United States Patent Application: 0080287555

There is, of course, a great deal of quite recent, though inexcusably tardy, verbal flailing about in the press and media concerning an issue simply stated in:

EPA limits carbon pollution from new power plants - CNN.com; "The Environmental Protection Agency is proposing new rules aimed at limiting the amount of carbon pollution coming from new power plants".

Note the qualifier "new power plants". Carbon regulations for existing power plants are, by reports, in the works, and due to come out at some later time in the not-too-distant future.

A great deal of, mostly emotional, editorializing has greeted that announcement by the EPA, also and most especially of course, in the Coal Country commercial press. Even supposedly straight reportage, as in:

EPA Enacts Power Plant Carbon Limits - News, Sports, Jobs - The Intelligencer / Wheeling News-Register

"New coal-fired power plants will need to install expensive technology to capture between 30 and 50 percent of their carbon dioxide and bury it underground. No coal-fired power plant has done that yet, in large part because of the cost. Virtually all new natural gas plants would meet the standard without additional controls",

is suspect, since we're not certain the captured CO2 is actually obliged to be buried "underground". If so, then the true intent of the new regulations is hinted at in "new natural gas plants would meet the standard without additional controls". That is because the places where it is most often proposed that the CO2 be buried "underground" is in natural petroleum and gas reservoirs, to help push out more oil and more gas.

Thus, mandated burying of Carbon Dioxide becomes a back-door subsidy of the oil and gas industries, with the costs of that subsidy saddled onto the backs of the consumers of abundant, and currently-affordable, Coal-based electric power. But, even with all of the wailing and figurative gnashing of teeth about the EPA's recent actions in the Coal Country public media, no one in the press seems yet to have the courage to fill you in on the details of that somewhat inconvenient truth.

Again, we don't know the specifics of the EPA's plan, having been treated only to generalizations that it could soon, perhaps, "triple" the cost of Coal-based electric power. And, nowhere in the press are we treated to another seemingly inconvenient truth, i.e.:

Carbon Dioxide is a valuable raw material resource, which can be reclaimed from whatever handy source, and, as seen for only one example in:

West Virginia Coal Association | Penn State May 14, 2013, CO2 to Methane | Research & Development; concerning: "United States Patent 8,440,438 - Electromethanogenic Reactor and Processes for Methane Production; 2013; Assignee: The Penn State Research Foundation; Biological processes for producing methane gas and capturing carbon from carbon dioxide are provided according to embodiments of the present invention ... . Electrons and carbon dioxide are provided to the plurality of methanogenic microorganisms (which) reduce the carbon dioxide to produce methane gas";

via a number of technical routes, even in addition to that of "United States Patent 8,440,438", be converted in energy-efficient ways into a substitute for the "natural" gas that everyone seems currently so entranced with.

Moreover, you're not being told by your press that some folks in other parts of the world, folks you're likely not real fond of, openly recognize the value of Carbon Dioxide, and, as seen, for just two examples in:

West Virginia Coal Association | Saudi Arabia 4th of July CO2 to Hydrocarbons | Research & Development; concerning: "US Patent Application 20130168966 - Method for Conversion of Carbon Dioxide into Hydrocarbons; Date: July 4, 2013; Inventors: Mazen Abdullah Ba-Abbad, et. al., Riyadh, Saudi Arabia; Assignee: King Saud University, Riyadh; Abstract: The present invention relates to a method for converting carbon dioxide into hydrocarbons"; and:

West Virginia Coal Association | Saudi Arabia and Texas CO2 to Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture; 2012; Assignee: Saudi Basic Industries Corporation, Riyadh (Saudi Arabia); Abstract: The invention relates to a process of making a syngas mixture ... comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst wherein the (resultant synthesis gas can) be combined with other processes, for example up-stream with other synthesis processes for making products like aliphatic oxygenates, olefins or aromatics";

are assertively developing the technology needed to collect Carbon Dioxide and convert it into more of the stuff we're already paying them through the nose to send us an endless stream of tanker ships full of.

