Process for the manufacture of hydrocarbons from carbon monoxide and hydrogen
We've made many reports concerning the Carbon conversion expertise developed and patented by the former, German-owned but Pittsburgh-based, Koppers Company.
We note, without reciting the full genealogy, that Koppers, ultimately, became a part of Krupp-Koppers, who were later, after having been acquired by Thyssen to become ThyssenKrupp, assimilated into the German conglomerate "Uhde Gmbh" - if we understand it all correctly.
While they were with us, though, as we've previously documented, Koppers did a lot of interesting things with Coal, and with the derivative products of Coal.
Koppers was actually, at one time, pretty well-known for making roofing sealants and wood preservatives from Coke oven tars, which isn't surprising since the German founder of the company, Heinrich Koppers, was an internationally-recognized expert in Coke oven design and construction, as seen in:
Heinrich Koppers - Wikipedia, the free encyclopedia; which tells us that: "Dr. Heinrich Koppers ... founded his own company, 'Heinrich Koppers AG', in 1901 to successfully exploit the patents he had been granted in the area of coke oven design".
And, after having founded the American branch of their company, Koppers learned, as seen in our report:
Pittsburgh & Germany 1940 Coal & Steam to Hydrocarbons | Research & Development; concerning: "United States Patent 2,220,357 - Synthetical Production of Liquid Hydrocarbons; 1940; Inventor: Michael Steinschlager, Germany; Assignee: Koppers Company, Pittsburgh, PA; Abstract: This invention relates to the synthetical production of liquid hydrocarbons by reacting gases containing hydrogen and carbon monoxide (which are made by) alternate blows of air and ... steam through ... carbonaceous fuel";
how to make a synthesis gas, suitable for the "production of liquid hydrocarbons", by gasifying Coal with air and steam.
Interestingly, should you read the full Disclosure of "United States Patent 2,220,357", you'll discover that Carbon Dioxide can be added to the blend of gases with which Coal is gasified, in which process that CO2 is chemically reduced into more of the Carbon Monoxide component of hydrocarbon syngas.
And, Koppers scientists in Germany then seemed to focus more of their attention on Carbon Dioxide, and its value as a source of Carbon in hydrocarbon synthesis processes, as seen in our report of:
Pittsburgh 1941 CO2 + Methane = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,266,989 - Manufacture of a Gas from CO2 and Methane; 1941; Inventor: Max Radtke, Germany; Assignee: Koppers Company, Pittsburgh, PA; Abstract: The present invention relates to the manufacture of gases suitable for the synthesis of higher hydrocarbons or the like, said gases containing definite volumes of carbon monoxide and hydrogen in a certain proportion, by reacting on methane ... with carbon dioxide or a mixture of carbon dioxide and steam, so that the methane ... is decomposed into hydrogen and carbon monoxide."
Such a blend of "hydrogen and carbon monoxide" is, again we remind you, better known as "synthesis gas", or "syngas"; and, which syngas, it has long been known, as demonstrated, for example, 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;
can be catalytically transformed and condensed into gaseous and liquid hydrocarbons.
Further, we submit, Max Radtke, of Germany, the inventor of "United States Patent 2,266,989 - Manufacture of a Gas from CO2 and Methane"; would, prior to 1941, have known that the needed Methane could itself be derived in the first place from Carbon Dioxide, via the Sabatier process, which was invented in neighboring France, and which, as seen in:
CO2 Solution Wins Nobel Prize - in 1912 | Research & Development; wherein Paul Sabatier himself, in his 1912 Nobel Prize acceptance speech, says: "Carbon monoxide and carbon dioxide are both changed immediately into methane, which can therefore be synthesized with the greatest ease",
had, decades before issuance of "United States Patent 2,266,989", been publicly awarded Europe's highest honor for scientific achievement.
In any case, we submit herein more confirmation of the fact, that, as in the seminal Fischer-Tropsch technology, "United States Patent 1,746,464 - Process for the Production of Paraffin-Hydrocarbons" cited above, blends of Carbon Monoxide and Hydrogen can be condensed into liquid hydrocarbons.
We see our subject, in fact, primarily as a refinement of that synthesis process.
The possible sources of the synthesis gas are noted only in passing, almost casually.
And, we think that to be significant:
In 1941, the year our subject United States Patent was issued, it almost seems to have been taken for granted that Carbon Dioxide can be reacted with Methane and that Coal can be reacted with Steam to form a hydrocarbon synthesis gas blends of Carbon Monoxide and Hydrogen from which liquid hydrocarbon fuels could be manufactured.
Further, this is also additional confirmation of the fact that such processes were known and understood by Pittsburgh's Koppers Company and, by extension, through issuance of an official US Patent, our United States Government, even somewhat before the award to Koppers of the above-referenced "United States Patent 2,266,989", all the way back during the early years of World War II.
