We have, over the long course of our reportage, more than thoroughly documented the incontrovertible fact that our most iconic and familiar representative of the Big Oil clan, ExxonMobil, and it's precedent Mobil Oil and Esso/Exxon companies, clearly know how to efficiently convert our abundant domestic Coal into anything, quite literally anything, we now mortgage our nation's financial future to the moneyed, alien powers of OPEC for the supply of.
Among their many technologies for so converting Coal into liquid hydrocarbon fuels, we remind you of one, in particular, that clearly states the truth, as in our report of:
West Virginia Coal Association | Mobil Converts Coal to High Quality Gasoline | Research & Development; concerning: "United States Patent 4,076,761 - Process for the Manufacture of Gasoline; 1978; Assignee: Mobil Oil Corporation, NY; Abstract: Synthesis gas comprising a mixture of carbon monoxide and hydrogen is derived from fossil fuels and catalytically converted in a first reaction zone to a mixture of methanol and dimethyl ether which in turn is converted in a separate reaction zone ... into a high octane gasoline fraction, a light hydrocarbon gas fraction which may be liquefied and a hydrogen-rich gaseous by-product which is recycled to the conversion of fossil fuels to synthesis gas or may be otherwise used. This invention is concerned with a process for converting coal ... to high quality gasoline."
The process of the above "United States Patent 4,076,761" is representative of indirect Coal conversion technology, wherein Coal is first gasified, that is, partially oxidized and transformed into a blend of, primarily, Carbon Monoxide and Hydrogen, "synthesis gas", or "syngas", which gas blend is then chemically condensed, over one or more of any number of known effective catalysts, into liquid and gaseous hydrocarbons.
Coal, due to its current abundance relative to other Carbon sources, is key to such processes; but, such gasification processes founded economically on Coal would then allow for inclusion of other, CO2-recycling and renewable, raw material resources to be included and utilized, as ExxonMobil themselves lately acknowledged, in our report of:
West Virginia Coal Association | Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development; concerning: "US Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass; 2010; Assignee: ExxonMobil Research and Engineering Company; Abstract: A process for the co-gasification of carbonaceous solids (coal) and biomass ... wherein the solid carbonaceous particles comprise coal (or) a coke derived from coal ... (and) wherein the biomass comprises biological matter selected from wood, plant matter, municipal waste, green waste, byproducts of farming or food processing waste, sewage sludge, black liquor from wood pulp, and algae."
Note that the above process of "US Patent Application 20100083575" allows as well for the inclusion in the raw material feed of "a coke derived from coal", and, be advised that they don't necessarily mean "coke" as we traditionally think of it.
Such "coke" can, as well, be taken to mean any carbonaceous residue derived from Coal, like that which might result from a direct Coal liquefaction processes, wherein a solvent is utilized to extract, in liquid form, a majority of the Carbon in Coal, but with some Carbon remaining in the insoluble residue.
Examples of such technologies can be seen in our reports of:
West Virginia Coal Association | Esso 1970 CoalTL | Research & Development; concerning: "United States Patent 3,488,279 - Two-stage Conversion of Coal to Liquid Hydrocarbons; 1970; Assignee: Esso Research and Engineering Company; Abstract: Coal is hydrogenated to produce liquid products in two stages. The first stage is an initial mild conversion by hydrogen-donor extraction followed by a second stage of catalytic hydrogenation using a cobalt molybdate catalyst and added molecular hydrogen. The present invention is directed to the conversion of a solid carbonaceous material such as coal into liquid products (which can be further) converted into gasoline"; and, the later:
West Virginia Coal Association | Exxon Multi-Stage Hydrogen Donor Coal Liquefaction | Research & Development; concerning, in part: "United States Patent 4,210,518 - Hydrogen-donor Coal Liquefaction Process; 1980; Assignee: Exxon Research and Engineering Company; Abstract: Improved liquid yields are obtained during the hydrogen-donor solvent liquefaction of coal ... . The Government of the United States of America has rights in this invention pursuant to Contract No. E(49-18)-2353 awarded by the U.S. Energy Research and Development Administration".