The above patent and patent application disclosures are not, by the way, idle intellectual exercises.

Information is at this point sketchy, limited to a few brief corporate news releases, and we will bring you a more complete report of the matter as soon as we are able, but:

Within the past week, "Saudi Basic Industries Corporation", aka "Saudi Arabia Basic Industries Corporation", aka "SABIC", who are the owners of the above-cited "US Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture", and who once had a pilot plant operating their Carbon Dioxide-recycling processes in Bahrain, have signed a design, engineering and construction contract with the Germany-based international industrial gas supplier, the Linde Group, to build what is being described as the world’s largest CO2 purification and liquefaction plant, which will extract CO2 from the exhaust gas of a petroleum-refining/petrochemical-manufacturing complex, and supply that CO2 to, by reports, three additional facilities, all of them sited in Saudi Arabia, the home of Mecca, where the waste Carbon Dioxide will be consumed in the synthesis of fuel alcohol Methanol and at least one other industrial commodity chemical.

Again, we'll get more info to you, with documentation, as soon as we are able to do so, but:

In brief, if you don't like paying a large portion of your income for imported oil, or the prospect of paying more of your income for currently-affordable Coal-based electricity because of CO2 Cap and Trade taxes, you will, we assure you, like these new developments, and, justifiably, the journalistic industry that is keeping the news and the truth of the matter from you, even less.

That said, we learn herein that the art and science of productively and profitably capturing and utilizing Carbon Dioxide is, throughout the World of Islam at least, continuing to progress and to become more energy efficient.

As seen in excerpts from the initial link in this dispatch to:

"United States Patent Application 20080287555 - Novel Process and Catalyst for Carbon Dioxide Conversion to Energy Generating Products

Patent US20080287555 - Novel process and catalyst for carbon dioxide conversion to energy ... - Google Patents

Novel process and catalyst for carbon dioxide conversion to energy generating products - Quaid-e-Azam University

November 20, 2008

(Note that this application has been around for a while, and has undergone revision. It might soon transition into an issued US Patent, in which case the links we enclose to it will ultimately cease to function. We'll attempt to keep apprised of developments, and update you accordingly.)

Inventors: Syed Tajammul Hussain, et. al., Pakistan

Assignee: Quaid-e-Azam University, Islamabad

Abstract: A catalytic process and a nano material for the conversion of moist carbon dioxide into methanol, propyne and oxygen (in which) hydrogen is produced from water in a catalytic reaction, when the moist carbon dioxide enters into the catalytic reactor, resulting in C--O and H--OH bond breakage at a relatively low temperature and at atmospheric pressure in a single step using a combination of catalytic materials comprising at least three metals dispersed on a catalyst support, preferably anatase form of titanium dioxide, to induce a multifunctional surface chemical reaction for the production of oxygenated products such as hydrocarbons of different chain lengths.

(Note, in the above, this is a process that can be conducted at energy-conserving "relatively low temperature" and "atmospheric pressure".)

Claims: A method of converting carbon dioxide into straight chain, C1-C4, hydrocarbons by contacting a mixture of catalytic materials comprising of ruthenium, cobalt and manganese or their salts thereof dispersed onto a catalyst support system with wet carbon dioxide gas. 

The method ... wherein said catalytic materials additionally include Platinum, Palladiumd, Cobalt, Silver, Gold, Indium, Cerium, Tungsten, Molybdenum, or Iron or their salts and combinations thereof.

(Note that not all of the above are required. The final "or" in the above should be highlighted; but, there is no doubt a most advantageous blend of the named components which Quaid-e-Azam University has determined, but which they likely hold as proprietary.)

The method ...  wherein said catalytic materials are doped by potassium, sodium, cerium and combinations thereof (and) wherein the concentration of said catalytic materials ranges between 1 and 25% of each weight by weight. 

