http://www.osti.gov/scitech/biblio/1164221

Coal can be efficiently converted into synthetic petroleum-type liquid hydrocarbon fuels - - and, any Carbon Dioxide emitted by such a process can be captured and as well be converted, via an initial synthesis of fuel alcohol Methanol, in a process of "artificial photosynthesis", into synthetic petroleum-type liquid hydrocarbon fuels.

Those facts have now been established and formally reported to the United States Department of Energy by the University of Texas at Arlington, "UTA", although that might not be made perfectly clear by the document we bring to you herein.

That document demonstrates that UTA has developed catalyst systems which enable, in processes powered by simple sunlight, the conversion of Carbon Dioxide, in combination with H2O, into such valuable products as substitute natural gas Methane, fuel alcohol Methanol, and hydrocarbon synthesis gas, that is, a blend of primarily Carbon Monoxide and Hydrogen which can be catalytically condensed, as via for one example the nearly-ancient Fischer-Tropsch synthesis, into liquid and gaseous hydrocarbon fuels.

First, at least one news release, as in:

Simpler, cheaper way to make liquid methanol fuel using CO2 and sunlight; "'Simpler, cheaper way to make liquid methanol fuel using CO2 and sunlight'; April 7, 2013; Researchers at University of Texas at Arlington have developed a novel means of creating methanol from sunlight and CO2. Most previous methods of producing methanol from carbon dioxide have involved lots of electricity, high pressures and high temperatures, and used toxic chemicals or rare earth elements like cadmium or tellurium. A team of researchers at the University of Texas at Arlington (UTA) has developed a new method they claim is safer, less expensive, and simpler than current approaches and can be scaled up to an industrial scale to allow some of the CO2 emitted from electrical power plants to be captured and converted into a useful fuel. ... Dr Krishnan Rajeshwar, a distinguished professor of chemistry and biochemistry and co-founder of the Center for Renewable Energy, Science & Technology, CREST, at UT Arlington, described the new methanol production process developed by his team as a photo-electrochemical version of photosynthesis that occurs in plants. The heart of this technique uses a thermal process to coat copper oxide (CuO) nanowires with another form of copper oxide (Cu2O) and submerging them in a solution rich in carbon dioxide. The CuO-Cu2O hybrid nanorod arrays were then subjected to sunlight – or simulated sunlight in the lab – to trigger a chemical reaction and produce liquid methanol. The team says the experiments generated methanol with 95 percent electrochemical efficiency and avoided the excess energy input, also known as overpotential, of other methods.When asked if this process might be used to create fuel for remote locations in Alaska and Canada, far from pipelines and roads, Dr. Rajeshwar thought it might be combined with the output of generators that make electricity, recovering the CO2 waste gas pollution to produce useful fuel";

has been published by the University of Texas system concerning the fact that Carbon Dioxide, whether recovered from the exhaust gases of a Coal-to-Oil process or "from electrical power plants", can be converted, on "an industrial scale", via an artificial "photo-electrochemical version of photosynthesis that occurs in plants", into "liquid methanol" at a "95 percent ... efficiency".

Those facts concerning Carbon Dioxide result in large part from participation by the University of Texas system with the United States Department of Energy in the USDOE's development of their "Green Freedom"(TM) Carbon Dioxide utilization technology, as we reported on for one example in:

Thank Goodness for Texas - and for Carbon Dioxide! | Research & Development | News; "Green Freedom (TM); Los Alamos National Laboratory and the University of Texas Permian Basin; 2009; Los Alamos National Laboratory developed Green Freedom as the shortest path to affordable, large-scale, clean, carbon-neutral, gasoline and jet fuel production. Ironically this practical but transformational concept depends on low-risk technology. Almost all the technologies already exist today and operate at large scale. ... Green Freedom is free of scaling limitations and most of its plant could be designed and built today because the principle focus would be on the unique integration of known technologies rather than their development. Green Freedom works by extracting carbon dioxide from the atmosphere and hydrogen from water to serve as feedstocks. Depending on the desired end product(s), there are converted, emissions-free, to fuel by any of a number of established methods, such as Fischer-Tropsch or through a methanol-to-gasoline based process. At the heart of Green Freedom is a new electro-chemical process that reduces the energy required to capture and recover production quantities of carbon dioxide from the atmosphere by 96%".

