The two, closely-related United States Patents at the core of this report are focused on the disclosure of an improved catalyst and process for reacting Carbon Monoxide with Hydrogen to make synthetic fuels.
The Japanese inventors don't dwell much on the sources of those two gases, but do mention, almost in passing, that: "a mixture of carbon monoxide and hydrogen, is produced through ... coal gasification".
And, their improvement lies, as explained in the full Disclosure, in the discovery and development of synfuel catalysts that are much more resistant to the presence of Sulfur in that "mixture of carbon monoxide and hydrogen", CO and H2, than those that had been already known to the "prior art".
That is a good thing, of course, especially if the CO and H2 are to be made directly from Sulfur-bearing Coal.
However, since the technology disclosed herein is focused and concerned primarily on the synthesis of liquid fuels, with "methanol" specifically mentioned, out of, generically, Carbon Monoxide and Hydrogen, we wanted to document that there are alternative sources for those two gases; and, different ways to obtain them, that might, in the long run, be more advantageous for us all.
By way of preamble, keep in mind, that, as seen in:
Carbon Dioxide Recycled in the Manufacture of Plastics | Research & Development; which includes incidental report of: "USP 4,564,513 - Process for the Production of Carbon Monoxide; 1986; Assignee: Bayer AG, Germany; Abstract: Carbon monoxide is produced in an improved process ... by the gasification of carbon with a mixed gas of oxygen and carbon dioxide";
we can make Carbon Monoxide by reacting on hot "carbon", i.e., Coal, with reclaimed Carbon Dioxide.
And, as seen in:
Chicago Hydrogen from H2O | Research & Development; about: "USP 4,793,910 - Photoelectrochemical Cell for Unassisted Photocatalysis; 1988; Assignee: Gas Research Institute, Chicago; Abstract: A multielectrode photoelectrochemical cell ... which ... contains two bipolar electrode panels for photoelectrochemical reactions such as water photolysis to produce H2 (and) O2";
we can make Hydrogen by using electricity derived from sunlight to "split" Water, H2O, into it's elemental constituents.
Then, once we have the Carbon Monoxide and Hydrogen, Japan herein tells us, in excerpts from the initial link in this dispatch, with an additional link and excerpts following, how, through a durable process, to efficiently convert them into liquid hydrocarbon fuels:
"United States Patent 6,534,553 - Hydrogenation of Carbon Monoxide Using Sulfide Catalysts
Date: March, 2003
Inventors: Muneyoshi Yamada and Naoto Koizumi, Japan
Assignee: Tohoku University, Sendai
Abstract: A method of producing synthetic fuels by hydrogenating carbon monoxide comprising contacting a feed gas containing carbon monoxide and hydrogen with a catalyst comprising: a supported metal sulfide comprising Palladium and at least one promoter selected from the group consisting of alkali metal, alkaline earth metal, and rare earth elements, and optionally solid acid.
(We know that "Palladium" sounds fancy, and expensive; and, it is. But, it's not as fancy or nearly as expensive as Platinum, for instance; and, it doesn't get used up or consumed in the reactions; though it can, in a way, "wear out", albeit slowly. It can thus be considered a part of the physical, durable, plant investment. And, the optional "solid acid" can, and likely does, imply use of relatively inexpensive zeolite minerals in a way similar to our frequently-cited ExxonMobil "MTG"(r), Methanol-to-Gasoline, process, wherein the Methanol is posited to be made from Coal.)
Claims: A method of producing methanol and/or dimethylether by hydrogenating carbon monoxide comprising contacting a feed gas containing carbon monoxide and hydrogen with a magnesia, silica or calcia supported metal sulfide catalyst comprising Palladium and at least one promoter selected from the group consisting of alkali metal, alkaline earth metal, and rare earth elements.
(And) wherein said catalyst is supported on magnesia (or) silica (or) calcia.
(And) wherein said feed gas contains from 1 to 10000 ppm of sulfur compounds.
(One caution: The "10000 ppm of sulfur compounds" that are allowed sounds like a lot; but, it is, actually, only one percent. Synthesis gas generated from high-Sulfur Coal might still have to be cleaned a little bit, just not as much as in older, related processes. The Sulfur does, in the course of catalysis, get precipitated, or otherwise separated, out; and, virtually none of it passes through to the hydrocarbon liquids. It is that precipitation and separation, though, that can deactivate, or "poison", the catalyst.)
(And) wherein a molar ration of hydrogen to carbon monoxide is from 1:1 to 5:1 and said feed gas is contacted with said catalyst at a temperature of 100 to 400 C. and at a pressure of 0.1 to 10 MPa.
(Note that those broad reaction conditions of temperature and pressure are what, in the trade, are called "mild"; and, are easily attainable. The chemical-industrial engineering component of this process is not demanding or out of the ordinary. Note, as well, the broad range of H2-CO ratios that can be accommodated in the feed gas, which enables broad tolerance in the composition of starting materials.)
A method of producing methanol and/or dimethylether by hydrogenating carbon monoxide.
(The "dimethylether", aka "DME", is, we remind you, a serviceable substitute for Diesel fuel.)
Background and Field: This invention relates to a process for hydrogenating carbon monoxide. More specifically, this invention relates to a process for producing synthetic fuels of low environmental impact from synthesis gas. In one aspect, this invention concerns a catalyst for use in the hydrogenation of carbon monoxide.
Various useful organic chemicals have been produced from carbon resources like ... coal ... and biomass in the following manner. Firstly, a synthesis gas, a mixture of carbon monoxide and hydrogen, is produced through a ... coal gasification. The synthesis gas is then allowed to react on specific catalysts at high temperature and at high pressure, thus converted to hydrocarbons or oxygenates.
