Research & Development

USDOE Low-rank Coal Liquefaction

 
We some time ago reported, without many details available to us at the time, on the "Encoal"(R) Process for converting low-rank coal into liquid fuels, and the work on development of such technology in Wyoming.
 
As it happens, that was one of our US Department of Energy's Coal-to-Liquid development projects, and our Federal Government does know quite a lot about using this technology to convert coal into liquids, with  improved solid fuels being produced as a useful by-product. .
 
Brief comment follows our excerpt from the evidentiary link:
 
"CCPI/Clean Coal Demonstrations; ENCOAL(R) Mild Coal Gasification Project
 
PROJECT FACT SHEET: US Department of Energy; Office of Fossil Energy

Project Summary

Operational Performance
The LFC(R) facility operated for more than 15,000 hours over a five-year period. Steady-state operation was maintained for much of the demonstration with availabilities of 90% for extended periods. The length of operation and volume of production proved the soundness and durability of the process.

By the end of the demonstration ... (over)  5 million gallons of (coal liquids) were produced and shipped to eight customers in seven states."

Those millions of gallons of liquid fuel, from a demonstration plant, were in addition to a refined, higher-Btu, cleaner, solid fuel that: "enabled reduction in SO2 emissions, reduction in NOx emissions" when used in a utility boiler application.

Again: Our US Government sponsored development of this coal liquefaction technology in the far, remote west. And, it works, and works well, on low-rank coal. How well would it work on high-rank Appalachian bituminous coal? And, why haven't any of us in the very heart of US Coal Country heard anything about it?

Japan Liquefies Coal with Wast Plastic


 
We are herein returning to a theme we've previously elaborated on to some extent:
 
Certain "wastes", including some waste plastics, can be liquefied with coal; and, in such co-liquefaction, the plastics (and, by extension, as we've elsewhere documented, other wastes of various sorts, including rubber and cellulose) contribute, as we have been led to understand it, some hydrogen to the overall process of hydrogenating a  material, such as coal, that is composed primarily of carbon, to form hydrocarbon gasses and liquids.
 
These Japanese coal scientists, though, notably, also used the hydrogen donor solvent, "tetralin", as we believe to be specified by WVU in their "West Virginia Process" of direct coal liquefaction.
 
In any case, for whatever reason, the co-liquefaction of coal with, supposedly waste, polyethylene plastic resulted in a synergy, as in other reference we've cited, wherein yields, as we understand the abstract, were significantly higher than would be expected if the coal and plastic were liquefied separately.
 
The excerpt:
 
"Coliquefaction of Coal with Polyethylene Using Fe(CO)5−S as Catalyst
 
Toshiyuki Kanno, Masahiro Kimura, Na-oki Ikenaga, and Toshimitsu Suzuki
[Unable to display image]Department of Chemical Engineering, Kansai University, Suita, Osaka 564-8680, Japan
Energy Fuels, 2000, 14 (3), pp 612–617
Publication Date (Web): March 7, 2000
Copyright © 2000 American Chemical Society
 
Abstract

The coliquefaction of Yallourn coal (YL) with polyethylene (PE) was carried out at 400 or 425 C under pressurized H2 in 1-methylnaphthalene or tetralin. In the coliquefaction without a catalyst, the conversion and the oil yield increased by 11−12% as compared to that of expected value from the additive values of respective runs. We considered that free radicals produced from YL coal were stabilized by the hydrogen abstraction from PE during the coliquefaction ... . The addition of a large amount of Fe ... catalyst ... increased the conversion and the hexane soluble oil yield in the homoliquefaction of YL coal or PE... ."

We were compelled to edit the abstract in the extreme, deleting much of what are, for us, far too technical details. Like much of what we have brought to your attention, the full report begs reading by qualified and competent individuals, experts who genuinely have our nation's best interests at heart. Maybe then all of us might finally benefit from the facts, that: Our domestic coal can be liquefied into the fuels and chemical manufacturing materials we need; and, from the synergies such coal liquefaction industry would offer us, including the opportunity to make productive use of some of our industrial and agricultural wastes, we could start to make the most efficient, most profitable, and cleanest, use of the resources we have been blessed with.

Australia Moves Forward

 
We've documented both the Australian plans for coal-to-liquid development, and the coal conversion expertise of Synthesis Energy Systems.
 
In this recent story, it's reported that both are now, together, planning additional coal-to-liquid projects, as in the attached and following:
 
"Friday, 04 December 2009
 
Coalworks Limited , an emerging Australian energy developer, and Synthesis Energy Systems Inc. ("SES") , a global industrial gasification company, intend to develop, through a strategic alliance, Coalworks' first coal gasification and liquefaction plant at Oaklands in New South Wales, Australia utilizing SES' proprietary U-GAS(R) gasification technology, which SES licenses from the Gas Technology Institute
 
Coalworks and SES have entered into a strategic alliance agreement which is based on the following key points:
 
  --  U-GAS(R) technology has been proven on a commercial scale with
      gasification plants in China
  --  The U-GAS(R) technology is ideal for sub bituminous coal like that is
      found in Oaklands
  --  The Oaklands coal resource is well suited for gasification and
      downstream value added products
  --  Oaklands coal would be converted to gasoline via a planned coal to
      liquids (CTL) plant
  --  The agreement provides a framework for feasibility and engineering
      design phases using commercially proven technologies and plant
      construction strategies"
 
We have previously documented the work of SES in China, and their "U-GAS"(R) coal conversion technology, which "has been proven on a commercial scale with gasification plants in China".
 
