WV Coal Member Meeting 2024 1240x200 1 1

New Jersey CO2 to High-Energy Alcohol

Note that we might be looking at a game-changer in this dispatch.
As we read the source document, there are nuances and implications inherent within it, that, even though our West Virginia Coal Association publishers don't like it when we do so, compel us to admonish the members of the Coal Country public press corps that are among our direct and primary addressees:
Given that the United States public have become de facto economic fiefs to Big Oil and OPEC, with Uncle Sam seeming to have accepted his role as beat cop on the take in the Persian Gulf, i.e., Big Oil's turf war enforcer; and, given that King Coal has been so harassed by the propagandized rabble that he's locked himself up in the castle keep and restricts his communications to sad notes tossed out the window promising to keep the lights on for us, it's far, far past time you in the Coal Country press got off your dead cans and started fulfilling your self-proclaimed fiduciary roles as open conduits for, and active transmitters of, the Truth:
Carbon Dioxide, as it arises in only a small way, relative to natural sources of emission, such as the earth's inexorable and inescapable processes of planetary volcanism, from our essential use of Coal in the generation of genuinely affordable and truly abundant electric power, is a valuable raw material resource.
As we most recently documented in:
"United States Patent Application 20120228150 - CO2 Decomposition Via Oxygen Deficient Ferrite Electrodes Using Solid Oxide Electrolyser Cell; September 13, 2012; Inventors: Bruce S. Kang, Huang Guo and Gulfam Iqbal, Morgantown, WV; (Presumed ultimate Assignee of rights: West Virginia University);
Abstract: Oxygen Deficient Ferrites (ODF) electrodes integrated with Yttria Stabilized Zirconia (YSZ) electrolyte, electrochemically decompose carbon dioxide (CO2) into carbon (C)/carbon monoxide (CO) and oxygen (O2) in a continuous process. The ODF electrodes can be kept active by applying a small potential bias across the electrodes. CO2 and water (H2O) can also be electrolyzed simultaneously to produce syngas (H2+CO) and O2 continuously that can be fed back to the oxy-fuel combustion. With this approach, CO2 can be transformed into a valuable fuel source allowing CO2 neutral use of the hydrocarbon fuels";
there exist technologies which can efficiently transform Carbon Dioxide, as reclaimed from whatever convenient source, along with Water, into hydrocarbon synthesis gas, "syngas", a blend of Hydrogen and Carbon Monoxide; which syngas can then be catalytically and chemically condensed, through long-known and well-established processes, such as the now-generic Fischer-Tropsch synthesis, into both liquid and gaseous hydrocarbons.
And, there are even other ways to go about it.
As confirmed by our report of:
"United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Assignee: The USA as represented by the USDOE;
Abstract: A method and system for synthesizing methanol from the CO2 in air using electric power. The CO2 is absorbed by a solution of KOH to form K2CO3 which is electrolyzed to produce methanol, a liquid hydrocarbon fuel. ... Other products ... are also formed which can be separated and recovered as valuable products";
Carbon Dioxide dissolved, perhaps in combination with chemical intermediaries and facilitators, in Water, can be electrolyzed and converted, with the Water, directly into Alcohol.
The Methanol product specified by the process of "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2" is valuable stuff to have. But, even though it can be converted, via, for one established example, ExxonMobil's MTG(r), Methanol-To-Gasoline, technology, as explained in our report of:
West Virginia Coal Association | ExxonMobil "Clean Gasoline from Coal" | Research & Development; concerning the ExxonMobil promotional brochure: "Methanol to Gasoline (MTG): Production of Clean Gasoline from Coal; So Advanced, Yet So Simple";
into Gasoline, that additional conversion step would add complexity and cost to the total Carbon Dioxide recycling process.
As we documented with, secondary references included, in our report of:

"United States Patent Application 20110177571 - Designer Calvin-Cycle-Channeled Production of Butanol; July, 2011; Inventor: James Weifu Lee, MD; Abstract: Designer Calvin-cycle-channeled and photosynthetic ... photosynthetic organisms for photobiological production of butanol and related higher alcohols from carbon dioxide and water are provided";

the alcohol "butanol" is much closer to Gasoline in energy content, and in other characteristics, than are Methanol or Ethanol; and, according to British Petroleum, via a separate reference included in that report, "it can be shipped in existing gasoline pipelines. And it contains more energy than does ethanol, which will improve mileage per gallon".

