Hydrocarbon synthesis process with two-stage coke gasification
Herein, again from more than half a century ago, we present an indirect Coal liquefaction technology developed by the petroleum industry, which, ultimately, results in the production of "high yields of ... high octane gasoline", with no, or very, very little, Carbon Dioxide being emitted from the process itself.
Though for multiple reasons unable to thoroughly analyze it all for you, we see it as being closely similar to another petroleum industry Coal liquefaction technology that was it's contemporary, and about which we earlier reported, in:
Texaco 1951 Coal + CO2 + H2O + O2 = Syngas | Research & Development; concerning: "United States Patent 2,558,746 - Carbon Monoxide and Other Gases from Carbonaceous Materials; 1951; Assignee: The Texas Company; 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. 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."
The point being, that: Any Carbon Dioxide generated by the process is recycled within the process and further converted into the desired Carbon Monoxide.
No, or, again, very, very little Carbon Dioxide is left un-reacted and un-utilized.
Comment, and additional links, follow excerpts from the initial link to:
"United States Patent 2,620,348 - Hydrocarbon Synthesis with Two-Stage Coke Gasification
Date: December, 1952
Inventors: Walter May and Sumner Sweetser, NJ
Assignee: Standard Oil Development Company, DE
Abstract: The present invention relates to the catalytic reaction between carbon monoxide and hydrogen to form valuable liquid products, and more specifically to a novel process for the preparation of synthesis gas.
More particularly, the present invention is concerned with improvements in the reaction based upon an improved two-stage process for preparing synthesis gas from coke or coal, and a two-stage process for reacting synthesis gas thus produced to give high yields of valuable high octane gasoline, preferably at low synthesis pressures.
(We must interrupt here to point out a few things. First, note the specification of "low synthesis pressures", with the potential for process economies that implies. Second, note that this is, similar to other technologies about which we have previously reported, a process which can convert both Coal and the semi-solid carbonaceous "coke" that is the by-product of some conventional petroleum refining processes. Such "petroleum coke", aka "residuals" or "resid", is co-produced in large quantities by the refining of some types of crude oil.
It is closely similar to Coal in it's composition, and, the petroleum industry has been routinely processing it into liquid fuels since before WWII.
Coal and petroleum coke are so much alike that it has been documented several times, that, not only can they both be converted into liquid hydrocarbon fuels, but, they can be so processed together, in the same processing train. One example of our reportage concerning that fact can be accessed via:
Mobil Co-Liquefies Coal and Oil Refinery Resids | Research & Development; concerning: "United States Patent 4,390,409 - Co-Processing of Residual Oil and Coal; 1983; Mobil Oil Corporation; Abstract: Coal and metals-containing residual oil are coprocessed under conditions whereby the coal is volatilized and solubilized, the residual oil is demetallized and substantially no coking of the residual oil occurs. The products obtained include metals-free distillates and metals-containing solid fuel. This invention relates to the co-processing of residual oil and coal".
And, we will further document those co-processing potentials in a number of reports to follow. The main point is, though, that the petroleum industry has, for many, many decades, been further converting one of their own products, a product very much like Coal in it's composition, into liquid hydrocarbon fuels.)
The synthetic production of liquid hydrocarbons from gas mixtures containing various proportions of carbon monoxide and hydrogen is a matter of record, and numerous catalysts, usually containing an iron group metal, have been described which are specifically active in promoting the desired reactions ... .
Most processes for the synthesis of hydrocarbons from synthesis gas obtained from coal ... involve the production of relatively pure oxygen for the partial combustion of these raw materials to form CO and H2 which are then reacted in a second step.
(Note: We've earlier documented that using purified Oxygen for the Coal gasification offers a number of advantages, and, that a number of economical ways exist to provide the Oxygen in a purified form; some of which supply the Oxygen in a way that's "metered", for want of a better term to describe it, so that preferentially more Carbon Monoxide, rather than Carbon Dioxide, is formed. Standard Oil themselves, in yet another technology that was contemporaneous with our subject herein, described such a process, as in our report of:
Standard Oil 1952 Oxygen Donor Coal Gasification | Research & Development; concerning: "United States Patent 2,592,377 - Manufacture of ... Carbon Monoxide and Hydrogen; 1952; Assignee: Standard Oil Development Company, DE; Abstract: The present invention relates to the manufacture of gas mixtures containing carbon monoxide and hydrogen from ... carbonaceous materials such as coal (and) cellulosic materials ... and more particularly to the manufacture of such gas mixture as are suitable for the catalytic synthesis of hydrocarbons. In accordance with the present invention the gasification of solid carbonaceous materials with steam is carried out in the presence of metal oxides supplying the heat required (and, the) metal oxide is intimately contacted with, and gives off its oxygen to, the fluidized solid carbonaceous charge of the gas generator".
And, we will further document those potentials, and those concerning the co-utilization of renewable and Carbon-recycling "cellulosic materials", as above, in additional reports to follow.
Standard Oil goes on, in the full Disclosure of our subject herein, United States Patent 2,620,348, to explain the value of using purified Oxygen in the coordinated reaction sequence at some considerable length; and, we won't replicate their complete explanation; but, it is worth the read for anyone genuinely interested in knowing the full facts about how Coal can be completely converted into hydrocarbons via the generation, and subsequent catalytic processing, of synthesis gas. - JtM)
It is one of the purposes of the present invention ... to provide a highly economical process of producing synthesis gas from coal ... in a multi-stage process and employ the (synthesis gas) in a multi-stage synthesis operation.
