WV Coal Member Meeting 2024 1240x200 1 1

CO2 as Raw Material - US National Lab

 

We've cited Brookhaven National Laboratory researchers Creutz and Fujita, on the subject of Carbon Dioxide utilization previously.
 
Herein, via the enclosed link and attached file, they present a much fuller outline of the potentials for actually using Carbon Dioxide, in needed productive and profitable ways, as opposed to the costly, perhaps ineffective, disposal and storage of it.
 
The excerpt from the enclosed link and attached file, with comment interspersed and following:
 
"Carbon Dioxide as a Feedstock
Carol Creutz and Etsuko Fujita
Chemistry Department; Brookhaven National Laboratory; Upton NY 11973-5000  

This report is an overview on the subject of carbon dioxide as a starting material for organic syntheses of potential commercial interest and the utilization of carbon dioxide as a substrate for fuel production. It draws extensively on literature sources, particularly on the report of a 1999 Workshop on the subject of catalysis in carbon dioxide utilization, but with emphasis on systems of most interest to us.

Atmospheric carbon dioxide is an abundant (750 billion tons in atmosphere), but dilute source of carbon (only 0.036 % by volume), so technologies for utilization at the production source are crucial for both sequestration and utilization. Sequestration-such as pumping CO2 into sea or the earth-- is beyond the scope of this report, except where it overlaps utilization, for example in converting CO2 to polymers. But sequestration dominates current thinking on short term solutions to global warming, as should be clear from reports from this and other workshops."
 
(As we've seen, geologic "sequestration", in depleted oil reservoirs. for instance, "dominates current thinking on short term solutions to global warming". Wouldn't long term, and sustainable, solutions be far more preferable, what we should really be looking for? - JtM)

The 3500 million tons estimated to be added to the atmosphere annually at present can be compared to the 110 million tons used to produce chemicals, chiefly urea (75 million tons), salicylic acid, cyclic carbonates and polycarbonates. Increased utilization of CO2 as a starting material is, however, highly desirable, because it is an inexpensive, non-toxic starting material. There are ongoing efforts to replace phosgene as a starting material. Creation of new materials and markets for them will increase this utilization, producing an increasingly positive, albeit small impact on global CO2 levels. The other uses of interest are utilization as a solvent and for fuel production and these will be discussed in turn.
 
(So, "increased utilization of CO2 as a starting material is ... highly desirable". And, another CO2 use "of interest" is "for fuel production". - JtM) 

"Principal current uses of carbon dioxide.  

Urea synthesis is currently the largest use of carbon dioxide in organic synthesis. Urea, C(O)(NH), is the most important nitrogen fertilizer in the world. It is also an intermediate in organic syntheses such as production of melamine and urea resins, used as adhesives and bonding agents. Salicylic acid is used in pharmaceuticals.
 
Cyclic organic carbonates, high melting, but extremely high boiling, serve as solvents for natural and synthetic polymers such as lignin, cellulose, nylon, polyvinyl chloride. They are extensively used in the production of polyacrylic fibers and paints. Ethylene and propylene carbonates have many uses in chemical synthesis; also they react with ammonia and amines to form carbarnates; from reaction with diamines they yield di(hydroxyethyl)carbamates which can further react with urea to form polyurethanes.
 
Novel insertions are under active investigation: incorporation of CO, into polymers-polycarbonates, polypyrones, lactone intermediates, and polyurethanes Of particular interest is the incorporation of carbon dioxide into polymers, an active area of research and very promising for future applications. However, the impact of new materials and processes in this area will ultimately depend on market forces, a factor than
can be frustrating to the researchers.
 
Carbon Dioxide as Solvent. Supercritical carbon dioxide is a hydrophobic solvent which can replace organic solvents in a number of applications. Its critical temperature is 31°C and it is of very low viscosity. When carbon dioxide is substituted for an organic solvent, solvent costs may be reduced and emission of toxic organics can be reduced.
 
