http://www.netl.doe.gov/publications/proceedings/01/carbon_seq/p18.pdf
We submit herein what is, from our point of view, another of what has become for us an interesting collection of documents regarding the true nature of, and potentials for, Carbon Dioxide; just in case anyone does find themselves disposed to assuming some sort of leadership, or at least informational, role in the growing debate about utility MACT issues and that kind of thing.
And, we think it reflects even more of what we have come to perceive as the complete disconnect between the public pronouncements made by the political branches of our United States Government concerning Carbon Dioxide, and what the technical branches of our United States Government actually know to be true about Carbon Dioxide.
Consider, that, all you ever hear in the news concerning the issue of CO2 is how it's a greenhouse gas accumulating in our atmosphere in dangerous quantities, and, how we're either going to have to Cap & Trade tax the people, primarily the operators of Coal-fired power plants, who produce it out of business, or enslave them, through mandated Geologic Sequestration, into the service of Big Oil and his secondary petroleum scrounging in nearly-depleted natural oil reservoirs.
But, if you dig into, as we have done, what our US Government scientists, who by and large don't care what the people who have to smile for the cameras and scrounge for political donations have to say about it, are themselves doing and saying about Carbon Dioxide, there are absolutely astonishing contradictions.
For instance, to beat it to death, as seen for just two examples in:
US Navy Awarded September, 2011, CO2 Recycling Patent | Research & Development; concerning: "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; 2011; Assignee: The United States of America as represented by the Secretary of the Navy; Abstract: A method of: introducing hydrogen and a feed gas containing at least 50 % carbon dioxide into a reactor containing a Fischer-Tropsch catalyst; and heating the hydrogen and carbon dioxide to a temperature of at least about 190 C. to produce hydrocarbons in the reactor"; and:
USDOE Converts CO2 to Gasoline | Research & Development; "United States Patent 4,197,421 - Synthetic Carbonaceous Fuels and Feedstocks; 1980; Assignee: The United States of America; Abstract: This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous sodium carbonate/bicarbonate solution, obtained from scrubbing atmospheric carbon dioxide with an aqueous sodium hydroxide solution, whereby the hydrogen generated at the cathode and the carbon dioxide liberated in the center compartment are combined thermocatalytically into methanol and gasoline blends";
our United States Departments of Defense and of Energy, by inference, assert that Carbon Dioxide is a valuable raw material resource, one from which we can synthesize liquid hydrocarbon fuels, including Gasoline.
While, on the other hand, what we might label as our "politicos" continue to push for productivity-limiting measures like subsidization of the Oil industry through mandated Geologic Sequestration and what we often label in our posts as "Cap and Trade Taxation".
And, we do confess that we use that label, "Taxation", with some deliberate inaccuracy, to add emotion to our personal contention that we, as a nation, would be far better off recycling our Carbon Dioxide.
If anyone is interested, the Smithsonian Magazine provides a more balanced and thoughtful discussion of the issue in:
The Political History of Cap and Trade | Science & Nature | Smithsonian Magazine.
Speaking of Geologic Sequestration, though, in passing, we note that some very recent documentation has come to light demonstrating exactly why there is such a push for it; and, providing us with even more reason to start thinking of our Carbon Dioxide as a valuable commodity, that, if anyone wants to get it from us, they darned well better be prepared to pay us for it and accept our terms for selling it to them.
But, we'll eventually get to that.
The Carbon Dioxide transformation and recycling technology we introduce herein is fairly well represented in the literature; and, further explication of it is another issue we will eventually get to.
The basics are a tad difficult to understand, and we've had to kick it around with our consultants a good bit, most especially given our own personal handicaps and limitations, in order to get enough of a basic technical grasp in order to feel halfway comfortable introducing it to you.
To wit, we see herein that two distinguished and accomplished scientists have done their own review of available literature, and, for their own reasons, come to the same conclusion we reached long ago and which we repeat, using one version of the refrain or another, in nearly every one of our reports concerning Carbon Dioxide:
They "propose that CO2 be considered a renewable resource", and, "specifically that it be recycled back to fuel".
Of perhaps even more interest is the fact that this document was not actually published in the traditional sense. It was, apparently, contracted for, and is made publicly available only on the web and only by the United States Department of Energy's National Energy Technology Laboratory.
Comment follows excerpts from the initial link in this dispatch to:
"Reductive Sequestration of Carbon Dioxide
by: Ted Mill, SRI (aka Stanford Research Institute; see: Theodore Mill and SRI International - an independent, nonprofit R&D organization dedicated to client success.)
and D. Ross, U.S. Geological Survey
Introduction: The United States currently meets 80% of its energy needs by burning fossil fuels to form
CO2. The combustion-based production of CO2 has evolved into a major environmental challenge that extends beyond national borders and the issue has become as politically charged as it is technologically demanding.
