EP2008005069 CATALYTIC HYDROGENATION OF CARBON DIOXIDE INTO SYNGAS MIXTURE

In a recent dispatch, accessible via:

West Virginia Coal Association | Saudi Arabia and Texas CO2 to Hydrocarbon Syngas | Research & Development;

we made report of:

"United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture; October 16, 2012; Inventors: Agaddin Mamedov, Texas, and Abdulaziz Al-Jodai, Riyadh, Saudi Arabia; Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, wherein the catalyst substantially consists of chromia/alumina. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be combined with other processes, for example up-stream with other synthesis processes for making products like aliphatic oxygenates, olefins or aromatics".
And, "United States Patent 8,288,446" is, obviously, the disclosure of a technical process which can efficiently convert, recycle, Carbon Dioxide into a hydrocarbon synthesis gas which, through long-known catalytic processes, can be chemically condensed into liquid hydrocarbons.

As too often happens, as we've noted on multiple previous occasions, the official, United States Patent and Trademark Office link we included in that dispatch, to the US Government's own electronic file of that document, as it is posted on the West Virginia Coal Association's web site, has proven unreliable, now fails to function properly, and now takes you to a different patent document altogether.

We included in that dispatch an additional link to a secondary site's record of that United States Patent; and, here is yet another:

US Patent # 8,288,446. Catalytic hydrogenation of carbon dioxide into syngas mixture - Patents.com.

It is, we assure you, quite real.

Carbon Dioxide can be efficiently converted - - it can be efficiently recycled via the intermediate production of a hydrocarbon synthesis gas - - into liquid hydrocarbons; no matter what some people of suspect interest and motivation would have you believe.

And, although the patent hasn't yet been awarded, we submit to you herein, by way of further confirmation of those facts, yet another variation of that Saudi Arabia technology for the effective recycling of Carbon Dioxide into some stuff that we should all be interested in how, using a wrongly-vilified natural resource we seem to have plenty of as the basic raw material, we can make for ourselves, right here, right now, in the USA.

As seen in:

"United States Patent Application: 0100190874 - Catalytic Hydrogenation of CO2 into Syngas Mixture

CATALYTIC HYROGENATION OF CARBON DIOXIDE INTO SYNGAS MIXTURE - Mamedov, Agaddin Kh M.

Date: July 29, 2010

Inventors: Agaddin Mamedov, et. al.; Texas and Riyadh, Saudi Arabia

Correspondence (and presumed eventual Assignee): SABIC (Saudi Basic Industries Corporation) Americas

Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, which catalyst substantially consists of Mn oxide and an oxide of at least one member selected from the group consisting of Crl Ni, La, Ce, W, and Pt. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be integrated with other processes, both up-stream and/or down-stream; like methane reforming or other synthesis processes for making products like alkanes, aldehydes, or alcohols."

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We'll keep our excerpts brief since little differs between "United States Patent 8,288,446" and "United States Patent Application 0100190874", wherein the catalytic elements are specified to be Manganese, "Mn", oxide, Nickel, "Ni"; Lanthanum, "La"; Cesium, "Ce"; Tungsten, "W"; and Platinum, "Pt". The "Crl", or, variously, "Cr1", is not a misprint, but refers to Chromium at a specific level of electrochemical reactivity. We don't understand it well enough to attempt explaining it; but, for more info, have a look at:

http://www.nist.gov/data/PDFfiles/jpcrd94.pdf; "Energy Levels of Chromium; National Bureaus of Standards; Washington, DC".

There is, in other words, nothing mystical or exceedingly rare needed to facilitate the "hydrogenation of carbon dioxide into" the reactive and chemically valuable "carbon monoxide" which is then available for "synthesis processes". And, "United States Patent Application 0100190874" seems to vary from the issued  "United States Patent 8,288,446", with both sharing the title of "Catalytic Hydrogenation of CO2 into Syngas Mixture", primarily in the selection of catalysts which can be utilized and in the ranges of hydrocarbons and other products that can thus be formed. However, given our limitations here, we simply cannot attempt to analyze or explain the subtleties for you further than that.

It's far past time some genuine experts were drafted to do so, if anyone at all is interested. 

However, to confirm for you that these technologies are not only real, but, that the Saudi's are quite serious about locking up the rights to pursue their reduction to practice, with resulting benefit, we present to you herein the International Patent Applications for these Carbon Dioxide recycling processes, which would secure, in essence, the exclusive worldwide rights to practice these technologies for profit and gain.

First, as excerpted from the initial and following links, we have:

"Publication No.: WO/2009/000494; International Application No.: PCT/EP2008/0050

(We note that this is, indeed, only a patent application; and, a well-aged one, at that. We have no doubt, that, given the official US Government affirmation of this as innovative and practical technology, the World Patent Organization will soon follow suit and issue an international patent on this technology. At that time, the links we enclose herein will, too, cease to function. But, when that occurs, we will, as soon as we become aware of the fact, make further report on the international patent itself.)

