WV Coal Member Meeting 2024 1240x200 1 1

CO2 Mitigation with Methanol

 
Methanol as an agent for CO2 mitigation
 
We again cite M. Steinberg, of Brookhaven National Laboratory, on the subject of Carbon Dioxide recycling into the liquid fuel, methanol, as a more economically-attractive and advantageous option to the current, costly and unproductive, proposalss for dealing with CO2 emissions from our coal-use facilities: sequestration and cap & trade.
 
The excerpt:

"M. Steinberg

Dept. Of Advanced Technology, Brookhaven National Laboratory, Upton, N.Y. 11973, USA


Abstract

The Carnol System consists of methanol production by CO2 recovered from coal fired power plants and natural gas and the use of the methanol as an alternative automotive fuel. The Carnol Process produces hydrogen by the thermal decomposition of natural gas and reacting the hydrogen with CO2 recovered from the power plant. The carbon produced can be stored or used as a materials commodity. A design and economic evaluation of the process is presented and compared to gasoline as an automotive fuel. An evaluation of the CO2 emission reduction of the process and system is made and compared to other conventional methanol production processes including the use of biomass feedstock and methanol fuel cell vehicles. The CO2 emission for the entire Carnol System using methanol in automotive IC engines can be reduced by 56% compared to the conventional system of coal fuel power plants and gasoline driven engines and by as much as 77% CO2 emission reduction when methanol is used in fuel cells for automotive purposes. The Carnol System is shown to be an environmentally attractive and economically viable system connecting the power generation sector with the transportation sector which should warrant further development."

We want to note that the several explications of the Carnol System we've forwarded propose, as does this one, obtaining Hydrogen, for the synthesis of fuels from CO2,  from methane. Other references document that the needed Hydrogen can be obtained from the electrolysis of water, from syngas generated from biomass, and from other industrial sources.

More CO2 Recycling to Liquid Fuel

We have introduced you previously to Brookhaven National Laboratory's "Carnol" process for recycling Carbon Dioxide. Herein is more detail, and a fuller explanation of how the Carbon Dioxide co-product of our coal-fired-power and coal-to-liquid-conversion facilities could, and should, be used as a valuable raw material resource.

The excerpt:

 
"The Carnol process system for CO2 mitigation and methanol production 
Meyer Steinberg

Engineering Research and Applications Division, Department of Advanced Technology, Brookhaven National Laboratory, Upton, NY 11973-5000, U.S.A.

Abstract

The feasibility of an alternative CO2 mitigation system and a methanol production process is investigated. The Carnol system has three components: (i) a coal-fired power plant supplying flue gas CO2, (ii) a process which converts the CO2 in the presence of He (Correction: "H", hydrogen, is intended by the author, not "He", helium - JtM) from natural gas to methanol, (iii) use of methanol as a fuel component in the automotive sector. For the methanol production process alone, up to 100% CO2 emission reduction can be achieved; for the entire system, up to 65% CO2 emission reduction can be obtained. The Carnol system is technically feasible and economically competitive with alternative CO2-disposal systems for coal-fired power plants. The Carnol process is estimated to be economically attractive compared to the current market price of methanol, especially if credit can be taken for carbon as a marketable coproduct."

We think it important to repeat a few passages:

"For the methanol production process alone, up to 100% CO2 emission reduction can be achieved; for the entire system, up to 65% CO2 emission reduction can be obtained."

"The Carnol system is technically feasible and economically competitive with alternative CO2-disposal systems for coal-fired power plants. The Carnol process is estimated to be economically attractive compared to the current market price of methanol, especially if credit can be taken for carbon as a marketable coproduct."

We can potentially convert, as we understand it, 100% of a coal plant's CO2 emissions into liquid fuel. That would result in an overall reduction of CO2 emissions of 65% for the complete coal-power and CO2-to-liquid-fuel recovery system. And, we get a liquid fuel, methanol, which we can convert into gasoline if we want to, in the bargain.