In any case, one objection that has been raised against the indirect conversion of Coal, or any Carbon source, into, as in the process of the above-cited process of "United States Patent 4,076,761 - Process for the Manufacture of Gasoline", well, Gasoline, is that it entails the generation of some amount of Carbon Dioxide in the synthesis gas generation, Coal gasification, step.
That's okay by us, since, as even Exxon affirms, as in our report of:
Exxon Coal + CO2 + H2O Combo Gasification & Conversion | Research & Development; concerning: "United States Patent 4,318,712 - Catalytic Coal Gasification Process; 1982; Assignee: Exxon Research and Engineering; Abstract: A carbonaceous feed material, a potassium compound ... and a sodium or lithium salt are introduced into a gasification reactor. The carbonaceous material is then gasified in the presence of the added potassium and sodium or lithium constituents. Claims: The process ... is one for the gasification of bituminous coal, subbituminous coal, lignite, organic waste materials or similar carbonaceous solids in the presence of added sodium and potassium compounds. It will be understood that the invention ... may be employed in ... gasification operations ... to promote the reaction of steam, hydrogen, carbon dioxide, or a similar gasification agent with (carbon)";
Carbon Dioxide can be reclaimed and then consumed as an agent of gasification for the Coal, and, for, just as in the later "US Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass", just about any Carbon-recycling "organic waste materials" we might want to toss in.
However, even though Carbon Dioxide can, both directly, through it's inclusion as an agent of Coal gasification, and indirectly, through the inclusion of "Biomass" as a co-feed raw material with Coal in the gasification, be consumed and recycled, for the sake of efficiency it seems better to produce as little as possible of it as a result of the Coal gasification itself.
That was the intent of one technology we recently reported, but as was developed more than half a century ago, as seen in:
West Virginia Coal Association | Texaco 1957 CO2-Free Syngas from Coal | Research & Development; concerning: "United States Patent 2,803,530 - Production of Carbon Monoxide from a Solid Fuel; 1957; Assignee: Texaco Development Corporation; Abstract: This invention relates to a process for the generation of carbon monoxide and hydrogen from a solid carbonaceous fuel. In one of its more specific aspects, this invention relates to an improved method for the reaction of powdered coal with oxygen and steam to produce carbon monoxide and hydrogen ... relatively free from carbon dioxide".
And, that was as well the intent of Mobil Oil, three decades later, as seen in excerpts from the initial link in this dispatch to:
"United States Patent 4,583,993 - Carbon Monoxide and Hydrogen from Carbonaceous Material
Date: April, 1986
Inventor: Nai Chen, New Jersey
Assignee: Mobil Oil Corporation, New York
Abstract: Hydrogen and carbon monoxide are produced from coal, char or other carbonaceous material in a processing combination comprising a catalytic CO generator employing as reactant materials, fluid carbon material and CO2 product of the reaction of steam with CO to produce hydrogen and CO2. CO2 produced in the process is relied upon as the primary endothermic heat source in the fluid CO generator.
(And, we must unfortunately interject here, since it isn't well-explained in the body of the text, that, when Mobil refers to "the reaction of steam with CO to produce hydrogen and CO2", they are alluding to the "water gas shift" reaction, which we have previously discussed, and, about which more can be learned via:
Water gas shift reaction - Wikipedia, the free encyclopedia; "The water-gas shift reaction (WGS) is a chemical reaction in which carbon monoxide reacts with water vapor to form carbon dioxide and hydrogen".
It is often specified for use in Coal gasification processes to increase the amount of Hydrogen, relative to Carbon Monoxide, in the product hydrocarbon synthesis gas.
Further, when they discuss "a catalytic CO generator employing as reactant materials, fluid carbon material and CO2", they are identifying a process and apparatus similar in concept to that described in our report of:
Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Assignee: Bayer Material Science, AG, Germany; The present invention relates to a novel generator for the reaction of carbon-containing raw materials and also to an improved process for the production of carbon monoxide gas (CO gas) having a high degree of purity using such a generator. Carbon monoxide gas is frequently produced in the art by means of a continuous process in which carbon-containing raw materials are reacted with oxygen and carbon dioxide";
and, they are specifying how any Carbon Dioxide which might be co-produced in the gasification process, whether by oxidation of Coal or via the water gas shift reaction, is consumed and utilized in the production of more Carbon Monoxide.)