As we also reported, in:

WVU and UTexas: Oil at $35 from Coal | Research & Development | News; concerning the news release:

"UT Arlington researchers' work could lead to $35-a-barrel oil; 2009; After a year of trying, University of Texas at Arlington researchers say they have succeeded in producing Texas intermediate-quality crude oil out of lignite. In a few years, the researchers predict, their discovery could lead to oil that costs $35 a barrel instead of the current $65 to $70. Richard "Rick" Billo, UTA's associate dean of engineering and research, explained the coal-to-oil project in a column a year ago. His team had three goals: 'To produce a quality oil out of coal; Get the production cost of that oil down to at least $35 per barrel; Come up with a concept for refining the oil.'  The group developed a microrefinery that can manufacture oil from coal without the huge financial cost associated with traditional refineries. ... UTA's methodology was based on work at the University of West Virginia, which holds patents on converting bituminous soft coal, a much higher grade than lignite, into crude oil";

the University of Texas at Arlington has been at work tweaking Coal-to-Oil technology developed by West Virginia University, as summarized, with additional reference links, in our report of:

WVU Coal Liquefaction System | Research & Development | News; which centered on: "United States Patent 8,597,503 - Coal Liquefaction System; 2013; Inventors: Alfred H. Stiller and Elliot B. Kennel, Morgantown, WV; Assignee: West Virginia University".

We, here, aren't technically astute enough to understand or describe how much Carbon Dioxide would be emitted from Coal-to-Oil processes like those developed by West Virginia University, especially since, if you examine the above report, and others to which that report makes reference to, you will discover that a variety of renewable, and naturally Carbon-recycling wastes, such as sewage treatment plant sludge and crop residues, can be added to the raw Coal feed for conversion into synthetic crude petroleum.

But, herein we see that the University of Texas at Arlington, in a project funded by the United States Department of Energy, reported that Carbon Dioxide reclaimed from a Coal-to-Oil process, like those discussed above, which could lead to the production of synthetic petroleum from Texas lignite Coal at a cost, perhaps, of $35 per barrel, can be reclaimed and efficiently converted into a number of valuable products - such as fuel alcohol Methanol, substitute natural gas Methane, and compounds which can and are being used in the manufacture of polymers and plastics, such as Formaldehyde.

They disclose, as well, that CO2, as recovered actually from any source, and Water can be photo-catalytically converted into a blend of Carbon Monoxide and Hydrogen, that is, hydrocarbon synthesis gas. 

Comment follows and is inserted within excerpts from the rather technically dense:

"Report Title: Final Report - Center for Renewable Energy Science and Technology (CREST)

http://www.osti.gov/scitech/servlets/purl/1164221

Principal authors: Dr. Richard E. Billo (and) Dr. Krishnan Rajeshwar

April 15, 2013


DOE Award Number: DE-FE0002829


Submitting organization: The University of Texas Arlington

The CREST research team conducted research that optimized catalysts used for the conversion of southwestern lignite into synthetic crude oil that can be shipped to nearby Texas refineries and power plants for development of transportation fuels and power generation. Research was also undertaken to convert any potential by-products of this process such as CO2 to useful chemicals and gases which could be recycled and used as feedstock to the synthetic fuel process. These CO2 conversion processes used light energy to drive the ... reactions involved.

The project was divided into two tasks: A CO2 Conversion Task, and a Catalyst Optimization Task.

The CO2 Conversion task was aimed at developing molecular and solid state catalysts for the thermal, electro- and photocatalytic reduction of CO2 to reduced products such as simple feedstock compounds (e.g. CO, H2, CHOOH, CH20, CH3OH and CH4).

(The above "CH3OH and CH4" are Methanol and substitute natural gas Methane. The other products, such as Carbon Monoxide and Hydrogen, are potentially important, as well, especially as intermediates on the way to higher value compounds, as seen following.) 