(The)1997 Kyoto Treaty on Global Warming was initiated in a major world-wide effort to curtail CO2 emissions. A major feature of this activity involves separation, collection and storage of a significant fraction of the 6-billion tons of CO2 currently produced worldwide each year. The annual U.S. production is about a third of that value, and sites considered for storing U.S. produced CO2 include depleted gas reservoirs, deep saline aquifers, depleted oil reservoirs, coal beds, and the deep ocean.
Although accumulating the captured gas in vast reservoirs seems a rational approach to the problem, a second, potentially more rewarding route is suggested here.
(The above statement is, we feel obviously, a politely-worded swipe at the Geologic Sequestration concept, with the phrase "seems a rational approach" feeling like that one might use to soothingly correct the behavior of a particularly dense child. As we've seen previously, other serious scientists label it "ridiculous".)
Because the nominal 2 billion tons of CO2 the U.S. produces annually represents the energy content of about 11 million barrels of oil per day, or roughly the U.S. daily import, we propose that CO2 be considered a renewable resource.
We propose specifically that it be recycled back to fuel by employing water as the hydrogen source, and the reductive chemical energy available from sunlight driven (electrochemical processes) or thermal reduction using abundant (Iron)-containing minerals (of a specific type).
(The employment of specific "(Iron)-containing minerals" in the chemical reduction and recycling of CO2 is the technical issue we will begin addressing in future reports.)
If the process can be successfully applied, it would not only satisfy concerns tied to global warming, but would also eliminate some fraction of the nation’s daily dependence on imported oil. This dependence is now a matter of renewed concern and uneasiness with impact on both national security and the economy.
The proposed process involves reductive capture of CO2 in a two-part scheme related in part to the Fischer Tropsch process, and employing common minerals with sufficient reduction and/or photoreduction potential to convert CO2 to formate and/or methanol and then to fuel-valued products.
(See, for just a few examples out of now many:
Japan Converts CO2 to Formic Acid | Research & Development; concerning: "United States Patent 7,479,570 - Process for the Reduction of Carbon Dioxide; 2009; Assignee: Japan Science and Technology Agency; Abstract: Carbon dioxide and water are mixed with an organometallic complex (of varied and specified compositions). This makes it possible to directly reduce carbon dioxide in water. A reducing process of carbon dioxide, comprising mixing carbon dioxide and water with an organometallic complex ... so as to reduce carbon dioxide so that formic acid or alkali salt thereof is formed"; and:
Japan Converts CO2 to Methanol | Research & Development; concerning: "United States Patent 7,488,404 - Process for Hydrogenating Carbon Dioxide; 2009; Inventor: Masayoshi Matsui; Abstract: A process for hydrogenating carbon dioxide to generate methanol".).
Thermochemical calculations show the overall scheme to be highly exothermic, and thus self-sustaining with the proper process design.
(As with some Coal conversion technologies we've documented for you, in other words, little or no external energy would need to be supplied to the process.)
Objectives: This paper explores the photochemical and thermochemical parameters associated with reduction of CO2 ... (and) the key kinetic steps required to effect reduction to methane and higher alkanes. With that information, the overall feasibility of using this process for sequestration of CO2 can be evaluated relative to other CO2 sequestration processes.
Background: Carbon dioxide and its aqueous counterparts, bicarbonate and carbonate, are inherently
highly stable (and) are the most stable carbon-containing substances on a per carbon basis at 25°C. The thermochemical gap separating them from organic compounds widens still further at higher temperatures, increasing the difficulty of reducing CO2 at higher temperatures. It therefore follows that high reduction potentials are required to convert CO2 and its aqueous ions to organic species. And although such reduction reactions are known, they are presently confined to the ... laboratory.
(The above might not be, strictly speaking, true. As in:
Iceland Methanol from CO2 in 2010 | Research & Development; concerning: "CRI breaks ground for the first CO2 to Renewable Methanol Industrial Scale Plant in the world: Carbon Recycling International (CRI) captures carbon dioxide from industrial emissions and converts carbon dioxide into clean Renewable Methanol (RM) fuel. RM can be blended with different grades of gasoline for existing automobiles and hybrid flexible vehicles. The capture of carbon dioxide results in a net reduction of carbon dioxide from power generation. It is a cost effective method and sustainable production of renewable fuel. The ground-breaking of the George Olah Plant took place on October 17 2009 in Svartsengi, Iceland. CRI will construct an Industrial Scale Plant to capture carbon dioxide from emissions and produce Renewable Methanol (RM)";
CO2 chemical reduction and recycling might no longer be "confined" just "to the ... laboratory".)