(So, using Carbon Dioxide in a solvent application could enable the "emission of toxic organics" to "be reduced". Sounds rather environmentally friendly, to us. - JtM)
 
Thermodynamic Barriers to CO2 Utilization. Carbon dioxide is a very stable molecule and accordingly energy must generally be supplied to drive the desired transformation. Thus high temperatures, extremely reactive reagents, electricity, or the energy from photons may be exploited to carry out carbon dioxide reactions:
 
The reaction, CH, + CO2, = 2 CO -I- 2 Hz, is called the carbon dioxide reforming of methane. (It) could significantly mitigate CO, produced in cement, lime and metal (iron, aluminum) production ... .
 
For electrochemical reduction of CO2 to methane, energy may be derived from a solar cell or nuclear power. Reduction may also be accomplished photochemically by utilizing a dye to absorb visible light, since carbon
dioxide itself does not absorb visible light. Interestingly, with vacuum ultraviolet irradiation of carbon dioxide yields oxygen and carbon monoxide.
 
Conversion of Carbon Dioxide to Fuels: Direct Hydrogenation

With abundant renewable energy sources carbon dioxide can be converted to fuels by reduction to methanol or methane. The value of a fuel is based on its energy content and its ease of transport and storage. ... The high energy density of carbon-based fuels and their availability as either gases, liquids, or solids are important reasons for the dominant position of fossil fuels in the current market place. Today carbon
dioxide is a by-product of fuel use, not a feedstock for fuel production. Utilization of CO2 converted to fuels using renewable or nuclear power produces no net emission of CO2 (when carbon dioxide produced by energy consumption in the reduction process is excluded) and it would complement the renewable production of fuels from biomass which is likely to be insufficient to meet future world demands. Catalysis can play an important role in this area. The objective is to develop strategies for reduction of CO2
that can be adapted to utilization at different sources and to attain fuel products widely utilizable with current and future technologies.
 
Hydrogenation of carbon dioxide to methanol is slightly exergonic, and to methane to a greater extent ... because of the favorable thermodynamics of water formation. 
 
Catalysis of hydrogenations leading ... to hydrocarbons is being successfully addressed. Reduction to carbon monoxide is also useful when the carbon monoxide-hydrogen mixtures can be used to augment feeds in industrial processes such as ethylene and methanol production. Methanol, lower hydrocarbons (methane, ethane, ethylene, etc), CO, and HCOOH have been prepared .
 
(So, reactions of CO2 "leading ... to hydrocarbons is being successfully addressed", as we have documented from Penn State University. - JtM) 
 
Copper on ZnO seems to be the most active catalyst for methanol production. Selectivity for methanol
production was found to be very high and direct methanol production from CO2 may be commercially feasible with an inexpensive source of H2. 
 
(The "inexpensive source of H2" is needed in direct hydrogenation reactions. There are alternatives. - JtM)   
 
Conversion of Carbon Dioxide to Fuels: Indirect Hydrogenation

Hydrogen (H2) may be replaced by electrons and protons, available, for example, in electrochemical reduction in aqueous media.
 
(In other words, as other researchers have noted, the Hydrogen needed for CO2 hydrogenation can be obtained through "electrochemical reduction". - JtM) 
 
Electrochemical reduction.
 
As noted earlier, direct electroreduction is achieved at high overvoltage. An unreactive metal or carbon electrode produces carbon dioxide radical anion ... . (Other) metals ... can direct CO2 reduction to hydrogenated products and at much smaller applied voltage ... . Particularly noteworthy is the work of Hori which showed that copper produces high yields of methane from aqueous bicarbonate at 0 C-and high yields of ethylene at 45 C.
 
Photochemical systems. 
 
Photochemical reduction systems require efficient light harvesting, usually by a so-called dye or sensitizer, and efficient charge separation and energy utilization. Transition metal complexes  ...  serve as sensitizers.
 
Electrocatalysis Photocatalytic Reduction. 
 
At present, electrochemical reduction of CO2 yields carbon monoxide, formate, methane, etc. with good current efficiencies and, in photochemical systems, quantum yields for carbon monoxide (and/or formate) are up to 40%.
 
There are many areas in which ongoing and future research can lead to new modes of carbon dioxide utilization. 
 
