PRODUCTION OF SYNTHESIS GAS RICH IN CARBON MONOXIDE
Since, as we recently reported in:
2011 Efficient Extraction of Flue Gas CO2 | Research & Development; concerning: "United States Patent 7,927, 572 - Purifying Carbon Dioxide and Producing Acid; 2011; Praxair Technology, Inc.; Abstract: Carbon dioxide is purified by processes employing NOx-rich sulfuric acid that can be formed by removal of SO2 from the carbon dioxide (and) wherein said gaseous feed stream of carbon dioxide is formed by combustion"; and:
The Reclamation and Reuse of Carbon Dioxide | Research & Development; concerning, in part: "United States Patent Application 20060051274 - Removal of Carbon Dioxide from Air; 2006; Abstract: The present invention is directed to methods for removing carbon dioxide from air (and, the) invention is particularly useful in processing hydroxide solvents containing CO2 captured from air";
the technologies exist which would enable us to reclaim and recover concentrated streams of Carbon Dioxide, either from the atmosphere itself or from the flue gases of, for instance, a Coal-fired power plant.
We've documented the rather astonishing potential utility of such reclaimed Carbon Dioxide, as, for just two out of now-many examples, in our reports of:
Chicago Recycles CO2 to Methanol | Research & Development; concerning: "United States Patent 4,609,441 - Electrochemical Reduction of Aqueous Carbon Dioxide to Methanol; 1986; Gas Research Institute, Chicago; Abstract: A method of producing methanol from carbon dioxide"; and:
Texaco Recycles CO2 to Methanol & Methane | Research & Development; concerning: "United States Patent 4,523,981 - Means and Method for Reducing Carbon Dioxide to Provide a Product; 1985; Texaco, Incorporated; Abstract: A process for reducing carbon dioxide to at least one useful product ... (including) formic acid (and/or) formaldehyde (and/or) methanol (and/or) methane".
Further, we've documented that Carbon Dioxide can serve as one of the agents of Coal gasification, which produces a synthesis gas, or "syngas", consisting primarily of Carbon Monoxide and Hydrogen, and compositionally well-suited for catalytic chemical condensation into liquid and gaseous fuels through a number of processes, such as those described 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;
which discloses the basic process of reacting Carbon Monoxide with Hydrogen to form liquid hydrocarbons; and, in:
Exxon Coal + CO2 + H2O Combo Gasification & Conversion | Research & Development; concerning: "United States Patent 4,318,712 - Catalytic Coal Gasification Process; 1982; Exxon Research and Engineering; A process for the catalytic steam gasification of coal (and) organic waste materials or similar carbonaceous solids in the presence of added sodium and potassium compounds (which) promote the reaction of steam, hydrogen, carbon dioxide, or a similar gasification agent with (carbon)";
which reveals that not only can Coal be gasified into a synthesis gas suitable for the Fischer-Tropsch process of ""United States Patent 1,746,464", but, that Carbon-recycling "organic waste" can be so gasified along with Coal and that Carbon Dioxide can serve as one of the agents for that gasification
Herein, we find additional confirmation of the Exxon carbon gasification technology disclosed in "United States Patent 4,318,712", as it applies especially to Carbon-recycling, and renewable, organic wastes; and, especially as it applies to the use of Carbon Dioxide as an agent for that gasification.
To emphasize that point, we submit one advance excerpt from the United States Patent we enclose via the initial link in this dispatch:
"(In) the present invention carbon dioxide is used as a reactant to convert oxygen-containing material to valuable synthesis gas."
Such "oxygen-containing material", they clearly specify, would include naturally CO2-recycling botanical wastes, as seen in our more complete excerpts from:
"United States Patent 3,850,588 - Production of Synthesis Gas Rich in Carbon Monoxide
Date: November, 1974
Inventor: Robert White, CA
Assignee: Chevron Research Company, San Francisco
A carbon-monoxide-rich synthesis gas is produced by feeding a mixture of carbon dioxide and an organic material to a reaction zone maintained at (specified temperatures). Suitable organic materials are compounds composed of carbon, hydrogen and oxygen in which the oxygen content is at least 10 weight percent. Alkali metal carbonates catalyze the reaction.
Background: The present invention relates to the production of synthesis gas. More particularly, it relates to the production of synthesis gas rich in carbon monoxide by the reaction of carbonaceous material with carbon dioxide.
The term "synthesis gas" is used herein to mean a gas comprising carbon monoxide and hydrogen. The synthesis gas produced in the process of the present invention is mainly carbon monoxide, that is, the gas produced usually contains more than 50 volume percent carbon monoxide on a dry gas basis.
Synthesis gas rich in carbon monoxide is especially useful in the synthesis of methanol.
It is also useful as a feed for a Fischer-Tropsch synthesis for the production of hydrocarbons.
Another use is the production of methane.
(We are compelled to interrupt here to remind you that, if, indeed, the Carbon Dioxide-based synthesis gas being described herein by Chevron were used for "the production of methane", then that CO2-based Methane could then be used in a process such as that described in:
Exxon 2010 CO2 + Methane = Liquid Hydrocarbons | Research & Development; concerning: "United States Patent 7,772,447 - Production of Liquid Hydrocarbons from Methane; 2010; ExxonMobil;
and be reacted with even more CO2; to form, through such reactions, "liquid hydrocarbons".)
According to the present invention, a process is provided for producing carbon-monoxide-rich synthesis gas which comprises contacting and organic material ... with added carbon dioxide at an elevated temperature in a reaction zone.