For example, the research team recycled CO (carbon monoxide) that was developed from this Task and used it as a feedstock for the production of synthetic crude in the Catalyst Optimization Task.

In the Catalyst Optimization Task, the research team conducted bench-scale experiments with the goal of reducing overall catalyst cost in support of several synthetic crude processes that had earlier been developed. This was accomplished by increasing the catalyst reactivity thus reducing required concentrations or by using less expensive metals. In this task the team performed parametric experiments in small scale batch reactors in an effort to improve catalyst reactivity and to lower cost. They also investigated catalyst robustness by testing lignite feedstocks that vary in moisture, ash, and volatile content.

Executive Summary: The CREST research team conducted research that optimized catalysts used for the conversion of southwestern lignite into synthetic crude oil that can be shipped to nearby Texas refineries and power plants for development of transportation fuels and power generation. Research was also undertaken to convert any potential by-products of this process such as CO2 to useful chemicals and gases which could be recycled and used as feedstock to the synthetic fuel process. These CO2 conversion processes used light energy to drive the endogonic reduction reactions involved. The project was divided into two tasks which are summarized below.

Task 2: CO2 Conversion: CO2 is an unavoidable by-product from any fossil fuel combustion process. Due to the environmental concerns about continued CO2 emissions into the atmosphere, technologies for the conversion of CO2 to useful, environmentally friendly products is paramount.

Other than sequestration, the only feasible long term solution is the reduction of CO2 into useful fuels, (i.e. alcohols and hydrocarbons).

Such technology could greatly reduce CO2 emissions or even close the carbon cycle - a carbon-neutral fuel cycle with respect to the atmosphere. This task was aimed at developing molecular and solid state catalysts for the thermal, electro- and photocatalytic reduction of CO2 to reduced products such as simple feedstock compounds (e.g. CO, H2, CHOOH, CH20, CH3OH and CH4). For example, we recycled CO that was developed from this Task and used it as a feedstock for the production of synthetic crude in Task 3.

Task 3: Catalyst Optimization: Several processes for converting lignite into synthetic crude (syncrude) were investigated by our group in the past three years. During this time, we developed a cost effective approach that used a catalytic reaction conducted under moderate temperature and pressure conditions. Our ultimate goal was to bring this process to a pilot scale somewhere close to a lignite mine in Texas. In support of this effort, we conducted bench-scale experiments with the goal of reducing overall catalyst cost. This was accomplished by increasing the catalyst reactivity thus reducing required concentrations or by using cheaper metals. In this task we performed parametric experiments in small scale batch reactors in an effort to improve catalyst reactivity and to lower cost. We also investigated catalyst robustness by testing lignite feedstocks that vary in moisture, ash, and volatile content.

The catalytic reduction of carbon dioxide (CO2) to fuels and organic compounds using light, electricity, or a combination of both, is not a new topic. References to this topic date back to the 1800s, although rapid progress was made only since the 1970s.

(One of the key achievements in "the 1970's" that seemed to spur development of technology "using light" to drive the conversion, the "deep reduction", of Carbon Dioxide into products like Methane and Methanol, as we read the literature, was that made at the USDOE's Brookhaven, New York, National Laboratory, about which we reported in:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development | News; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Inventor: Meyer Steinberg, NY; Assignee: The USA as represented by the USDOE; A method and system for synthesizing methanol from the CO2 in air using electric power. The CO2 is absorbed by a solution of KOH to form K2CO3 which is electrolyzed to produce methanol, a liquid hydrocarbon fuel. (Any) source of electrical power may be employed (but) solar energy generated power, would be preferred".

That technology suggested the use of photovoltaic energy to drive the CO2-to-Methanol conversion, and more recent developments have both improved on those processes and shown that solar light energy itself, without conversion into electricity, can also be used to convert CO2 into hydrocarbons.)

A (Ruthenium-organic) complex has been the primary one used in our studies on homogeneous photochemical reduction of CO2. As shown schematically (in included illustrations) these species are thermodynamically capable of reducing CO2 (to form methanol and methane).

