http://www.osti.gov/scitech/biblio/1127211

We bring to you herein a fairly recent publication from the Morgantown, WV, and Pittsburgh, PA, National Energy Technology Laboratory - a component of the United States Department of Energy.

It documents an active program of development by the USDOE, directed toward the improvement of established technology for converting Carbon Dioxide, as recovered from whatever handy source, into fuel alcohol Methanol.

 We're enclosing two links to the document, the one above, leading to a synopsis, and another to a different file of it, leading to the full report, as follows:

http://www.osti.gov/scitech/servlets/purl/1127211.

Additionally, due to the importance we ascribe to it, we will be forwarding an electronic file of the full report to the West Virginia Coal Association.

By way of introduction to the technology reported herein by the USDOE, we remind you, that, as seen in our report of:

Sweden Makes Public Report of CO2 to Motor Fuel Recycling | Research & Development | News; concerning the Swedish newspaper article:

"Iceland As A Green Saudi ArabiaMarch 12, 2013Recently, they shipped the first load to oil company Argos in Holland, for low level blending in gasoline. Vulcanol is just a name for methanol, regular wood spirit. It is the production method which makes this fuel especially interesting. It is made using renewable electricity, water and captured CO2";

they are, in Europe, already making Methanol out of Carbon Dioxide on an industrial, commercial basis.

And, as can be learned via:

USDOE Confirms CO2 to Methanol Economic Viability | Research & Development | News; concerning the USDOE report:

"SANDIA REPORT SAND2009-7489; November 2009; Final Report on “Fundamentals of Synthetic Conversion of CO2 to Simple Hydrocarbon Fuels” (LDRD 113486); Prepared by: Sandia National Laboratories, Albuquerque, New Mexico and Livermore, California; Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000. (A) detailed process analysis comparing the potential for chemical and conventional engineering methods to provide a route for the conversion of CO2 and water to fuel has been completed. No apparent “showstoppers” are apparent in the synthetic route";

our United States Department of Energy determined that such CO2-to-Methanol operations could, indeed be economically viable.

And, as seen in:

USDOE Finances September, 2012, CO2 to Methanol | Research & Development | News; concerning: "United States Patent Application 20120225956 - Catalysts for the   Reduction of Carbon Dioxide to Methanol;
Date: September 6, 2012; Assignee: Trustees of the Leland Stanford Junior University, California; Abstract: A catalytic composition is provided for methanol production.   The composition includes an alloy of at least two different metals M and M',   where M is selected from Nickel, Palladium, Iridium, and Ruthenium, and M' is   selected from Gallium, Zinc, and Aluminum. A molar ratio of M to M' is in the   range of 1:10 to 10:1, and the alloy is configured to catalyze a reduction of CO2 to methanol. Government Interests: This invention was made with Government support under Grant No. DE-AC02-76SF00515, awarded by the Department of   Energy. The Government has certain rights in this invention";

the USDOE has invested some of the tax dollars collected from all of us into the development of better catalysts for promoting the Carbon Dioxide-to-Methanol conversion.

In addition to the catalyst blend specified in the above USDOE-sponsored "United States Patent Application 20120225956 - Catalysts for the Reduction of Carbon Dioxide to Methanol", as seen in our report of:

Conoco Converts CO2 to Methanol and Dimethyl Ether | Research & Development | News; concerning: "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates; 2003; Assignee: ConocoPhillips Company; Abstract: A catalyst and process for converting carbon dioxide into oxygenates. The catalyst comprises copper, zinc, aluminum, gallium, and a solid acid. Claims: A catalyst composition comprising: copper; zinc; aluminum; gallium; and a solid acid (wherein) said solid acid (comprises) a zeolite (specified as) ZSM-5. A catalyst composition for converting carbon dioxide to methanol and dimethyl ether. The present invention relates generally to the conversion of carbon dioxide to oxygenates. In another aspect, the invention concerns a catalyst for converting a feed comprising carbon dioxide and hydrogen into methanol and dimethyl ether";

other catalyst blends, based on, primarily, Copper and Zinc have been developed by private industry to promote the synthesis of Methanol from Carbon Dioxide.

And, herein, we learn that our United States Department of Energy, as embodied in the Pittsburgh, PA, and Morgantown, WV, National Energy Technology Laboratory, has begun to work with those Copper-based Carbon Dioxide "hydrogenation" catalysts, as well, and has found ways to improve them, and to, thereby, improve the efficiency of converting Carbon Dioxide into fuel alcohol Methanol.

We advise that the full document is highly technical, and is supported by charts and graphs. Our excerpts will thus be relatively brief, and, we'll attempt to summarize the import of it all in comments following those excerpts from, as accessible via the links:

"Adsorption and Deactivation Characteristics of Cu/ZnO-Based Catalysts for Methanol Synthesis from Carbon Dioxide

Date: December 31, 2013

Authors: Sittichai Natesakhawat, et. al.

