Herein, we're just submitting more evidence of just how far advanced, almost totally unknown to us common folk in United States Coal Country, the science and technology for converting our abundant domestic US Coal into anything and everything we now squander our national and personal treasures, and mortgage our grandchildren's futures, to keep buying from those bastions of democracy and exemplars of American ideals, the beloved and always-beneficent nations of OPEC, has become.
We've many times documented the development of a complete body of Coal-to-Hydrocarbon technology that had been developed by the former Gulf Oil Corporation, once of Pittsburgh, PA, as, for just one example, in:
West Virginia Coal Association | Pittsburgh's Gulf Oil Liquefies & Gasifies Coal | Research & Development; concerning: "United States Patent 4,159,236 - Combining Coal Liquefaction and Gasification; 1979;
Assignee: Gulf Oil Corporation, Pittsburgh; Abstract: The prior art has disclosed a combination coal liquefaction-gasification process wherein ... the gasification zone (produces) the exact hydrogen requirement of the (total) process. The present invention provides ... improvement in the ... efficiency of the combination process. This invention relates to a process wherein coal liquefaction and ... gasification operations are combined synergistically to provide an elevated ... efficiency. The liquefaction process produces for sale a significant quantity of both liquid fuels and hydrocarbon gases".
Gulf Oil Corporation ceased to exist in 1985, when it merged with Standard Oil of California, SOCAL, and the new entity was re-branded as Chevron.
And, we've documented in a number of reports how SOCAL had apparently been developing Coal conversion technologies of their own, with rights to their developments being reassigned to the newly-formed Chevron, as seen in our report of
West Virginia Coal Association | Chevron Improves Direct Coal Liquefaction | Research & Development; concerning: "United States Patent 4,379,744 - Coal Liquefaction Process; Date: April, 1983; Inventors: Joel Rosenthal and Arthur Dahlberg, CA; Assignee: Chevron Research Company, San Francisco; Abstract: This invention is a process for liquefying coal in at least two stages, comprising (a) heating a slurry comprising a solid particulate coal, and an externally supplied dispersed dissolution catalyst in the presence of hydrogen in a first reaction zone to substantially dissolve the coal and provide a first effluent slurry having a normally liquid portion comprising solvent and dissolved coal and containing undissolved solids and dispersed dissolution catalyst; and (b) contacting at least a portion of said normally liquid portion containing undissolved solids and dispersed dissolution catalyst with hydrogen in a second reaction zone in the presence of a second externally supplied hydrogenation catalyst under hydrogenation conditions ... to produce a second effluent slurry having a normally liquid portion. Preferably, the dispersed dissolution catalyst in the first hydrogenation zone is added as an emulsion of aqueous soluble compounds of transition elements, e.g. from Groups IV-B, V-B, VI-B or Group VIII of the Periodic Table".
We included the above example since it specifies the use of catalysts - - note especially "VI-B" - - which can be "transition elements", that represent a potentially significant expense in Coal-to-Petroleum conversion processes.
We'll note that we've previously documented how other petroleum companies have developed the technology to recover and recycle valuable catalysts in their own Coal conversion processes, as, for one example, in:
West Virginia Coal Association | Exxon Recovers and Recycles Coal Conversion Catalyst | Research & Development; concerning: "United States Patent 4,157,246 - Hydrothermal Alkali Metal Catalyst Recovery Process; 1979; 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. ... 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";
where it was seen that our US Government thought it to be of value to reduce "the overall cost of" Coal conversion processes, and financed the development, by Exxon, of a means of doing so through the recovery and recycling of "the metal constituents" of the catalysts used in their Coal conversion technologies.
And, we see herein that Chevron, too, has taken it upon themselves to reduce the costs of their own Coal liquefaction processes, by providing for the recovery of catalysts used in their own, proprietary Coal-to-Liquid techniques.
As seen in excerpts from the initial link in this dispatch to the quite recent:
"United States Patent 8,628,735 - Process for Recovering Metals from Coal Liquefaction Residue Containing Spent Catalysts
January 14, 2014
Inventor: Rahul Bhaduri, CA
Assignee: Chevron USA, Inc., San Ramon
Abstract: In one embodiment, this invention is directed to a method of recovering metals from a metals bearing material comprising: reducing the particle size of at least a portion of the metals bearing material; mixing the metals bearing material in an acid solution to form a first slurry containing at least alkaline earth metal compounds; separating the at least alkaline earth metal compounds from the first slurry to form a first filtrate and a metals bearing material; leaching metals from the metals bearing material to form a pressure leach solution containing transition metals; precipitating and recovering transition metals from the pressure leach solution. In another aspect, the invention relates to a method for recovering metals from a deoiled and dried coal liquefaction residue that contains spent catalyst originating from a Group VIB metal sulfide catalyst.