Steinberg's economic "kicker" seems to be one we've earlier suggested: The methanol system is economically attractive "if credit can be taken for carbon as a marketable coproduct". We presume him to refer to the market for trading carbon credits, established by Cap & Trade legislation.

In any case, we reaffirm that Carbon Dioxide is a valuable by-product of our coal use, and we can find profitable ways to use it. We shouldn't punish our coal industries for making the opportunity possible.

Carbon Dioxide as a Feedstock - Brookhaven Nat. Lab

 
We've introduced you to the work at Brookhaven National Laboratory, and Meyer Steinberg's postulations, concerning the capture and use of Carbon Dioxide as a raw material which can be used to make more liquid fuels.
 
Herein, two of Steinberg's BNL colleagues address the same issue.
 
The excerpt:
 
(Please note that this excerpt, as is true of many we present you, was heavily footnoted with original literature references. For the sake of clarity and efficiency in transmission, we remove those footnotes and associated links. We urge you to log, through the primary links we do enclose, onto the web sites themselves so that you can avail yourself of all the information available.)

"Carbon Dioxide as a Feedstock

Carol Creutz and Etsuko Fujita

Brookhaven National Laboratory

This chapter 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 the report of a 1999 workshop on the subject of catalysis in CO2 utilization, but with emphasis on systems of most interest to us.

Atmospheric carbon dioxide is an abundant (750 billion tons of carbon in the 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 the seas or the earth—is beyond the scope of this chapter, except where it overlaps utilization—for example, in converting CO2 to polymers. Yet sequestration dominates current thinking on short term solutions to global warming, as should be clear from reports of this and other workshops. (By extrapolation, geologic sequestration of CO2 is short-sighted.) The net anthropogenic increase of 13,000 million tons of carbon dioxide estimated to be added to the atmosphere annually at present can be compared to the 110 million tons of CO2 used to produce chemicals, chiefly urea (75 million tons of CO2), salicylic acid, cyclic carbonates, and polycarbonates. Increased utilization of CO2 as a starting material is, however, highly desirable, because it is an inexpensive, nontoxic 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 relatively small, impact on global CO2 levels. The other uses of interest are utilization as a solvent and for fuel production, and these are discussed in turn.

PRINCIPAL CURRENT USES OF CARBON DIOXIDE

Urea synthesis is currently the largest use of carbon dioxide in organic synthesis. Urea, C(O)(NH2)2, is the most important nitrogen fertilizer in the world. Urea is also an intermediate in organic syntheses such as the production of melamine and urea resins, which are used as adhesives and bonding agents. Carbon dioxide is also used to produce salicylic acid, which is found in pharmaceuticals, and cyclic organic carbonates, high melting, but extremely high boiling solvents for natural and synthetic polymers such as lignin, cellulose, nylon, and poly vinyl chloride. The latter are used extensively in the production of polyacrylic fibers and paints. Ethylene and propylene carbonates have many uses in chemical synthesis—among them reactions with ammonia and amines to form carbamates and subsequent reactions with diamines to yield di(hydroxyethyl) carbamates, which can react further with urea to form polyurethanes."

Those are just some of the current uses of Carbon Dioxide. And, although they are currently, relative to CO2 emissions, small uses, the potential seems to be there to expand the applications, especially since versatile modern plastics, such as polycarbonates and polyurethanes, can be made with CO2 as a starting material. Urea, the largest current consumer of CO2, as well, can be used not just as a fertilizer, but as a base material from which some types of plastics can formulated.

The author indicates that capture of CO2 at the production source is crucial to the successful use of CO2 as a base material for further synthesis. We'll note that other research we've reported to you suggests otherwise: That CO2 can feasibly be extracted from the atmosphere for practical use.

And, of course, as we've extensively documented, among other CO2 uses of interest mentioned is it's employment "for fuel production".

