http://www.ems.psu.edu/~elsworth/courses/egee580/2010/Final%20Reports/co2_electrochem.pdf


As you know, presuming you to have followed our reports over the past several years, The Pennsylvania State University has devoted considerable effort into the development of technologies that would enable us to begin treating the Carbon Dioxide byproduct of our essential and vital use of Coal for the generation of electrical power as what it truly is:

An available and cheap source of Carbon which can be productively utilized, through a variety of ways, in the synthesis and manufacture of a wide range of organic products, including hydrocarbon fuels.

Our reports on the development of CO2 utilization technologies at Penn State have included some concerning the "tri-reforming" of Carbon Dioxide, with Methane and H2O; an inadequate compilation of which can be accessed via our report of:

More Penn State CO2 Recycling with Methane | Research & Development | News; wherein we included links to several reports, including: "Catalytic Tri-reforming of Methane Using Flue Gas from Fossil Fuel-based Power Plants"; "Tri-reforming A New Process Concept for Effective Conversion and Utilization of CO2 in Flue Gas from Electric Power Plants"; and, "Tri-reforming of Methane: a Novel Concept for Catalytic Production of Industrially Useful Synthesis Gas with Desired H2/CO Ratios".

And, since Methane is required for the reactions with, and the consequent productive consumption and use of, Carbon Dioxide in such "Tri-reforming" processes, we documented that Penn State has that base covered as well, as, for one example, seen in:

Penn State Solar CO2 + H2O = Methane | Research & Development; concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; The Pennsylvania State University; Efficient solar conversion of carbon dioxide and water vapor to methane."

Further, in point of fact, Penn State's use of photocatalysis in the productive recycling of Carbon Dioxide is actually conducive to the generation of a far broader range of valuable hydrocarbons than just Methane, as explained in their recent application for a United States Patent on their light-based technology for CO2 utilization, which we reported in:

Penn State Seeks CO2 Recycling Patent | Research & Development; concerning: "United States Patent Application 20100213046 - Nanotube ... Photocatalytic Conversion of Carbon Dioxide; 2010; The Penn State Research Foundation; Abstract: Nitrogen-doped titania nanotubes exhibiting catalytic activity on exposure to any one or more of ultraviolet, visible, and/or infrared radiation, or combinations thereof (and) use of nitrogen-doped titania nanotubes in catalytic conversion of carbon dioxide alone or in admixture with hydrogen-containing gases such as water vapor and/or other reactants as may be present or desirable into products such as hydrocarbons and hydrocarbon-containing products, hydrogen and hydrogen-containing products, carbon monoxide and other carbon-containing products, or combinations thereof. Claims: A method for photocatalytically converting carbon dioxide into reaction products comprising any one or more of hydrocarbons and hydrocarbon-containing products, hydrogen and hydrogen-containing products, carbon monoxide and other carbon-containing products, or combinations thereof".

As should be apparent from those, and our other reports concerning Penn State's study and development of Carbon Dioxide recycling technologies, their efforts in that arena have been somewhat comprehensive, as will be further emphasized in a number of reports to follow.

In fact, our sense of things here, now, is that Penn State seems to have been, and is, devising a rather complete and integrated suite of technologies that, taken in total, would provide not only for the productive recycling of Carbon Dioxide, but, would also enable the more efficient utilization of our abundant Coal in the synthesis of liquid hydrocarbon fuels, with some of Penn State's processes having direct application to WVU's "West Virginia Process" for direct Coal liquefaction.

We'll re-address the above commentary a little further on; but, our subject herein concerns one route for the productive recycling of Carbon Dioxide about which we've reported from other sources, but which we haven't yet documented as having been examined by Penn State.

That route is the process known somewhat generically as "Syntrolysis"; which is, the co-electrolysis of Carbon Dioxide and Water, or Steam, H2O, to form a synthesis gas, or "syngas", composed of Hydrogen and Carbon Monoxide, which syngas is suitable for catalytic condensation, as via the Fischer-Tropsch synthesis, for one example, into various hydrocarbons.

