We've documented a number of times that Carbon Monoxide can be manufactured in a pretty direct way, by what might seem the rather self-evident reaction between Carbon Dioxide and hot Coal, as represented by the simple equation: CO2 + C = 2CO; and, as seen for just one instance in:
Solar Power Converts CO2, H2O and Coal to Hydrocarbon Syngas | Research & Development; concerning:
"US Patent 4,177,120 - Photolytic Process for Gasification of Carbonaceous Material; 1979; Process and apparatus are disclosed for converting carbon dioxide to carbon monoxide by subjecting the carbon dioxide to radiation in the presence of carbonaceous material such as coal to form carbon monoxide."
In the above process, the endothermic reaction between CO2 and Coal is driven by focused radiant Solar heat energy, thus obviating the need to partially oxidize Coal to obtain the needed heat, and forestalling in that way the incidental co-production of any CO2 in such a partial oxidation of the Coal.
There is a bit more to utilizing such reactions on an industrial basis, as we have documented, and as we will further document; but, not a lot.
And, there are other processes which can lead to the production of CO from CO2, as seen most recently in our report:
Colorado Recycles Carbon Dioxide | Research & Development; wherein is documented, among several:
"United States Patent Application 0080245672 - Methods to Generate Hydrogen and Sequester CO2; October, 2008; Abstract: A carbon dioxide negative method of manufacturing renewable hydrogen and trapping carbon dioxide from the air or gas streams (which comprises, among other things) chemically reducing carbon dioxide by reacting hydrogen gas produced by the system with carbon dioxide trapped by the system to produce carbon monoxide, a precursor for other synthetic processes".
We've also already documented a number of times that Carbon Monoxide, CO, once so produced, as above, from Carbon Dioxide, can be directly utilized as a valuable raw material in manufacturing processes directed towards the synthesis of liquid hydrocarbon fuels and organic chemicals, including various plastics.
One example would be:
Standard Oil Carbon Monoxide + Water = Gasoline | Research & Development; which provides details of:
"United States Patent 4,559,363 - Process for Reacting Carbon Monoxide and Water; 1985; Abstract: A process for reacting carbon monoxide and water in the presence of a cadmium-containing catalyst ... for the direct production of gasoline".
Herein, we see that our own United States Government agrees and acknowledges that Carbon Monoxide, once we have it, perhaps, as in the process noted above, of "US Patent 4,177,120 - Photolytic Process for Gasification of Carbonaceous Material", made by reacting Carbon Dioxide with hot Coal, is a valuable and versatile raw material.
We can, indeed, as in the above-noted process of US Patent 4,559,363, react Carbon Monoxide with Water; but, instead of Gasoline, to synthesize various Alcohols.
As seen, with comment, concerning, especially, the catalysts employed, appended, in our excerpts from the initial link in this dispatch to:
"United States Patent 4,656,152 - Catalyst for Producing Lower Alcohols
Date: April, 1987
Inventor: Jerome Rathke, et. al., Illinois
Assignee: The United States of America, as represented by the Secretary of the USDOE
Abstract: A process and system for the production of the lower alcohols such as methanol, ethanol and propanol involves the reaction of carbon monoxide and water in the presence of a lead salt and an alkali metal formate catalyst combination. The lead salt is present as solid particles such as lead titanate, lead molybdate, lead vanadate, lead zirconate, lead tantalate and lead silicates coated or in slurry within molten alkali metal formate. The reactants, carbon monoxide and steam are provided in gas form at relatively low pressures below 100 atmospheres and at temperatures of 200-400C. The resulted lower alcohols can be separated into boiling point fractions and recovered from the excess reactants by distillation.
The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the U.S. Department of Energy and Argonne National Laboratory.
Claims: A catalyst combination for the reaction of carbon monoxide and water to produce lower alcohols, said catalyst combination comprising a lead heteropolyatomic salt in mixture with a metal formate ... .
Background and Field: The present invention relates to the catalytic production of the lower alcohols, methanol and mixtures of methanol with ethanol and propanol, by the reaction of carbon monoxide with liquid water or steam. The process is of particular advantage in that ethanol may be produced directly from carbon monoxide without resorting to a separate and additional process for the conversion of methanol to ethanol. Moreover, carbon monoxide can be provided as a by-product from the ... partial oxidation of coal or other carbonaceous material, or from typical coal gasification processes ... .
Previous processes for the production of methanol from carbon monoxide have involved the reaction of carbon monoxide with hydrogen.