With some rather small sacrifice in mileage, Butanol, unlike Methanol or Ethanol, can serve as a direct, 100% replacement for Gasoline without any significant changes in fuel handling infrastructure or automotive engine operational management systems.

The downside, as we see it, to the process disclosed in the above "United States Patent Application 20110177571 - Designer Calvin-Cycle-Channeled Production of Butanol", is that it entails the use of special Algae, or other "photosynthetic organisms", to accomplish the biologically-leveraged chemical processing.

That's fine wherever climate conditions would provide long outdoor cultivation seasons and plenty of sunlight to drive the photosynthetic processes; maybe better than fine, since the microorganisms involved produce some useful things in addition to the Butanol, and the needed physical plant for all of it might be relatively simple and straightforward, though large, relative to an industrial chemical manufacturing facility.

As clearly indicated by WVU's "United States Patent Application 20120228150 - CO2 Decomposition Via Oxygen Deficient Ferrite Electrodes Using Solid Oxide Electrolyser Cell", the technology for the indirect recycling of Carbon Dioxide via production of an intermediate hydrocarbon synthesis gas is becoming much more efficient and practical. And, the same is true for Carbon Dioxide recycling technologies based, as is the USDOE's "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2", on the direct, electricity-driven interactions between CO2 and H2O.

One group who have been diligently pursuing such improvements in electrolytic Carbon Dioxide conversion technologies are the Princeton University scientists, Andrew Bocarsly and Emily Barton Cole, now partnering with a small group of other accomplished Carbon technology scientists in the company, "Liquid Light", which we explained more fully in our report of:

"US Patent Application 20100187123A1 - Conversion of Carbon Dioxide to Organic Products; 2010; Inventors: Andrew B. Bocarsly and Emily Barton Cole, NJ; Government Interests: This invention was made with United States government support from Natural Science Foundation Grant No. CHE-0606475. The United States Government has certain rights in this invention. The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell ... to produce therein a reduced organic product (and) where the at least one product is methanol, isopropanol, formic acid, formaldehyde, glyoxal or ethanol".

And, which we further documented in:

States Patent Application 20110114502 - Reducing Carbon Dioxide to Products; 2011; Inventors: Emily Barton Cole (and) Andrew Bocarsly, et. al., NJ, DC and CA:
Abstract: A method for reducing carbon dioxide to one or more products is disclosed. The method may include steps (A) to (C). ... A method for reducing carbon dioxide to one or more products, comprising the steps of: (A) bubbling said carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell, wherein ... wherein said products (of the Carbon Dioxide chemical reduction) comprise one or more of acetaldehyde, acetone, carbon, carbon monoxide, carbonates, ethanol, ethylene, formaldehyde, formic acid, glyoxal, glyoxylic acid, graphite, isopropanol, methane, methanol, oxalate, oxalic acid and polymers containing carbon dioxide".
And, herein, we see that, in a US Patent Application just made recently accessible to the public, Cole, Bocarsly and their Liquid Light colleagues have refined and improved their CO2-recycling techniques, and established a technology for the direct and efficient conversion of Carbon Dioxide in aqueous solution into the much more valuable alcohol, as in the above-cited "US Patent Application 20110177571", "Butanol".
Comment follows excerpts from the initial link in this dispatch to:
"United States Patent Application 20120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water
Date: May 31, 2012
Inventors: Emily Barton Cole, Andrew Bocarsly, et. al., NJ and DC
(Though not disclosed in this early publication, there is little doubt that the ultimate Assignee of rights will be the company, Liquid Light.)
Abstract: Methods and systems for electrochemical production of butanol are disclosed. A method may include, but is not limited to, steps (A) to (D). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte, a catalyst, and a cathode. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a product mixture. Step (D) may separate butanol from the product mixture.
Claims: A method for electrochemical production of butanol, comprising: (A) introducing water to a first compartment of an electrochemical cell, said first compartment including an anode; (B) introducing carbon dioxide to a second compartment of said electrochemical cell, said second compartment including a solution of an electrolyte, a catalyst, and a cathode; (C) applying an electrical potential between said anode and said cathode in said electrochemical cell sufficient for said cathode to reduce said carbon dioxide to a product mixture; and (D) separating butanol from said product mixture.
The method ... wherein said butanol includes at least one of 1-butanol or 2-butanol.

