MIT and Coal Conversion Economics


We present the enclosed and attached from a surprising Friend of Coal, the Massachusetts Institute of Technology, for a couple of reasons.
 
First, we have lately been documenting the "Tri-reforming Process", as described by Penn State University, and others, as a technology which can productively recycle the Carbon Dioxide byproduct of our coal-use industries into valuable fuels and chemicals.
 
Penn State's technology specifies the use of Methane as a co-reactant with Carbon Dioxide, and we wanted to again document that, although Methane can be synthesized from Carbon Dioxide via Sabatier-type processes, it can also be generated from coal.
 
Although anyone who has spent any time in coal country should know that fact almost intuitively, we feel compelled to document, authoritatively, each and every of our assertions, since the science of coal conversion seems to have many, some surprising, opponents and detractors.
 
We note, as well, and will, in future dispatches, further document, that, once Methane, or "Synthetic Natural Gas", is produced from coal, not only can it serve as a reactant for Carbon Dioxide to make useful organic products in the Tri-reforming Process, it, too, can be directly converted into liquid fuels and organic chemical manufacturing raw materials; most especially Methanol, which itself is a valuable liquid fuel and can be further catalyzed, as we have tediously documented, into gasoline.
 
In any case, some excerpts from the attached and enclosed, with comment interspersed and following:
 
"Thermodynamic Analysis of Coal to Synthetic Natural Gas Process  

Lei Chen, Rane Nolan, Shakeel Avadhany
 
Supervisor: Professor Ahmed F. Ghoniem
 
Mechanical Engineering, MIT  and Materials Science and Engineering, MIT
77 Massachusetts Avenue, Room 3-335
Cambridge, MA 02139-4307
Submitted: May 11th, 2009
 
Abstract Natural gas is a clean energy source of the fossil fuels that dominates today’s energy supply. The Coal-to-Synthetic Natural Gas (SNG) concept has been successfully demonstrated as a feasible energy production concept. As a final report for term project of Fundamentals of Advanced Energy Conversion, the scope of this research includes a state-of-the-art technologies review for Coal-to-SNG, the thermodynamic parametric study of main components in this process, and the efficiency assessment of the overall energy system implementing different gasification technologies, as well as the novel hydromethanation process. ... Hydromethanation is a promising novel route with about 70% energy efficiency; however it is still under development because of the technique challenges on catalysts."
 
(In the available literature, "challenges on catalysts" in coal conversion processes are frequently noted; primary among those challenges being carbon deposition. Without citation, we submit that catalyst reactivation techniques have been developed. Catalyst deactivation seems to be a known and quite solvable problem. - ) 
 
"According to the United States Department of Energy, 90% of all new baseload power plants will be fueled by natural gas. The sudden increase in demand for natural gas will make its price point skyrocket. This presents an opportunity for novel ways to introduce supply into the market. One of these novel ways includes the conversion of coal, an abundant fossil fuel resource in the U.S., to SNG (Synthetic Natural Gas). SNG can be produced from coal, petroleum coke, biomass, or solid waste. The carbon containing mass is gasified and then converted to methane, a large component of natural gas."
 
(That categorical statement, "coal ... is gasified and then converted to methane",  is all we really need to document from this MIT report, for the purpose of supporting our thesis that the Methane needed for Carbon Dioxide recycling can be obtained from coal. But, as we will further document in future correspondence, not only can the methane extracted from coal be used to reform CO2 into liquid fuels, it can itself be directly catalyzed into liquids, including Methanol, which, aside from being a valuable liquid fuel in it's own right, is an extraordinarily versatile raw material for the manufacture of gasoline and plastics.)
 
"From a national security standpoint, SNG presents a means to alleviate the reliance on imported energy resources by making the most of an abundant American resource. SNG could be liquefied and transported throughout the U.S. via existing pipeline infrastructure already in-place."
 
(That "abundant American resource" would, of course, be coal.)
 
"A Coal-to-SNG system converts solid hydrocarbons such as coal, biomass or petroleum coke into SNG. A conventional approach for Coal-to-SNG is by a process of gasification, gas shift, and methanation. This “indirect” approach has been demonstrated in the Great Plains Synfuel Plant for 20 years and proven to be successful in application. More recently, advancements have been made on the “direct” gasification approach by the Great Point Energy. This mechanism involves hydromethanation and circumvents the
processes of gasification and water gas shift.
 
The hydromethanation, or catalytic steam gasificaiton technology, is considered to be more energy-efficient than the traditional methanation processes. This process was initially developed by Exxon in the 1970s using potassium carbonate (K2CO3) as a catalyst. However the process is still under development and not commercialized."
 