The present invention is based on my finding that carbon dioxide reacts with hydro-carbonaceous material containing at least 10 weight percent of combined oxygen at a surprisingly fast reaction rate to form carbon monoxide.
(In) the present invention carbon dioxide is used as a reactant to convert oxygen-containing material to valuable synthesis gas.
A principal reaction of the present invention can be schematically illustrated as follows:
CH2O + CO2 = 2CO + H2O (where CH2O is a carbohydrate).
A concurrent reaction of (the) evolved water with the feed is also experienced in my process.
The reaction of the organic feed as herein with CO2 proceeds at a sufficiently rapid rate to be attractive for the conversion of certain oxygen-containing carbonaceous material, particularly when large quantities of CO2 are easily available for use as a reactant.
(According to most news reports, we have so much CO2 that we're willing to pay to have it scooped up and shipped to Texas, to be stuffed down an old oil well for the putative purpose of "sequestration".)
It is particularly preferred to carry out the reaction of CO2 with the oxygen-containing organic material in the presence of an alkali metal catalyst, preferably a carbonate, such as potassium or sodium carbonate. I have found that (such) a catalyst greatly accelerates the reaction rate of the carbon dioxide ... ."
By organic feeds containing oxygen ... as used herein, is meant to include ... cellulose.
(Note: As can be learned in one of our previous reports, accessible via:
USDOE Algae Recycle CO2 into Liquid Fuels | Research & Development; concerning: "Liquid Fuels from Microalgae; 1987; Research Organization: National Renewable Energy Laboratory (NREL), Golden, CO; USDOE; Abstract: The goal of the DOE/SERI Aquatic Species Program is to develop the technology to produce gasoline and diesel fuels from microalgae. The algae can be grown ... using the resources of sunlight, saline water, nitrogen, phosphorus, and carbon dioxide. The algae can convert these raw materials into proteins, carbohydrates, and lipids (and) harvested cells then are subjected to an extraction process to remove the lipids. Although microalgae lipids represent the premium energy product, the energy trapped in the other biomass constituents can also be used; e.g., the cell residue after lipid extraction";
Algae can be grown using effluent Carbon Dioxide as a primary nutrient. They produce, in their biological recycling of that Carbon Dioxide, both "lipids", which can be extracted and used to produce "gasoline and diesel fuels, and, a "cell residue" remaining after the "lipids" are extracted for use in making liquid fuels. That "residue" could consist, primarily, of "cellulose".
Thus, a residue remaining after the biological recycling of Carbon Dioxide done to produce, through "lipids", "gasoline and diesel", can then be reacted, through our subject Chevron process of "United States Patent 3,850,588", with Carbon Dioxide, and be made to form a "synthesis gas" that is "especially useful in the synthesis of methanol (and) the production of hydrocarbons".)
I have found that particularly suitable and representative organic feed materials for the process of the present invention includes ... wood (and) solid waste material .. referred to as garbage.
The term "solid waste material" is used herein to include solid municipal waste or common garbage, sewage, industrial waste such as sawdust, and agricultural waste such as corn husks or other discarded cellulosic material.
I have found that using simulated solid municipal waste, goo conversion rates to synthesis gas can be obtained in the process of the present invention. Sanitary valuable products are also produced making possible the alleviation of an important disposal and pollution problem.
(We can employ, in other words, a Coal-use "waste", CO2, to alleviate a "pollution problem".)
Claims: (A) process for the production of a synthesis gas rich in carbon monoxide which comprises reacting in a reaction zone maintained at an elevated temperature a solid organic feed material with carbon dioxide."
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Again, that "synthesis gas", made from CO2-recycling organic waste materials, such as "sawdust, and agricultural waste", by reacting those renewable, but troublesome, resources with Carbon Dioxide, is specified herein by Chevron to be suitable for "the synthesis of methanol (and) the production of hydrocarbons.
We believe there to be other CO2-recycling potentials inherent in this process, as well, centering on the specified use of "metal carbonates" to catalyze the gasification reactions between Carbon Dioxide and the Carbon-recycling wastes.
Such "metal carbonates" might well be what we would obtain from a "scrubber" using alkali or alkaline metal hydroxides or oxides to strip Carbon Dioxide either from the atmosphere or from flue gases.
As also seen in:
The Reclamation and Reuse of Carbon Dioxide | Research & Development; which presents, among others:
"United States Patent Application 0070187247 - CO2 Recovery from Alkaline Solvents; 2007; The present invention relates to methods for recovering a hydroxide based sorbent from carbonate or another salt by electrochemical means (wherein the hydroxide has been used to remove) carbon dioxide from the air";
certain common metal hydroxides can be used to gather Carbon Dioxide from various gas mixtures and are converted thereby into "carbonates”.
If we don't want to regenerate the absorbent for immediate reuse, as in the above process, then we could send them instead to a process such as that of our subject Chevron process of "United States Patent 3,850,588 - Production of Synthesis Gas", where, in catalyzing reactions between Carbon Dioxide and Carbon-recycling biological materials, it might be contributing more CO2 to the reactions, and be being converted back into CO-absorbing compounds in any case.
The sum of it all, though, is:
Carbon Dioxide, as it arises in only a very small way, relative to natural sources of emission such as volcanoes, from our varied and productive uses of Coal, is a valuable raw material resource.
We can, as demonstrated by Chevron herein, use Carbon Dioxide to convert CO2-recycling biological wastes into a "synthesis gas" suitable for the "synthesis of methanol" and the "production of hydrocarbons".