Claims: A method for producing separate streams of hydrogen and carbon monoxide of relatively high purity from a char like product selected from the group consisting of coal, char product of coal solvation (and) char product of coal volatilization ... which comprises:
- passing a char product of fluidizable particle size comprising carbonaceous material and metal deposits which will promote the formation of CO obtained at an elevated temperature to a fluidized char particle carbon monoxide generation zone in admixture with preheated carbon dioxide wherein the primary source of endothermic reaction heat to form CO is supplied by said fluid char particles and said preheated carbon dioxide;
- separating a product of said CO generation zone into a carbon monoxide rich stream and an unreacted carbon dioxide rich stream;
- recovering a portion of the carbon monoxide thus produced as a product of the process;
- passing another separated portion of said produced carbon monoxide in admixture with steam to catalytic water gas shift reaction zone maintained under conditions to produce hydrogen and carbon dioxide;
- separating a hydrogen rich stream from a carbon dioxide rich stream produced in said shift reaction zone;
- recycling carbon dioxide product of said shift reaction zone admixed with CO2 separated from the CO product of said CO generator zone through indirect heating zones to heat the mixed CO2 stream to an elevated temperature before passing said fluid char particle to the CO generation zone;
- separating unreacted fluid char particles from said CO generation zone;
- and passing the separated fluid char particles to a heating zone to maintain the heat of said particles at elevated temperature.
The method ... wherein the char product passed to said CO generation zone comprises fluidizable particles of coke at an elevated temperature obtained from either one or both of a fluid coking operation or a fluid coke partial burning operation.
(Note: In the above claim, we again see where Coal conversion and standard petroleum refinery practices merge, and, where they can be coordinated and made to complement each other. The "fluidizable particles of coke ... from ... a fluid coking operation" are among the carbonaceous "resids" generated by some conventional petroleum refining processes, i.e., "fluid coking", about which more can be learned via:
http://www.exxonmobil.com/
Petroleum Coke Tutorial; "Fluid coking is a continuous process in which heated coker feeds are sprayed into a fluidized bed of hot coke particles which are maintained at 20-40 psi and 500C. The feed vapors are cracked while forming a liquid film on the coke particles. The particles grow by layers until they are removed and new seed coke particles are added".
And, interestingly, "FCC bottoms" arising from "ExxonMobil's FCC process" are mostly carbon residues, very much like Coal, or coke derived from Coal; and, the "FCC process" is a more or less standard petroleum refining practice, that, as seen in:
Fluid Catalytic Cracking | Refining | Technologies | KBR: A Global Engineering, Construction and Services Company; "FCC is used for the conversion of ... residues to ... high octane gasoline and distillates";
is intended to convert already highly carbonaceous feed materials, i.e., heavy petroleum refinery "residues", into somewhat more useful things.
Should you be motivated to follow up with independent study of your own, don't be misled by overuse of the standard abbreviations. The "FC", fluid coking, is not the same as the "FCC", fluid catalytic cracking.
Thus, the processes of Coal conversion and Petroleum refining are, in many ways, complementary and congruent; and, can be integrated with each other in ways that enhance the productivity of both, as further emphasized in the following claims.
The method ... wherein a liquid product of fluid coking, either with or without hydrogenation thereof is used as a solvent for coal in a coal solubilization operation and a solubilized coal product comprising coal particles is thereafter passed to a fluid coking operation in admixture with hot coke particles obtained from a fluid coke partial burning operation.
The method ... wherein the reaction of carbon dioxide with carbonaceous particle material is accomplished in the presence of adding oxygen to the reaction.
(As in the above-cited Bayer process of "US Patent 7,473,286 - Carbon Monoxide Generator".)
Background: The present invention is concerned with producing a clean gas composition of hydrogen and carbon monoxide from coal which is free of sulfur and nitrogen. A further object of this invention is to produce separate streams of hydrogen and carbon monoxide which can be blended to form any desired ratio thereof for syngas conversion with a Fischer-Tropsch synthesis containing catalysts.
