United States Patent: 4269784
We've documented numerous times that Carbon Dioxide can be converted into the more reactive and, thus, more desirable, Carbon Monoxide through the seemingly-obvious expedient of reacting CO2 with hot Coal; the reaction proceeding according to the formula: CO2 + C = 2CO.
Just to again document that fact, it is confirmed, for just one example, in our report of:
West Virginia Coal Association | Sweden CO2 + Coal = Carbon Monoxide | Research & Development; concerning: "United States Patent 2,607,667 - Reduction of CO2-Containing Gases; 1952; Assignee: Stora Kopparbergs Bergslags Aktiebolag, a corporation of Sweden; Abstract: The reduction of CO2-containing gases for metallurgical purposes has hitherto as a rule been carried out in such a way, that the starting gas is blown through an electrically-heated layer of charcoal.Because of charcoal being much more expensive than coke it has for a long time been desired to replace the charcoal by the less expensive coke in this reduction process. On account of the high temperature required when using coke for reduction purposes the difficulty arises that the ash constituents of the coke will sinter and that satisfactory arrangements for discharging sintered slag or ashes so far are not available.According to a preferred embodiment of the invention the desired volume and thereby the required time of contact between the gas and the pieces of coke is attained by providing a layer of coke of large extent in the direction of the flow of the gas and that the entire column of coke in the path of the gas flowing through the cupola is supplied with electric energy, so that the entire column will become heated to the desired reduction temperature. Claims: The method of reducing gases rich in carbon dioxide comprising the steps of forming a vertically extending and continuously sinking elongated column of substantially greater length than diameter of a carbonaceous reducing agent containing readily sintering ash constituents (i.e., hot Coal), supplying a reducing agent to the top of said column and discharging combustion residues from the bottom of said column, introducing the gas to be reduced (i.e., Carbon Dioxide) into said column from above the top thereof, drawing the reduced gas from the lower end of said column, and heating the column through substantially the entire length thereof to a temperature not exceeding the sintering temperature of the ash constituents of the said carbonaceous reducing agent (i.e., again, Coal, and/or Carbon-recycling Charcoal) by passing electrical current vertically through substantially the entire length of said column."
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There are a lot of variations that have been developed on that same theme, and the Swedes themselves had even designed another, earlier one, as can be learned via:
Method for reducing the carbonic acid in carbonic acid containing gases to carbon monoxide: "United States Patent 1,851,473 - Method For Reducing Carbonic Acid ... To Carbon Monoxide; March, 1932; Frans Martin Wiberg, Sweden";
the disclosure of which really just describes a prior version of the technology, similar to others developed in the United States, wherein the Coal, and/or renewable and CO2-recycling wood Charcoal, is kept hot by blowing it alternately with air or Oxygen, and then with CO2, with the resultant reaction: CO2 + C = 2CO, occurring. As we read the descriptions of such earlier processes, there is, of course, some CO2 produced when the Coal or Charcoal is "blown" with air to heat it up to the point where the CO2 reaction can occur; but, enough Carbon Dioxide is converted into Carbon Monoxide during the following "blow", as they typically phrase it, with Carbon Dioxide, that there is a net reduction of CO2, albeit with a certain amount of inefficiency.
There are other ways, too, to convert Carbon Dioxide into Carbon Monoxide, with an intriguing one seen in our report of:
Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development; concerning: "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company, Cleveland; Abstract: A process for the electrocatalytic reduction of carbon dioxide comprises immersing a transition metal complex with square planar geometry into an aqueous or nonaqueous solution which has been acidified to a (specified) hydrogen ion concentration ... , adding the carbon dioxide, applying an electrical potential of from about -0.8 volts to about -1.5 volts ... , and reducing the carbon dioxide to carbon monoxide."
And, make no mistake, the "transition metal complex" reduces the energy needed to electrolyze Carbon Dioxide, as dissolved in an acid solution, so much, to "-0.8 volts to about -1.5 volts", that you could probably generate enough photovoltaic power even on a cloudy day in Coal Country to get the job done.
And, we do have a little Carbon Dioxide in Coal Country to work with, as well, don't we? Or, have reports of it's abundance been exaggerated as much as those for that other, newly-famous, vapor, shale gas?
In any case, once we have Carbon Monoxide, preferably made from Carbon Dioxide, as we've documented, for just one example, in:
Standard Oil Carbon Monoxide + Water = Gasoline | Research & Development; concerning: "United States Patent 4,559,363 - Process for Reacting Carbon Monoxide and Water; 1985; Abstract: A process for reacting carbon monoxide and water in the presence of a cadmium-containing catalyst is disclosed. It is a general object of the present invention to provide a method for the direct production of gasoline";
we can react that Carbon Monoxide, CO, in the presence of certain catalysts, with pretty much nothing but Water, and thereby effect, to repeat for emphasis, the "direct production of gasoline".
We've made report of some other, similar, CO and H2O, reaction processes, with various alcohols being the end product. But, herein, just so it's clear, another Big Oil "standard" bearer confirms the fact that we can synthesize liquid hydrocarbons out of nothing but Carbon Monoxide, as we can make from Carbon Dioxide, and Water. As seen in excerpts, with a personal note to the Coal Country journalists among our audience appended, from the initial link in this dispatch to:
"United States Patent 4,269,784 - Process for Converting CO and H2O into Hydrocarbons
Date: May, 1981
Inventor: Gerald Doyle, NJ
Assignee: Exxon Research and Engineering Company, NJ
Abstract: A homogeneous process for preparing hydrocarbons from CO and H2O, D2O or T2O employing a soluble ruthenium catalyst. The process comprises contacting CO and H2O, D2O or T2O in the presence of a homogeneous aqueous solution containing a catalytically effective amount of a water-soluble ruthenium compound and heating the solution to temperatures of from 200 to 500C at pressures of from 0.1 to 100 MPa, the products are C9 to C60 hydrocarbons.