An example of our earlier reportage concerning that sort of technology can be accessed via:

More USDOE CO2 "Syntrolysis" | Research & Development; concerning the: "Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas; 2007; Idaho National Laboratory, USDOE; and Ceramatec, Inc., Utah; Abstract: An experimental study has been completed to assess ... simultaneously electrolyzing steam and carbon dioxide for the direct production of syngas. Syngas, a mixture of hydrogen and carbon monoxide, can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes. Based on the results obtained to date, coelectrolysis of steam and carbon dioxide for direct production of syngas appears to be a promising technology that could provide a possible path to reduced greenhouse gas emissions and increased energy independence, without the infrastructure shift that would be required for a hydrogen-based transportation system".

And, the process of CO2-H2O co-electrolysis for the generation of hydrocarbon synthesis gas is now more formally recorded in a recently-issued United States Patent, as we reported in:

West Virginia Coal Association | Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Assignee: Ceramatec, Inc., Salt Lake City; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell. Synthesis gas is also produced by the coelectrolysis of carbon dioxide and steam in a solid oxide fuel cell or solid oxide electrolytic cell. The synthesis gas produced may then be further processed and eventually converted into a liquid fuel suitable for transportation or other applications".

Herein, we learn that Penn State has, as well, examined, and confirmed the validity of, with some caveats, such co-electrolysis, Carbon Dioxide recycling, processes, as in our excerpts from the initial link in this dispatch to:

"Electrochemical Conversion of Carbon Dioxide to Hydrocarbon Fuels

J. Beck, R. Johnson, and T. Naya; 2010

(Studied and reported as a requirement of course work for "EME 580 Spring 2010" under the supervision of Dr. Derek Elsworth, who, as can be learned via:

Derek Elsworth; "is a professor in the Department of Energy and Mineral Engineering (at Penn State University). His interests are in the areas of computational mechanics, rock mechanics, and in the mechanical and transport characteristics of fractured rocks, with application to geothermal energy, the deep geological sequestration of radioactive wastes and of CO2, and instability and eruption dynamics of volcanoes".)

The electrochemical pathway for the production of energy dense hydrocarbons from renewable electricity, water and captured CO2 has been proposed as a means of producing fuels from renewable electricity sources while sequestering CO2 at the same time. However, few studies have investigated the feasibility of this technology, and none have been found to provide an in-depth analysis of its industrial implementation. The purpose of this study is to analyze the feasibility of applying the technology with respect to three major issues: the production of hydrocarbon fuels, the storage of excess renewable or grid electricity, and the sequestration or reduction of CO2 emissions. The first section of this report introduces the technological aspects of the CO2 electrochemical cell, which in many ways is similar to a water electrolysis cell but has the ability to create a potentially more useful fuel than hydrogen. Second, many aspects as to how this system can be integrated into future energy systems are introduced, such as working alongside renewable electricity production to store electrical energy when in excess or off-peak to form syn-gas, which can be a precursor to many other liquid fuels or to generate a light chain hydrocarbon such as methanol. Next, a few pathways for conversion of syn-gas are investigated for producing long-chain hydrocarbons such as Fischer-Tropsch diesel is discussed. The CO2 and energy balance is examined to estimate how many CO2 credits can be obtained, and to what degree this technology compares with existing renewable energy systems. Lastly, the economic factors are investigated, such as how much renewable electricity will cost, where CO2 will be captured and at what cost, and at what expected value the final products can be sold.

Chemical energy carriers are the most effective transportation fuels, as depicted by the United States transportation sector being dependent upon petroleum for 93% of the total fuel used for transportation in 2007. Electrolytic hydrocarbons have the ability to reduce emissions from the transportation sector by displacing fossil derived energy while providing the ability to reduce petroleum imports.

The viability of this technology could be great in that it could easily be implemented into the current hydrocarbon infrastructure in comparison to its water-electrolysis counterpart (i.e., elemental Hydrogen).

It is also apparent that renewable energy systems will not be able to support base-load power generation (and) thus there will be an ample supply of CO2 emissions that can be captured. This premise is exemplified by current U.S. electric power generation which is 48% coal powered, 21% natural gas powered, 20% nuclear and the last 11% is made up through renewable and other sources.

