Production of carbon monoxide and other gases from carbonaceous materials
As we've documented in many previous reports, the former, so ubiquitous that it was almost iconic, Texaco Corporation, which finally disappeared into the maw of the Chevron conglomerate over the course of the last decade, had worked, since the 1940's, on the development of an extensive portfolio of Carbon conversion technologies focused on the transmutation of just about anything that contained Carbon into liquid hydrocarbon fuels.
The primary focus of their Carbon conversion efforts centered on an initial transformation of the Carbon source into synthesis gas, or "syngas", a blend of Carbon Monoxide and Hydrogen that could then, through catalytic technology developed most famously by Franz Fischer and Hans Tropsch, as in:
Fischer & Tropsch Awarded 1930 US CoalTL Patent | Research & Development; concerning: "United States Patent 1,746,464 - Process for the Production of Paraffin-Hydrocarbons; 1930;
be converted into synthetic liquid and gaseous hydrocarbon substitutes for nearly any product derived conventionally from natural petroleum.
Texaco did, in fact, not really that long after the seminal US Patent 1,746,464, as immediately above, was issued to Fischer and Tropsch, develop their own, closely similar, technology, as disclosed in:
"United States Patent 2,286,814 - Manufacture of motor fuel
Date: June, 1942
Inventor: L.C. Kemp, Texas
Assignee: The Texas Company, New York, NY
Abstract: This invention relates to the manufacture of motor fuel and has to do more particularly with the production of motor fuel, such as gasoline, from mixtures of carbon monoxide and hydrogen."
And, Texaco then spent the better part of the next half century developing a collection of technologies that could produce such "mixtures of carbon monoxide and hydrogen", from, as noted, just about anything that contained Carbon, starting with, as seen, variously, in our reports of:
Texaco 1950 Coal + Steam = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,516,974 - Gasifying Carbonaceous Material; 1950; Texaco Development Corporation; Abstract: The present invention relates to gasification of solid fuels and is more particularly concerned with the conversion of carbonaceous materials into a gaseous product of high heating value composed primarily of carbon monoxide and hydrogen ... . In accordance with the present invention a stream of combustible gases, predominantly hydrogen and carbon monoxide, is produced by the reaction of water vapor with carbon"; and:
Texaco 1948 CO2 + CH4 = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,448,290 - Process for the Production of Synthesis Gas; 1948; The Texas Company; Abstract: This invention relates to a continuous method of manufacturing water gas involving the reaction of a gaseous hydrocarbon with carbon dioxide and steam so as to produce carbon monoxide and hydrogen";
both Coal and Carbon Dioxide, and, as we will learn in other reports to follow, just about everything in between. And, don't be misled by the fact that their process of "US Patent 2,448,290", as immediately above, needs Methane, CH4, the "gaseous hyrocarbon" specified in the full Disclosure to be reacted with Carbon Dioxide, since, as in:
More Texaco Carbon-Recycling Methane from Coal | Research & Development; concerning: "United States Patent 3,888,043 - Production of Methane; 1975; Texaco Incorporated; Abstract: Continuous process for the production of a gaseous stream comprising at least 90 mole % of methane (dry basis) from a sulfur containing hydrocarbonaceous fuel without polluting the environment ... wherein said hydrocarbonaceous fuel is a liquid hydrocarbon selected from the group consisting of ... coal oil; ... coal tar, ... ; and mixtures thereof (and/or) coke-oven gas (and/or) organic material selected from the group consisting of carbohydrates, cellulosic materials, ... (and/or) a pumpable slurry of solid carbonaceous fuels selected from the group consisting of coal (and) concentrated sewer sludge";
Texaco knew how to make it, too, out of virtually anything composed primarily of Carbon.
In any case, subsequent to issuance of the above-cited "United States Patent 2,516,974 - Gasifying Carbonaceous Material", Texaco continued to work on their Coal gasification technology, and were, not long afterward, able to demonstrate that, not only could Coal be converted into a blend of Carbon Monoxide and Hydrogen suitable for catalytic condensation, as via their own process of the above ""United States Patent 2,286,814 - Manufacture of Motor Fuel", into liquid hydrocarbons; but, that Carbon Dioxide itself, reclaimed from whatever soure, could be added to the blend of gases with which Coal was reacted in order to form that blend of Carbon Monoxide and Hydrogen, i.e., hydrocarbon synthesis gas.
As seen, with comment inserted and appended, in excerpts from the initial link in this dispatch to:
"United States Patent 2,558,746 - Carbon Monoxide and Other Gases from Carbonaceous Materials
Date: July 3, 1951
Inventor: Leon Gaucher, NY
Assignee: The Texas Company, NYC
Abstract: This invention relates to a process and apparatus for the generation of gases comprising carbon monoxide from carbonaceous materials. In one of its more specific aspects it relates to a process and apparatus for the generation of a mixture of carbon monoxide and hydrogen, suitable as a feed for the synthesis of hydrocarbons, from powdered coal.
The synthesis of hydrocarbons by the interaction of carbon monoxide and hydrogen is well known.
A number of processes are known to be effective for liquid hydrocarbon synthesis.
The present invention is concerned with the generation of a mixture of carbon monoxide and hydrogen (and) is particularly suited to the production of a feed gas for the synthesis of hydrocarbons.