Publication Date: December 31, 2008; International Filing Date: June 6, 2008

Applicants: Saudi Basic Industries Corporation, Riyadh, Saudi Arabia

Inventors: Aggadin M. Mamedov (for United States only)

(Keep in mind that Mamedov, though seeming to be listed officially in the full record of this document as a resident or citizen of Saudi Arabia, is identified in "United States Patent 8,288,446" as a resident of Texas. And, he seems to be Saudi Basic Industries' designated US representative.)

Title: Catalytic Hydrogenation Of Carbon Dioxide Into Syngas Mixture

Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, wherein the catalyst substantially consists of chromia/alumina. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be combined with other processes, for example up-stream with other synthesis processes for making products like aliphatic oxygenates, olefins or aromatics.

EP2008005069 CATALYTIC HYDROGENATION OF CARBON DIOXIDE INTO SYNGAS MIXTURE

(The separate links we include, as above, although appearing identical, seem designed and intended through the code they disguise to take you to different segments of the patent application publication. We include them for the sake of assurance and accuracy. They might prove for you redundant.)

Claims: Process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, characterized in that the catalyst substantially consists of chromium as active substituent, optionally at least one alkali metal or alkaline earth metal as promoter, and alumina as support.

Process ... wherein the catalyst contains from 5 to 30 mass% of chromium (and) from 0.2 to 30 mass% of at least one member selected from the group consisting of Lithium, Potassium, Cesium and Strontium.

Process ... wherein the catalyst is a spent chromia/alumina dehydrogenation catalyst.

(We explained the significance of "spent chromia/alumina dehydrogenation catalyst" in our report of "United States Patent 8,288,446". In brief sum, there are synergies between this CO2 recycling process and rather standard petroleum refining techniques and technologies.)

Process ... wherein the spent catalyst has been pre- treated with a gaseous mixture containing hydrogen at about 500-700 C under atmospheric pressure during 1-8 hours.

(There are many ways available, with more being developed all the time, to extract Hydrogen from Water, H2O, through the application of environmental energy. We've documented quite a few for you already, though we won't clutter up our presentation herein with more links. We will be making further report on even more advanced, and more economical, Hydrogen generation technologies in the future.)

Process .. wherein the contacting step is carried out ... with a contact time of from 0.5 to 6 seconds.

(This is, as above, a fast, high-production rate process.)

Process ... wherein the feed mixture contains hydrogen and carbon dioxide in a ratio of from 1 to 5 (and) wherein the syngas has a stoichiometric number of from 0.1 to 3.0.

(The feed mixture is variable so that the syngas composition can be adjusted to target production of specific hydrocarbons in the catalytic synthesis stage.)

Process ... herein the feed mixture further comprises methane.

(Methane isn't, strictly speaking, necessary; but, might be desirable in order to adjust the Hydrogen-Carbon Monoxide ratios in the product synthesis gas. If so, we remind you that, as seen, for only two out of now many, many examples in:

West Virginia Coal Association | Massachusetts Coal and Carbon-recycling Wastes to Methane | Research & Development; concerning: "United States Patent 8,202,913 - Process for Gasification of a Carbonaceous Feedstock; 2012; Assignee: Greatpoint Energy, Inc., MA: Abstract: The present invention relates to processes and continuous processes for preparing ... methane via the catalytic gasification of carbonaceous feedstocks in the presence of steam. The present invention relates to processes for preparing ... methane via the catalytic gasification of carbonaceous feedstocks (including) coal (and) "biomass" ... including plant-based biomass and animal-based biomass"; and:

West Virginia Coal Association | Switzerland & Chicago Photo-Convert CO2 into Methane | Research & Development; concerning: "United States Patent 4,847,231 - Mixed Ruthenium Catalyst; 1989; Assignee: Gas Research Institute, Chicago; Abstract: A catalyst having a mixture of Ru and RuOx ... is suitable for the heterogeneous catalytic gas phase direct methane production from hydrogen and carbon dioxide at mild temperatures as low as 25 C and atmospheric pressure";

we can make any needed Methane from Coal; from naturally CO2-recycling, and renewable, biological wastes; or, even, from Carbon Dioxide itself.)

Process for making a chemical product using a syngas mixture as an intermediate or as feed material, which process comprises a step of carbon dioxide hydrogenation ... (which "making a chemical product" can include) aliphatic oxygenates production, olefin synthesis, aromatics production, or ... methanol production. 

EP2008005069 CATALYTIC HYDROGENATION OF CARBON DIOXIDE INTO SYNGAS MIXTURE;

The invention relates to a catalytic process for producing a syngas mixture from carbon dioxide, more specifically to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a chromium-containing catalyst."