(Exxon! Yet again! But, why is their "more energy-efficient" "hydromethanation" process for coal gasification not, apparently, being reduced to practice, except, perhaps, in China?)
 
"Hydromethanation (Catalytic steam gasification) - The direct method of Coal-to-SNG is a process that performs the same function as the indirect method, except eliminates three of the six steps. With less steps of energy conversion, there is an increase in end-to-end efficiency of producing SNG from the coal. ... In this process, gasification and methanation occur in the same reactor in the presence of a catalyst. Steam is the only gasification agent used so that gas shift and methanation steps are no longer necessary."
 
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Note that we have many times documented the use of steam, as above, as an agent that can help to effect the "methanation" of both Coal and CO2. Herein, it seems that steam serves to eliminate other, costly, steps in the conversion process.
 
MIT's report continues with many calculations, illustrations, chemical descriptions and references that are far beyond our scope, and our limited grasp.
 
However, we can close with one clear quote:
 
"Traditional coal-to-SNG process has been demonstrated to be feasible in synthetic fuel production."
 
If we want to obtain Methane from Coal, for the Tri-reforming of Carbon Dioxide, we can do so. And, as we will further document, if we do extract Methane from Coal, we can as well directly convert that Methane into liquid fuels compatible with our current transportation infrastructure.

And More Japan CO2 Recycling

 
As with research and development of coal liquefaction and carbon dioxide conversion technologies we've cited from other nations, there seems to be, in Japan, one persistent champion of CO2 recycling: Kiyohisa Ohta, of Mie University's Environmental Preservation Center.
 
We submit herein a series of three reports, with links and excerpts, the first one attached as a file. All are authored, in part, by Ohta, and they demonstrate that Carbon Dioxide is, indeed, a resource of value that we should devote ourselves to finding ways in which it can be more profitably utilized, rather than, temporarily and at great unproductive cost, be disposed of.
 
First up is the most recent. The other links and excerpts follow, documenting that the science for recycling, for utilizing, Carbon Dioxide is, in Japan, understood and undergoing continuous improvement. 
 
We have edited heavily, and added comments interspersed and following:.
 
"Electrochemical and Photoelectrochemical Reduction of Carbon Dioxide in Metal Powder-Suspended Methanol
 
Yousuke Ueno, Satoshi Kaneco, Tohru Suzuki, Hideyuki Katsumata and Kiyohisa Ohta 

1 Department of Chemistry for Materials, Faculty of Engineering, Mie University, Japan
2 Environmental Preservation Center, Mie University, Japan
 
Abs. 66, 206th Meeting, © 2004 The Electrochemical Society, Inc

1. Introduction 
... carbon capture prefers a relatively pure stream of the gas. Pathways for carbon capture come from potential sources such as several industrial processes which produce highly concentrated streams of CO2 as a byproduct, power plants which emit more than one-third of CO2 emissions worldwide and the production method of hydrogen fuels from carbon-rich feedstocks. CO2 can be removed from the gas streams by physical and chemical absorption. Recently, the chemical absorption using amines represents the most widely deployed commercial technology for capture. However, in other commercial applications, the typical solvents for physically absorbing CO2 include glycol-based compounds and cold methanol.
 
(Keep in mind that methanol can be itself synthesized from Carbon Dioxide, or Coal. But, Penn State University, as documented, has been at work on "Tri-reforming" technology which, as our limited capacity allows us to understand it, enables the use of raw flue gas in similar CO2 transformations, and the costs of purifying and concentrating CO2 are thus eliminated. Also recall that Sandia National Lab has, as have others, been developing economical technologies to extract nearly-pure CO2 from the atmosphere. - JtM)
 
Methanol is a better solvent of CO2 than water, particular at low temperature, because the solubility of
CO2 in methanol is approximately five times that in water at ambient temperature and eight to fifteen times that in water at temperatures below 0 oC. Therefore, methanol has been industrially used as the physical absorbent of CO2 in Rectisol method at low temperature. Currently, over 70 large-scale plants apply the Rectisol process.
 
Recently, many investigators have actively studied the electrochemical reduction of CO2.
 
Results and discussion
In the electrochemical reduction of CO2 at Pb electrode in methanol without the copper powder, the main reduction products from CO2 were carbon monoxide and formic acid. However, in the presence of copper
powder, hydrocarbons such as methane and ethylene were formed by the electrochemical reduction of CO2 in methanol. ... The same phenomena were observed at Zn electrode." 
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Again, we were compelled to edit out much discussion, which includes the now-obligatory genuflections to the dangers of human-derived CO2. But: Carbon monoxide, as produced herein, has applications in hydrocarbon syntheses, including those targeted on fuel production; and, formic acid, among other things, can be used in fuel cells. Methane and ethylene, as we've documented, can be used to synthesize liquid fuels. Methane, especially, can be combined, "reformed", with even more Carbon Dioxide to create more complex hydrocarbons, including Methanol. 
 
