As we've noted previously, there exists in the published literature a vast amount of information concerning the ways and means by which a gaseous blend of Carbon Monoxide and Hydrogen can be chemically reacted over a catalyst, and be made thereby to synthesize gaseous and liquid, and even solid, hydrocarbons.
Such hydrocarbon synthesis is generically, but not necessarily universally, nor always accurately, referred to as "Fischer-Tropsch" synthesis, after the most famous of the earlier developers of the art, whose core invention is documented in our report of:
West Virginia Coal Association | Fischer & Tropsch Awarded 1930 US CoalTL Patent | Research & Development; which contains a link to the basic United States Patent on their process: "United States Patent 1,746,464 - Process for the Production of Paraffin-Hydrocarbons; 1930; Franz Fischer and Hans Tropsch, Germany; It is generally known that the oxides of carbon can be converted into methane by catalytic reduction (see Sabatier, Die Katalyse in der organischen Chemie, Leipzig, 1914) ... . ... (we) now have found that, instead of methane, its homologues (and) higher homologues which are easily liquefiable (or) liquid ... are obtained".
More about the Fischer-Tropsch process and it's history can be learned via:
Fischer–Tropsch process - Wikipedia, the free encyclopedia; "The Fischer–Tropsch process, or Fischer–Tropsch synthesis, is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. It was first developed by Franz Fischer and Hans Tropsch ... in 1925".
Fischer and Tropsch worked with Coal as their primary raw material, from which to derive the "mixture of carbon monoxide and hydrogen". And, as we saw most recently in our report of:
West Virginia Coal Association | Celanese Co-Gasifies Coal and CO2-Recycling Algae | Research & Development; concerning: "United States Patent Application 20130144087 - Co-Gasification of Aquatic Biomass and Coal; 2013; Assignee: Celanese International Corporation; Abstract: The invention also relates to co-gasification processes for forming syngas from aquatic biomass and a fossil fuel. In one aspect, the invention is to a process for producing syngas, comprising: introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide; and feeding aquatic biomass with carbon dioxide derived from the syngas (and) wherein the fossil fuel comprises coal";
effort continues to be made by major corporations to improve the technology for converting Coal into such synthesis gas mixtures "of carbon monoxide and hydrogen", effort focused on incorporating elements of sustainability and Carbon recycling into such Coal-to-hydrocarbon conversion processes.
In any case, again as we've noted previously, there exists a rather vast body of technical literature describing and defining the ways and means by which "carbon monoxide and hydrogen" can be converted into hydrocarbons. And, that body of knowledge continues to grow more sophisticated, with recent literature even identifying specific catalysts which can preferentially synthesize specific hydrocarbons, or ranges of hydrocarbons, from blends of "carbon monoxide and hydrogen", without ever mentioning from what source such "synthesis gas" might be derived.
And, before presenting too many reports on that recently-developed technology for processing synthesis gas blends of Carbon Monoxide and Hydrogen, technology which represents, essentially, evolution of the original Fischer-Tropsch Coal conversion methods, we wanted to again anchor the core technical concept of first converting Coal, with or without sustainable, renewable, and Carbon-recycling, resources into synthesis gas, and, thence, into hydrocarbons.
Shell Oil has been kind enough to help us along in that effort, via their recent, as excerpted from the initial link in this dispatch:
"United States Patent 8,308,983 - Process to Prepare a Gas Mixture of Hydrogen and Carbon Monoxide
Patent US8308983 - Process to prepare a gas mixture of hydrogen and carbon monoxide - Google Patents
Process to prepare a gas mixture of hydrogen and carbon monoxide - Shell Oil Company
Date: November 13, 2012
Inventors: Guillaume Fournier, et. al., The Netherlands
Assignee: Shell Oil Company, Texas
Abstract: The invention is directed to a process to prepare a gas mixture of hydrogen and carbon monoxide from an ash containing carbonaceous feedstock. The process involves a partial oxidation obtaining liquid ash and a gas mixture comprising hydrogen, carbon monoxide and solids. The liquid ash is separated from the gas mixture and the temperature of the gas mixture is reduced in the absence of the separated ash. The gas mixture is passed through a vertically positioned diptube wherein water is added to the gas mixture flowing through the diptube to obtain a gas/water mixture. The liquid is separated from the gas/water mixture. The gas thus obtained is passed together with an amount of liquid water through a venturi mixer and scrubbed.