The method ... wherein said catalytic materials are in the form of powder, discs or pallets (pellets?) (with a)particle size ranging between 10 and 100 nanometer. 

The method ... wherein said catalytic materials are heated to between 50 and 1000 C, more preferably between 400-800 C., prior to contacting them with wet carbon dioxide.

(In truth, the preferred "400-800 C" range is getting pretty hot. The "800 C", for instance, equates to

about 1472 degrees Fahrenheit, which is, very roughly, half the melting point of Iron.

However, as can be learned via:

Solar thermal energy - Wikipedia, the free encyclopedia; and related articles linked to in that core reference, such temperatures are well within the range of solar "furnaces", even large-scale solar furnaces, one  example of which is provided as having been operated in the mountains of France for a number of decades. It seems unlikely, though, that such solar thermal collectors and concentrators would prove practical in the often cloudy confines of West Virginia, Pennsylvania and most other outposts of US Appalachian Coal Country, at least for the purposes of continuous production over the course of seasons, which is one reason the often-touted concept of solar thermal electricity generation seems, for the most part, impractical.

It might, however, be practical in the southwest desert of the Unites States, where Carbon Dioxide could, as seen for just one example in our report of:

West Virginia Coal Association | Columbia University August 2012 Practical CO2 Air Capture | Research & Development; concerning: "United States Patent 8,246,731 - Systems and Methods for Extraction of Carbon Dioxide from Air; 2012; Assignee: The Trustees of Columbia University in the City of New York; Abstract: The present invention describes methods and systems for extracting ... carbon dioxide (CO2), particularly from the air. ... Methods are also described for extracting and/or capturing CO2 via exposing air containing carbon dioxide to - - a basic solution which absorbs carbon dioxide and produces a carbonate solution. The solution is causticized and the temperature is increased to release carbon dioxide, followed by hydration of solid components to regenerate the base";

be captured from the atmosphere and then be subjected to the thermo-chemical processing being disclosed herein by Pakistan, with the resultant products then distributed to the rest of the United States of America.

Such long-distance transport of what is, essentially, Solar energy, stored in the form of chemicals, seems feasible, since, as proposed and explained by way of example in:

http://pre.ethz.ch/publications/0_pdf/books/Solar_Thermochemical_Process_Technology.pdf; "'Solar Thermochemical Process Technology'; Swiss Federal Institute of Technology, Zurich, and Paul Scherrer Institute, Villigen, Department of General Energy Research";

it makes a great deal of economic sense, it's much more efficient, to use the abundant Solar heat energy available in Australia to make chemical and chemical energy products, and ship those as fuel or raw materials to Japan, rather than to try to use Solar heat for the generation, for instance, of electricity for such long-distance transmission.

And, by way of extrapolation, if we had our druthers, we would a lot druther fill up our trusty old Ford or Chevy in West Virginia or Pennsylvania with liquid fuel synthesized from Carbon Dioxide in Arizona or Nevada via Solar chemical processes, than with the same stuff synthesized in, and imported from, Saudi Arabia or, as herein, what is officially titled The Islamic Republic of Pakistan.)

The method ... wherein said catalyst support system comprises of anatase form of titanium dioxide, silica, zeolite, alumina, magnesium oxide, carbon and combinations of thereof.

(There is nothing, absolutely nothing, very exotic or hugely expensive in any of that; and, nothing we can't source right here in the USA.)

The method ...  wherein said catalyst support system has a surface area (and) particle size (as specified, and) wherein said catalytic materials are in the form of powder, discs (etc.). 

The method ... wherein said wet carbon dioxide has the temperature between 80-90 C prior to contacting with said catalytic materials (and) wherein said straight chain hydrocarbon (produced) is methanol.

Field and Background: This invention relates to a process for conversion of carbon dioxide using a supported synthetic catalyst mainly composed of a mixed oxide of ruthenium, cobalt and manganese, into methanol, propyne and oxygen as main products, and an apparatus thereof.