Ohta, and other colleagues, have been at this work for quite some time, as evidenced by the following, earlier report, wherein efficiency improvements for the conversion of Carbon Dioxide, into hydrocarbons appropriate for a variety of uses, including further processing into fuels, are documented:
 
 
The excerpt:
 
"Electrochemical Reduction of Carbon Dioxide to Hydrocarbons with High Efficiency
 
Satoshi Kaneco, Kenji Iiba, Syo-ko Suzuki, Kiyohisa Ohta, and Takayuki Mizuno
[Unable to display image]Department of Chemistry for Materials, Faculty of Engineering, Mie University, Japan
J. Phys. Chem. B, 1999, 103 (35), pp 7456–7460
August 13, 1999
Copyright © 1999 American Chemical Society
 
The electrochemical reduction of CO2 with a Cu electrode in LiOH/methanol-based electrolyte was investigated. A divided H-type cell was employed, the supporting electrolytes were ... lithium hydroxide in methanol and potassium hydroxide in methanol. The main products from CO2 were methane, ethylene, carbon monoxide, and formic acid. The maximum current efficiency for hydrocarbons (methane and ethylene) was of 78% ... the efficiency of hydrogen formation, a competing reaction of CO2 reduction, was depressed to below 2% at relatively negative potentials. On the basis of this work, the high efficiency electrochemical CO2 to hydrocarbon conversion method appears to be achieved. ... This research can contribute to the large-scale manufacturing of fuel gases from readily available and inexpensive raw materials, CO2-saturated methanol from industrial absorbers ... ."
 
Again, the Methanol, in which this "high efficiency electrochemical CO2 to hydrocarbon conversion" takes place, can itself, as we have documented, be synthesized from either Carbon Dioxide or Coal - your choice. But, in any case, it is noted that "high efficiency ... CO2 to hydrocarbon conversion ... (is) ... achieved" and these results "can contribute to the large-scale manufacturing of fuel gases from readily available and inexpensive raw materials", i.e., Carbon Dioxide.  
 
We wonder why we haven't been informed of the good news.
 
In any case, Ohta's trail reaches even further back, and we believe we've cited Ohta, et.al., a few other times, in earlier and separate dispatches, as well. A full review of his literature might be rewarding. In any case, following, it's reported that, more than 15 years ago, it was known that CO2 could be broken apart electrochemically, at temperatures and conditions easily achievable in industrial practice. As in:
 
 
"Electrochemical reduction of carbon dioxide in methanol at low temperature 

A. Naitoh, K. Ohta, T. Mizuno, H. Yoshida, M. Sakai and H. Noda

Chubu Electric Power Co. Ltd., Nagoya, 461, Japan

Department of Chemistry for Materials, Mie University, Mie, Tsu, 514, Japan

April 1993

Abstract

The electrochemical reduction of carbon dioxide in methanol has been investigated at low temperature. The electrolysis with a copper cathode and a platinum anode was performed in methanol ... . By the electrochemical reduction in methanol  ... carbon monoxide, methane and ethylene ... were produced from carbon dioxide at 0°C. At −15°C, 24.0% carbon monoxide, 39.1% methane and 4.4% ethylene were obtained. Under the optimal experimental conditions, the Faradaic efficiency of hydrocarbons such as methane and ethylene were better than that obtained in aqueous catholyte."

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A large percentage of "carbon monoxide" might not initially sound all that exciting. But, it is, unlike Carbon Dioxide, highly reactive and most definitely can be used in the syntheses of organic chemicals - additional hydrocarbon fuels included. 

But, note: We do obtain a high percentage of Methane. With that, we can, as per the Penn State University process, "Tri-reform" more Carbon Dioxide into more, and more useful, hydrocarbons.


A choice we all have, it seems, is to reclaim and recycle our Carbon Dioxide into valuable and versatile "Hydrocarbons with High Efficiency", rather than to tax our coal industries out of existence for making it for us, or to force them to stuff it all down a leaky geologic sequestration rat hole.

Colorado Converts CO2 to Methane


 
In light of our recent dispatches concerning Penn State University, and the work there, of Chunsan Song and Craig Grimes, on the practical recycling, into valuable hydrocarbons, of Carbon Dioxide, through the process of "Tri-reforming", we wanted to further substantiate that the Methane which is, in Penn State's technology, required for the reforming of CO2, can itself be synthesized from CO2.  
 