Comment is inserted within, and follows excerpts from, the initial link in this dispatch to:
"United States Patent 2,244,710 - The Manufacture of Hydrocarbons from Carbon Monoxide and Hydrogen
Date: June, 1941
Inventor: Herbert Kolbel, Germany
Assignee: Koppers Company, Pittsburgh, PA
Abstract: The present invention relates to the manufacture of hydrocarbon mixtures suitable for use as motor fuel or as lubricating means, by the reaction of a gas containing hydrogen and carbon monoxide ...
The main object of my invention is to provide such improvements which will render possible the immediate manufacture of valuable hydrocarbon mixtures by the use of ordinary coke water gas or gases of similar composition without a previous conversion of such gases.
(Note, that, all the way back in 1941, "coke water gas", that is, a blend of Carbon Monoxide and Hydrogen synthesis gas produced by the Steam-gasification of Coal, could already be described as "ordinary".)
For the synthesis of hydrocarbon mixtures from hydrogen and carbon monoxide or gases (water gas) containing such compounds, cobalt or nickel catalysts are preferably used.
Such catalysts give a high yield of valuable hydrocarbons.
The normal water gas made from coke and produced in the well-known discontinuous water gas process contains, however, carbon monoxide and hydrogen in the proportion of approximately 1:1 to 1:1.25. If such a gas is to be completely utilized for the catalytic production of hydrocarbons, as is necessary from an economical point of view, said gas has to be suitably treated before coming into contact with the catalyst.
It is, for instance possible to convert a part of the carbon monoxide into carbon dioxide and to separate the latter from the gases, or to add hydrogen from another source to the normal water gas ... . Such a treatment of the water gas results, however, in considerably increased costs for the production of synthesis gas.
(We interrupt to note that the basic cost structure for hydrocarbon fuels, against which syngas-derived petroleum substitutes would be measured, has certainly changed since the early years of WWII, when this patent issued, and the above statement could, and should, now elicit a "so what?". But, if additional Hydrogen "from another source" would help, then we remind you, that, as seen, for example, in:
USDOE Algae Make Hydrogen for Coal and CO2 Hydrogenation | Research & Development; concerning: "Photosynthetic Hydrogen and Oxygen Production by Green Algae; E. Greenbaum and J. W. Lee; Oak Ridge National Laboratory; Tennessee; Symposium on Hydrogen Production, Storage and Utilization; American Chemical Society; 1999; Report Number ORNL/CP-103431; USDOE Contract Number: AC05-96OR22464; 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"; and:
NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,045,315 - Solar Photolysis of Water; 1977; NASA; Abstract: Hydrogen is produced by the solar photolysis of water";
the issue of producing Hydrogen economically is one that has, since 1941, been pretty much dealt with, and, thus, the "costs for the production of synthesis gas" from either, as herein, "United States Patent 2,244,710", Coal, or, as in the above-cited "United States Patent 2,266,989 - Manufacture of a Gas from CO2 and Methane", Carbon Dioxide, using externally-supplied supplemental Hydrogen shouldn't be seen as quite the economic barrier it was back then.)
Now, the process of the present invention principally consists in manufacturing useful hydrocarbon mixtures by treating a synthesis gas consisting of water gas or other gases which contain carbon monoxide and hydrogen but not in the proportion of one volume carbon monoxide to two volumes of hydrogen, said synthesis gas being freed almost completely from the dangerous sulphur compounds in the usual manner in two stages in the presence of catalysts, namely in a primary stage in the presence of a catalyst containing iron and then in a second stage in the presence of a catalyst containing cobalt or nickel whereby the hydrocarbons in the first stage are removed before treatment of the gas in the second stage. According to my invention the residual gas of the first stage of the process may also be mixed with an adjustable quantity of untreated synthesis gas if necessary in order to obtain for the second stage of the process a gas mixture of the desired composition.
(We are compelled to summarize at this point. What Kolbel goes on to explain is the fact, that, the initial Iron catalyst produces hydrocarbons from the syngas in such a way that a residual amount of un-reacted synthesis gas is also produced, but, one in which the relative amount of Hydrogen, to Carbon Monoxide, is increased, so that the subsequent synthesis of additional hydrocarbons in the second stage, over a Nickel or Cobalt catalyst, is actually enhanced; and, the mix of product hydrocarbons is improved. Further, the initial Iron catalyst, which is more easily re-refined and renewed, reacts with, and removes, Sulfur compounds from the syngas, so that they can't react with and poison the secondary Cobalt or Nickel catalyst. And, although Kolbel does say that some untreated synthesis gas can be added to the second stage, to adjust, in essence, the Hydrogen-Carbon Monoxide ratios, perhaps a better choice would be to add either Hydrogen or Carbon Monoxide separately, as needed, from an essentially Sulfur-free source, such as those described in:
Germany 98% Pure Carbon Monoxide from Coal, CO2 and O2 | Research & Development; concerning: "Carbon Monoxide from Coke, Carbon Dioxide and Oxygen;1986; Lurgi GmbH, Frankfurt (Germany); Abstract: Many valuable organic chemicals-both as intermediate or final products-can be made from high purity carbon monoxide (CO). In order to provide a source of inexpensive CO ... , a very attractive new scheme has been developed. This is very competitive indeed when compared to processes using natural gas or oil as feedstock. According to this concept merely two process steps are required to convert coke to high purity CO. The purpose of the first process step is to gasify coke using a mixture of CO2 and O2 as gasification agent while the second one serves to remove sulfur compounds and residual CO2";
wherein a nearly-pure stream of Carbon Monoxide is manufactured from Coal and Carbon Dioxide; and:
Florida Hydrogen and Sulfur from H2S | Research & Development; concerning: "United States Patent 6,572,829 - Photocatalytic Process for Decomposing Hydrogen Sulfide; 2003; Assignee: University of Central Florida; Abstract: System for separating hydrogen and sulfur from hydrogen sulfide (H2S) gas produced from oil and gas waste streams";
wherein solar energy is used to extract both commercially-valuable Sulfur and the needed Hydrogen from a deadly toxin, which is now being produced in rather shocking and dangerous quantities from the new abundance of wells producing gas from deep shale deposits in certain parts of Appalachia and surrounding areas; more about which can be learned in our report of:
Another essential feature of the process according to the present invention resides in the fact that the industrial use of the iron catalyst in connection with the synthesis of the hydrocarbons is rendered possible in an exceptionally economical way and moreover products are obtained which are superior to the hydrocarbon mixtures formed by means of cobalt or nickel catalysts exclusively.