There are several other motivations ... for producing chemicals from carbon dioxide:

1. Carbon dioxide is an inexpensive, nontoxic feedstock that can frequently replace toxic chemicals ... .

2. Carbon dioxide is a renewable feedstock compared to oil ... .

3. The production of chemicals from carbon dioxide can lead to new industrial productivity.

4. New routes to existing chemical intermediates and products could be more efficient and economical than current methods.

5. The production of chemicals from carbon dioxide could have (an) impact on the global carbon balance.

Conversion and utilization of carbon dioxide are important subjects in the field of chemistry for the production of ultra-clean transportation fuels ... . Several technologies have been proposed for improving the efficiency of energy conversion and utilization of carbon dioxide. Examples of conventional techniques for hydrogenating carbon dioxide in order to fix carbon dioxide include photo-electrochemical techniques utilizing natural energy, such as sunlight, and biochemical techniques utilizing microorganisms.

(Concerning the above-mentioned use of  "sunlight, and ... microorganisms" for recycling Carbon Dioxide, see, for just two recent examples, our reports of:

West Virginia Coal Association | New York City CO2 to Methane via Artificial Photosynthesis | Research & Development; concerning: "US Patent Application 20120208903 - Conversion of Carbon Dioxide to Methane Using Visible Light; 2012; Assignee: Research Foundation of City University of New York";

and, in addition to our report cited in introductory comments concerning "US Patent 8,440,438 - Electromethanogenic Reactor and Processes for Methane Production":

West Virginia Coal Association | California Bugs Convert More CO2 into Methane | Research & Development; concerning: "United States Patent 7,807,427 - Methods and Compositions for Production of Methane Gas; 2010; Assignee: The Regents of the University of California; Abstract: The present invention provides methods and compositions for sustained methane production from atmospheric CO2 and solar energy from the sun. In general the methods involve culturing cyanobacteria in a first culture vessel and collecting and diverting the photosynthesis products, including glucose or acetic acid, to a second culture vessel including methanogenic bacteria. The photosynthesis products are then used as nutrients by the methanogenic bacteria in the second culture vessel in the production of methane".)

The most common of the reaction used is the Sabatier Reaction and Water Gas Shift Reaction. The Sabatier reaction or Sabatier process involves the reaction of hydrogen with carbon dioxide at elevated temperatures and pressures in the presence of a nickel catalyst to produce methane and water. Optionally ruthenium on alumina makes a more efficient catalyst.

(Regarding more recent developments related to the above-cited, century-old, Nobel Prize-winning "Sabatier process", see our report of:

West Virginia Coal Association | NASA Improves CO2 to Methane Conversion | Research & Development; concerning: "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2012; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen ... so as to produce a product stream comprising water and methane. Government Interests: This invention was made with support from the U.S. government under U.S. Contract No. NNX10CF25P sponsored by the National Aeronautics and Space Administration".)

A large volume of prior art exists in attempts to create an efficient system for converting carbon dioxide into useful products. Given below are some relevant patents issued in this art. 

The U.S. Pat. No. 6,248,795: Process of preparing a mixture of dimethyl ether and methanol from carbon dioxide, Jun and Lee. This invention relates to the process of preparing from carbon dioxide a mixture of dimethyl ether and methanol which are useful as clean fuel or raw materials in the chemical industry. More particularly, this invention relates to the process of preparing dimethyl ether and methanol in high yield without by-products such as hydrocarbons by means of chemical conversion of carbon dioxide.

