http://prod.sandia.gov/
The United States Department of Energy confirmed, in November, 2009, that it is now both technically and economically feasible to begin synthesizing the fuel alcohol Methanol from Water and Carbon Dioxide.
Carbon Dioxide, in other words, as it arises in only a small way, relative to all-natural and un-taxable sources of CO2 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, a strategically critical, raw material resource.
That fact should by now be evident to our readers, since, as seen in our report of:West Virginia Coal Association | Sweden Makes Public Report of CO2 to Motor Fuel Recycling | Research & Development; concerning the news story: "Iceland As A Green Saudi Arabia; March 12, 2013; Recently, 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 from the nearby geothermal power plant HS Orka";
they are already synthesizing Methanol from Carbon Dioxide on an industrial, commercial basis in the European nation of Iceland, and, as seen in our report of:
West Virginia Coal Association | : Saudi Arabia and CO2: The Rich Get Richer | Research & Development; concerning the news release: "'SABIC Unit Plans World’s Largest CO2 Purification Plant'; United Jubail Petrochemical Company, an affiliate of Saudi’s SABIC, has awarded a construction contract for the plant to Germany’s Linde Group. By Aarti Nagraj, August 21, 2013; An affiliate of Saudi Basic Industries Corporation (SABIC) announced that it has awarded a construction contract to build the world’s largest carbon dioxide (CO2) purification and liquefaction plant in the Kingdom. United Jubail Petrochemical Company (United), a manufacturing unit of SABIC, has given the engineering, procurement and construction contract for the project to Germany’s The Linde Group, it said in a statement. ... The plant will be designed to compress and purify about 1,500 tons per day of raw carbon dioxide coming from ethylene glycol plants. The purified gaseous CO2 will then be supplied through pipes to three SABIC-affiliated companies for enhanced methanol and urea production, the statement said. Methanol is a basic commodity for the chemical industry, and urea is used for fertilizer production. The plant will help save an estimated 500,000 tons of CO2 emissions each year, SABIC stated. Yousef Al-Zamel, SABIC executive vice president, Chemicals Strategic Business Unit, said: “It will add to SABIC’s business portfolio of industrial gas products. This is the first of many other similar projects to be executed next year";they are getting ready to do it in a big way in the OPEC Kingdom of Saudi Arabia.
And, as seen for a few examples in our reports of:
West Virginia Coal Association | USDOE "Green Freedom" CO2 Recycling | Research & Development; concerning the USDOE CO2-recycling program so advanced they gave it a trade name: "Green Freedom (TM) - A Concept for Producing Carbon-Neutral Synthetic Fuels; November, 2007; Jeffrey Martin and William Kubic; Los Alamos National Laboratory, NM; Introduction: We have developed a low-risk, transformational concept, called Green Freedom (TM), for large scale production of carbon-neutral, sulfur-free fuels and chemicals from air and water. Green Freedom (TM) utilizes carbon-neutral power to recover carbon dioxide from the atmosphere; split water into hydrogen; and, convert hydrogen and carbon dioxide into synthetic fuels and organic chemicals. Green Freedom's (TM) synthesis-gas process is based on ... current technologies that are in wide use. (Those technologies include) a process to separate carbon dioxide from the atmosphere and produce useful hydrogen as a byproduct; a process to generate supplemental hydrogen by splitting water; and, a carbon neutral power source. Many useful organic chemicals can be produced ... (and we) have developed Green Freedom (TM) concepts for evaluation specifically for production of methanol and gasoline. Making gasoline from air and water sounds exotic, but now practical technology has been developed to implement known chemical pathways for producing fuel from these abundant raw materials";
and:
West Virginia Coal Association | USDOE Calls for CO2 Recycling Revolution | Research & Development; concerning the thesis: "Initial Case for Splitting Carbon Dioxide to Carbon Monoxide and Oxygen; 2007;