The method ... wherein said product mixture includes butanol and at least one of formic acid, acetic acid, methanol, ethanol, acetone, or propanol.
(All of the above, for some separate and various reasons, are worthwhile byproducts to have.)

The method ... wherein said solution of electrolyte includes potassium chloride.
A method for electrochemical production of butanol, comprising:
(A) introducing water to a first compartment of a first electrochemical cell, said first compartment including an anode;
(B) introducing carbon dioxide to a second compartment of said first electrochemical cell, said second compartment including a solution of an electrolyte, a catalyst, and a cathode;
(C) applying an electrical potential between said anode and said cathode in said first electrochemical cell sufficient for said cathode to reduce said carbon dioxide to an intermediate product mixture;
(D) separating a two-carbon intermediate from said intermediate product mixture;
(E) introducing said two-carbon intermediate to a second electrochemical cell, wherein:
(i) said second electrochemical cell including an anode in a first cell compartment and a cathode in a second cell compartment and:
(ii) said cathode reducing said two-carbon intermediate to a product mixture; and:
(F) separating butanol from said product mixture.
The system ... wherein said second electrochemical cell is configured (to produce) 2-butanol with approximately 99% selectivity.
Description and Summary: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical production of butanol from carbon dioxide and water.

A mechanism for mitigating emissions is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use will be possible.

However, the field of electrochemical techniques in carbon dioxide reduction has many limitations, including the stability of systems used in the process, the efficiency of systems, the selectivity of the systems or processes for a desired chemical, the cost of materials used in systems/processes, the ability to control the processes effectively, and the rate at which carbon dioxide is converted.

A method for electrochemical reduction of carbon dioxide to produce butanol may include, but is not limited to, steps (A) to (D). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte, a catalyst, and a cathode. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a product mixture. Step (D) may separate butanol from the product mixture.

Another method for electrochemical reduction of carbon dioxide to produce butanol may include, but is not limited to, steps (A) to (F). Step (A) may introduce water to a first compartment of a first electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the first electrochemical cell. The second compartment may include a solution of an electrolyte, a catalyst, and a cathode. Step (C) may apply an electrical potential between the anode and the cathode in the first electrochemical cell sufficient for the cathode to reduce the carbon dioxide to an intermediate product mixture. Step (D) may separate a two-carbon intermediate from the intermediate product mixture. Step (E) may introduce the two-carbon intermediate to a second electrochemical cell. The second electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode may reduce the two-carbon intermediate to a product mixture. Step (F) may separate butanol from the product mixture.

A system for electrochemical reduction of carbon dioxide to produce butanol may include, but is not limited to, a first electrochemical cell including a first cell compartment, an anode positioned within the first cell compartment, a second cell compartment, a separator interposed between the first cell compartment and the second cell compartment, and a cathode and a catalyst positioned within the second cell compartment. The system may also include a carbon dioxide source, where the carbon dioxide source is coupled with the second cell compartment and is configured to supply carbon dioxide to the cathode for reduction of the carbon dioxide to an intermediate product mixture. The system may also include an extractor configured to separate a two-carbon intermediate from the product mixture. The system may further include a second electrochemical cell configured to receive the two-carbon intermediate. The second electrochemical cell may include a first cell compartment, an anode positioned within the first cell compartment, a second cell compartment, a separator interposed between the first cell compartment of the second electrochemical cell and the second cell compartment of the second electrochemical cell, and a cathode positioned within the second cell compartment of the second electrochemical cell. The cathode of the second electrochemical cell may be configured to reduce the two-carbon intermediate to butanol.