And, though the technology starts with coal gasification, don't lose sight of the fact that this is being undertaken so that "coal would be converted to gasoline via a planned coal to liquids (CTL) plant".

Cure for CO2 Headache

 
We've thoroughly documented that the Carbon Dioxide by-product of our coal use could, and should, be viewed as a useful, even valuable, resource from which we can manufacture more liquid fuels, and raw materials for our plastics and chemicals industries.
 
As the enclosed report, from collaborating researchers in both Spain and Japan, reveals, there are multiple technical ways in which the relatively inert CO2 can be processed, made more reactive, so that the carbon it contains can be utilized in the synthesis of valuable products, even medicine.
 
We have edited our excerpt in the extreme. Like much of what we send you, the complete information begs reading by competent individuals able to bring the information to the attention of those who most deserve to learn of it: The citizens of the United States, and most especially those citizens resident in US Coal Country.
 
The excerpt: 
 
"Electrochemical approaches to alleviation of the problem of carbon dioxide accumulation
 
C. M. Sánchez-Sánchez, V. Montiel, D. A. Tryk, A. Aldaz, and A. Fujishima

Grupo Electroquímica Aplicada, Departamento de Química Física, Universidad de Alicante, Ap. 99, E-03080, Alicante, Spain
 
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
 
Abstract: The electrochemical reduction of CO2, which includes a number of different specific approaches, may show promise as a means to help slow down the accumulation of this greenhouse gas in the atmosphere. Two types of approaches are examined briefly here. First, CO2 can be used as a reagent in the electrocarboxylation reaction to produce organic carboxylic acids, for example, the pharmaceutical ibuprofen. Second, CO2 can be converted to a fuel, either directly or via synthesis gas. The latter can be produced with reasonably good energy efficiency in a gas-diffusion, electrode-based cell even at present with existing electrocatalysts. Oxygen gas is produced as a by-product. Further work is needed to improve the selectivity and efficiency in this and other approaches.
 
Chemists have been working on various ways to prevent the accumulation of atmospheric CO2, including removal, sequestration, utilization, and conversion into fuels [1]. In particular, electrochemical researchers have been making sizable efforts to develop ways to transform CO2 into useful substances such as fuels or chemicals. The past decade or two have seen the growth of the subject, with promising results of electrochemical approaches.
 
This report tries to portray some of the principal electrochemical approaches to the CO2 problem that have been proposed by various research groups. We begin by explaining two generic electrochemical methods of utilizing CO2. The first involves the coupling of CO2 to electrochemically reduced organic molecules (electrocarboxylation), with the goal being to find new routes to synthesize chemicals that are interesting from a pharmacological point of view. The second is the direct electrochemical reduction of CO2, with the goal being to obtain hydrocarbons, alcohols, or other fuels. This second method can in turn be divided into two groups, according to whether metals or transition-metal complexes are used as catalysts."
 
(These scientists, like many we cite for you in our reports, are compelled to use, in places, highly-technical language, and we don't, because of our own limitations and lack of understanding, excerpt much of it directly for you. But, two things in the foregoing are quite clear, are stated categorically by these scientists: "CO2 can be used ... to produce ... organic carboxylic acids (like) ibuprofen. Second, CO2 can be converted to a fuel." That message comes through quite clearly. We wonder when everyone will start receiving it. - JtM) 
 
"The utilization of CO2 in the carboxylation of various types of organic compounds has been known for many years....
 
Electrochemical reductive carboxylations have been described for a large number of substrate types, including ketones, acetylenes, olefins, alkyl halides, and heterocyclic compounds. However, the most important scale-up processes are related to the synthesis of nonsteriodal antiinflammatory drugs (NSAIDs).
 
Direct electrochemical approaches to convert CO2 to various types of fuels have been investigated for several decades. ... Moreover, the reduction of carbon dioxide in the potentials at which the cathodic reaction occurs is normally accompanied by hydrogen evolution."
 
(So, "reduction of carbon dioxide" is "normally accompanied by hydrogen evolution". If we are blessed to receive both Carbon and Hydrogen, what can be made of them? Hydrocarbons? - JtM)  
 
Investigations on the direct electrochemical reduction of CO2 can be categorized into two groups according to the type of catalytic system:
 
1. Heterogeneous catalytic systems using cathodes of bulk or particulate metals, which show particular selective product properties. Their general properties are long-term reliability and acceptable mechanical, thermal, and chemical stability.