(Concerning the above, see our report of:

West Virginia Coal Association | Korea CO2 to Methanol & Dimethyl Ether | Research & Development; concerning: "United States Patent 6,248.795 - Dimethyl Ether and Methanol from Carbon Dioxide; 2001; Inventor: Ki Won Jun and Kyu Wan Lee, Daejeon, KR; Assignee: Korea Research Institute of Chemical Technology; Abstract: This invention relates to the process of preparing from carbon dioxide a mixture of dimethyl ether and methanol which are useful as clean fuel or raw materials in the chemical industry. More particularly, this invention relates to the process of preparing dimethyl ether and methanol in high yield without by-products such as hydrocarbons by means of chemical conversion of carbon dioxide".

"Syed Tajammul Hussain, et. al." cite quite a few other patented CO2-to-Methanol processes, as well, many of which we have already reported to you, others of which we might eventually get to.)

Summary: In one aspect, the present invention provides a method to produce hydrogen from water by breaking the hydrogen-oxygen bond at relatively low temperature and at atmospheric pressure in a single step. In another aspect, the present invention includes a heterogeneous catalytic material which breaks hydrogen-oxygen bond of water during the process. 

In another aspect, the present invention includes a heterogeneous catalytic material which breaks the carbon-oxygen bond of carbon dioxide and hydrogen-oxygen bond of water simultaneously during the process. 

In another aspect, the present invention includes a supported trimetallic catalytic materials which breaks carbon-oxygen bond at low temperature and at atmospheric pressure. At the surface of this catalytic material the hydrogen, oxygen and carbon react to form oxygenated products and hydrocarbons. The oxygenated hydrocarbon can be methanol, or high molecular weight oxygenated products depending on the concentration of the catalyst materials and temperature of reaction, the hydrocarbon gas can be propyne and other hydrocarbons.

The carbon dioxide can be obtained as an industrial byproduct, thus providing a mean to recycle the carbon dioxide that would otherwise be released as an atmospheric pollutant, to form useful chemicals.

In another aspect, the present invention includes a simple process for industries for the conversion of carbon dioxide to useful chemicals. The process includes the flow of carbon dioxide through a container filled with water and this moist gas is injected onto the catalyst surface where a surface reaction takes place at 400 C or lower and at atmospheric pressure for conversion of carbon dioxide to value added chemicals (such as) oxygenated products and hydrocarbons of different chain lengths".

-----------------------

In truth, this US Patent Application is well-aged; and, it has undergone significant revision, most of which, as we read it, was in the deletion of specific claims which, again as we interpret it, infringed on already established and claimed Carbon Dioxide recycling art.

That fact, in and of itself, is revelatory, in that CO2-to-Hydrocarbon technologies exist which can be infringed upon.

But, aside from the fact that it is again herein confirmed that Carbon Dioxide, which arises in only a small way relative to some natural sources of emission, such as the Earth's inexorable processes of planetary volcanism, from our essential use of Coal in the generation of abundant and truly affordable electric power, is a valuable raw material resource. It can be reclaimed from whatever handy source, and then be efficiently converted, as herein, into fuel alcohol and hydrocarbons, there is another point being made:

That value of Carbon Dioxide as a raw material for the synthesis of valuable fuels and chemicals is being recognized and acknowledged in some other places in this big world where the democratic values and individual rights we claim to cherish here in the USA aren't really priorities.

While our own formulators of public policy and our own vendors of public information focus on counter-productive nonsense like that encapsulated in our introductory citation of news concerning the fact, that: "The Environmental Protection Agency is proposing new rules aimed at limiting the amount of carbon pollution coming from new power plants", our economic competitors and, even, our ideological adversaries are going about the straightforward business of exploiting an important fact to their advantage, i.e.:

Carbon Dioxide is a valuable raw material resource.

Carbon Dioxide can be recovered from whatever convenient source and, then, as per the subject of our dispatch herein, "United States Patent Application 20080287555 - Novel Process and Catalyst for Carbon Dioxide Conversion to Energy Generating Products", it can be converted into such seemingly-desirable things as fuel alcohol and hydrocarbons.

They know that to be true in Islamabad.

And, it's far past time the fact was made clearly known to Washington, DC.


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