James E. Miller; Sandia National Laboratories; Albuquerque, NM; Abstract: The United States presently imports ... more than 20 million barrels of petroleum that it consumes daily. The largest fraction of this consumption ... is for transportation. Unfortunately, much of the non-domestic oil extraction, which we both directly and indirectly rely on, is from fields in unstable parts of the world. The national security and economic implications of our dependence upon foreign oil ... prompts a search for alternative sources of liquid fuels.Independence from problematic oil producers can be achieved to a great degree by applying decades-old synfuel technologies to convert non-conventional resources such as coal ... into liquid fuels.(And), if we adopt revolutionary thinking about energy and fuels, it may be possible to the meet the future fuel challenges while maintaining our traditional hydrocarbon fuel framework. We must recognize that hydrocarbon fuels are energy carriers, not energy sources. The energy stored in a hydrocarbon is released for utilization by oxidation to form CO2 and H2O. Furthermore, just as H2O can be “reenergized” by applying energy to split water back into H2 and O2, hydrocarbons can be recycled by capturing CO2 (and H2O) and 're-energizing' them back into hydrocarbon form. In this document, the concept of (using) thermochemical cycles to split CO2 into CO and O2 as a starting point for synthetic fuel production is introduced and potential advantages of this approach are discussed. The most general way to convert CO2 and H2O into a fuel is through the intermediate production of synthesis gas or 'syngas'. Syngas is roughly a 1:2 mixture of CO and H2 whose exothermic conversion to fuel and other products is currently commercially practiced. Stated concisely, one key route to converting CO2 and H2O into fuel is the following 'reenergizing' reaction:2CO2 + 4H2O → 2CO + 4H2 + 3O2. Herein, we begin to document and expand on the case for splitting carbon dioxide into CO and O2 as an attractive (option). (Thus,) the discussion herein is primarily limited to a comparison of water splitting and carbon dioxide splitting as the key steps in fuel production from CO2 and water";
our USDOE began laying the rational and technical foundations for recycling Carbon Dioxide, to produce primarily Methanol, several years ago. Further, those foundations have led to, as seen in:
West Virginia Coal Association | USDOE Converts Atmospheric CO2 into Gasoline | Research & Development; concerning: "United States Patent Application 20100205856 - Method of Producing Synthetic Fuels and Organic Chemicals from Atmospheric Carbon Dioxide; Date: August 19, 2010; Inventors: William Kubic and Jeffrey Martin, Los Alamos, NM; Assignee: Los Alamos National Security LLC, NM (USDOE);
Abstract: The present invention is directed to providing a method of producing synthetic fuels and organic chemicals from atmospheric carbon dioxide. Carbon dioxide gas is extracted from the atmosphere, hydrogen gas is obtained by splitting water, a mixture of the carbon dioxide gas and the hydrogen gas (synthesis gas) is generated, and the synthesis gas is converted into synthetic fuels and/or organic products. Government Interests: This invention was made with government support under Contract No. DE-AC52-06NA25396 awarded by the U.S. Department of Energy. The government has certain rights in the invention.Claims: A method for producing a chemical product comprising the steps of: extracting carbon dioxide gas from the atmosphere; producing hydrogen gas; combining said carbon dioxide gas and said hydrogen gas to produce a synthesis gas; and converting said synthesis gas to said product (and)wherein said product is selected from the group consisting of fuel, diesel fuel, jet fuel, gasoline, petrochemicals, plastics, butane, methanol, ethylene, propylene, aromatic compounds, petrochemical derivatives, derivatives thereof, and mixtures thereof";
the development of a complete, direct technology that enables the conversion of Carbon Dioxide, captured, as in "a method of producing synthetic fuels and organic chemicals from atmospheric carbon dioxide", from the atmosphere itself, into a full range of hydrocarbon fuels and chemicals.The above-cited "United States Patent Application 20100205856 - Method of Producing Synthetic Fuels and Organic Chemicals from Atmospheric Carbon Dioxide" arose, we are convinced, from the "Green Freedom (TM)" project, as noted above, which, insofar as we have been able to determine from web-accessible documents, was undertaken by both the Los Alamos and Sandia National Laboratories, which would include, we believe, the Lawrence Livermore Lab in California, and which, as indicated, centered on the conversion of Carbon Dioxide and Water into Methanol.
