engines pending the eventuality of reasonably-priced fuel cells. It would be even better if hydrogen vehicles were plug-in hybrids in order to minimize the use of hydrogen in the vehicle. There are still issues with hydrogen for transportation, such as fuel tanks, but a way to produce modestly-priced hydrogen is the essential first step that can be addressed if a carbon monoxide catalyst can be developed. In this way, the country could move off of imported oil and reduce greenhouse gas emissions from transportation.

    This may not work, or the development of a catalyst to convert carbon monoxide into carbon and oxygen could lead to a disruptive technology. The author is not a researcher on catalysts. Those with catalysts backgrounds are encouraged to propose this type of project to ARPA-E, and ARPA-E is encouraged to pursue research projects to investigate and develop catalysts that could convert carbon monoxide to carbon and oxygen.

    The opinions expressed here are solely those of the author and do not reflect the position of any other organization.

     

    Readers Comments

    Date Comment
    Roger Arnold
    6.30.09
    Yes, a perpetual motion machine would indeed be a wonderful solution to our energy problems. The DOE should be funding efforts to overthrow those nasty laws of thermodynamics!

    Chris, as you say, you are not a researcher on catalysts. A fundamental rule of catalysts is that they change the equilibrium concentrations or the energy balance of reactions in which they participate. They only change the speed of the reactions, and enable reactions to proceed at lower temperatures than what would be feasible in the absence of the catalyst.

    There is no possibility of catalyzing the splitting of CO into C and O, because energy is needed to do so, and catalysts don't supply energy.

    Water, BTW, is not a "fuel" in gasification. It's the source of hydrogen, yes, but the energy to liberate the hydrogen from water comes from the oxydation of carbon -- the true fuel for the reaction.

    Roger Arnold
    6.30.09
    Oops, sorry, meant to say that catalysts do not
    Roger Arnold
    6.30.09
    Arghhh, what's wrong with my typing fingers. Apparently I can't even close the bolding properly... Catalysts do not change the equilibrium concentrations or the energy balance of reactions ..

    Len Gould
    7.6.09
    An intriguing approach. My question regarding Roger's comment is "Has Roger identified a game-breaking flaw in the author's logic, or has the author simply missused the term catalyst when he should have identified a different term?". Personally, I think the only thermodynamic flaw Roger has pointed out is the energy balance issue, and IF that were the only flaw, perhaps the necessary input energy could be found somewhere else? Arggg. Now I see Roger's point. It would require at least ALL the energy provided by re-combining the H with the O to provide the needed energy to the reaction to separate the C from the O.

    Len Gould
    7.6.09
    Might still be an interesting process if the required energy were provided from concentrated solar.

    Roger Arnold
    7.6.09
    Ouch! You're right, Len. A chemical system to enable photolytic reduction of CO to C + O2 is entirely within the rhelm of possibility. It could even prove to be a technological "breakthrough" of exactly the sort that ARPA-E was set up to encourage.

    It wouldn't be a single catalyst, of course; it would have to be a system of enzymes and intermediates that operate together to enable sunlight to drive the reaction. An alternative type of photosynthesis, in effect. But that could be quite interesting. And it isn't too much of a breech for someone to label the system, informally, as "a catalyst for reduction of carbon monoxide" to carbon and oxygen.

    I came down on Chris too hard, too quickly. My appologies, Chris.

    Len Gould
    7.7.09
    I see that in 1973, Michael Mentzoni published a paper at http://www.iop.org/EJ/abstract/0022-3727/6/4/314 in the abstract of which he discusses using microwaves at a frequency of 9·361 GHz to separate C from O in carbon monoxide... Certainly not much help initially, as generating the microwaves MUST take more energy than available from the H2 out of the process. If only sunlight could be cheaply down-converted to microwaves (or natural sunlight could do the job of the microwaves?)

