Energy Citations Database (ECD) - - Document #804531
The documents we enclose in this dispatch are further evidence that our own United States Department of Energy knows one heck of a lot about the conversion, the recycling, of Carbon Dioxide into hydrocarbon fuels; but, that they are, or at least were, trying to avoid talking too much about it.
The initial link in this dispatch takes you to a "Progress Report" concerning the course of a research project, undertaken for the USDOE by the University of Oklahoma, focused on the production of synthesis gas, suitable for catalytic condensation into liquid hydrocarbons, by reacting Methane with Carbon Dioxide.
That concept shouldn't be unfamiliar to you, presuming you to have followed our posts thus far.
It is a process and technology that, as we have documented, has been known of since before WWII, as we documented in:
1939 CO2 + CH4 = Hydrocarbons | Research & Development; concerning: "US Patent 2,180,672 - Process for Converting Gaseous Hydrocarbons; 1939; Phillips Petroleum, Oklahoma; This invention relates to processes for the conversion of normally gaseous hydrocarbons into organic products of higher molecular weight and more specifically to the conversion of methane and higher gaseous hydrocarbons together with oxides of carbon into such organic products ... . An object of the present invention is the production of hydrocarbons suitable for motor fuel ... from gaseous hydrocarbons of lower molecular weight by reacting them with oxides of carbon ... (in a process wherein) carbon dioxide ... may be mixed directly with the gaseous hydrocarbons ... predominating in methane".
Further, the study and development of such technology continues today, as seen in:
Exxon 2010 CO2 + Methane = Liquid Hydrocarbons | Research & Development; concerning: "United States Patent 7,772,447 - Production of Liquid Hydrocarbons from Methane; 2010; Assignee: ExxonMobil; Abstract: (A) process for converting methane to liquid hydrocarbons ... (by) contacting a feed containing methane and ... H2O (and) CO2 with a (specified) catalyst"; and, in:
WVU CO2 + CH4 = Hydrocarbon Syngas | Research & Development | News; concerning: "New Catalysts for Syngas Production from Carbon Dioxide and Methane; Mahesh V. Iyer; West Virginia University; 2001".
Keeping in mind that the Methane needed to recycle Carbon Dioxide can be obtained, as ExxonMobil themselves tell us, as in:
Exxon Converts 99% of Coal to Methane | Research & Development | News; concerning: "United States Patent 4,077,778 - Process for the Catalytic Gasification of Coal; 1978; Exxon Research and Engineering Company; Abstract: A process for the production of synthetic natural gas from ... coal (wherein) the synthetic natural gas (consists) essentially of methane";
from Coal; or, as 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; 2009; Efficient solar conversion of carbon dioxide and water vapor to methane";
from Carbon Dioxide itself;
we see herein that the University of Oklahoma and our own United States Department of Energy again confirm that such Methane can, indeed, be reacted with Carbon Dioxide, reclaimed from whatever source, and be made through such reactions to form a synthesis gas, consisting of Hydrogen and Carbon Monoxide, suitable for catalytic condensation into liquid hydrocarbon fuels.
As a forward, we must note that the University of Oklahoma herein, and somewhat predictably, insists on referring to "natural gas" as the co-reactant for Carbon Dioxide, albeit natural gas with a high Methane content. But, again, as documented above, "natural gas" is far, far from our only source of Methane, and, for reasons we point out, such "natural gas" may be a relatively unattractive source for the Methane.
Somewhat discouraging comment is appended to excerpts from the initial and followings links herein to:
2 Mb View Document or Access Individual Pages; DOI: 10.2172/804531
Title: Novel Catalyst Development and Process Optimization for CO2 reforming of CH4.
Progress report for the period March 1, 1999 - December 31, 1999.
Date: May, 2002
Authors: Daniel Resasco and Miguel Bagaiewicz
Research Organization: University of Oklahoma; Sponsor: United States Department of Energy
USDOE Contract Number: FG02-99ER45759
The CO2 reforming of CH4 (has) been intensively investigated for the production of synthesis gas as a complementary process of the well-established steam reforming. The ... H2/CO product ratio, which is lower than that of steam reforming, make this process attractive for some applications. The primary difficulty associated with the applicability of the CO2 reforming process is finding a suitable catalyst that will not deactivate under the conditions needed for this reaction.
Since the reforming reaction is highly endothermic, high operating temperatures are required to obtain significant conversions. At such high temperatures and in the presence of high concentrations of carbon-containing compounds, the catalyst is susceptible to deactivation, primarily by carbon deposition.