We thus submit the enclosed link and following excerpt by way of even further confirmation that Methane can be synthesized from Carbon Dioxide.
 
Comment follows:
 
"Methanation of carbon dioxide by hydrogen reduction using the Sabatier process in microchannel reactors  
 
Kriston P. Brooks, Jianli Hu, Huayang and Robert J. Kee

Pacific Northwest National Laboratory, Richland, WA 99352, USA

Engineering Division, Colorado School of Mines, Golden, CO 80401, USA

July 2006 


Abstract

This paper describes the development of a microchannel-based Sabatier reactor for applications such as propellant production on Mars or space habitat air revitalization. Microchannel designs offer advantages for a compact reactor with excellent thermal control. This paper discusses the development of a Ru–TiO2-based catalyst using powdered form and its application and testing in a microchannel reactor. The resultant catalyst and microchannel reactor demonstrates good conversion, selectivity, and longevity in a compact device. A chemically reacting flow model is used to assist experimental interpretation and to suggest microchannel design approaches. A kinetic rate expression for the global Sabatier reaction is developed and validated using computational models to interpret packed-bed experiments with catalysts in powder form. The resulting global reaction is then incorporated into a reactive plug-flow model that represents a microchannel reactor."

First, mention of the Nobel Prize-winning "Sabatier process" should not be unfamiliar to any of our readers. We remind you that this Carbon Dioxide conversion and recycling technology is now being employed and further developed by NASA, as we have documented, although NASA isn't named in this Abstract. We have already quite thoroughly documented for you NASA's, and the USDOD's, development of CO2 recycling technologies.

And, so, we can make the useful product, Methane, from Carbon Dioxide, in a "compact device" that "demonstrates good conversion, selectivity, and longevity".

Then, once we have made Methane, from Carbon Dioxide, we can use it, in the "Tri-reforming" process described by Chunsan Song, at Penn State University, and others, as we have documented in these reports, to convert even more Carbon Dioxide into valuable hydrocarbons.

Note: This comes from yet another of our Federal, tax dollar-supported US National Laboratories and a school within a public, state university that was founded specifically on the profitability of the mining industry. 

Doesn't it seem so strange to you, as it does to us, that we citizens of US Coal Country haven't heard anything about any about it?

Finally, isn't it interesting how, in the body of the Abstract itself, neither Carbon Dioxide nor Methane is mentioned, even once? That, when those two resources are what this entire study is all about.

Methane Misdirection

 
We have been documenting the fact that Carbon Dioxide, rather than being an intractable pollutant, an obnoxious gas that we must punish our coal industries for producing, is, instead, a valuable raw material resource from which we can manufacture liquid fuels and useful industrial chemicals.
 
Toward that end, we have lately been reporting on the "Tri-reforming" process, as described by multiple sources, but most thoroughly by Penn State University, wherein Carbon Dioxide can be reacted with Methane to synthesize valuable and versatile liquid fuels and chemical manufacturing raw materials.
 
We have documented that Methane, needed for the reforming of CO2 into liquid fuels, can itself be manufactured from CO2, and from coal.
 
However, much as the true, "raw material", nature of Carbon Dioxide has, we would contend deliberately, been obscured, and CO2 itself demonized, we have discovered that the valuable Methane, too, has been subjected to some concerted effort to make it also appear as a pollutant that must be collected and somehow disposed of, rather than as a resource which could, and should, be used to it's fullest potential as a co-reactant for CO2 in the manufacture of liquid hydrocarbons.
 
As evidence, we enclose two links, the one above and another below, and two excerpts following, which detail the International "Methane to Markets Partnership".
 
They describe themselves as follows:
 
"The Methane to Markets Partnership is an international initiative that advances cost-effective, near-term methane recovery and use as a clean energy source. The goal of the Partnership is to reduce global methane emissions in order to enhance economic growth, strengthen energy security, improve air quality, improve industrial safety, and reduce emissions of greenhouse gases."
 
Note that they define Methane, not as a valuable hydrocarbon raw material, but, more as an "emission" - a "greenhouse" pollutant. And, even though they acknowledge Methane to be "a clean energy source", their goal is "to reduce global methane emissions in order to enhance economic growth".
 
In the extensive body of their web site, they do talk about using Methane in it's traditional role as "natural gas", but only in a limited way. It is mostly an exposition about the policies and arts of collecting Methane, from it's many sources, and it's disposal.
 
