WV Coal Member Meeting 2024 1240x200 1 1

Texaco 1953 CO2-Free Coal Syngas

Synthesis gas generation

We've already submitted many reports on the extensive development of innovative Coal conversion and Carbon recycling technologies by the once-famous Texaco, aka "The Texas Company".

Such have included:

Texaco 1950 Coal + Steam = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,516,974 - Gasifying Carbonaceous Material; 1950; Assignee: 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 ... hydrogen and carbon monoxide (are) produced by the reaction of water vapor with carbon"; and, the later:

Texaco Recycles CO2 to Methanol & Methane | Research & Development; concerning: "United States Patent 4,523,981 - Means and Method for Reducing Carbon Dioxide to Provide a Product; 1985; Assignee: Texaco, Incorporated, NY; Abstract: A process for reducing carbon dioxide to at least one useful product  (including) formic acid (and/or) formaldehyde (and.or) methanol (and/or) methane".

Herein, we submit information concerning refinements made by Texaco on the type of technology described in their somewhat earlier ""United States Patent 2,516,974", as cited above.

In this later development, they describe how hydrocarbon synthesis gas can be generated from Coal, and other Carbon sources, in a way which doesn't lead to the co-production of any appreciable amount of Carbon Dioxide, and, which process results in a stream of nearly-pure Carbon Monoxide and Hydrogen, which would seem almost ideally suited for further catalytic processing into various sorts of hydrocarbons.

As seen, with comment and other links inserted and appended, in excerpts from the initial link herein to:

"United States Patent 2,655,443 - Synthesis Gas Generation

Date: October, 1953

Inventor: Frederic Moore, CA

Assignee: The Texas Company (Texaco), NY

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 hydrocarbon synthesis.

In general liquid hydrocarbons are most effectively produced by the interaction of carbon monoxide and hydrogen at an elevated temperature and pressure in the presence of a suitable catalyst, usually an element of the iron group of the periodic table of the elements.

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.

Various solid carbonaceous fuels may be used, e.g., coal.

An object of this invention is to provide a process for the generation of carbon monoxide and hydrogen from carbonaceous materials.

Another object is to provide a process particularly suited to the generation of a feed gas for the synthesis of hydrocarbons from coal.

The method and apparatus of my invention provides a high rate of carbon reaction, resulting in efficient carbon utilization. Handling of slag is accomplished without particular difficulty due to the improved method and apparatus by which the slag is maintained in molten condition.

In the gasification of carbonaceous material with oxygen, particularly solid fuels, the reaction between the oxygen and the fuel results in the production of carbon dioxide according to the equation: C + O2 = CO2.

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: CO2 + C = 2CO.

Steam also reacts with heated carbon to produce carbon monoxide and hydrogen: H2O + C = CO + H2.

These reactions are endothermic and require heat from another source. Heat for the endothermic reactions may be supplied from the exothermic 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 the carbon dioxide is consumed by reaction with carbon.

The water gas shift reaction: CO + H2O = CO2 + H2; also takes place in the generator. The water gas shift reaction has little influence on the thermal balance (and, the) quantity of hydrogen in the product gas may be controlled by control of conditions affecting the water gas shift reaction.

The present invention will be described, for the sake of simplicity, with reference to coal as a fuel. It will be understood that coal is used as a specific example and the apparatus and method described is not necessarily limited to the use of coal.

(A fact that we recently confirmed by report of Exxon's more contemporary take on this half-century-old technology, as seen in:

Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development; concerning: "United States Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass;  2010; ExxonMobil Research and Engineering Company, NJ; Abstract: A process for the co-gasification of carbonaceous solids (coal) and biomass in which the biomass material is pyrolyzed to provide a biomass pyrolysis oil and biomass char or coke which are then mixed with the carbonaceous solid to form a slurry. This slurry is then heated if necessary to achieve a viscosity which can be processed conveniently in the gasifier. The heat required for pyrolyzing the biomass can conveniently be obtained from the heat exchanger used to cool the hot synthesis gas product emerging from the gasifier. (And) wherein the solid carbonaceous particles comprise 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.")

In accordance with this invention, coal is crushed and charged into the reaction zone in suspension with steam. Oxygen is introduced into the reactor separately and brought into intimate contact with the particles of coal. Preferably the oxygen-containing gas has an oxygen concentration of 90 per cent by volume or greater and is preheated prior to introduction into the reactor.