Methanol is a very basic compound of Carbon and Hydrogen, and, as seen for one example in:
West Virginia Coal Association | ExxonMobil Coal to Methanol to Gasoline | Research & Development; concerning both: "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification;
1982; Assignee: Exxon Research and Engineering Company; Abstract: Methanol is produced by gasifying a carbonaceous feed material with steam ... wherein said carbonaceous feed material comprises coal"; and:
"United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation;
Abstract: The conversion of methanol to gasoline";
no matter what it's made from, Methanol is well-suited to serve as a starting point from which to synthesize other, more complex, hydrocarbon compounds. We don't wish though to presuppose how the USDOE's Carbon Dioxide recycling technology has evolved, since "United States Patent Application 20100205856 - Method of Producing Synthetic Fuels and Organic Chemicals from Atmospheric Carbon Dioxide" seems to suggest that a range of products can be generated directly, via an intermediate synthesis gas, from Carbon Dioxide.
Nonetheless, Methanol is both a product and a raw material of already-immense, and perhaps increasing, industrial value and utility. And, herein, we learn that our United States Department of Energy, as embodied in their western United States National Laboratories, established the fact, several years ago, that:
Not only is it perfectly feasible on a technological basis to convert Carbon Dioxide, as recovered perhaps especially from the atmosphere, into Methanol, it is cost-effective and economical to do so.
As seen in excerpts from the initial link in this dispatch to the USDOE document:
"SANDIA REPORT SAND2009-7489; November 2009
Final Report on “Fundamentals of Synthetic Conversion of CO2 to Simple Hydrocarbon Fuels” (LDRD 113486)
("LDRD" = "Lab-Directed Research and Development". For a time, at least, the USDOE's National Laboratories were accorded the privilege of establishing some of their own research priorities in addition to those which might have been dictated from Washington, DC. Also, should the initial link we enclose in this dispatch to the USDOE's electronic file of this report fail to function, we have downloaded a full copy and will be forwarding it separately to the West Virginia Coal Association.)
Manos Mavrikakis, Christos T. Maravelias, Constantine A. Stewart, James E. Miller, and Richard A. Kemp
(Mavrikas and Maravelias were/are visiting scientists from the University of Wisconsin.)
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.
Abstract: Energy production is inextricably linked to national security and poses the danger of altering the environment in potentially catastrophic ways. There is no greater problem than sustainable energy production. Our purpose was to attack this problem by examining processes, technology, and science needed for recycling CO2 back into transportation fuels.
This approach can be thought of as “bio-inspired” as nature employs the same basic inputs, CO2/energy/water, to produce biomass. We addressed two key deficiencies apparent in current efforts.
First, 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.
Opportunities to improve current processes have also been identified and examined. Second, we have also specifically addressed the fundamental science of the direct production of methanol from CO2 using H2 as a reductant.
Energy production, or more precisely the conversion of resources to useful forms of energy, is the largest human enterprise on the planet. As such, it is inextricably linked to national security and quality of life, but also poses the danger of altering the environment in potentially catastrophic ways. Thus, there is no greater problem than sustainable energy production.Sandia scientists are just beginning to attack this problem in new ways by developing processes and technology for recycling CO2 back into liquid transportation fuels, thus helping to ensure domestic and battlefield energy supplies as well as mitigate global climate change. This approach can be thought of as “bio-inspired” as nature employs the same basic inputs, CO2/energy/water, to produce biomass (and) recycling CO2 via some type of reductive process to regenerate transportation fuels, or a suitable fuels precursor, (has) the volume necessary
to reduce or stabilize CO2 levels in the atmosphere.
As well, generating fuels from a noncrude oil source also aids in the economic stability and security of the United States.
(The above statement would apply to Coal, as well.)
CO2 is an energy-depleted molecule - the conversion of a hydrocarbon to CO2 and H2O is a significantly downhill, exothermic process. In order to return this oxidized molecule to a usable fuel, it must be converted (reduced) back into a suitable precursor. In order to do this, one can use electrons (electrochemistry) or an appropriate reducing agent such as H2. In the work discussed in this report, we assume that the reducing agent is H2, most likely eventually derived from photo-splitting of water.