In accordance with some embodiments of the present disclosure, an electrochemical system is provided that generally allows carbon dioxide and water to be converted to butanol.
In some embodiments, the production of butanol from carbon dioxide and water may occur in a one-stage or a two-stage process. In the one-stage process, butanol may be produced with low yields and low selectivity. In the two-stage process, butanol may be produced with improved reaction rates, yield, and selectivity as compared to the direct conversion of carbon dioxide and water to butanol in the one-stage process.

Butanol (which includes the isomer 2-butanol, also called sec-butanol, and the isomer 1-butanol, also called n-butanol) is an industrial chemical used around the world. Industrially, butanol is produced via gas phase chemistry, using oil and natural gas as feedstocks.
In addition to using non-renewable oil and natural gas as feedstocks, the overall process of industrially synthesizing butanol using current techniques requires a large amount of energy, which generally comes from natural gas. The combustion of natural gas contributes to the concentration of carbon dioxide in the atmosphere and thus, global climate change.

Additional production techniques for butanol include production of butanol via biological pathways. However, such biological processes can be resource intensive due to the large amounts of land, fertilizer, and water necessary to grow the crops used to sustain fermentation processes.
(The above as in our comments concerning "United States Patent Application 20110177571 - Designer Calvin-Cycle-Channeled Production of Butanol".)

In some embodiments of the present disclosure, the energy used by the system may be generated from an alternative energy source to avoid generation of additional carbon dioxide through combustion of fossil fuels.
(We won't include any more reference links. We've documented in numerous earlier reports that parts of US Coal Country have plenty of Wind, Hydro, and, even, Geothermal energy potentials.)
In general, the embodiments for the production of butanol from carbon dioxide and water do not require oil or natural gas as feedstocks. Some embodiments of the present invention thus relate to environmentally beneficial methods and systems for reducing carbon dioxide, a major greenhouse gas, in the atmosphere thereby leading to the mitigation of global warming. Moreover, certain processes herein are preferred over existing electrochemical processes due to being stable, efficient, having scalable reaction rates, occurring in water, and having selectivity of butanol.

Advantageously, the carbon dioxide may be obtained from any source (e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself).
Most suitably, the carbon dioxide may be obtained from concentrated point sources of generation prior to being released into the atmosphere. For example, high concentration carbon dioxide sources may frequently accompany natural gas in amounts of 5% to 50%, exist in flue gases of fossil fuel (e.g., coal, natural gas, oil, etc.) burning power plants, and high purity carbon dioxide may be exhausted from cement factories, from fermenters used for industrial fermentation of ethanol, and from the manufacture of fertilizers and refined oil products.
Certain geothermal steams may also contain significant amounts of carbon dioxide. The carbon dioxide emissions from varied industries, including geothermal wells, may be captured on-site. Separation of the carbon dioxide from such exhausts is known. Thus, the capture and use of existing atmospheric carbon dioxide in accordance with some embodiments of the present invention generally allow the carbon dioxide to be a renewable and unlimited source of carbon."
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And from which "carbon dioxide ... a renewable and unlimited source of carbon", we can make the Alcohol, Butanol, which is so high in energy content, and otherwise so chemically compatible with conventional fuel handling systems, that it can serve, with little penalty, as a direct substitute for Gasoline.
In sum, and in brief:
Carbon Dioxide is a valuable raw material resource.
We can reclaim Carbon Dioxide, from whatever source, or sources, which might be convenient to us, and then, using freely-available environmental energy, efficiently convert that Carbon Dioxide into a liquid hydrocarbon fuel that is able to serve as a direct, or nearly direct, replacement for Gasoline.
All the rest of it:
Cap and Trade taxes levied against our vital Coal-use industries, our ongoing national economic enslavement to the alien powers of OPEC, the War On Coal, are self-defeating, criminally deceptive and exploitive nonsense.
We now have the means to - - as embodied in the Disclosure of our subject, "United States Patent Application 20120132538 - Electrochemical Production of Butanol from Carbon Dioxide and Water", and it's far, far past time to - - put a stop to all of it.