This research was carried out at Brookhaven National Laboratory under contract DE-AC02-98CH10886
with the U.S. Department of Energy and was supported by its Division of Chemical Sciences, Office of Basic Energy Sciences."
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So, there are almost half a dozen known processing routes for Carbon Dioxide that would yield liquid and gaseous fuels, fertilizer, and plastics manufacturing raw materials; and, at the same time, reduce the need for some hazardous raw materials, such as "phosgene", and, subsequently "emission of toxic organics can be reduced". 
 
Naw. Let's just waste a lot of money, instead, to stuff it all down leaky geologic storage rat holes.
 
And, note: This research was conducted by a US Government Lab, and it was paid for with our tax dollars under  USDOE contract DE-AC02-98CH10886. Why haven't we US taxpayers, especially those of us resident in US Coal Country, been told about any of it? Why haven't these opportunities been published and promoted? Why is it that all we hear about is Cap & Trade and Sequestration?

CO2 Capture from Ambien Air - Columbia University

 

We have cited Frank Zeman, of Columbia University, previously, in his collaborations with other scientists, including Klaus Lackner, also at Columbia, on the subject of Carbon Dioxide utilization.
 
Herein, he describes further refinement of technology that would enable the economically-feasible capture of Carbon Dioxide from the atmosphere itself. Although his concerns are primarily on CO2 emissions from dispersed sources, and he presents that capture from concentrated point sources might be more efficient, his discussion reveals opportunity for other options, as we describe, following the excerpt:
 
"Energy and Material Balance of CO2 Capture from Ambient Air
 
Frank Zeman
[Unable to display image]Columbia University, Department of Earth and Environmental Engineering, New York, New York 10027
Environ. Sci. Technol., September 26, 2007; Copyright © 2007 American Chemical Society 

Abstract

Current Carbon Capture and Storage (CCS) technologies focus on large, stationary sources that produce approximately 50% of global CO2 emissions. We propose an industrial technology that captures CO2 directly from ambient air to target the remaining emissions. First, a wet scrubbing technique absorbs CO2 into a sodium hydroxide solution. The resultant carbonate is transferred from sodium ions to calcium ions via causticization. The captured CO2 is released from the calcium carbonate through thermal calcination in a modified kiln. The energy consumption is calculated as 350 kJ/mol of CO2 captured. It is dominated by the thermal energy demand of the kiln and the mechanical power required for air movement. The low concentration of CO2 in air requires a throughput of 3 million cubic meters of air per ton of CO2 removed, which could result in significant water losses. Electricity consumption in the process results in CO2 emissions and the use of coal power would significantly reduce to net amount captured. The thermodynamic efficiency of this process is low but comparable to other “end of pipe” capture technologies. As another carbon mitigation technology, air capture could allow for the continued use of liquid hydrocarbon fuels in the transportation sector."

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First, Zeman refers to "large, stationary sources" of CO2 emissions, without specifying what those might be. Coal-fired power plants are the obvious targets, but it must be emphasized and repeated that they are not the only industrial point sources; with cement kilns, and various chemical and petroleum processors, being significant rivals. Moreover, as we've documented, natural point sources, such as volcanoes, and dispersed natural sources, wherever rotting vegetation might be accumulated, i.e., swamps, the Tundra in summer, etc., dwarf the emissions of coal utilization industry.

Second, he proposes a wet scrubbing system for ambient air processing that is likely archaic compared to other CO2 air capture proposals, such as Sandia National Laboratory's "Sunshine to Petrol" development, as we've documented, which proposes the use of, primarily, solar power both to capture CO2 from the atmosphere and to recycle it into more liquid hydrocarbon fuels.

Third, to emphasize the foregoing, Zeman envisions only fossil fuel-generated power as the energy source for his CO2 capture scenario, as in:

"Electricity consumption in the process results in CO2 emissions and the use of coal power would significantly reduce to (the?) net amount captured." 

As we have documented from other sources, that is not the only way to go about it, and it is an extraordinarily narrow view.

The purpose of our citing Zeman in this report is: Air capture of Carbon Dioxide is technically feasible and potentially practical, as documented herein.