    Len Gould
    7.7.09
    Sandia's "Sunshine to Petrol" project http://www.sandia.gov/news/resources/releases/2007/sunshine.html proposes to convert 2 CO2 into 2 CO + O2 using only solar energy. From there they propose using the CO to produce either liquid fuels (methanol etc) or H2 ? Last news Dec 2007,

    Richard Vesel
    7.7.09
    Gentlemen,

    Let's look at the overall process from a slightly higher altitude:

    2 H2O + energy --> 2 H2 + O2

    This is accomplished in any number of ways, and basing it around a process which requires one to turn the H2O into steam, run it through a gasifier, hope for some miracle catalyst or process to reverse the formation of CO back such that the O may be recovered - well, it seems to me that it's a long route to a nearby destination.

    How about just taking the sunlight to generate electricity for direct consumption, already available at costs below $3/w (on large scales) - OR - if a transportable fuel is required, make H2 or CH4 (using biocarbon, not fossil carbon). I like the methane route, because we already have all the infrastructure for methane in place.

    Regards, RWVesel

    Mel Zwillenberg
    7.7.09
    I once taught thermodynamics to mechanical engineering students, and he would get an F- in my class!

    First of all, catalysts change the rate of reactions but do not vchange the equilibrium composition, and the equilibrium composition of a mixture of carbon and oxygen is a mixture of CO2 and CO, depending on the relative proportions of C and O2.

    Secondly, the reaction 2CO -> 2C + O2 is endothermic (absorbs heat), so energy must be input to make it go. When carbon reacts with oxygen to form CO, energy is released, and to reverse the reaction, the same amountof energy must be input. More energy is released when CO reacts with oxygen to form CO2, but Mr. Neil does not want CO2 to be produced.

    IThe reactions proposed are a net consumer of energy. If you want to input energy to make them go, it would be simpler and more efficient to simply use that external energy directly.

    Efstratios Psarianos
    7.7.09
    Is it just me, or are Richard Vesel and I the only ones who came up with the flaw in the flaw in Mr. Neil's reasoning? I mean, halfway through the article, the fact that energy has to be added INTO the system top make it work struck me as the obvious counterargument.

    No matter what, 2H2O + energy = 2H2 + O2. Always. No matter what path one follows from start to finish.

    Really, guys ... F- to you all, with Mr. Vesel as the gold-star exception. For Heaven's sake, they teach this kind of elementary energy-balance in high school!

    And Mr. Neal: best have someone technically proficient review chemistry-based issues before you publish. By way of analogy, I myself would be embarassed to have invented a 'perpetual money machine' and have it shot down by economists. And that despite the fact that I might confuse a few into believe in it for a while.

    Don Hirschberg
    7.7.09
    Before I could respond others had awarded well-deserved F’s to the author as well as to several of those making comments. I’ve seen some clever perpetual motion schemes that took some effort to expose but this one has no guile at all.

    I have often been accused of being a “negative thinker”, or being unable to think “outside the box.” Unfortunately my accusers cannot comprehend that science and arithmetic are as useful in telling us what cannot be done as what might or can be done.

    Thermodynamics is much simpler than economics. Two economists can say contradictory things and each gets a Nobel prizes for his brilliant theory. Not so in the simple world of thermodynamics. Alas they would have your scalp.

    Chris Neil
    7.8.09
    For simpliciity, I didn't include a second reaction that is going on in the gasifier:

    C + O2 --> CO2 + Energy

    This reaction, commom burning of carbon, is the reaction that provides the energy needed to run the gasifier. That is, some of the carbon is used to provide energy and some of the carbon is used to split hydrogen out of water. The gasification process can be turned, to a certain extent, to produce more energy or more hydrogen and carbon monoxide. Normally, about 30% of the carbon is being used in this first reaction to produce energy. That leaves lots of room for producing more energy if it is necessary.

    Most of the comments state that catalysts won't change the energy required for this reaction. Roger Arnold says in the first comment that catalyts can change the temperature at which a reaction occurs. This is what I am to accomplish. If it would take 1,000 degrees to convert carbon monoxide into carbon and oxygen without a catalyst but 500 degrees with a catalyst, then this could be successful since the gasifer gets to something like 500 degrees.