(An included illustration) assists in placing the various parts of the novel fuel supply into perspective. The renewable electricity source would come from off-peak hours on an electrical grid when renewable electricity cannot be readily consumed. Waste CO2, most likely from a coal power plant or gasification plant, is piped to the plant. The only other precursor to the reaction is water which is directly fed into the electrolysis cell.

(We have previously reported on the potentials for utilizing "renewable electricity ... from off-peak hours on an electrical grid when renewable electricity cannot be readily consumed" in, for one example:

West Virginia Coal Association | Germany & Pennsylvania Hydrogen from Hydropower | Research & Development; concerning: "United States Patent 6,864,596 - Hydrogen Production from Hydro Power; 2005; Assignees: Voith Siemens Hydropower Generation GmbH and Incorporated, Germany and York, PA; Abstract: A turbine installation configured for large scale hydrogen production includes a foundation structure separating an upper elevation headwater from a lower elevation tailwater. The foundation structure defines a water passageway extending therethrough between an inlet adjacent the headwater and an outlet adjacent the tailwater. A runner is supported for rotation by the foundation and disposed in the water passageway intermediate the inlet and the outlet so that water flowing through the passageway as a result of head differential causes rotation of the runner. A generator is supported by the foundation and connected to the runner by a rotary shaft for generating electrical power as the runner rotates. An electrolyzer is electrically coupled to the generator for receiving the electrical power and producing hydrogen. A control system is capable of sensing the remaining hydrogen storage capacity and performing an economic comparison analysis to determine whether operating the turbine to produce additional hydrogen or to supply a utility grid with power provides the highest economic return."

Note, too, the mention of "a coal ... gasification plant", which could well be one that itself is generating, through Coal gasification, it's own synthesis gas, i.e., Carbon Monoxide and Hydrogen, for liquid hydrocarbon fuel production, with Carbon Dioxide as a byproduct. And, please, make special note of the following excerpted passages, which confirms other of our reportage on the issue.)

It is important to appreciate that the sequestration of CO2 from coal power plants is not the only possible route toward the required CO2 reductions goals, as eliminating the carbon contributions from the petroleum sector would achieve even a greater reduction in CO2 emissions ... .

The potentially viable method of CO2 electrolysis to hydrocarbons could utilize waste CO2 from coal power plants to produce liquid transport fuels to off-set petroleum consumption, thus mitigating CO2 emissions from the transportation sector.

(In other words, if we were to establish such a Coal power plant Carbon Dioxide recycling technology; and, if Cap and Trade taxes were ever slapped on Big Oil's automotive fuels, we could start selling him Cap & Trade Carbon credits.)

The process proposed here produces hydrocarbons or syngas through the electrochemical reduction of CO2. The cell consists of two sections, the anode and the cathode. Water is fed into the anode, where it is split into O2 gas and hydrogen ions.

The ions are transported by solution through the membrane and into the cathode. These ions then react with the CO2 gas which is fed into the cathode, generally producing water and some form of reduced carbon product. A variety of products can be produced (including) carbon monoxide, methane, ethylene, methanol, and formic acid.

(Our report herein is already overlong, so we won't clutter it further here by referencing our past reports documenting how valuable each and every one of those products are. They all could have direct applicability to the straightforward synthesis of more hydrocarbons; the conversion of Coal into hydrocarbons; and, the recycling of even more Carbon Dioxide. We will reference, however, this report, and the available product slate, in reports to follow.)

A basic schematic of the likely system is shown (in provided illustrations). The feed streams would consist of CO2, water, and electricity. For this analysis the CO2 would likely be captured at a coal fired power plant operating under sequestration and purchased as feed. While this could provide a cheap source of reactant, the stream would probably contain trace amounts of NOx and SOx. The NOx could lead to acidic conditions in the cell, changing the reaction conditions and possibly increasing the material corrosion of the cell. Presence of SOx would be more detrimental to operation, as it is a well-known catalyst poison. For these reasons the CO2 feed would likely have to be filtered and the contaminants removed. This would further increase the capital and energy costs of the system, though it is not included in this analysis.