Recently, however, the possibility of large-scale, process-level CO2 reduction has become more viable following two separate published accounts describing the reduction of CO2 with common minerals. The first is a report by McCollom (2000) who discussed experiments in hydrothermal media with dissolved CO2 and the mineral olivine, which showed that bicarbonate ion was immediately reduced to formate at 300C and 350 bar. These conditions are at pressures above the water saturation curve and therefore there was no headspace in the reactor. McCollom suggested that absence of headspace stopped the reduction at formate, since further reduction to alkanes is highly favored thermodynamically. McCollom et al. (1999) confirmed this speculation in other work using a system purposefully containing a headspace, in which reduction of aqueous formate to a broad array of hydrogen-rich Fischer Tropsch-like products in the C2 - C35 range, including alkanes, alkenes, and oxygenated products, readily took place at 175C.
(We will, in the future, make specific report of the above-cited works and references.)
The second account of a mineral-based conversion describes sunlight-driven production of formic acid from CO2 at ambient temperatures. In this case, Ohta et al. (2000) worked with a selection of common (Iron)-containing silicate rocks ... which were powdered and suspended in CO2-saturated water. When the mixtures were irradiated by sunlight at ambient temperatures, formic acid was formed ... .
Photoreduction of CO2 on irradiated semiconductor surfaces has been widely reported to give a range of C1 and C2 products, including CO, formate, methanol, methane, formaldehyde, xalic acid and glyoxal.
CO2 photoreductions are observed on a variety of metal oxides, including WO3, TiO2, ZnO, as well as on GaP, ZnS and CdS.
(See, concerning "CO2 photoreductions", for example:
Penn State Solar CO2 + H2O = Methane | Research & Development; "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; Materials Research Institute, The Pennsylvania State University; 2009; Efficient solar conversion of carbon dioxide and water vapor to methane and other hydrocarbons is achieved.")
.Approach: The existing literature on CO2 reductions shows that the reactions do work and can be modified to produce varying proportions of C1 and C2 products. However, efficiencies vary widely and the factors controlling selectivity and band gap energies are not well understood. Nor is it clear how the work of Ohta et al. with ferrous minerals relates to the semiconductor oxide processes. Despite these important gaps in understanding these two reduction processes, we propose a scheme to create fuel-valued products from process CO2.
The concept effectively utilizes the carbon cycle (as illustrated) to link energy available in the mineral phase (either thermally or photolytically) to that required in the reduction process. The core of the conversion is the central loop in which CO2 is reduced either thermally or through solar irradiation to formic acid ... .
The hydrogen source is water in the feed mixture.
Photoreduction of CO2 to formate using mineral surfaces would be a practical first step for sequestration if: (1) overall photoefficiency were comparable to that of other photoreductions, or about 10-15%; (2) if the active mineral photocatalysts were abundant and easily processed; and (3) if a photoreactor can be designed to efficiently utilize sunlight over a broad range of solar conditions.
Conversions of CO2 are highly exothermic, with the production of methane being the most heat-yielding. Thus, a self-sustaining operation should be attainable with the proper process design.
In summary, it appears that the practical sequestration of CO2 through conversion to formic acid and fuel-valued materials is feasible.
The sensible utilization of the concept will depend on the balance between the fuel value provided by reduction of CO2 and the energy requirements for reduction. The energy requirements are directly tied to the basic thermochemistry and kinetics of the individual steps in the sequence, including the two thermal
and one photochemical step. The program proposed here is designed to develop the necessary kinetic and photochemical parameters to evaluate the commercial potential of CO2 recycling."
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Our thoughts are, that, "the energy requirements for reduction" comprise an area where those concerned with and/or in one way or another affected by Carbon Dioxide emissions could come together. Those concerned with CO2 emissions are generally those proponents of environmental energy, which, while it might be abundant at certain places in various forms, i.e., wind, solar, hydro, still needs converted into some more easily transmittable and useable form.
That "form" is most often just electricity; but, herein we again see that environmental energy could be harnessed to drive the conversion of an accused environmental pollutant into various hydrocarbon compounds, which would in turn prevent environmental disruptions incurred by the extraction of those same types of hydrocarbon compounds from the natural deposits where they occur.
Sounds like a win-win-win to us - with Coal-based electric power, and it's customers, somewhere in that winning circle.
Again, and in sum:
Carbon Dioxide is "a renewable resource", and "the practical sequestration of CO2 through conversion to formic acid and fuel-valued materials is feasible".
Sounds like a decent place for all of us to start leading from.