Two types of natural gases, one with almost no CO2 and the other with a high content of CO2 were chosen to investigate whether a single reactor or a combination of them can competitively produce Syngas. Addition of CO2 and water to the inlet and intermediate streams is considered as means of adjusting conditions to reach the desired Syngas ratio.
(Note: Carbon Dioxide, from whatever source, can, in some cases, be added, depending upon the amount of Carbon Dioxide that is already, naturally, contained by "America's Clean Energy Alternative". And, that relates to one of our points in our opening comments: Why bring "natural gas" that is already contaminated with high levels of Carbon Dioxide to the surface, anyway, the Marcellus Shale Gas tulip frenzy currently afflicting certain segments of our Coal Country press notwithstanding? That CO2 is already naturally "sequestered"; and, we can make all of the Methane we might want or need out of Coal or Carbon Dioxide. We don't have to release CO2 from natural sequestration.)
Specifically, the purpose of this study was to identify under which conditions (pressure, temperature, amount of water in the feedstock, and reactors scheme) the reforming of natural gas using steam and/or CO2 is thermodynamically and economically optimal.
During this project a process thermodynamics analysis of the CO2 reforming of methane aiming at the selection of optimal process conditions for the production of Syngas was studied.
The constraints are given by the following specifications:
High methane conversion.
The lowest possible CO2 content in the (final) product.
The highest possible Syngas production rate.
A low usage of steam is preferred.
(The above reference to "usage of steam" concerns "tri-reforming" processes, such as, for example, seen in:
1944 CO2 + H2O + CH4 = Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent 2,355,753 - Catalytic Apparatus; 1944; The M.W. Kellogg Company, NJ; Abstract: The present invention relates generally to improvements in ... the production of a synthesis gas adapted for use in the synthesis of various ... hydrocarbons ... by the interaction of methane with carbon dioxide, or with steam, or with a mixture of carbon dioxide and steam"; and, the much later:
Minnesota & WV CO2 + CH4 + H2O = Syngas | Research & Development; concerning: "United States Patent 6,254,807 - Control of H2 and CO Produced in Partial Oxidation Process; 2001; Lanny Schmidt, Minneapolis, and Paul Witt, Dunbar, WV; The invention was made with government support under DOE Grant No. DE-FG02-88ER13878-A02. Abstract: A process for enhancing H2 or CO production in a partial oxidation reaction by feeding H2O or CO2 with the feed hydrocarbon (wherein) the ratio of (product) H2:CO is manipulated by the addition of either water or CO2 to the partial oxidation (of the feed hydrocarbon, which is) preferably methane".
Further, as indicated especially by the above USP 6,254,807, Steam can be added in lesser or greater quantities to the blend of Carbon Dioxide and Methane, to effect in desired ways the ratios of Carbon Monoxide and Hydrogen in the synthesis gas thus produced. However, according to the University of Oklahoma, in their full dissertation, a "low usage of steam is preferred" in order to minimize costs.)
It is concluded that a process at atmospheric pressure is more convenient due to a higher methane conversion, Syngas yield, H2/CO ratio, as well as reduced carbon formation when compared with a process at a higher pressure.
(A lower-pressure, and thus lower-cost, process for reacting Methane with CO2, is, it seems, better.)
Conclusions: Optimal conditions of temperature and pressure as well as water addition and CO2 recycling have been investigated (and) the following conclusions are made:
When using Terrell gas, recycling CO2 increases the yield, the water required, the duty, and the methane conversion at constant desired H2/CO ratios. The cost of CO2 separation and recycling needs to be considered.
For California gas processing, and working at low desired Syngas H2/CO ratios, recycling CO2 is not enough to get high yields and conversion.
Thus, external CO2 is needed."
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Some explanations, not provided, at all in the full report, are needed. It is almost as if they wished to keep the details secret.
"Terrell gas", again not explained in the document, is, according to other web-based references, a "standardized" label applied to natural gas close in composition to that produced in and around the town of Terrell, Texas. It is characterized by having a relatively high natural Carbon Dioxide content, and, thus, no "external CO2" needs to be supplied.
"California gas", a similar standardized label that should be self-explanatory, is low in natural CO2 content.
And: "Thus, external CO2 is needed".