Herein, we have addressed two key deficiencies that have become apparent as work proceeds in other laboratories. First, prior to our work a detailed process analysis comparing the potential for nanotechnology and conventional engineering methods, e.g., in the form of catalysts and active materials in a chemical plant environment, to provide a viable route for the conversion of CO2 and water to fuel, to that provided by nature, i.e., biomass, had not been completed. Understanding the possible advantages and/or disadvantages of the two
routes is a key to establishing credibility as well as to identifying key hurdles and the most fruitful directions for research. Also, it is critical to understand whether there are any “showstoppers” or serious technical hurdles in the synthetic routes. Second, we more specifically address the science of applying nanotechnology to the direct production of methanol from CO2, either chemically or electrochemically, using water, or H2 derived from water, as a reductant.
In particular, the use of density functional theory (DFT) to examine the fundamental steps in the conversion of CO2 into a small organic molecule, methanol, has been performed. Interactions of CO2 with the Cu surface present in heterogeneous catalysts have been studied.
Another aspect of our work that was performed in conjunction with the University of Texas in the area of metal
nanoparticles grown within an electrically-conducting polymer matrix will be covered in another SAND report when complete, and as such those results are not reported here.
SYNTHETIC PRODUCTION OF METHANOL: PROCESS ANALYSIS
Summary: Energy security and global climate change are two intertwined problems that demand attention. The vision for the “hydrogen economy” is a proposed solution that is based on the application of sustainable energy sources to split water. However, many technical and infrastructure challenges remain for hydrogen that do not exist for hydrocarbon fuels.
Integrating CO2 capture and conversion into liquid fuels produces a new vision that promises the benefits of hydrogen while preserving many of the advantages of the hydrocarbon economy.
In this section, we study the production of methanol from H2/CO2 and H2O/CO mixtures. We present two alternative processes that are based on the combined action of two reversible reactions: water gas shift (WGS) and methanol synthesis (MS) on a Cu/ZnO/AlO3 catalyst. Detailed flowsheet simulations and economic evaluations under multiple scenarios indicate that both processes can be economically feasible in the near future, while having energy efficiencies that are significantly better than their biological counterpart.
(Note that the USDOE specifies that Hydrogen is required herein, and suggests that it is becoming practical to generate Hydrogen from Water in processes powered by Solar energy, i.e., from the "photo-splitting of water". And, as seen in our report of:
West Virginia Coal Association | USDOE and Delaware Sunshine Extracts Hydrogen from Water | Research & Development; concerning: "United States Patent Application 20130175180 - Devices and Methods for Increasing Solar Hydrogen Conversion Efficiency in Photovoltaic Electrolysis; 2013; Assignee: University of Delaware; Abstract: Devices and methods for photovoltaic electrolysis are disclosed. A device comprises a photovoltaic cell element and an electrolysis compartment. The photovoltaic cell element is configured to convert a portion of solar energy into electrical energy and to pass another portion of the solar energy. Government Interests: This invention was made with Government support ... by the Department of Energy. The Government may have certain rights in this invention. A method for photovoltaic electrolysis comprising: receiving solar energy with a photovoltaic cell element; converting a portion of the received solar energy into electrical energy with the photovoltaic cell element; passing another portion of the received solar energy through the photovoltaic cell element; receiving with an aqueous electrolyte the other portion of the solar energy passing through the photovoltaic cell element; transmitting the electrical energy generated by the photovoltaic cell element to a pair of electrodes; and electrolyzing the aqueous electrolyte with the pair of electrodes. This invention relates generally to electrolysis, and more particularly to devices and methods for increasing solar hydrogen conversion efficiency in photovoltaic electrolysis. Photovoltaic (PV) electrolysis allows the generation of hydrogen gas (H2) and oxygen gas (O2) from water using solar energy";
the USDOE, and it's contractors, are improving the technologies for generating Hydrogen from Water in processes that rely on Solar energy to drive them.