Liquid or solid carbonaceous fuels may be used, e.g., ... coal; the method and apparatus is especially useful when powdered coal is used as the feed material.
An object of this invention is to provide a process for the generation of carbon monoxide and hydrogen (and) to provide a process particularly suited to the generation of a feed gas for the synthesis of hydrocarbons from coal.
In the gasification of carbonaceous material with oxygen, particularly solid fuels, the reaction between oxygen and fuel results in the production of carbon dioxide ... .
The oxidation reaction, being highly exothermic, releases large quantities of heat.
The carbon dioxide, so produced, in contact with hot carbon, in turn, reacts with the carbon to produce carbon monoxide.
Steam also reacts with heated carbon to produce carbon monoxide and hydrogen.
(Note: The above explanations are accompanied in the full document by illustrative chemical equations; one of which, that somehow inexplicably escaped the notice of our usually-impeccable US patent examiners, is in error and conflicts with the above statements, which, according to our consultants, are accurate.)
Heat for the endothermic or reduction reactions may be supplied from the oxidation reaction. Thus, in a gas generator there should be a free transfer of heat between the zone in which carbon dioxide is formed and the zone in which carbon dioxide is reduced by reaction with carbon.
(Note the implications: Carbon Dioxide can be converted into the reactive and quite useful Carbon Monoxide through reactions with hot Coal.)
The heat released by the exothermic reactions may be utilized to supply heat for the exothermic reactions.
(The above confirms a fact we have documented numerous times previously, as, for just two examples, in:
ExxonMobil Self-Powered Coal Conversion | Research & Development; concerning: "United States Patent 3,254,023 - Heat Balancing in Organic Reactions; 1966; Socony Mobil Oil Company; Abstract: This invention relates to a method of carrying out an exothermic chemical reaction and an endothermic reaction in a single reaction zone wherein the heat evolved in the exothermic reaction is utilized to effect the endothermic reaction"; and:
1963 Self-Powered Coal Conversion | Research & Development; concerning: "United States Patent 3,107,985 - Coal (and it's) Autogenous Hydrogenation; 1963;
The second phase of the reactions are increased if the concentrations of carbon dioxide produced in the exothermic zone is high. Therefore, the size of the reactor many be reduced or the degree of conversion obtainable in given reactor may be increased if the purity of free oxygen added is great enough to generate a high concentration of carbon dioxide.
(So, a lot of Carbon Dioxide is a good thing. And, here's a thought: Instead of structuring the reactor so that "a high concentration of carbon dioxide" is generated, why don't we just add some Carbon Dioxide, as we could recover from a Marcellus Shale gas cleaning and stripping facility, where, as we've documented in previous reports, a great deal of it is likely to be just separated and blown off into the atmosphere?)
Claims: A process for the generation of carbon monoxide and hydrogen from a solid carbonaceous fuel by reaction with oxygen and steam."
----------------------
And, we abbreviate our excerpts so that we can explain something that we deliberately de-emphasized in our excerpts.
A full read will reveal that Texaco spells out a process wherein the internal production of Carbon Dioxide is maximized, so that Carbon Dioxide is then available for further reactions with hot Coal to make larger quantities of Carbon Monoxide.
Some of that Carbon Monoxide is reconverted into CO2 in a "water gas shift" reaction, which generates more the Hydrogen needed to mix with the Carbon Monoxide, in order to formulate a gas blend "particularly suited" as Texaco specifies "for the synthesis of hydrocarbons".
We submit that we could, instead, heat the Coal by some non-oxidative means, perhaps, as in:
USDOE Hydrogasifies Coal with Solar Power | Research & Development | News; concerning: "United States Patent 4,415,339 - Solar Coal Gasification Reactor; 1983; Assignee: The USA, as represented by the Department of Energy; Abstract: Coal (or other carbonaceous matter, such as biomass) is converted into a duct gas that is substantially free from hydrocarbons. The coal is fed into a solar reactor, and solar energy is directed into the reactor onto coal char, creating a gasification front and a pyrolysis front";
by using some form or another of freely-available environmental energy; and, then, we could add Carbon Dioxide recovered from an external source, perhaps a "green" Corn ethanol fermentation and distillation facility, to make more of the desired Carbon Monoxide through reaction with the hot Coal.
Further: Some of the Carbon Dioxide generated, and then utilized, in this Texaco system arises from employment of the water gas shift reaction, wherein Carbon Monoxide is reacted with Water, H2O, to make extra Hydrogen.
We submit, that, instead, any extra needed Hydrogen could be obtained via a process such as seen in:
More NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,051,005 - Photolytic Production of Hydrogen; 1977; Assignee: United Technologies Corporation; The invention described herein was made in the course of a contract with the National Aeronautics and Space Administration; Abstract: Hydrogen and oxygen are produced from water in a process involving the photo-dissociation of molecular bromine with radiant energy at wavelengths within the visible light region";
which would also, coincidentally, co-generate, through the use of environmental energy, at least some of the "free oxygen" needed by our subject Texaco process herein, of "United States Patent 2,558,746", to generate, from Coal, Carbon Dioxide and Water, as Texaco specifies with official US Government affirmation of the fact, "a mixture of carbon monoxide and hydrogen ... suited to the ... synthesis of hydrocarbons".