(Note mention of the "Group VIB metal" catalyst, as in our above-cited report concerning: "United States Patent 4,379,744 - Coal Liquefaction Process; Date: April, 1983; Inventors: Joel Rosenthal and Arthur Dahlberg, CA; Assignee: Chevron Research Company".)
Claims: A method of recovering metals from a coal liquefaction residue containing a spent catalyst comprising: (a) deoiling and drying the coal liquefaction residue to form an ash feed; (b) reducing the particle size of the ash feed; (c) mixing the ash feed in a weak acid solution to form a first slurry containing at least alkaline earth metal compounds; (d) separating the at least alkaline earth metal compounds from the first slurry to form a first filtrate and a metals bearing material; (e) pressure leaching metals from the metals bearing material in the presence of ammonia and air to form a pressure leach slurry containing transition metals; (f) precipitating and recovering transition metals from the pressure leach slurry.
The method ... wherein step (b) comprises comminution of the ash feed to a particle size distribution wherein at least 70% of the metal bearing materials passes 200-mesh (and) wherein a coal liquefaction residue comprises inorganic material, ash and a spent catalyst (and) wherein the spent catalyst comprises one or more transition metals selected from the group consisting of Group VIB metals and sulfides thereof (and) wherein the spent catalyst comprises molybdenum (and) wherein the ash feed contains about 0.1% to 10% molybdenum by weight.
The method ... wherein the acid solution ... is a weak acid solution selected from the group consisting of weak solutions of sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid (and) wherein step (c) is carried out at a temperature 35 C and 80 C for a time between about 1 to 4 hours (and) wherein the first filtrate of step (d) comprises solubilized alkaline earth metals and materials consisting of ash, insoluble organic matter and spent catalyst.
The method ... wherein the coal liquefaction residue comprises 0.1 to 10% Mo by weight (and) wherein the coal liquefaction residue comprises 40 to 60% by weight insoluble organic matter and is 40 to 60% by weight ash (and) wherein at least 70% of the Group VIB transition metals are leached into solution.
The method ... wherein the Group VIB transition metal is molybdenum and wherein at least 75 wt. % of said molybdenum is leached into solution in the form of ammonium molybdate.
Background and Field: The invention relates to a process for recovering metals from residues produced from coal liquefaction processes.
In a coal liquefaction process, valuable liquid products of lighter molecular weights are obtained from heavy hydrocarbonaceous materials such as coal, tar sands and the like, using a transition metal catalyst, e.g., molybdenum disulfide. As the process progresses, most of the molybdenum typically becomes concentrated in the metals bearing materials, solid residue or heavy bottoms. Various approaches have been introduced to recover the transition metal components from the spent coal liquefaction catalysts.
Summary: In one embodiment, this invention is directed to a method of recovering metals from a metals bearing material comprising: reducing the particle size of at least a portion of the metals bearing material; mixing the metals bearing material in an acid solution to form a first slurry containing at least alkaline earth metal compounds; separating the at least alkaline earth metal compounds from the first slurry to form a first filtrate and a metals bearing material; leaching metals from the metals bearing material to form a pressure leach solution containing transition metals; precipitating and recovering transition metals from the pressure leach solution. In another aspect, the invention relates to a method for recovering metals, from a deoiled and dried coal liquefaction residue."
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Note that the catalyst herein, "the Group VIB transition metal", is actually specified to be "molybdenum", which, as seen for example in:
West Virginia Coal Association | More Dow Chemical Direct Coal Hydrogenation | Research & Development; concerning: "United States Patent 4,172,814 - Emulsion Catalyst for Hydrogenation Processes; 1979; Assignee: The Dow Chemical Company, MI; Abstract: In the catalytic hydrogenation of a substance in a water-immiscible organic liquid medium, a metallic hydrogenation catalyst is conveniently and effectively dispersed in the reaction mixture by addition as an emulsion of an aqueous solution of a salt of the metal in the liquid medium. The method is particularly applicable to the liquefaction of coal. (The) process for hydrogenating a hydrogenatable organic substrate ... wherein the metal (catalyst) is molybdenum";is often specified as the metal catalyst of choice in direct Coal hydrogenation/liquefaction processes.
In any case, the technicalities of the full Disclosure are likely beyond the interest of most of our readers, as they are beyond ours, or at least beyond our ability to succinctly explain them.
Our primary intent in submitting it to you is this:
Whether you're being told about it or not by your public media, the art and science of converting our abundant Coal into substitute petroleum - - into products that could mean many more American jobs and far greater security and prosperity for the United States of America - - continue to advance and improve.
Maybe when our public dissemination of knowledge finally starts to advance and improve, we can start to put such Coal liquefaction technologies to work, and start thereby to build better lives for ourselves and a better future for our entire nation.