CO2 to Fuel


 
Here we have some research performed by one of our own, US, institutions of higher learning, and a respected one at that, confirming, as we've been reporting from other credible sources, that there are, indeed, cost-effective ways to capture the Carbon Dioxide by-product of our coal use, and to then convert it into valuable, much-needed, liquid transportation fuels.
 
The excerpt: 

"Selective Solar-Driven Reduction of CO2 to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell

 Emily E. Barton, David M. Rampulla and Andrew B. Bocarsly
[Unable to display image]Department of Chemistry, Princeton University, Princeton, New Jersey 08544
J. Am. Chem. Soc., 2008, 130 (20), pp 6342–6344
DOI: 10.1021/ja0776327
Publication Date (Web): April 26, 2008
Copyright © 2008 American Chemical Society
 

With rising atmospheric CO2 levels, there has been increasing interest in artificial photosynthetic schemes for converting this greenhouse gas into valuable fuels and small organics. Photoelectrochemical schemes for activating the inert CO2 molecule, however, operate at excessive overpotentials and thus do not convert actual light energy to chemical energy. Here we describe the selective conversion of CO2 to methanol at a p-GaP semiconductor electrode with a homogeneous pyridinium ion catalyst, driving the reaction with light energy to yield faradaic efficiencies near 100% at potentials well below the standard potential."

Methanol, as all should by now know, is an excellent liquid fuel in it's own right; and, it can, through at least one established and commercialized process, be converted into gasoline.

CO2 to Fuel - USC

 
Chemical Recycling of Carbon Dioxide to Methanol and Dimethyl Ether: From Greenhouse Gas to Renewable, Environmentally Carbon Neutral Fuels and Synthetic Hydrocarbons
 

It should be getting plain as day that the Carbon Dioxide co-produced by our coal utilization - whether coal is employed to generate power or to synthesize much-needed liquid fuels and industrial chemicals - is a valuable by-product of our coal use; and, we should thus focus some dedicated attention on establishing the infrastructure we need to reclaim and utilize it. 
 
The excerpt:
 
"George A. Olah, Alain Goeppert and G. K. Surya Prakash
[Unable to display image]Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089-1661
J. Org. Chem., 2009, 74 (2), pp 487–498
DOI: 10.1021/jo801260f
Publication Date (Web): December 8, 2008
Copyright © 2008 American Chemical Society
 

Nature’s photosynthesis uses the sun’s energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time can new fossil fuels be formed naturally. In contrast, chemical recycling of carbon dioxide from natural and industrial sources as well as varied human activities or even from the air itself to methanol or dimethyl ether (DME) and their varied products can be achieved via its capture and subsequent reductive hydrogenative conversion. The present Perspective reviews this new approach and our research in the field over the last 15 years. Carbon recycling represents a significant aspect of our proposed Methanol Economy. Any available energy source (alternative energies such as solar, wind, geothermal, and atomic energy) can be used for the production of needed hydrogen and chemical conversion of CO2. Improved new methods for the efficient reductive conversion of CO2 to methanol and/or DME that we have developed include bireforming with methane and ways of catalytic or electrochemical conversions. Liquid methanol is preferable to highly volatile and potentially explosive hydrogen for energy storage and transportation. Together with the derived DME, they are excellent transportation fuels for internal combustion engines (ICE) and fuel cells as well as convenient starting materials for synthetic hydrocarbons and their varied products. Carbon dioxide thus can be chemically transformed from a detrimental greenhouse gas causing global warming into a valuable, renewable and inexhaustible carbon source of the future allowing environmentally neutral use of carbon fuels and derived hydrocarbon products."

We've made mention of George Olah, and his work at the Loker Institute, previously. We bet even this good ole' Southern California beach boy would agree with us West Virginia hillbillies that our Carbon Dioxide is a valuable raw material resource. We shouldn't be wasting time and money stuffing it all down geologic sequestration rat holes to subsidize Big Oil's petroleum scavenging; or, attempting, through crooked Cap & Trade schemes, to tax the coal-based industries, and the good people who depend for their livelihoods on those coal-based industries, out of existence.