    Don Hirschberg
    7.8.09
    Come on fellas, give it up.

    What this article proposes has been known to be impossible for over a hundred years. Yet such schemes piled up at the Patent Office. So, long ago they had to institute a blanket polilcy to grant no patents to schemes that violated the laws of thermodynamics. A perpetual motion machine is as undebatable as is a flat earth.

    Chris Neil
    7.9.09
    The thermodynamists criticized my analysis, saying that I was making a perpetual motion machine.

    The reactions, with an energy component are:

    H2O + EnergyH2O -> H2 + O Reaction 1

    C + O -> CO + EnergyCO Reaction 2

    C + O2 -> CO2 + Energy CO2 Reaction 3 – Burning Carbon

    The thermodynamists that the system was impossible or that it was a perpetual motion machine because they didn’t know that about reaction 3. The thermodyamists thought that the energy relationship was that the amount of energy used to split the water came from the energy given off when the carbon monoxide was formed, as shown below. They thought that to reverse the carbon monoxide would require the entire amount of energy already given up.

    EnergyH2O = EnergyCO Wrong thermodynamic Equation

    The energy required to split the water actually comes from both the reaction forming carbon monoxide and the burning of carbon to form carbon dioxide (reaction 3). In fact, most of the energy input into the system comes from the burning of carbon in Reaction 3. The amount of energy given off converting carbon to carbon monoxide is fairly small.

    Energy H2O = Energy CO + Energy CO2 Right Thermodynamic Equation

    What I have proposed is to reverse Reaction 2 and split the carbon monoxide back into carbon and oxygen. The thermodynamists have assured me that the amount of energy required to do this reaction is the same amount of energy that was given off in forming the carbon monoxide, with or without a catalyst. That is,

    CO + EnergyCO -> C + O Reaction 4

    I believe that this thermodynamic analysis continues to support that this is a viable process. Not as good as I had hoped, but still very useful way to reduce fuel use and emissions. If a catalyst had been able to magically convert carbon monoxide into carbon and oxygen, the process would have reduced fuel use and carbon emissions by about 70%. The other 30% of the fuel was burned to create the energy needed to split the water. To emphasize: most of the energy is used to split water.

    There is not a lot of energy given off when carbon is made into carbon monoxide. Therefore, it won’t take a lot of energy to split carbon monoxide back into carbon and oxygen; far less than required to split water. The amount of fuel that must be burned in order to split the water and split the carbon monoxide might increase to something like 50% of the fuel, but that means that the process would use only 50% as much fuel as a conventional IGCC and have 50% less carbon emissions.

    For example, suppose the gasifier in a conventional IGCC plant normally operated at 1,000° and produced hydrogen, carbon monoxide and carbon dioxide. The temperature and pressure could be increased to the point that carbon monoxide would split into carbon and oxygen, say 1,300° by using a greater proportion of fuel (carbon) to be burned to givee off energy and carbon dioxide. At this point, as soon as the carbon monoxide was produced, it would convert back into carbon and oxygen. Some of this carbon would react with water to split it into hydrogen and oxygen. Some would be burned to create energy and CO2. The net result of raising the temperature and pressure to the point that carbon monoxide would split into carbon and oxygen, however, is that only about half as much fuel would be required. Most of the energy is being used to split water into hydrogen and oxygen; not that much more would be needed to split carbon monoxide into carbon and oxygen. A conventional IGCC has a heat rate of about 8,500 Btu per kWh. The carbon monoxide recycling approach might have a have a heat rate of 4,000 Btu/kWh to 5,000 Btu/kWh. Re-using the carbon monoxide would represent a significant improvement in fuel use and carbon emissions.

