Exxon Recovers and Recycles Coal Conversion Catalyst

United States Patent: 4157246

Without citing any of our past reports, as now accessible on the West Virginia Coal Association's web site,   concerning the fact, we herein again confirm, as disclosed by the-now ExxonMobil, and as affirmed by our United States Government's technically-expert patent examiners, that:

The conversion of Coal, into more versatile hydrocarbons, can be made more efficient and more economical by the recovery and recycling of various metal compounds used to catalyze the hydro-conversion reactions.

And, almost by now in fulfillment of expectations, our US Government used our tax money to finance Exxon’s development of this commercial refinement in Coal gasification and liquefaction technology.

Brief comment follows excerpts from the link to:

"United States Patent 4,157,246 - Hydrothermal Alkali Metal Catalyst Recovery Process

Date: June, 1979

Inventors: James Eakman, et. al., TX

Assignee: Exxon Research and Engineering Company, NJ

Abstract: In a coal gasification operation or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein solid particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles primarily in the form of water soluble alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water ... and in the presence of added carbon monoxide.

(We apologize for interrupting so early in the excerpts, but, what the heck: Since Carbon Monoxide is required for this Coal conversion catalyst recovery process, to make the total process more economical, we remind you, as in: USDOE Recycles CO2 to Methanol with Solar Power | Research & Development | News; concerning: United States Patent: 6066187 - Solar Reduction of CO2; 2000; The red shift of the absorption spectrum of CO2 with increasing temperature permits the use of sunlight to photolyze CO2 to CO"; and, as in: More Pre-WWII CO2 Recycling | Research & Development; wherein is detailed: "United States Patent 2,128,262 - Carbon monoxide manufacture;1938"; which confirms that "substantially pure" Carbon Monoxide can be manufactured by the simple expedient of passing Carbon Dioxide through red-hot Coal; we can utilize both environmentally-derived energy and/or Coal to convert Carbon Dioxide, recovered from whatever convenient source, into the Carbon Monoxide required herein by Exxon, to recover Coal conversion catalysts from Coal gasification residues.)

During the treating process the water insoluble alkali metal compounds comprising the insoluble alkali metal residues are converted into water soluble alkali metal formates. The resultant aqueous solution containing water soluble alkali metal formates is then separated from the treated particles and any insoluble materials formed during the treatment process, and recycled to the gasification process where the alkali metal formates serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. This process permits increased recovery of alkali metal constituents, thereby decreasing the overall cost of the gasification process by reducing the amount of makeup alkali metal compounds necessary.

Government Interests: The government of the United States of America has rights in this invention pursuant to Contract No. E(49-18)-2369 awarded by the U.S. Energy Research and Development Administration.

Claims: In a process for the conversion of a solid carbonaceous feed material in the presence of an alkali metal-containing catalyst into liquids and/or gases wherein particles containing alkali metal residues are produced, the improvement which comprises: 

(a) treating said particles containing said alkali metal residues in a reaction zone with a calcium or magnesium-containing compound in the presence of liquid water ... and in the presence of added carbon monoxide thereby converting water insoluble alkali metal constituents in said residues into water soluble alkali metal formates and producing an aqueous solution containing water soluble alkali metal constituents consisting primarily of alkali metal formates; and 

(b) using said alkali metal constituents from said aqueous solution in said conversion process as at least a portion of the alkali metal constituents comprising said alkali metal-containing catalyst.

(And) wherein said conversion process comprises gasification (and/or) wherein said conversion process comprises liquefaction.

(And) wherein at least a portion of said alkali metal-containing catalyst comprises potassium carbonate (and) wherein said particles containing said alkali metal residues are treated with a calcium-containing compound (and) wherein said calcium-containing compound comprises calcium hydroxide.

(And) using said alkali metal constituents from said aqueous solution in said conversion process as at least a portion of the alkali metal constituents comprising said alkali metal-containing catalyst. 

A process ... wherein said conversion process comprises gasification. 

A process ... wherein said conversion process comprises liquefaction. 

A process ... wherein said carbonaceous feed material comprises coal.

Background and Field: This invention relates to the conversion of coal and similar carbonaceous solids in the presence of alkali metal-containing catalysts and is particularly concerned with the recovery of alkali metal constituents from spent solids produced during coal gasification and similar operations and their reuse as constituents of the alkali metal-containing catalysts.

Summary: The present invention provides an improved process for the recovery of alkali metal constituents from char particles produced during coal gasification and other conversion processes carried out in the presence of an alkali metal-containing catalyst ... .

In accordance with the invention, it has now been found that substantial amounts of alkali metal constituents can be effectively recovered from particles containing alkali metal residues produced during coal gasification and related high temperature conversion processes primarily in the form of alkali metal formates by treating the particles with a calcium or magnesium-containing compound in the presence of water ... and in the presence of added carbon monoxide.

Under these conditions the calcium or magnesium-containing compound and the carbon monoxide react with both water soluble and water insoluble compounds in the alkali metal residues to produce water insoluble precipitates and an aqueous solution containing primarily alkali metal formates. These alkali metal formates are then used in the conversion process as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst. Preferably, such use is achieved by recycling the solution directly to the conversion process.

The process of the invention ... makes possible substantial savings in gasification and other conversion operations carried out in the presence of alkali metal-containing catalysts and permits the generation of product gases and/or liquids at significantly lower cost than would otherwise be the case.

(The) process of the invention provides an alkali metal recovery system which makes it possible to recover alkali metal constituents from alkali metal residues produced during catalytic gasification ... and at the same time enables inexpensive alkali metal sulfates to be used as a source of makeup alkali metal compounds thereby lowering the overall cost of the conversion process"

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We'll close our excerpts there, but will note that Exxon illustrates and explains some examples of this US Government-financed technology in the full Disclosure, one of them being, specifically, as it can be applied, as they state, in the: "production of methane by the gasification of a bituminous coal ... with steam"; again, as just one of it's potential applications in the conversion of Coal, as Exxon otherwise states herein, "into liquids and/or gases".

And, what the heck, as long as we're on the subject, once we have Methane, as herein economically produced by Exxon, via the "catalytic gasification" of Coal, we can, as seen for just one instance in:

More Penn State CO2 Recycling with Methane | Research & Development | News; wherein we made report of: "Catalytic Tri-reforming of Methane Using Flue Gas from Fossil Fuel-based Power Plants; Wei Pan, Jian Zheng, Chunshan Song; The Pennsylvania State University"; which explains that "Tri-reforming is a new process designed for the direct production of synthesis gas (suitable for the catalytic synthesis of liquid hydrocarbons) by reforming methane (with the) flue gas from fossil fuel-based electric power plants without pre-separation of CO2";

react Exxon's Coal-derived Methane with even impure and contaminated Carbon Dioxide, and form, via that reaction, a synthesis gas; the composition of which can be tailored for catalytic condensation into a specific variety of desired liquid hydrocarbon fuels and chemicals.

And, to belabor the point:

Based on the statement above, that the "government of the United States of America has rights in this invention pursuant to Contract No. E(49-18)-2369 awarded by the U.S. Energy Research and Development Administration"; We the People own at least a share of this technology, which helps to enable the efficient conversion of our abundant Coal into Methane, and, also, through their specification, noted above, of "liquefaction", into hydrocarbon liquids.