(The report goes on to explain that catalyst systems are available to effect the rather efficient reduction of Carbon Dioxide into products like carbon monoxide and formic acid, "CO, ... CHOOH", etc., but, that, to efficiently effect what is referred to as the "deep reduction" of CO2, to form Methane and Methanol, better catalysts were needed, which UTA developed out of organic Ruthenium compounds. However, as seen for just one example in our report of:

Korea Improves Solar CO2 to Methane Catalysis | Research & Development | News; concerning: "United States Patent Application 20130192975 - Method of Manufacturing a Porous Gallium (III) Oxide Photocatalyst for Preparation of Hydrocarbons; 2013; Assignee: Korea Advanced Institute of Science and Technology, Daejeon, Korea; Abstract: The present invention relates to preparation of porous gallium (III) oxide (Ga2O3) photocatalyst for production of hydrocarbons (and) a process of producing hydrocarbons using the porous gallium oxide photocatalyst ... . A method for production of hydrocarbons, comprising reacting the porous gallium (III) oxide photocatalyst manufactured by the method (disclosed) with CO2 and water as raw materials under a light source (and) wherein the hydrocarbons (produced) comprise methane";

there are other elements, as well, that can effectively serve to catalyze the light-driven "deep reduction" of Carbon Dioxide into fuels like substitute natural gas Methane.)

The rate of the reaction between the photoexcited (Ruthenium complex) and CO2, depends on the reactant concentrations, the photon flux, the lifetime of the excited state complex and, importantly, the ability of the excited-state complex to transfer an electron to the CO2. These simple complexes lack the chemical functionality to lower the activation barriers involved and are only capable of delivering a single electron each towards these multi-electron reactions. It is also worth noting that the initial conversion of CO2 to CO is the energy “hog” in the overall process and consumes a minimum of 1.33 eV. Much of the progress associated with the conversion of CO2 to CO and formate has revolved around electro- and photocatalytic strategies for minimizing the additional overpotential over and above this minimum threshold.

Although many homogeneous catalysts have been developed for both electrochemical and photochemical systems, only few are capable of deeper reduction than the two-electron reduced products of CO2, such as CO and formic acid. We found out that out of 72 molecular electrocatalytic systems for CO2 reduction, 71 are metal complexes and the final product in the majority is CO ... .

We have examined the homogeneous photochemical (reduction) of CO2 using a (Ruthenium complex) and pyridine as a co-catalyst in aqueous solution (which we) hypothesized ... could ...  drive the pyridine catalyzed CO2 to methanol reaction.

We demonstrated that (two Ruthenium complexes, as specified) are competent electrocatalysts for CO2 reduction to methanol ... .

Photogeneration of Syngas and Methane on (Platinum based catalysts): Syngas(or “synthetic gas”) is the name given to a gas mixture that contains varying amounts of CO and H2 gases. Common examples of producing syngas include the ... gasification of coal ... . Thermally mild (i.e., low temperature) alternatives for producing this transportable chemical fuel mixture is obviously very significant from an energy perspective. Value is even further if the production process can be driven via a renewable solar energy source from a source greenhouse gas material such as CO2".

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The above "Syngas", we remind you, can be catalytically, chemically condensed, as has long been known, into a full range of liquid and gaseous hydrocarbons, and is the basis of the Fischer-Tropsch process for making hydrocarbon fuels from Coal, wherein the Coal is first gasified to provide such "Syngas".

We'll close there, since those excerpts should suffice to impress upon you how seriously what is now the plain reality of the fact that Carbon Dioxide - - whether recovered from the exhaust stream of a Coal-fired power plant or from a Coal liquefaction, Coal-to-Oil, process - - can be efficiently consumed and utilized, in processes powered by, among other "renewable" energy sources, solar light energy, in the synthesis of both liquid and gaseous hydrocarbon fuels and chemicals. And, that plain reality is being treated on a practical basis both by universities pretty much founded on and supported by the petroleum industry, as herein the University of Texas Arlington, and by the United States Department of Energy.

Way past time we started taking that reality seriously here, in the heart of US Coal Country, isn't it?


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