(The above issues have been addressed by the above-cited Ceramatec, Inc., of Salt Lake City, and others, as we will more thoroughly document in later reports.)

The water feed could be standard industrial water. This would need to be filtered, but since it is standard procedure for electrolysis cells it should not increase the system costs. Since most of the systems require an aqueous electrolyte a management system would need to be in place to control the pH and conductivity of the solution. This provides an issue, as this is common in alkaline electrolysis but not in PEM electrolysis. For a PEM cell the advantage is that the more expensive membrane material usually reduces the need for an electrolyte solution, removing the need for the additional processing equipment found in alkaline cells. Since our cell would likely require both this would further increase the capital and operating costs of the system.

(In point of fact, the above issues as well have been addressed and dealt with by others, a significant contributor to which developments has again been Ceramatec, Inc., of Utah, the corporate assignee of rights to the above-cited "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water". Gas separation via practical "membrane" technology has been resolved, as we will document, again in future reports.)

CO2 Electrochemical Reduction as Energy Storage: When comparing the CO2 electrolysis liquid fuel products to other energy storage forms, it is apparent that a liquid hydrocarbon fuel is a much more efficient energy carrier by weight and volume than thermal, mechanical, battery and hydrogen energy storage. The CO2 electrochemical liquid fuels are comparable to fossil fuels and biochemical fuels. Yet, storage of electrical energy to a liquid fuel has a downside of not being accessible for electricity regeneration to provide grid stability, dispatchability and peak power reduction unless it is used as a fuel-based back-up such as a diesel generator (which would be less than ideal). An upside of storing energy as a hydrocarbon is that the CO2 electrochemical cell can run at any time, thus providing the renewable energy source a pathway for economic viability to gain revenue when renewable power is in excess or being generated at off-peak hours. An integrated CO2 electrochemical hydrocarbon transportation sector complements renewable systems by providing a flexible use for excess renewable electricity while reducing overall emissions from fossil based transportation fuels.

With current small-scale technology for CO2 electrochemical reduction, the conversion of electrical energy to chemical energy is adequate to produce liquid fuels economically.

(The above summary statement should be committed to memory; as should the one following.)

For every barrel of diesel or gasoline produced from the CO2 electrolysis facility, one barrel of imported oil will be displaced.

(With that in mind, we remind you of our earlier report:

Coal TL vs. Hidden Oil Costs | Research & Development; concerning: "NDCF report: the hidden cost of imported oil; The National Defense Council Foundation, an Alexandria, Virginia-based research and educational institution has completed its year-long analysis of the "hidden cost" of imported oil. The NDCF project represents the most comprehensive investigation of the military and economic penalty our undue dependence on imported oil exacts from the U.S. economy";

and, urge you to remember that we are paying a lot, really a lot, more for the privilege of importing foreign oil, through military expenditures and lost US jobs and taxes, than the price at the gas pump indicates.)

Electricity is the highest quality energy carrier, but one of the most troublesome aspects of the electric power industry is that electricity must be produced when it is needed and used once it is produced. Furthermore, electricity may not play a major role in transportation due to the high cost and low energy density of batteries. With the overarching goals of U.S. energy policy makers to increase the use of domestic renewable energy, energy storage options must be considered for various reasons. Energy storage mechanisms can also mitigate over-generation of electricity when generation is high and demand is low.

Many proponents of renewable energy do not realize that energy storage is key for making raw, intermittent renewable power technically feasible. Energy storage is seen to the grid operator as a load, as there are efficiency losses for storing and dispatching this energy.

(The above "energy storage" concept, has been addressed by others, as well, in addition to our above citation of "United States Patent 6,864,596 - Hydrogen Production from Hydro Power", as seen, for example, in our report of:

West Virginia Coal Association | Hydrogen for Coal and CO2 Conversion from Wind Power | Research & Development; concerning: "United States Patent 7,199,482 - System and Method for Controlling Wind Farm Power Output; 2007; Assignee: General Electric Company; Abstract: A method for controlling variability in power output of a wind farm supplying power to a grid includes monitoring a power output level of the wind farm. The monitored power output level is compared to a target power output level. A command is issued to increase or decrease electrical power consumption by an electrolyzer system electrically coupled to the wind farm to maintain a net power output level by the wind farm based upon the comparison";

wherein the "electrolyzer"s noted in both the above could well be the "CO2 electrochemical cell" discussed herein by Penn State, which would convert Carbon Dioxide into a "variety of" energy-carrying and energy storage "products", such as "carbon monoxide, methane, ethylene, methanol, and formic acid".)