We have been unable to find even one mention, in this multinational effort, of Methane's potentials for use as an industrial chemical manufacturing raw material; or as a starting point for methanol manufacture; or, for it's potential as a co-reactant, with Carbon Dioxide, to make liquid fuels, the details of which we have thoroughly documented.
 
There are more than thirty listed members of the "Partnership", including the United States and, among the others, Canada, China, Germany and Russia.
 
Significantly, we find no OPEC members, that we recognize, on their roster.
 
Perhaps more significantly, the United States is represented in the Partnership not by the Department of Energy, but by the EPA, as follows:
 
 

"The Methane to Markets Partnership is an international initiative that advances cost-effective, near-term methane recovery and use as a clean energy source. The goal of the Partnership is to reduce global methane emissions in order to enhance economic growth, strengthen energy security, improve air quality, improve industrial safety, and reduce emissions of greenhouse gases."

Methane is a greenhouse gas pollutant only when it arises from uncontrolled sources, such as the Arctic tundra in the summer, the Everglades Swamp and the Oklahoma feed lots of cattle headed for slaughter. Otherwise, it's a useful byproduct of industrial processes. At some sites, for instance, Methane emitted by coke ovens, driven off the coal being coked, was reclaimed and used as supplemental fuel in nearby steel furnaces.

Anyone who grew up, back in the day, in West Virginia, before electric stoves became prevalent, and brewed some coffee or heated some beans, likely did so with the kind assistance of the Methane in natural gas.

And, we now know, as we've documented thoroughly, and will document further: Methane can be reacted with Carbon Dioxide to synthesize liquid fuels.

This "Partnership" is, we are compelled to suspect, yet more deliberate misdirection; a deception intended to deny us access to one of the valuable raw material resources available to us, including coal and CO2, which, if properly utilized, could enable the United States of America to achieve domestic liquid fuel self-sufficiency. 

The "Markets" this organization wants to direct Methane into, are not, via technologies such as Penn State Tri-reforming with Carbon Dioxide, our local filling stations.

Why?

Swiss Low-Energy CO2 Recycling

 
Herein, from Switzerland, following on our reports of Swiss and Israeli collaboration in the technology of Carbon Dioxide recycling, we have even further confirmation that energy, and thus cost, barriers to the reclaiming of Carbon Dioxide, and it's conversion into valuable liquid fuels and chemicals, can be overcome.
 
We submit this as "foreign" confirmation of the evidence attesting to that fact which has been published, as we've documented, by Penn State University, the United States Department of Defense and the United States Department of Energy, and others, since prophets, it seems, do have no honor in their own land.
 
Excerpt as follows: 

"Methanation and photo-methanation of carbon dioxide at room temperature and atmospheric pressure

K. Ravindranathan Thampi, John Kiwi & Michael Grätzel
Institut de Chimie Physique, Ecole Polytechnique Fédérate, CH-1015 Lausanne, Switzerland

The Sabatier reaction: CO2+4H2 right arrow CH4+2H2O ... is an important catalytic process of wide industrial and academic interest. It is applied to syngas conversion and the treatment of waste streams. Methane is one of the most important carbon resources of the world, serving as an energy vector as well as a feedstock for higher-value chemicals. Despite its favourable thermodynamics, the eight-electron reduction of CO2 to CH4 by hydrogen is difficult to achieve: high-energy intermediates impose large kinetic barriers, and the formation of side products is common. Intensive investigations during the past decade have therefore been aimed at improving the activity and selectivity of methanation catalysts. Although significant progress has been made in this field, elevated temperatures and pressures are still required for methane generation to proceed at significant rates and yields. Here we report the selective conversion of CO2 to methane at room temperature and atmospheric pressure, using highly dispersed Ru/RuO loaded onto TiO2 as a catalyst. The reaction rate is sharply enhanced through photo-excitation of the support material."

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We're not including the authors' extensive list of supporting documentation. And, their presentation of the Sabatier reaction seems, to us, an oversimplification. But, you should get the picture: CO2 is a raw material resource, not a pollutant.

Interestingly, as we will shortly document for you, even though these Swiss researchers refer to Methane as "one of the most important carbon resources of the world", a great deal of international effort is being applied to convince people otherwise, and to make Methane appear as just another "greenhouse gas", similar to Carbon Dioxide, that must somehow be disposed of.

We'll comment further on that situation in a pending dispatch. But, herein, we have documented yet again that the science for recycling Carbon Dioxide, like the science for liquefying Coal, is quite real and undergoing continuous improvement in various places throughout the world.

It's far past time we started reducing those sciences to commercial practice in US Coal Country.