And, since the CO2 can be captured from the atmosphere, collection facilities can be located at dispersed sites where environmental, carbon-neutral energy, i.e., solar, wind, hydro, etc., can be harnessed to effect bothand it's subsequent conversion into commercially valuable hydrocarbon compounds. the capture of CO2 from the atmosphere

We don't have to burn more fossil fuel, and thereby generate more CO2, to accomplish the recycling of CO2.

And, Zeman does acknowledge that "air capture could allow for the continued use of liquid hydrocarbon fuels in the transportation sector".

"Liquid hydrocarbon fuels" which definitely could, and we assert should, be increasingly synthesized from Coal, and from recycled Carbon Dioxide.

ExxonMobil Coal to Gasoline via Methanol

 
We've reported on and referenced many times the ExxonMobil "MTG"(r), Methanol To Gasoline, process, and documented some earlier reports of the technology's development, including sequential documents from each company, Exxon and Mobil, prior to their merger, recording what seemed to be their independent development of carbon conversion techniques.
 
We've even suggested that, as Exxon and Mobil, separately, developed coal liquefaction and gasoline synthesis technologies, their congruent interests in coal conversion science, along with shrinking supplies of traditional petroleum resources, might have spurred their merger.
 
Herein, we present a document, and reference one we earlier sent you, that mark their trail even more clearly.
 
First, the technical Abstract of a US Patent, assigned to Exxon, for a process to produce Methanol, from Coal, as excerpted from the above link:
 
Title: Production of methanol via catalytic coal gasification
 
Author(s): Calvin, W.J.; Goldstein, S.S.; Marshall, H.A.
 
Date: September 1982; OSTI ID: 6787393; US Patent 4348487; Application 317358 filed November 1981
 
Patent Assignee: Exxon Research And Engineering Co
 
Abstract: Methanol is produced by gasifying a carbonaceous feed material with steam in the presence of a carbon-alkali metal catalyst and added hydrogen and carbon monoxide at a temperature between about 1000/sup 0/ F and about 1500/sup 0/ F and at a pressure in excess of a 100 psi to produce a raw product gas comprising methane, ... carbon dioxide, carbon monoxide, hydrogen and hydrogen sulfide. The raw product gas is withdrawn from the gasifier and treated for the removal of steam, particulates, hydrogen sulfide and carbon dioxide to produce a treated gas containing primarily carbon monoxide, hydrogen and methane. The treated gas is separated into a methane-rich gas stream and a gas stream containing primarily carbon monoxide and hydrogen. The gas stream containing primarily carbon monoxide and hydrogen is passed to a methanol synthesis reactor where the carbon monoxide is reacted with the hydrogen in the presence of a methanol synthesis catalyst to form methanol. Methanol product is recovered from the effluent exiting the methanol synthesis reactor thereby leaving a gas comprised of carbon monoxide, hydrogen, methane and carbon dioxide. A portion of this gas is passed to a steam reforming furnace wherein at least a portion of the methane is reacted with steam to produce hydrogen and carbon monoxide which is then passed from the steam reforming furnace into the gasifier. Preferably, at least a portion of the methane-rich gas produced in the separation step is used as fuel for the steam reforming furnace."
 
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Note, as an aside, that "methane-rich gas", which they propose using as both a co-reactant and a process fuel, is produced in their gasification system, and recall that technologies exist, such as "Tri-reforming", as reported by Penn State University, which can combine Methane with Carbon Dioxide in a CO2-recycling process that itself synthesizes higher hydrocarbons suitable for refining into liquid fuels.
 
In light of the above, also recall that, in an earlier dispatch, we reported on Mobil's later development of the technology to convert Methanol into Gasoline, as in "Aromatics, light olefins and gasoline from methanol", by Haag, et. al., of Mobil R&D in Princeton, NJ.
 
We know this dispatch is redundant, relative to the various other reports of Exxon and Mobil developments we've presented. But, the only way we have to emphasize the truth, the validity, of viable technology that would enable the United States to achieve liquid fuel self-sufficiency by utilization of her vast coal resources, is by repetition.

Just as Exxon and Mobil combined their names when they merged, we'll close by combining the titles of the two reports referenced herein: Consider this to be a disclosure of the technology to synthesize "gasoline from methanol (produced) via catalytic coal gasification".