(Again, "oxygenates" implies alcohols, like Methanol and Ethanol.)
These organic chemicals thus obtained will suppress the emission of toxic substances when used as fuel, since they contain little sulfur and nitrogen compounds owing to their distinctive manufacturing processes. In particular, methanol, which is mostly produced from synthesis gases and used as an alternative fuel or a gasoline additive, has recently received much attention as a hydrogen source for the fuel cell. In the stream of rising environmental-conscious, an improved manufacturing method with higher productivity is desired.
Summary: The object of the present invention is to provide a method for hydrogenating carbon monoxide with high productivity under mild conditions and with a simple manufacturing process. It is another object of the present invention to provide sulfide catalysts with high durability, especially excellent sulfur tolerance in the production of synthetic fuels."
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We'll take the opportunity to document for you here, that, since Methanol is one of the two primary products of our subject technology, then, as seen in:
ExxonMobil Coal to Methanol to Gasoline | Research & Development; about: "USP 4,035,430 - Conversion of Methanol to Gasoline; 1977; Mobil Oil Corporation; Abstract: The conversion of methanol to gasoline";
we can, indeed, then convert that Methanol into Gasoline.
However, Tohoku University's the lead scientists, with an additional colleague, continued to develop their Carbon Monoxide hydrogenation technology; and, just months later, they were awarded another US Patent for a somewhat improved version, as in:
"United States Patent: 6605647 - Hydrogenation of Carbon Monoxide Using Sulfide Catalysts
Date: August, 2003
Inventors: Muneyoshi Yamada, Naoto Koizumi, and Yosuke Takahashi, Japan
Assignee: Tohoku University, Sendai
Abstract: A method of producing synthetic fuels by hydrogenating carbon monoxide comprising contacting a feed gas containing carbon monoxide and hydrogen with a metal sulfide catalyst comprising: at least one element selected from the group consisting of Rhodium, Palladium, Platinum, and Hafnium; and optionally solid acid.
Claims: A method of producing a synthetic fuel by hydrogenating carbon monoxide consisting essentially of contacting a feed gas containing carbon monoxide and hydrogen with a metal sulfide catalyst comprising at least one element selected from the group consisting of Rh, Pd, Pt, and Hf, wherein the synthetic fuel is methanol or dimethyl ether.
The method ... wherein said feed gas contains from 1 to 10,000 ppm of sulfur compounds.
A method of producing a synthetic fuel by hydrogenating carbon monoxide consisting essentially of contacting a feed gas containing carbon monoxide and hydrogen with a catalyst consisting of a solid acid and a metal sulfide comprising at least one element selected from the group consisting of Rh, Pd, Pt, and Hf, wherein the synthetic fuel is methanol or dimethyl ether.
Background and Summary: This invention relates to a process for hydrogenating carbon monoxide. More specifically, this invention relates to a process for producing synthetic fuels having low environmental impact from synthesis gas.
Useful organic chemicals have been produced from carbon resources like ... coal ... and biomass in the following manner. Firstly, synthesis gas, a mixture of carbon monoxide and hydrogen, is produced through the ... coal gasification. The synthesis gas is then allowed to react on specific catalysts at high temperature and high pressure, thus converted to hydrocarbons like alkane and alkene, and oxygenates like alcohol and ether.
(The rather generic "alkane and alkene" can be components of Gasoline blending stock.)
These organic chemicals thus obtained can suppress the emission of toxic substances when used as a fuel, since they do not contain sulfur compounds and nitrogen compounds owing to their distinctive manufacturing processes.
(Again: Nearly all of any Sulfur in the starting feed materials, prior to their gasification, will be precipitated or otherwise separated out of the product stream by various stages of the overall process.)
Summary: The object of the present invention is to provide a method of hydrogenating carbon monoxide with high productivity under mild conditions and with simple manufacturing process. It is another object of the present invention to provide sulfide catalysts with high durability, especially excellent sulfur tolerance in the production of synthetic fuels."
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So, Japan has developed for us a technology that has high "durability" and "excellent sulfur tolerance"; a technology which would enable us to, through "a simple manufacturing process", make a much-needed variety of liquid "hydrocarbons" out of "a mixture of carbon monoxide and hydrogen" that is "produced through ... coal gasification"; all of which is accomplished in a way which should be acceptable, even at this time "of rising environmental-conscious"ness.
Gosh, darn, it seems tough to embellish on all of that. But, of course, we will try.
As noted in our introductory comments, and, if we really want to express "environmental-conscious"ness, while at the same time conserving and extending our vital Coal resources, then, we can make the needed Hydrogen and Carbon Monoxide, as seen, additionally, in:
Germany Makes Economical Hydrogen from H2O | Research & Development; concerning: "United States Patent Application 20090026089 - System and Method for Splitting Water; 2009; Hermsdorfer Institut, Germany; Abstract: The present invention relates to a system and a method for cleaving water by means of hyperpolarisation ... economically into hydrogen and oxygen"; and, in:
1915 CO2 Recycling | Research & Development; concerning: "United States Patent 1,163,922 - Producing Carbon Monoxid from Carbon Dioxid; 1915; Charles Hillhouse, NYC, NY; This invention relates to the production of carbon monoxid (CO) gas (by) mixing powdered carbon and carbon dioxid (CO2) gas under sufficiently high temperature";
by "economically ... cleaving water", and, by reacting "carbon dioxid (CO2) gas" with "powdered" Coal.