    David Smith
    7.9.09
    While we're giving out F-'s, how about a big fat F- to the Obama Administration for wasting taxpayer dollars and/or incurring more useless debt in support of these intellectually imploded schemes? Or does that Cult of Idiocy really believe they can change the laws of physics? I suspect it is the latter, given that the underlying impetus for these schemes - the cultish belief in anthropogenic climate change via CO2 emissions - is the poster child for violating the laws of physics.

    David Smith Moscow, ID USA

    Richard Vesel
    7.10.09
    Mr. Neal,

    Regarding your last expanded comment. My response is: Why bother???

    You are simply identifying the fact that you are playing a zero-sum game (ideally). With process inefficiencies included, you are going to get a nagative result - your proposed mechanism will net less useful energy out than just burning the carbon directly. You propose scavenging energy from the C + O2 --> CO2 reactions to reverse the CO formation. It is more efficient, and yields the SAME net CO2 output to just continue with 2CO + O2 --> 2CO2.

    PLEASE, learn the science and numbers behind what you are considering before putting it forth as a legitimate proposal.

    Regards, RV

    Richard Vesel
    7.10.09
    Sorry - Mr. Neil, not Neal...my apologies for the misspelling

    Len Gould
    7.13.09
    As skewed is the proposal is the dragging in of the Obama administration and the Global Warming debate. Honestly, some people can see conspiracies to incompetence in anything which doesn't add more dollars to their own pockets.

    Jerry Watson
    7.13.09
    Wow, I realize I am not much of a writer but Energy Pulse published this? I have actually worked at an IGCC plant. I was a control room operator and then an operations team leader before being promoted into energy trading for a utility. I am not an engineer but I recognize this as article as being ridiculous on several levels. First the CO produced at an IGCC plants is a good thing since the reaction is completed in gas turbine and produces KWs as does the burning of the hydrogen. A great syngas gasifier for power production would produce only CO and Hydrogen with very little CO2. The CO and hydrogen would be separated and the CO used as fuel for a combustion turbine to generate power and the hydrogen reformed with more carbon to produce the more valuable liquid fuels. Secondly, IGCC’s are not fueled by water at all they are carbon fueled. In simple terms carbon is more reactive than hydrogen and in the oxygen starved gasifier carbon strips the oxygen from the water to form CO and CO2. The Carbon process is exothermic and hydrogen process endothermic. The reaction is not even self-sustaining additional heat energy is needed and provided by the formation of CO and CO2 with the oxygen and carbon supplied to the gasifier Working at the IGCC plant was one of the most enjoyable times in my career but it left me with one huge answered question. Why? The IGCC heat rate is attainable with high temp supercritical units as are the emissions reductions for far less capital input. IGCC is a great way to bring a large chunk of dollars into a rate base to recover and make a return on without adding a lot of total megawatts, which I feel is at least unethical. I think that gasification is a great thing if CO2 emissions do not matter and it is used for its original purpose which was to produce hydrogen to be used in the production of liquid fuels. The Chinese intend to do just that using the massive Mongolian reserves to supply the coal to make liquids fuels. It is a valid concept the water-CO2 shift that produces hydrogen from a carbon fuel source. The hydrogen separated from the water can then be reformed with carbon to produce liquid fuels. However, a gasifier is not a CO2 abatement tool on the contrary is a device to more rapidly and fully use carbon resources to produce energy and liquid fuels with the side effect of massive CO2 production. It is a trade off device to swap carbon and energy for hydrogen. I even agree with the original DOE funding because the potential heat rate looked impressive however the plants efficiencies have turned out not to be very impressive. It is simply a complex and capital intensive way of burning coal with little if any advantage over state of the art steam plants. Now for some reason we can’t say “hey you know it really doesn’t produce the expected results.” It needs further research to produce a process that gives a return that justifies the additional capital outlay. Gasification may have some advantages in CO2 sequestration but separating and storing the CO2 upstream of the turbine will further reduce efficiency. At some point generators will be better served to purchase PRB coals and coke them just burning the volatile components as fuel source and rebury the coke (carbon).



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