In contrast, the reaction of carbon monoxide and water to form methanol is thermodynamically more favorable than the corresponding carbon monoxide and hydrogen reaction. However, prior workers have been unable to realize this advantage at low process pressures by directly reacting carbon monoxide with water in the presence of these known catalysts. Consequently, the elevated process pressures with required thick-walled equipment negates many advantages of the carbon monoxide-water reaction.
The prior processes for the production of methanol from carbon monoxide have produced little ethanol. Subsequent process steps and operations are required for the further conversion of methanol to ethanol. Ethanol is a particularly desirable alcohol as it can be employed not only as a fuel but also as a raw material for the production of ethylene, a chemical used in large quantities in the industrialized countries. In addition, mixtures of methanol with ethanol and propanol are desirable as gasoline extenders.
Summary and Description: Therefore in view of the above it is an object of the present invention to provide an improved catalyst for the reaction of carbon monoxide with water to produce methanol and other lower alcohols.
It is a further object to provide a process for the production of methanol from carbon monoxide and water in which a relatively inexpensive catalyst permits the reaction at low pressures.
It is also an object to provide a process for the production of methanol in which ethanol is also directly produced.
In other aspects of the present invention, a process is provided for producing a lower alcohol from the reaction of carbon monoxide and water. The process involves passing a gas mixture of carbon monoxide and steam into contact with a catalyst combination including a lead salt, that is essentially not reduced to lead metal by carbon monoxide, and a co-catalyst comprising metal formates or precursors to metal formates under the reaction conditions. These catalysts promote the reaction of carbon monoxide and water to form a lower alcohol typically including methanol, often ethanol and in some instances propanol."
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Note, as in the full Disclosure, that "carbon monoxide can be provided as a by-product from the ... partial oxidation of coal", which is exactly the sort of process described, for one instance, in:
More Pre-WWII CO2 Recycling | Research & Development; concerning: "US Patent 2,128,262 - Carbon Monoxide Manufacture; 1938; Abstract: An object of this invention is to provide an efficient and economical process for the manufacture of carbon monoxide of high purity by the reduction of carbon dioxide (which is accomplished by passing) carbon dioxide through (hot) coke".
We must as well call your attention to the improved catalysts employed in the process of our subject, United States Patent 4,656,152, which include, as specified: "metal formates".
Such "metal formates", we submit, would be formed by reacting the suitable metal with Formic Acid; which Formic Acid, as seen in:
Japan Converts CO2 to Formic Acid | Research & Development | News; wherein is detailed: "United States Patent 7,479,570 - Process for the Reduction of Carbon Dioxide; 2009; Abstract: Carbon dioxide and water are mixed with an organometallic complex (of varied and specified compositions). This makes it possible to directly reduce carbon dioxide in water ... so that formic acid or alkali salt thereof is formed";
can itself be made from Carbon Dioxide.
Then, since Alcohols are being manufactured via the process herein of "United States Patent 4,656,152", from Carbon Monoxide, which can be made from Carbon Dioxide, we remind you of our report:
Monsanto Recycles CO2 to Methanol | Research & Development; which includes information about the: "United Stares Patent 5,371,183 - Preparation of Urethane from Polyamine and Carbon Dioxide; 1994; Assignee: Monsanto Company, St. Louis; Abstract: The present invention provides a process for preparing urethanes and carbonates from an ... alcohol, carbon dioxide and a hydrocarbyl halide";
wherein is explained how a range of quiet useful plastics can be synthesized by reacting various of those CO2 and CO-derived alcohols with even more Carbon Dioxide; in which plastics, any CO2 used to synthesize Carbon Monoxide for the production of Alcohols via the process herein of "USP 4,656,152", along with any CO2 added to those Alcohols, as in the process above of "USP 5,371,183", would be permanently, and profitably and productively, "sequestered".
Further, again and finally, once we have the "methanol and mixtures of methanol with ethanol", as herein synthesized from such CO2-derived Carbon Monoxide in reactions with Water, we can, as seen in:
Coal and CO2 to Gasoline and Plastics via Methanol | Research & Development; which catalogues, among others similar: "US Patent 4,981,491 - Production of Ether-Rich Fuel; 1991; Mobil Oil Corporation; Abstract: Methanol or other alcohol is converted to high octane gasoline components ... . This invention relates to techniques for converting crude methanol or other ... alcohols to ... gasoline range hydrocarbons";