That is, precisely, what it is.

Portugal Recycles CO2 with Water and Sunlight

 
This translation from the original Portuguese might, in places, be phrased a little awkwardly, but the message is precise: Using sunlight and water, we can convert Carbon Dioxide into hydrocarbon fuels, and some other useful substances.
 
Comment follows:
 
"Electrochemical and photocatalytic reduction of carbon dioxide for fuel cell utilization
 
M.R. Gonçalves, J.A.D. Condeço, T.C.D. Pardal D.M. Roncero, B.L. Aguado and C.A.C. Sequeira
Affiliations:
OMNIDEA, Lda Travessa António Gedeão, Portugal
Instituto Superior Técnico, Lisboa, Portugal
Universidad de Valladolid - Facultad de Ciencias, Valladolid

Abstract
 
The electroreduction of CO2 at various metal electrodes yields many kinds of organic substances, namely CO, CH4, C2H6, EtOH, etc. However, hydrocarbons are favourably produced on Cu electrode and so, many studies have been reported. 
 
The photochemical reduction of carbon dioxide by sunlight irradiation and under mild experimental conditions is also a very attractive method because of the needless of an electric source and an expensive apparatus. As for the direct use of solar energy, the production of fuel and organic raw materials on heterogeneous photocatalysts have been reported by numerous investigators.

In this paper, the photochemical reduction of carbon dioxide and water on microparticles of semiconductor oxides (TiO2, SiO2) and copper powder, illuminated by sunlight (500-1000 W/m2) for 100-200 hours at normal temperature and atmospheric pressure, was investigated and evaluated.
.
X-ray diffraction, gas chromatography, and other chemical and physical methods, allowed the analysis of the results. Methane and hydrogen were produced with reasonable yields, particularly for particles of larger surface area per unit weight. It was assumed that the electron holes available at the semiconductor/solution interface promote the H2O discharge to O2, and then both resulting H+ ions and conduction band electrons initiate the H+/CO2 reductons on the active sites ... that are responsible for the hydrogen and methane productions. Our results on the carbon dioxide reduction by electrochemical/chemical ways are very encouraging for the CO2 fixation and conversion to useful hydrocarbons and alcohols."
 
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To simplify it: Portugal knows how to convert CO2, "at normal temperature and atmospheric pressure", into "useful hydrocarbons and alcohols" by, basically, mixing it with water and exposing it to sunlight.
 
The proprietary key seems to be catalysis by oxides of titanium and silicon, and copper powder, with none of those being very exotic.
 
We suppose then, that the energy - "sunlight" - and raw material - "oxides of ... silicon, and copper", i.e., beach sand and recycled water pipes -  costs wouldn't be that excessive; presuming the CO2, noxious pollutant it has been portrayed to be, is obtained free of charge; and, unless we would prefer to pay to ship it to, and to have it pumped down, a leaky, drying-up old oil well. 
 
Note that this Portuguese research seems to support similar findings reported by multiple US DOE' National Labs, as we've reported. And, it confirms the results of Swiss developments we recently sent you, as in: "'Methanation and photo-methanation of carbon dioxide at room temperature and atmospheric pressure'
by Thampi, Kiwi & Grätzel; Institut de Chimie Physique, Ecole Polytechnique Fédérate, Switzerland"; and which is now posted on the West Virginia Coal Association's web site, in their R&D Blog.
 
And, again, as we've documented from multiple other sources, once we've synthesized the Methane, "CH4", and the "alcohols", as above, from CO2, we can make a lot of other things, up to and including gasoline, from them.

Methane to Gasoline

 
Subsequent to our recent posts documenting that Methane can be generated both by the gasification of Coal and by the Sabatier conversion of Carbon Dioxide, we wanted to document that, once so obtained, Methane can also, in addition to being Tri-reformed with more CO2 into more complex and more useful hydrocarbons, be directly converted into liquid fuels - up to, and including, gasoline.
 
Enclosed are a sequence of three links, the first attached above, and three excerpts detailing the known and established processing steps that would, once we have made Methane from Coal or CO2, enable us to convert it into gasoline.
 