(We'll interrupt at some unfortunate length to explain a few things.
First, "D2O or T2O" refer to the isotopic forms of Water formed with the Deuterium and Tritium isotopes of Hydrogen. They will react chemically in precisely the same way as plain old H2O; and, since there is absolutely no nuclear chemistry or radioactive alchemy involved in any of this, their specification herein seems a needless, and needlessly distracting, waste of ink.
Second, the product "C9 to C60 hydrocarbons", as can be learned via:
Selective Fischer-Tropsch Catalyst for Producing C9-C16 Hydrocarbons; and:
FACT SHEET: Petroleum Fuels: Basic Composition and Properties;
comprise a broad range, from what are considered Diesel oils up to petroleum refining "resids". They can all, for the most part, be subjected to the standard petroleum refining process known as "hydrocracking" to produce, ultimately, distillate fuels such as Gasoline. The heavier, "C60", "resid"-type products could, we submit, also be forwarded to an associated process, such as that described in our report of:
West Virginia Coal Association | 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; Assignee: 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";
and be co-converted with Coal into both distillate fuels and a few other things. And, in fact, there are a number of technologies established for the co-processing of such heavy resids and Coal, which we will more fully document in future reports.
Further, the pressure range specified, "0.1 to 100 MPa", i.e., one-tenth to one hundred "mega-pascals", is quite broad. As can be learned via:
Pascal (unit) - Wikipedia the free encyclopedia; the "0.1 MPa" would be about atmospheric pressure, standardized at 14.5 pounds per square inch. The "100 MPa", thus, would be a very high pressure condition at about 14,500 PSI, and, likely impractical for any genuine industrial process. Why such a broad specification would be permitted by the USPTO is beyond us; and, it might mean that this process will work, no matter what the pressure is.
Finally, a "ruthenium catalyst" is specified, and, as can be learned via:
Ruthenium - Wikipedia, the free encyclopedia and USGS Minerals Information: Platinum-Group Metals;
Ruthenium is a Platinum Group metal that we don't produce any of in the United States. However, Canada and South Africa do have plenty, and we could likely get it without too much trouble, especially since it is already used as a catalyst in some petroleum refineries. It's expensive; but, it serves only as a catalyst and wouldn't get "used up" or consumed to an appreciable extent in the process.)
Claims: A process for preparing C9 to C60 aliphatic hydrocarbons ... which comprises:
- contacting Carbon Monoxide and water ... in the presence of a homogeneous aqueous solution containing a catalytically effective amount of water-soluble ruthenium compound selected from the group consisting of ruthenium halide, ruthenium acetyl acetonate and a complex salt of (ruthenium, as specified).
- heating the solution to temperatures of from 200 to 500C at pressures of from 0.1 to 100 MPa.
The process ... wherein the pressure is from 5 to 20 MPa.
(The above is a much more industrially-reasonable pressure range than indicated in the Abstract.)
The process ... wherein the temperature is from 200 to 350C.
A process for preparing C9 to C60 aliphatic hydrocarbons ... which comprises:
contacting CO and water ... in the presence of a homogeneous aqueous solution containing a catalytically effective amount of ruthenium trichloride; and
heating the solution to temperatures of from 200 to 500C at pressures of from 0.1 to 100 MPa.
Background and Field: This invention relates to the synthesis of hydrocarbons from carbon monoxide and water. More particularly, CO and H2O are contacted with a water-soluble ruthenium catalyst in an aqueous solvent.
Summary: It has been discovered that hydrocarbons can be prepared from CO and H2O by employing a homogeneous ruthenium-containing catalyst.
The homogeneous process of the invention provides good yields of hydrocarbon mixtures under relatively mild reaction conditions and exhibits higher activity than similar reactions utilizing heterogeneous metal catalysts (and) produces ... higher molecular weight hydrocarbons in a single step using inexpensive and easily-handled starting materials."
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We must note that there are formulas and equations related to the Disclosure, and likely attached to the document in the USPTO's hard copy files, that are not available in the electronic file we are compelled by circumstances to rely upon. Presumably, they would make clear the disposition of the Oxygen contained in the Carbon Monoxide and H2O, when the Carbon and the Hydrogen are chemically combined into the "higher molecular weight hydrocarbons". At this point, that is not clear to us.
But, again, we can make the Carbon Monoxide - - from which we can, according to the Disclosure of our subject herein, Exxon's "US Patent 4,269,784 - Process for Converting CO and H2O into Hydrocarbons", synthesize hydrocarbons suitable as petroleum refinery feedstock using little else but Water - - via a process like that disclosed, for yet another example, in our report of:
Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Assignee: Bayer Material Science; A generator including a ... desulfurising device ... for a continuous process in which carbon-containing raw materials are reacted with oxygen and carbon dioxide (and) to provide a continuous process for the production of CO gas by the gasification of coal";
by reacting Carbon Dioxide, harvested from whatever convenient source, with some of our abundant Coal.