Claims: A process to prepare a gas mixture of hydrogen and carbon monoxide from an ash containing carbonaceous feedstock comprising the following steps:
(a) partial oxidation of the ash containing carbonaceous feedstock with an oxygen containing gas thereby obtaining liquid ash and a gas mixture comprising hydrogen, carbon monoxide and solids;
(b) separating more than 90 wt % of the liquid ash from the gas mixture, wherein step (a) and (b) are performed in a reactor vessel provided with horizontally firing burner nozzles, which nozzles discharge a gas mixture comprising hydrogen, carbon monoxide and solids into a gasification chamber as present in the reactor vessel, and wherein liquid ash is present on an interior wall of the gasification chamber, wherein the gas mixture is discharged through an opening at the upper end of the gasification chamber and the liquid ash is discharged via an opening at the lower end of the gasification chamber;
(c) reducing the temperature of the gas mixture, in the absence of the separated ash, from a temperature above 1000 C to a temperature below 900 C by contacting the gas mixture with a gaseous and/or liquid quench medium;
(d) passing the gas mixture obtained in step (c) through a vertically positioned diptube wherein water is added to the gas mixture flowing through the diptube to obtain a gas/water mixture;
(e) separating the liquid water from the gas/water mixture by passing the gas/water mixture through a water bath as present at the lower end of the diptube wherein the gas is discharged to a space above the water bath and effluent water is discharged from the water bath via a discharge conduit fluidly connected to said water bath;
(f) passing the gas obtained in step (e) together with an amount of liquid water through a venturi mixer; and:
(g) passing the gas obtained in step (f) upwardly through a scrubber in which the gas contacts a stream of downwardly moving liquid water thereby obtaining a scrubbed gas mixture of hydrogen and carbon monoxide and used water, wherein part of the used water is used in step (d) as the water added to the gas mixture.
A process ... wherein part of the used water of step (g) is reused in step (g) itself, part is used in step (d) and part is used in step (f).
A process ... wherein the downwardly water stream has an initial pH of between 6.5 and 7.5 as it is supplied to the scrubber (and) wherein the scrubber in step (g) is provided with a gas inlet device which directs the gas substantially upwardly and the liquid as present in the gas substantially downwardly.
A process according to (the claims), wherein the carbonaceous feedstock is coal.
A process ... wherein ash is separated from the effluent water by means of a decanter centrifuge thereby obtaining a wet ash and a stream of water poor in ash.
A process ... wherein the stream of water is recycled to step (c), step (e) and/or to step (g).
A process ... wherein the feedstock to step (a) contains a calcium compound and wherein the decanter centrifuge is nitrogen blanketed to prevent oxidation of sulphur components as present in the effluent water.
(Now, if anyone is still wondering why Shell Oil would devote this much detail to a Coal gasification process, we remind you of what they themselves state, as seen in our report of:
West Virginia Coal Association | Shell Oil Converts Coal and CO2-Recycling Biomass to Gasoline | Research & Development; concerning, in part:
"United States Patent 4,499,209 - Fischer-Tropsch Catalyst and Preparation of Hydrocarbons from Syngas; 1985; Assignee: Shell Oil Company, Houston; Abstract: A Fischer-Tropsch catalyst is ... used in the preparation of hydrocarbons from a H2/CO mixture. A process for the preparation of hydrocarbons by catalytic reaction of carbon monoxide with hydrogen"; and:
"United States Patent 7,678,952 - Process to Prepare a Gasoline; 2010; Assignee: Shell Oil Company, Texas; Abstract: A process to prepare a gasoline fuel by contacting a Fischer-Tropsch product with a catalyst system of an acidic matrix (as specified)";
the end goal to be, i.e., "gasoline".)
Background and Field: The invention is directed to a process to prepare a gas mixture of hydrogen and carbon monoxide from an ash containing carbonaceous feedstock."