The high capital cost of energy storage technologies is a hidden cost of renewable energy and needs to be addressed when states decide to integrate large fractions of renewable power into the grid.

CO2 Electrochemical Reduction as Energy Storage: When comparing the CO2 electrolysis liquid fuel products to other energy storage forms, it is apparent that a liquid hydrocarbon fuel is a much more efficient energy carrier by weight and volume than thermal, mechanical, battery and hydrogen energy storage. The CO2 electrochemical liquid fuels are comparable to fossil fuels and biochemical fuels. Yet, storage of electrical energy to a liquid fuel has a downside of not being accessible for electricity regeneration to provide grid stability, dispatchability and peak power reduction unless it is used as a fuel-based back-up such as a diesel generator (which would be less than ideal). An upside of storing energy as a hydrocarbon is that the CO2 electrochemical cell can run at any time, thus providing the renewable energy source a pathway for economic viability to gain revenue when renewable power is in excess or being generated at off-peak hours. An integrated CO2 electrochemical hydrocarbon transportation sector complements renewable systems by providing a flexible use for excess renewable electricity while reducing overall emissions from fossil based transportation fuels.

(Make special note of the following statement, excerpted from page 26 if you're interested in the full discussion and explanatory graphics.)

With current small-scale technology for CO2 electrochemical reduction, the conversion of electrical energy to chemical energy is adequate to produce liquid fuels economically.

Models for CO2 Electrolyzer: The CO2 reduction process can make a wide variety of products. We prepared four electrolysis models: the syn-gas/Fischer-Tropsch (F-T) model, the methanol model, the hydrogen model, and the methane model. In the syn-gas/F-T model we assume that we produce syngas from the electrolyzer and convert it to fuels via the F-T process. The products are diesel, gasoline, and kerosene, with diesel as the primary desired product."

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We'll close our excerpts there so that we can address the above statement asserting, that: "the conversion of electrical energy to chemical energy (through the conversion of Carbon Dioxide and Water into hydrocarbon synthesis gas) is adequate to produce liquid fuels economically".

In point of fact, the full discussion goes on concerning the "caveats", our term, we mentioned in our opening comments, which caveats imply that such technology might not "produce liquid fuels economically".

We don't include them herein because we think they're specious and likely included simply for the sake of the appearance of rigor in a scientific dissertation.

Left entirely unanalyzed are the positive, broad-scale, and perhaps indirect, economic effects of displacing OPEC oil imports, and of preventing negative Cap and Trade taxation schemes and parasitic Geologic Sequestration scams, through the positive recycling of Carbon Dioxide into "diesel, gasoline, and kerosene".

As we also noted in our opening comments, this dissertation, with it's exposition of understood and assimilated CO2 recycling technology, seems to us another facet in a rather complete and comprehensive body of fuel synthesis technologies that have been and are being developed at the Pennsylvania State University; technologies that rely on our Coal Country resources of Coal, CO2, Water and some environmental energy sources to provide for both the production of various hydrocarbon fuels and the reduction of accused greenhouse gas pollutants.

We will, as noted, continue to report to the best of our abilities, in a sadly piecemeal fashion, on those Penn State developments, as they become accessible to us.

Our varied personal disabilities and other insufficiencies prevent us from grabbing a notebook, jumping in a car and driving to the Happy Valley environs of State College, PA, and directly interviewing some of the Penn State principals, like Craig Grimes, Chunsan Song, Harold Schobert, and, as herein, Derek Elsworth, that are up to their necks in the issues.

But, some Coal Country journalist, one who actually and truly gives a hoot about their local people, their local economy and their local environment, really ought to get their butt out of their cushy chair behind their impressive desk in their cozy office and do exactly that.


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