DOE Contract Number: DE-FE0004000

Research Organization: National Energy Technology Laboratory - In-house Research; National Energy Technology Laboratory (NETL), Pittsburgh, PA, and Morgantown, WV

Sponsoring Organization: United States Department of Energy Office of Fossil Energy

Abstract: The adsorption and deactivation characteristics of coprecipitated Cu/ZnO-based catalysts were examined and correlated to their performance in methanol synthesis from Carbon Dioxide hydrogenation. The addition of Ga{2}O{3} and Y{2}O{3} promoters is shown to increase the Cu surface area and CO2/H2 adsorption capacities of the catalysts and enhance methanol synthesis activity.

Infrared studies showed that CO2 adsorbs spontaneously on these catalysts at room temperature ... as carbonate species. These weakly bound species desorb completely from the catalyst surface by 200 C ... .

Gallium and Yttrium promotion improves the catalyst stability by suppressing the agglomeration of Cu and ZnO particles under pretreatment and reaction conditions.

Introduction: Due to ever-increasing concerns over energy demands and global warming, current research activities are driven by a pressing need to develop new, efficient technologies for mitigating CO2 emissions.

Thermocatalytic hydrogenation of CO2 offers an attractive route to utilize CO2 as an inexpensive raw material to produce value-added methanol, which can be used directly as a fuel or further converted to various commodities.

While many catalytic systems including supported precious metal catalysts have been investigated, Cu/ZnO-based catalysts remain the most promising system for methanol synthesis from CO2.

ZnO is an important component because it prevents agglomeration of Cu particles, thus leading to the large Cu surface area needed for methanol catalysis. However, information about the crystal structure and morphology of ZnO, the synergy between Cu and ZnO, and how these properties affect the stability of such catalysts is lacking. Additionally, the role of ZnO on the adsorption and activation of CO2 is still unclear.

Therefore, an understanding of adsorption and deactivation characteristics of Cu/ZnO-based catalysts will help identify key parameters controlling their overall performance, both in activity and resistance to sintering, and will subsequently facilitate rational design of robust methanol synthesis catalysts for CO2 reuse.

Previously, we have demonstrated that CO2 hydrogenation to methanol over Cu-based catalysts is a structure-sensitive reaction. There is a linear correlation between turnover frequency for methanol formation and Cu crystallite size. An activity enhancement observed with smaller Cu particles may be attributed to larger numbers of open planes and edge/defect sites that can bind more strongly with key reaction intermediates (i.e., formates).

In the present contribution, we report a study of adsorption and deactivation characteristics of coprecipitated Cu/ZnO-based catalysts for methanol synthesis from CO2.

We investigated the nature of adsorbed species on the surface of reduced catalysts upon exposure to CO2 and H2 using temperature-programmed desorption (TPD) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The sintering behavior of prepared catalysts was also examined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution transmission and scanning transmission electron microscopy (HRTEM/STEM), Cu surface area and dispersion measurements using N2O decomposition, and temperature-programmed reaction (TPReaction).

A promotional effect of Ga2O3 and Y2O3 addition on the CO2/H2 adsorption capacities and catalyst stability is discussed.

Under the reaction conditions used in this study, the products from CO2 hydrogenation are methanol, carbon monoxide, and water vapor. ... As the reaction temperature is increased, methanol selectivity decreases whereas CO selectivity increases. These results indicate that the formation of CO via the reverse water-gas shift reaction (CO2 + H2 → CO + H2O) becomes more appreciable at higher temperatures, therefore leading to a decrease in methanol selectivity.

Conclusions: The crystallinity, morphology, and particle size of ZnO have a strong impact on the performance of coprecipitated Cu/ZnO-based catalysts for methanol synthesis from CO2 hydrogenation.

The incorporation of Ga2O3 and Y2O3 as textural promoters delays the crystallization of ZnO during
synthesis and produces an amorphous-like structure. The catalysts containing amorphous ZnO exhibit significantly higher activity and stability than their counterparts with crystalline ZnO.


The synergy between Cu and ZnO may be associated with an intimate contact between the two components, which creates additional adsorption sites for CO2 and H2. A large amount of spherical ZnO nanoparticles ... are found in the Ga and Y-promoted catalysts and they aid in preventing Cu particles from agglomeration during exposure to the pretreatment and reaction conditions. ZnO is an essential component because it acts as a hydrogen reservoir for methanol synthesis on Cu crystallites and stabilizes them against sintering".

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In sum: Our USDOE Morgantown, WV, and Pittsburgh, PA, labs have improved the process for converting Carbon Dioxide into such useful substances as Methanol and "carbon monoxide".