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We're not organic chemists and, as previously noted, we have lost access to knowledgeable advisors with whom we used to consult on such matters. But, we assure you:

The synthesis gas mixture described herein could be directly condensed, as via the Fischer-Tropsch, and a number of other, related, catalytic processes into familiar and conventional liquid hydrocarbon fuels, including Diesel and the blending components for Gasoline.

But, some of the generic organic chemical products, i.e., "olefin" and "aromatics", can also, we assure you, be utilized and consumed in the manufacture of certain types of plastics, wherein the Carbon Dioxide first consumed in the process of our subject, "International (Patent) Application No.: PCT/EP2008/0050; Catalytic Hydrogenation Of Carbon Dioxide Into Syngas Mixture", would be forever, chemically and productively, "sequestered".

And, we remind you that, since "methanol" is one of the CO2-recycling products directly specified, such Methanol, as seen, for only one example, in our report of:

West Virginia Coal Association | Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984;

Assignee: Mobil Oil Corporation; Abstract: A process for producing a wide slate of fuel products from coal is provided by integrating a methanol-to-gasoline conversion process with coal liquefaction and coal gasification (wherein) coal is gasified under oxidation conditions to produce a synthesis gas which is converted to methanol. The methanol is converted to gasoline by contact with a zeolite catalyst";

no matter which of our precious natural resources we choose to make it from, whether, as immediately above, Coal, or, as via the process of "International (Patent) Application No.: PCT/EP2008/0050 - Catalytic Hydrogenation Of Carbon Dioxide Into Syngas Mixture"; Carbon Dioxide, can be directly converted into that stuff we've demonstrated our willingness to fight foreign wars and mortgage our grandchildren's future to keep ourselves supplied with in the here and now: Gasoline.

In any case, Saudi Basic Industries are also, as they are in the United States of America, seeking international patent protection to secure the world rights to the alternate version of their CO2-recycling technology, as seen in:

EP2008003258 CATALYTIC HYDROGENATION OF CARBON DIOXIDE INTO SYNGAS MIXTURE

"Publication No.: WO/2008/131898; International Application No.: PCT/EP2008/003258

Publication Date: June 11, 2008; International Filing Date: April 23, 2008

Applicants: Saudi Basic Industries Corporation, Riyadh, Saudi Arabia

Inventors: Aggadin M. Mamedov (for United States only), et. al.

Title: Catalytic Hydrogenation Of Carbon Dioxide Into Syngas Mixture

Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, which catalyst substantially consists of Mn oxide and an oxide of at least one member selected from the group consisting of Cr1, Ni, La, Ce, W, and Pt. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be integrated with other processes, both up-stream and/or down-stream; like methane reforming or other synthesis processes for making products like alkanes, aldehydes, or alcohols."

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A couple of us here remember an old movie about WWII. There is a scene in it, where, prior to the attack on Pearl Harbor, while the United States still maintained diplomatic relations with Japan during their aggressive Asian colonial empire building, a small group of people, including a couple of military officers, were standing by some piers on the ocean, talking.

One of the officers said to the others, and we generalize:

"You see those ocean barges tied up to the pier? They're being loaded up with all kinds of junk, wrecked automobiles, everything and anything metal. And, they're all headed for Japan. You watch, in a few years, the Japanese are going to be shooting pieces of old Buick's back at us."

If anyone takes a drive today or tomorrow along one of our Coal Country rivers and passes by a Coal-fired electric power plant, take a look at the exhaust stacks. Nowadays, you won't be able to see much coming out of them; but, imagine that you can see the Carbon Dioxide wafting up into the clear blue sky and drifting away in the breeze - maybe imagine it as being colored green, since that's the color of all the forest trees and food crops it nourishes, as well as being the color of money.

And, you watch:

In a few years, OPEC's going to be selling that CO2 back to us. We'll be filling up our cars with old Coal Country Carbon Dioxide; at, what, 4, 5, 6 bucks a gallon?

And, unless our Coal Country press gets off their dead cans and starts informing the public about the truth of the matter, we will, no doubt, even when that starts happening, still be whining about the threat of Cap & Trade taxes or okey-dokey giving our Carbon Dioxide away to Big Oil, and paying to ship it to him, so that he can, under the modesty veil of "geologic sequestration", use it to scrounge more profit out of his leaky and nearly-depleted natural petroleum reservoirs.

If we don't want to convert it, recycle it, into hydrocarbons ourselves, we could and should at least be collecting it and selling it for profit to those who do.  

Folks: It's way, way past time we all woke up and smelled the coffee; and, made up a big fresh pot for our Coal Country press.

Carbon Dioxide is a valuable raw material resource. We need to start thinking of it and treating it that way.

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