Finally, an important advantage of the iron catalyst against the cobalt or nickel catalysts is it's low manufacturing cost. This fact has a special effect when treating the gases which are not completely freed from dangerous sulphur compounds. Iron as well as cobalt and nickel catalysts are poisoned by the sulphur compounds fairly soon. As, however, the synthesis gas according to the present invention first of all comes into contact with the cheap and easily replaceable iron catalysts and gives off nearly all the dangerous sulphur compounds to these iron catalysts, the valuable cobalt or nickel catalysts of the second stage of the process are taken care of and their full efficiency is maintained.
Claims: A process to enable gases containing sulphur to be treated for the manufacture of hydrocarbons from carbon monoxide and hydrogen by leading the synthesis gas mixture first of all over an iron catalyst and then over a catalyst of the group consisting of cobalt and nickel comprising passing over the iron catalyst first of all a gas mixture which is free from sulphur and after the iron catalyst has attained it's full efficiency changing over to passing over the iron catalyst the has mixture containing sulphur."
-------------------------
The above, as we will more fully document in future reports, has led to other methods of treating gases containing Hydrogen Sulfide, as suggested in:
Hydrogen sulfide - Wikipedia, the free encyclopedia; "Hydrogen sulfide is commonly found in natural gas, biogas and LPG. It can be removed in a number of ways. (For instance) Gas is pumped through a container of hydrated iron (III) oxide, which combines with hydrogen sulfide. In order to regenerate iron(III) oxide, the container must be taken out of service, flooded with water and aerated. On completion of the regeneration reaction the container is drained of water and can be returned to service";
and, as we've begun to address more specifically, as in:
Georgia Tech By-Product Sulfur from Coal Syngas | Research & Development; concerning: "Electrochemical Polishing of Hydrogen Sulfide from Coal Synthesis Gas; Advanced coal-fired power systems `95 review meeting, Morgantown, WV; June,1995; Report Number: DOE/PC/94207--96/C0547;
Moreover, as in the above citation of our report concerning "United States Patent 6,572,829 - Photocatalytic Process for Decomposing Hydrogen Sulfide"; and, variously, as seen in:
West Virginia Coal Association | Exxon Liquefies More Coal with Hydrogen Sulfide | Research & Development; concerning: "United States Patent 4,149,959 - Coal Liquefaction Process; 1979; Exxon Research and Engineering Company; A coal liquefaction chargestock is first treated with a gaseous mixture comprising ... hydrogen sulfide ... and thereafter subjected to coal liquefaction conditions";
we really could start to see the Hydrogen Sulfide byproduct of Coal gasification as yet another sort of profit center accruing to processes dedicated primarily to the conversion of Coal into hydrocarbons.
All of which might make the process of our subject herein, "United States Patent 2,244,710 - The Manufacture of Hydrocarbons from Carbon Monoxide and Hydrogen", developed all the way back in 1941 to enable the production of Sulfur-free hydrocarbons from Sulfur-containing synthesis gas derived from Coal, seem a little archaic.
But, that's our point:
Seventy-one years ago, in Pittsburgh, Pennsylvania, for all practical purposes back in the Dark Ages, a technology had been developed to produce essentially Sulfur-free liquid hydrocarbon fuels out of Coal.
How far behind the times are our local newspapers that - - especially given our current statues of economic servants indentured to OPEC and Big Oil - - such information - - concerning the fact that Coal can be efficiently converted into environmentally-friendly, Sulfur-free liquid hydrocarbons - - has not yet reached the headlines - - or, at least the editorial pages, with demands that such Coal utilization technology be, finally and at long last, implemented and commercialized - - of those local, supposedly Coal Country, newspapers?