(Now, since this Texaco process of forming a hydrocarbon synthesis gas from Coal, perhaps along with another Carbon source, since the process "is not necessarily limited to the use of coal", does specify the use of purified Oxygen, here's a thought:

As we've previously reported, via, for just one example:

USDOE Algae Recycle CO2 into Liquid Fuels | Research & Development; concerning, primarily: "Liquid Fuels from Microalgae; 1987; USDOE; Abstract: Aquatic Species Program is to develop the technology to produce gasoline and diesel fuels from microalgae. A technical and economic analysis, "Fuels from Microalgae," demonstrates that liquid fuels can be produced from mass-cultured microalgae at prices that will be competitive with those of conventional fuels by the year 2010. The algae can be grown ... using the resources of sunlight ... and carbon dioxide (and, they) convert these raw materials into proteins, carbohydrates, and lipids";

it is possible to cultivate certain strains of Algae in various sorts of what are, in other reports of similar and related concepts, labeled as "bio-reactors", and feed them, basically, Coal combustion exhaust gas emissions laden with Carbon Dioxide. The Algae convert the CO2 into "lipids", which can be extracted and converted rather directly into "gasoline and diesel"; and, various residual "proteins and carbohydrates" - a "biomass", in other words, composed of Algae cellular debris such as specified by ExxonMobil in "United States Patent Application 20100083575" as a perfectly suitable co-feed with Coal for a gasification process, and, thus, which would also qualify for use in our subject Texaco process of  "United States Patent 2,655,443 - Synthesis Gas Generation", which "is not necessarily limited to the use of coal".

And, as specified in the full "Liquid Fuels from Microalgae" document, and nearly all the others similar we've reported to you, as, for instance, in:

 

USDOE Algae Make Hydrogen for Coal and CO2 Hydrogenation | Research & Development; concerning: "Photosynthetic Hydrogen and Oxygen Production by Green Algae; Oak Ridge National Laboratory; 1999; Abstract: Photosynthesis research at Oak Ridge National Laboratory is focused on hydrogen and oxygen production by green algae in the context of its potential as a renewable fuel and chemical feed stock";

those same Algae, in the normal course of their routine business of reprocessing Carbon Dioxide via photosynthesis, will also generate recoverable and useful quantities of Oxygen, as specified for use in the CO2-free, Oxygen-supplemented, Steam-gasification of Coal described herein by Texaco.)

The exothermic reaction or burning which takes place upon contact between coal and oxygen releases heat which is utilized in a very effective and efficient manner in this invention to supply heat for ensuing endothermic reactions.

Gases comprising carbon monoxide, carbon dioxide and hydrogen result from the oxidation of carbon in the presence of steam. The steam and the carbon dioxide (further) react with the (thus) highly heated carbon in the coal to produce the desired carbon monoxide and hydrogen.

Due to the novel manner in which reactants are fed into and gaseous products are withdrawn from the reactin zone, efficient heat transfer and effective reaction conditions are obtained. This efficient heat transfer (to the CO2-Coal and H2O-Coal reactions) is also thought to be enhanced by effective mixing and unimpeded radiation from exothermic to endothermic points of reaction.

Claims: (A) process for the production of a gaseous mixture comprising hydrogen and carbon monoxide from a solid carbonaceous fuel by reaction with steam and oxygen."

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And, again, such a "gaseous mixture comprising hydrogen and carbon monoxide", "a feed gas for the synthesis of hydrocarbons", made so efficiently and cleanly from Coal and Carbon-recycling biological materials, with virtually no co-production of Carbon Dioxide, would be ideal for the Fischer-Tropsch, and related and derivative, processing, as described in

Mobil Upgrades Fischer-Tropsch Fuel | Research & Development | News; which makes report of: "United States Patent 4,041,094 - Upgrading Products of Fischer-Tropsch Synthesis; 1977; Assignee: Mobil Oil Corporation; Abstract: Upgrading of Fischer-Tropsch synthesis product is obtained ... to effectively and more efficiently convert synthesis gas, and thereby coal ..., to highly valued hydrocarbons such as motor gasoline with high octane number, petrochemical feedstocks, liquefiable petroleum fuel gas, and aromatic hydrocarbons";

which processing would convert them, and thus our abundant domestic Coal, and renewable and sustainable biological products, into anything, quite literally anything, we now rely on scarce and costly natural petroleum, and it's often hostile and economically predatory foreign producers, for the supply of.