2. Homogeneous and heterogeneous catalytic systems using transition-metal complexes as catalysts. Attractive features are high selectivity and low operating potentials, but at the price of limited stability.
 
These catalytic systems ... carry out the electrochemical reduction of CO2, ... (and) ... In aqueous solution, C1-type compounds (e.g., carbon monoxide, formic acid, methanol, methane) are produced."
 
(If we get carbon monoxide, we can use it in processes, like Fischer-Tropsch synthesis, to make liquid fuels. Formic acid, among other uses, can be employed in fuel cells. Methanol is a valuable liquid fuel in it's own right, but can serve as a raw material from which we can make gasoline and plastics. Methane can be used in it's traditional role as "natural gas", or, like methanol, be employed in the synthesis of other valuable organic chemicals. - JtM)
 
"In the case of aqueous media, metal electrodes used in the electroreduction of CO2 can be divided in different groups according to the nature of the main product.
 
A. Hydrocarbons and alcohols (Cu).
B. Carbon monoxide (Au, Ag, Zn, Pd, and Ga).
C. Formic acid (Pb, Hg, In, Sn, Bi, Cd, and Tl). 
 
Shibata and coworkers have developed an important line of research involving the electrochemical synthesis of urea by simultaneous reduction of CO2 and nitrite or nitrate ... .
 
... various compositions of synthesis gas can be produced. ... useful to synthesize methanol ... .  
 
It is, of course, necessary to compare such an electrochemical method for producing synthesis gas with purely chemical ones such as steam reforming of methane or partial oxidation of methane, which is used in industry as a method of producing synthesis gas, and carbon dioxide reforming of methane. Although the electrochemical route costs more energy, this is because it includes the energy cost of producing the hydrogen.
 
It appears possible that the electrochemical reduction of CO2 could be applied to new energy storage systems that could contribute to the alleviation of the accumulation of atmospheric CO2. As one example, CO2 reduction shows great potential in the production of pharmaceuticals and fine chemicals. ...  A second example is the reduction of CO2 to produce fuels or synthesis gas."
 
----------
 
Multiple options exist, it seems, to make valuable, profitable, use of coal's major by-product. Further comment from us, at this point, seems pointless. We'll close by noting the Spanish and Japanese authors include a very substantial reference list, which confirms even further that the science of CO2 utilization, like the science for converting coal into liquid fuels, is, in certain circles, well-known and well-understood. What isn't known or understood, at all, by us, is why those sciences haven't been publicized and explained to the people who most deserve to have that knowledge; the people who could and would do the most with it: The citizens of the United States of America, and, most especially, those citizens resident in US Coal Country.

CO2 and Fuel from Air

 
First of all, as we understand online references we've accessed, "silanes" are relatively common industrial chemicals, encompassing a range of formulas. But, they are, basically, the silicon-hydrogen counterparts of carbon-hydrogen compounds such as methane. The technicalities are far beyond us, but it seems they can be made by, essentially, reacting commodity hydrochloric acid with a variety of abundant silicon-containing minerals. Beach sand is a common silicon-containing mineral, but we've no idea if it's inertness would allow it to be a feasible raw material, or not.
 
But: Silicon is as common as, literally, dirt; and, hydrochloric acid is nearly so.
 
In any case, once you've made silane, or bought it from one of it's multiple major industrial suppliers, you can collect some Carbon Dioxide and make the gasoline and plastics raw material, Methanol, out of it.
 
As per the excerpt, comment appended:
 
"Conversion of Carbon Dioxide into Methanol with Silanes over N-Heterocyclic Carbene Catalysts
 
Siti Nurhanna Riduan, Yugen Zhanj, Dr. Jackie Y. Ying; Inst. of Bioengineering; Singapore
 
Abstract: Carbon Dioxide was reduced with silane using a stable organocatalyst to provide methanol under very mild conditions. Dry air can serve as feedstock, and the organocatalyst is much more efficient than transition metal catalysts for this reaction. This approach offers a very promising protocol for chemical CO2 activation and fixation."
 
There are multiple items of import to be gleaned from our sparse extract of the abstract. And, we're compelled to oversimplify them, thus: With a product you can, in essence, make from beach sand and stomach acid, you can make liquid fuel, "methanol", out of "dry air".
 
Left unstated is that this is a productive recycling of Carbon Dioxide, as opposed to an expensive, and deceptive, "disposal" of it. Also unstated are the possibilities of siting such an operation at the business end of a coal plant's smokestack, where the CO2 would be more concentrated, and waste heat would be available to help drive the process.
 
And, note: We have cited these researchers, and/or their colleagues, in small and isolated Singapore, previously, on the subject of true Carbon Dioxide utilization. They are at work figuring out how to do the best they can with what they have to work with. In their case, it's "dry air".
 
We are blessed with abundant coal and concentrated smoke stack emissions.
 
  1. California Recycles CO2
  2. CO2 Recycling Proposal
  3. Germany Improves Coal Liquefaction
  4. Penn State Improves Coal LIquefaction

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