Their technology for so productively utilizing Carbon Dioxide requires a supply of elemental, molecular Hydrogen, and, as seen for only one example in:

Japan Hydrogen from Water and Sunlight | Research & Development | News; concerning yet another light-driven water-splitting Hydrogen production technology from Japan's Panasonic Corporation: "United States Patent 7,909,979 - Water Photolysis System and Process; 2011; Assignee: Panasonic Corporation; Abstract: The present invention provides a water photolysis system comprising: a casing into which incident sunlight can enter (and in which water) vapor is decomposed into hydrogen and oxygen by the photocatalyst particles, which are excited by the sunlight";

the technologies are becoming available to extract Hydrogen from the abundant water molecule in processes powered by freely-available environmental energy.

As far as the "carbon monoxide" is concerned, it is being generated from Carbon Dioxide by the "reverse water gas shift conversion", or, more simply, "reverse conversion", as described for one example, in:

France Efficient CO2 to Carbon Monoxide Conversion | Research & Development | News; concerning: "United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst; 2003; Assignee: Air Liquide (France); Abstract: The invention concerns a method for producing carbon monoxide by reverse conversion, in gas phase, of carbonic acid gas and gaseous hydrogen while minimising the production of methane. The invention is characterised in that the reaction is carried out at a temperature between 300 and 520 C and under pressure between 10 to 40 bars in the presence of an iron-free catalyst based on zinc oxide and chromium oxide. Said method is preferably carried out continuously and comprises preferably the following steps which consist in: a) preparing a gas mixture rich in carbon dioxide and in hydrogen ... between 300 and 520 C; b) reacting said gas mixture, forming carbon monoxide and water vapour, by passing said mixture through a catalytic bed based on zinc oxide and chromium oxide maintained under pressure between 10 and 40 bars".

And, once we have Carbon Monoxide, as generated from Carbon Dioxide, we can, as seen in:

Conoco Hydrogenates More Carbon Monoxide | Research & Development | News; concerning: "United States Patent 6,730, 708 - Fischer-Tropsch Processes and Catalysts Using Aluminum Borate; 2004; Assignee: ConocoPhillips Company; Abstract: A process is disclosed for the hydrogenation of carbon monoxide. The process involves contacting a feed stream comprising hydrogen and carbon monoxide with a catalyst system in a reaction zone maintained at conversion-promoting conditions effective to produce an effluent stream, preferably comprising hydrocarbons";

react that CO2-based Carbon Monoxide with even more Hydrogen, and thereby generate a complete range of needed "hydrocarbons".

Further, since Methanol is the primary desired product generated from Carbon Dioxide herein by our USDOE's Morgantown and Pittsburgh labs, since, as they put it: "hydrogenation of CO2 offers an attractive route to utilize CO2 as an inexpensive raw material to produce value-added methanol, which can be used directly as a fuel or further converted to various commodities"; we remind you that, as can be learned via:

ExxonMobil Coal to Methanol to Gasoline | Research & Development | News; concerning both:

"United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Assignee: Exxon Research and Engineering Company; Claims: A process for the production of methanol from a carbonaceous feed material (by) gasifying said carbonaceous feed material with steam ... and added hydrogen and carbon monoxide (and) wherein said carbonaceous feed material comprises coal"; and:

"United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation; Claims:  (A) method for converting methanol to gasoline boiling products in a plurality of sequentially arranged catalyst beds";

one of the "commodities" into which Methanol - - no matter which of our precious natural raw material resources, whether Coal, as in the above-cited: "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification", or, Carbon Dioxide, as discussed and described by our subject herein, the USDOE report: "Adsorption and Deactivation Characteristics of Cu/ZnO-Based Catalysts for Methanol Synthesis from Carbon Dioxide" - - can be "further converted" is Gasoline.

The work described herein by USDOE scientists in Morgantown and Pittsburgh actually represents an improved understanding of, and improved catalytic technology for, the conversion of Carbon Dioxide into, preferentially, Methanol, with identification of process variations that can enable the generation of valuable Carbon Monoxide as a byproduct.

We rather expect that the very recent innovations described in this work will result in an application for patent protection on the technology, with rights to be assigned to the United States Government. If and when such an application results, we will bring news of it to you. However, for now, it should be worthy enough to note, that:

Coal Country scientists in the employ of our United States Government have, in research paid for with the taxes contributed by all of us, again demonstrated an important fact that we ignore at our economic peril:

Carbon Dioxide - - as it arises in only a very small way, relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of truly abundant and truly affordable electric power - - is a valuable, maybe even a precious, raw material resource.

We can, as shown by work very recently performed in Morgantown, WV, and Pittsburgh, PA, based on the enhancement of catalysts originally developed by ConocoPhillips, reclaim Carbon Dioxide from whatever convenient source, and, then, we can efficiently convert that Carbon Dioxide into such immensely valuable industrial and fuel commodities as Methanol.


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