It is also a purpose of the present invention to disclose a process for preparing synthesis gas of any desired composition for a two-stage hydrocarbon synthesis operation.
(Note, we've documented several times, as, for one example, in:
More WV DuPont 1955 Coal and Steam to Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,716,598 - Carbon Monoxide and Hydrogen (from) Carbonaceous Solids; 1955; Inventor: Douglas Moses, Charleston, WV; Assignee: E..I. DuPont and Company, DE; Abstract: This invention relates to a process for the preparation of carbon monoxide and hydrogen by at least partial oxidation of comminuted solid carbonaceous materials, and is more particularly directed to the preparation of hydrogen, gaseous mixtures containing hydrogen and nitrogen, and gaseous mixtures containing hydrogen and carbon monoxide by the partial oxidation of powdered coal. An object of the present invention is to provide an improved process for the preparation of synthesis gas from coal ... containing principally hydrogen (or) carbon monoxide and hydrogen ... wherein the purity and/or the ratio of constituents can be accurately controlled";
that, the Coal gasification reaction can be structured so as to allow for, depending on the final synthesis products desired, the generation of a hydrocarbon syngas of variable and "desired composition".)
It is a further purpose of the present invention to provide a two-stage hydrocarbon synthesis process wherein a synthesis gas derived from coal ... may be converted into valuable hydrocarbons of high octane value at relatively low pressures in a substantially once-through operation.
In accordance with the present invention, more effective utilization of coal ... used in the production of synthesis gas for the synthesis operation is obtained ... by employing a two-stage ... gasification unit coupled with a two-stage synthesis unit ... .
The two gasification reactors are operated to give product gas streams of different compositions.
In the first, a gas of relatively high hydrogen to carbon monoxide ratio is produced ... (since both) Steam and ... oxygen are supplied ... .
The second stage gasification unit is operated to give a product gas of low hydrogen to carbon monoxide ratio.
This is done by feeding it with carbon dioxide ... .
The product gas from the second gasification ... is then blended with the gas from the first synthesis stage so that the hydrogen to carbon monoxide ratio of the mixture passing to the second synthesis stage is suitable for further synthesis operation.
(In other words, and we have been compelled to edit our excerpts in the extreme, there are two Coal gasifiers and two hydrocarbon synthesis units operating in coordinated tandem; and, any Carbon Dioxide arising from either the first gasification, or either of the two hydrocarbon syntheses, is collected, and directed into the second gasifier, the product of which is combined with the tail gas from the first synthesis unit, after the Carbon Dioxide has been removed from it. It's complicated the way Standard Oil writes it out, but makes sense after you study it for a while. Someone fully-functional and genuinely qualified could quickly correct any of our misrepresentations and spell it out clearly for you. The bottom line is that any CO2 generated anywhere in the system is consumed in the making of more Carbon Monoxide. And, the different synthesis gases generated by the separate gasifiers can be blended to make a final synthesis gas of a composition suitable for the synthesis of various hydrocarbons, most especially the specified "high yields of valuable high octane gasoline".)
Claims: An improved process for the catalytic synthesis of hydrocarbons from CO and H2 which comprises passing steam and carbonaceous solids to an initial gasification stage (and reacting the syngas in) an initial hydrocarbon synthesis reaction zone ... .
The process .. wherein CO2 is removed from ... said synthesis stages (and) supplied to said second stage gasification zone."
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The end result of it all being "high octane gasoline", from Coal, with virtually no emission of Carbon Dioxide.
And, as in our above citation of "United States Patent 2,592,377 - Manufacture of ... Carbon Monoxide and Hydrogen", wherein "cellulosic materials" can be gasified, in a process closely related and very similar to that of our subject, "United States Patent 2,620,348", along with Coal, the very real potential exists to make of these processes a technology that actually consumes, indirectly, through the process of the botanical photosynthesis that gives rise to the "cellulosic materials", Carbon Dioxide, in a process founded on Coal and that results in the production of "gasoline".
That fact was actually further confirmed in the year following issuance of both US Patents "2,592,377" and "2,620,348" by Standard Oil themselves, as seen in our earlier report of:
Standard Oil Co-Gasifies Coal & Carbon-Recycling Biomass | Research & Development; concerning: "United States Patent 2,633,416 - Gasification of Carbonaceous Solids; 1953; Assignee: Standard Oil Development Company; The present invention relates to the production of gases from non-gaseous carbonaceous materials and, more particularly, to the production of gas mixtures containing carbon monoxide and hydrogen ... from such solid carbonaceous materials as ... various coals (and) cellulosic materials".
And, the upshot of it all is this:
Via "a highly economical process of producing synthesis gas from coal", we can consume some sustainable and Carbon-recycling "cellulosic materials", with Coal, and, through an "improved process for the catalytic synthesis of hydrocarbons", make "valuable high octane gasoline", with no emission of CO2.
Maybe we here are missing something important, but, is there anything about any of this that those of us resident in United States Coal Country wouldn't like?
Is there anything that wouldn't be of great economic benefit to all of us resident in United States Country, all of us resident in the United States of America?
Nope?
We didn't think so.
So:
Why, for what possible reason, haven't we been told, at some point during the last half a century since these technologies were certified, via the Patent Office, by our own United States Government, as being practical and viable, anything about any of it by the people most responsible for bringing us the news?