We submit, yet again, that processes exist, such as seen in:
Pittsburgh USDOE Converts CO2 to Methane & Methanol | Research & Development; concerning: "Visible Light Photoreduction of CO2; 2009; National Energy Technology Laboratory, USDOE, Pittsburgh, PA; Abstract: A series of ... Titanium Dioxide (catalysts) have been synthesized, characterized, and tested for the photocatalytic reduction of CO2 in the presence of H2O (and) the primary reaction product is CH4";
which would enable us to use environmental energy to effect the "photocatalytic reduction of CO2 (and) H2O" into "CH4", i.e., Methane, that would have absolutely no Carbon Dioxide mixed with it, as would natural gas, whether from California or Texas, or Marcellus Shale.
Thus, nothing else but "external CO2", perhaps captured, as in
Efficient Capture of Atmospheric CO2 | Research & Development; concerning: "US Patent 7,993,432 - Air Collector ... for Capturing Ambient CO2; 2011; Assignee: Kilimanjaro Energy, Inc., WI; An apparatus for capture of CO2 from the atmosphere comprising an anion exchange material formed in a matrix exposed to a flow of the air. A process for removing CO2 from atmospheric air at a location remote from where the CO2 was generated";
economically from the atmosphere itself, could be added to the process developed herein by the University of Oklahoma for our United States Department of Energy, and be reacted with Methane, perhaps synthesized as in the above-cited USDOE-Pittsburgh technology from Carbon Dioxide itself, and be made thereby to form a blend of Carbon Monoxide and Hydrogen, a "synthesis gas" as the University of Oklahoma and our USDOE specify, "which is ... attractive for some applications".
And, which "applications", we submit, would include those such as and similar to that described, plainly and directly, in:
Fischer–Tropsch process - Wikipedia, the free encyclopedia; wherein we learn that: "The Fischer-Tropsch Process (or Fischer–Tropsch Synthesis) is a set of chemical reactions that convert a mixture of carbon monoxide and hydrogen into liquid hydrocarbons."
However, we did note that some "discouraging comment" would be forthcoming, and, it is this:
The document we enclose as the centerpiece of this dispatch is only a "Progress Report" for a nine-month period of the contract in 1999. There is, as we have so far been able to determine in multiple searches of USDOE document data bases, no "final report" available.
That, even though the University of Oklahoma scientists who were the lead investigators are otherwise apparently well-accomplished investigators of Methane-Carbon Dioxide reforming technology, as witnessed in other publications, such as:
Energy Citations Database (ECD) - - Document #659075: "Effect of promotion with Sn on supported Pt catalysts for CO2 reforming of CH4; Journal of Catalysis, August, 1998; D. Resasco, et. al., University of Oklahoma; Abstract: The reforming of CH4 with CO2 (dry reforming) was studied ...over SiO2 and ZrO2 supported Pt-Sn catalysts."
Where is the final report of "USDOE Contract Number: FG02-99ER45759", which makes disclosure of research confirming that Methane, perhaps synthesized, as we've separately documented, from Carbon Dioxide, can be reacted with Carbon Dioxide, and be made through such a reaction to form a "synthesis gas" likely suitable for Fischer-Tropsch, and related, catalytic condensation into "liquid hydrocarbons"?
We US citizens paid for that research through our taxes.
Each and every one of us US citizens, especially those of us resident in US Coal Country, with our livelihoods threatened by Cap & Trade tax extortions and mandated CO2 Geologic Sequestration scams, deserves to have a copy of that full, US tax-paid report delivered to us by the US Postal Service.
Or, at the very least, a Coal Country journalist should get a copy, by hook or by crook, and fill us all in on it.
And, make no mistake, the people of Oklahoma, where this good information was developed by research paid for by every US citizen's tax money, and, where, like Texas, they used to produce, and profit from, a lot of oil, know all about these potentials for recycling Carbon Dioxide in the synthesis of hydrocarbon fuels.
Or, at least their elected representatives are aware enough to know about them, as circumstantially evidenced by:
Oklahoma Conservation Commission - WQ Carbon Sequestration Enhancement Act; concerning the:
"Oklahoma Carbon Sequestration Enhancement Act; The Oklahoma Legislature finds that: Increasing levels of carbon dioxide in the atmosphere have led to growing interest in national and international forums for implementing measures to slow and reverse the buildup of such atmospheric constituents. These measures may include, but are not limited to, the establishment of systems of trading in carbon dioxide credits or adoption of practices, technologies, or other measures which decrease the concentration of carbon dioxide in the atmosphere ... including, but not limited to ... improved practices for the capture and sequestration of carbon dioxide emissions through carbon dioxide injection in marginally producing oil and/or gas wells and abandoned oil and/or gas wells".