First, from Australia, we have:
 
"Homogeneous Conversion of Methane to Methanol. 1. Catalytic Activation and Functionalization of Methane
 
Kausala Mylvaganam, George B. Bacskay, and Noel S. Hush
[Unable to display image]School of Chemistry, University of Sydney,  Australia
J. Am. Chem. Soc., 1999, 121 (19), pp 4633–4639; Copyright © 1999 American Chemical Society 

Abstract

The recent announcement by Periana et al. (Science 1998, 280, 560) of 70% one-pass homogeneous catalysis of methane-to-methanol conversion with high selectivity in sulfuric acid solution under moderate conditions represents an important advance in the selective oxidation of alkanes, an area of considerable current interest and activity. The conversion is catalyzed by bis(2,2‘-bipyrimidine)Pt(II)Cl2. In this work, the thermodynamics of the activation and functionalization steps of the related cis-platin-catalyzed process in H2SO4 are calculated using density functional techniques, including the calculation of solvation free energies by a dielectric continuum method. It is concluded that electrophilic attack by CH4 on an intermediate which may be regarded as a tetracoordinate solvated analogue of a gas-phase, T-shaped, three-coordinate Pt(II) species, followed by oxidation of the resulting methyl complex to a methyl bisulfate ester, is thermodynamically feasible. ... While the alternative mechanism of oxidative addition does not appear to be thermodynamically feasible when using Pt(II) catalysts, catalysis by a Pt(IV) species is predicted to be, on thermodynamic grounds, a viable alternative pathway."

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So, we start out on the trail of Methane to Methanol conversion with "pathway"s that are "thermodynamically feasible" and are  "predicted to be ... viable".

Then, we have from these same Australian researchers:

 
"Homogeneous Conversion of Methane to Methanol. 2. Catalytic Activation of Methane ... the Shilov Type Reaction
 
Kausala Mylvaganam, George B. Bacskay, and Noel S. Hush
[Unable to display image]School of Chemistry, University of Sydney,  Australia
J. Am. Chem. Soc., 2000, 122 (9), pp 2041–2052; Copyright © 2000 American Chemical Society
 
Abstract

The C−H activation of methane catalyzed by cis- and trans-platin in aqueous solution has been studied by density functional based computational methods. ... The revised results provide evidence for the thermodynamic feasibility of oxidative addition of methane.".

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We were compelled to edit out a very great deal of far too technical detail in the second abstract. Suffice it to say that the "oxidative addition of methane", which yields Methanol, has had it's "thermodynamic feasibility" demonstrated. That's a good thing.

It's a "good thing" because, once the Methane, which has been synthesized from Coal or Carbon Dioxide, has been converted into the valuable liquid fuel and organic chemical manufacturing raw material, Methanol, that Methanol can be converted into gasoline, as follows:

 
We've cited Mobil, and Exxon, and even some of these same researchers, on this topic before, but repetitive emphasis is, we believe, necessary.
 
The excerpt:
 
"Aromatics, light olefins and gasoline from methanol: Mechanistic pathways with ZSM-5 zeolite catalyst

W.O. Haag, R.M. Lago and P.G. Rodewald

Mobil Research and Development Corporation, Princeton, NJ 08540


September 2001

Abstract

The conversion of methanol to hydrocarbons with zeolite ZSM-5 as catalyst provides a novel route to gasoline as well as to olefins and aromatics as chemical raw materials. The reaction is acid-catalyzed and involves alkylation of olefins and aromatics as major methanol conversion steps, accompanied by olefin isomerization, polymerization/cracking, cyclization and aromatization via hydrogen transfer. Shape-selective control of the aromatics produced results from the use of the medium pore size zeolite ZSM-5. It is shown that the true kinetic pathways are often disguised by diffusion/desorption effects. Ethylene is most likely the first olefinic hydrocarbon formed."

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So, we know from multiple, earlier-cited, sources, that we can convert both Coal and Carbon Dioxide into Methane.

As documented herein, once we have the Methane, we can convert it into Methanol. And, once we have the Methanol, we can convert it into Gasoline.