---------------------------
We'll leave it at that. Shell has actually developed what might be seen as an immense body of Coal, or Carbon, conversion technology; much of representing, as seen in:
"United States Patent: 7597067 - Process to Reduce the Temperature of a Hydrogen and Carbon Monoxide Containing Gas and Heat Exchanger for Use in said Process; 2009; Inventors: Franciscus Gerardus Van Dongen, et. al., The Netherlands; Assignee: Shell Oil Company, Houston; Abstract: A process to reduce the temperature of a hydrogen and carbon monoxide containing gas by contacting the gas with a metal alloy surface having a lower temperature than the temperature of the gas, wherein the metal alloy surface has between 0 and 20 wt % iron, between 0 and 5 wt % aluminium, between 0 and 5 wt % silicon, between 20 and 50 wt % chromium and at least 35 wt % nickel, wherein the metal alloy surface maintains it lower temperature than the temperature of the gas by making use of coolant water";
sophisticated refinements on synthesis gas handling. The above "United States Patent 7,597,067", for instance, enables both the recovery of heat from the synthesis gas for recycling and use elsewhere in the total Coal conversion system and the adjustment of the temperature of the synthesis gas, prior to entering an exothermic Fischer-Tropsch reactor, to enable better control over the mix of hydrocarbons produced, much like that in one Shell syngas technology about which we reported earlier, via:
West Virginia Coal Association | Shell Hydrogenates Coal Syngas, Recycles CO2 | Research & Development; concerning: "United States Patent 5,431,703 - Method of Quenching Synthesis Gas; 1995; Assignee: Shell Oil Company, Houston; Abstract: The invention is a process for quenching a first synthesis gas mixture containing synthesis gas, molten fly ash, water and carbon dioxide and producing additional synthesis gas (by) passing first synthesis gas mixture into a ... mixture of pulverized coal in a ... carbon dioxide carrier gas (and) endothermically reacting the pulverized coal with the water and the carbon dioxide to produce additional synthesis gas. The invention is a process (which includes) endothermically reacting the pulverized coal with the water vapor and the carbon dioxide in the first synthesis gas mixture thus producing additional synthesis gas consisting of hydrogen and carbon monoxide";
wherein it was seen that any Carbon Dioxide that might be co-produced anywhere in a hydrocarbon synthesis system could, too, be further recycled in the system and consumed in the production of more hydrocarbon synthesis gas, while at the same time cooling, "quenching", an initial run of syngas.
And, there is even more to Shell's syngas technologies, some of it related to the claim in the above "United States Patent 8,308,983 - Process to Prepare a Gas Mixture of Hydrogen and Carbon Monoxide" which concerns "separating more than 90 wt % of the liquid ash", and, what might be productively done with that recovered "ash", in a way related to that disclosed in our report of:
West Virginia Coal Association | Shell Oil Coal Conversion Residues to Construction Aggregates | Research & Development; concerning: "United States Patent 4,917,732 - Flyash Treatment; 1990; Assignee: Shell Oil Company, Houston; Abstract: A process for production of a flyash-slag composite is described in which, in one embodiment, slag particles are tumbled with an aqueous suspension of finely divided clay, flyash and a cementitious material are added, and the mixture is tumbled to produce the desired composite. A process for producing a flyash-slag composite comprising discrete particles of slag dispersed in a solid mixture comprising (a) tumbling slag particles with an aqueous suspension of finely divided clay, under conditions effective to provide aggregation, the ratio of slag to said clay, by weight, being from about 15 parts to about 40 parts slag per part of clay, and forming a mixture comprising aggregates of slag and clay in said suspension; (b) adding flyash derived from the gasification of coal to said mixture while tumbling said mixture under said conditions, said flyash particles being added in a ratio of from about one part to about 5 parts flyash per part of slag, by weight, and forming a flyash-aggregate mixture";wherein Shell Oil posits that Coal gasification and conversion Ash can be utilized and consumed in the making of materials useful in construction.
Again, as we go along, we'll be addressing some sophisticated technology and knowledge that's been developed relative to the catalytic processing of gas blends of Carbon Monoxide and Hydrogen, and the products that can be made from such synthesis gas with high degrees of productivity and selectivity; and, we wanted herein to again demonstrate that such Carbon Monoxide and Hydrogen can be made in efficient processes, with a low potential for pollution, from by far our most abundant Carbon resource: Coal.