Further, the USDOE is suggesting herein that Carbon Dioxide conversion into Methanol is contiguous with the conversion of Carbon Monoxide into Methanol. If Hydrogen is available, then the conversion of Carbon Dioxide first into Carbon Monoxide may proceed automatically via the Reverse Water Gas Shift reaction, or Reverse Conversion, as explained in our report of:
West Virginia Coal Association | France Efficient CO2 to Carbon Monoxide Conversion | Research & Development; 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 (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".Otherwise, if it is desirable to add Carbon Monoxide to the Carbon Dioxide, then, as seen for one example in our report of:
West Virginia Coal Association | Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Assignee: Bayer Material Science, AG, Germany; The present invention relates to a novel generator for the reaction of carbon-containing raw materials and also to an improved process for the production of carbon monoxide gas (CO gas) having a high degree of purity ... . Carbon monoxide gas is frequently produced in the art by means of a continuous process in which carbon-containing raw materials are reacted with oxygen and carbon dioxide ... . Suitable fuels which meet the above-mentioned demands and which can be reacted successfully in terms of technology and economy to CO gas in the process described herein are, for example ... coal";
we can make any Carbon Monoxide that might be desirable from CO2 and a little of our abundant Coal.)
Energy resources are the foundation for developed economies and are inextricably linked to national security, social stability, and quality of life. Hence, global demand and competition for petroleum as a transportation fuel is projected to continue to climb even as supplies of conventional oil decline. Less-conventional resources such as coal ... .
Hydrocarbon fuels are ideal energy carriers, but they can no longer be thought of as primary energy sources.
Rather, it is necessary that we take the realistic view that our conventional hydrocarbon fuels are in fact “stored sunlight” and “sequestered carbon.” That is, petroleum, coal and other fossil fuels are the end result of a long process that began with a biological organism capturing sunlight and using it to drive chemical conversions of CO2 and H2O to hydrocarbons and oxygen (photosynthesis).
We presented two process designs for the production of methanol from H2/CO2 and H2O/CO. The two alternatives can be integrated with thermochemical processes for the splitting of H2O and/or CO2, leading to technologies that can change the way we view renewable energy.
The integrated processes satisfy the twofold objective of fomenting the use of renewable energy (in this case concentrated solar power) while reducing CO2 emissions trough recycling. Simulations of the proposed alternatives feature methanol yields significantly better than those reported in the literature.
Based upon current methanol prices, sensitivity analysis indicates economic feasibility (and) even if the cost is twice as high, the processes can be economically attractive if the price of methanol increases moderately.Conclusions: We presented two process designs for the production of methanol from H2/CO2 and H2O/CO.
The two alternatives can be integrated with thermochemical processes for the splitting of H2O and/or CO2, leading to technologies that can change the way we view renewable energy. The integrated processes satisfy the twofold objective of fomenting the use of renewable energy (in this case concentrated solar power) while reducing CO2 emissions through recycling."
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In other words, and in sum:
Our own United States Department of Energy says that we have the technologies in hand to, as a practical matter, convert, through reactions with Hydrogen, Carbon Dioxide into Methanol.
Further, based on their analyses, the USDOE says that converting Carbon Dioxide into Methanol would be economically feasible even if the "cost" of doing so "is twice as high" as it appears to be, and is downright "economically attractive if the price of methanol increases" only a little bit.
Is there anywhere in this great nation, especially in US Coal Country, where Cap & Trade CO2 taxes would be "economically attractive", at all?
And, given that Methanol, as via the above-cited ExxonMobil process of "US Patent 4,035,430 - Conversion of Methanol to Gasoline", can be efficiently and directly converted into more conventional types of liquid hydrocarbon fuels, is there anywhere in this great nation where another Middle East OPEC war would be considered "economically", much less morally, "attractive"?
As taught by our United States Department of Energy, we could, and should, start to view and treat Carbon Dioxide as a valuable raw material resource; a resource which could enable us to put more of our fellow citizens to work while we improved both our national economy and our natural environment; all while we became more able to walk away from expensive brawls with the OPEC gang out behind the bar in the Persian Gulf Alley.
And, it's far past time someone found the will within themselves to bring the USDOE's lesson herein home to us.