(Note, especially, the above: "hydrogen and carbon monoxide from coal which ... can be blended to form any desired ratio thereof", with the implication that, through various catalytic processes, like and conceptually related to the "Fischer-Tropsch synthesis", such "syngas" can be chemically condensed into virtually "any desired" hydrocarbon.)
Summary: The present invention contemplates an integrated operation comprising one or more steps including solubilizing coal, fluidized coal volatilization, fluid coking, conversion of coke obtained from one or more or a combination of the above to CO and the generation of CO2 employed in said CO generator by use of the well known water gas shift reaction. Hydrogen produced in the process may be used in part to hydrogenate a coal solubilizing liquid passed to the coal solubilizing step.
(The "coal solubilizing liquid" is "the hydrogen-donor solvent" of the Exxon's technology disclosed in our earlier report concerning: "US Patent 4,210,518 - Hydrogen-donor Coal Liquefaction Process".)
The integrated operation is particularly desirable in utilizing metal contaminated carbonaceous materials which are products of one or more of the herein described operations involving coal, tar sands, residual oils and combinations thereof. Coke and char products of these operations are laden with metals selected from the group consisting of iron, nickel, vanadium and copper. The metals, iron and nickel, are particularly desirable for promoting the reactions herein particularly desired. Thus the build-up of metals, iron and nickel, on the coke particles circulated from the fluid coker to the CO generator and back to the fluid coker is not an undesirable expedient on the overall combination.
The present invention particularly contemplates processing char or coke residue particles obtained as herein defined by contacting the coke particles with CO2 in the presence of a reducing catalyst to produce a (CO) carbon monoxide rich gaseous product stream. In this CO producing operation, a fluid coke particle system is preferably employed for effecting the desired highly endothermic reaction in the presence of (CO2) carbon dioxide heated to an elevated temperature as herein described. The primary source of CO2 used in the combination operation of this invention is that recovered from a shift reactor system comprising the reaction of carbon monoxide (CO) with water (steam).
The present invention contemplates the blending of the hydrogen and CO produced in the operation and the conversion of the blend to methanol and thence to an olefinic or aromatic product. It also contemplates the conversion of the blend as by Fischer-Tropsch synthesis to produce hydrocarbon products in single or multiple stage operation. More importantly, it contemplates the use of ZSM-5 type crystalline zeolites to convert Fischer-Tropsch syngas conversion products."
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The "ZSM-5 type crystalline zeolites" are the catalysts which are key to ExxonMobil's "MTG"(r), technology, wherein Methanol, which they most often posit to be made from Coal, but which, as in:
USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Assignee: The USA as represented by the USDOE; A method and system for synthesizing methanol from the CO2 in air using electric power";
can also be made from Carbon Dioxide, is converted into Gasoline.
More about "MTG"(r) can be learned via:
ExxonMobil "Clean Gasoline from Coal" | Research & Development; concerning the ExxonMobil promotional piece: "Methanol to Gasoline (MTG): Production of Clean Gasoline from Coal; So Advanced, Yet So Simple".
Finally, we must note that our consultants advise that Mobil's specified use of the water gas shift reaction to provide necessary Hydrogen will result in some material imbalances.
In sum, even though the system can be made to be Carbon Dioxide-free, doing so will result in production of excess Carbon Monoxide, relative to what can be consumed through reactions with the system-produced Hydrogen, in the "Fischer-Tropsch"-type syntheses.
Hydrogen, thus, might have to be added, which seems okay to us, since, as seen in:
NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,045,315 - Solar Photolysis of Water; 1977; NASA; Hydrogen is produced by the solar photolysis of water";
there are economical ways to make additional Hydrogen.
Or, we might have to extract some of the excess product Carbon Monoxide, which seems okay to us, as well, since, as seen in:
USDOE Carbon Monoxide + H2O = Alcohol | Research & Development; concerning: "United States Patent 4,656,152 - Catalyst for Producing Lower Alcohols; 1987; USDOE; A process and system for the production of the lower alcohols such as methanol ... involves the reaction of carbon monoxide and water";
we have the technology in hand to mix any excess Carbon Monoxide with nothing, essentially, but Water, and to thereby make more Methanol, for use in ExxonMobil's MTG(r) process to make more Gasoline.