United States Patent Application: 0030113244
We first refer you to our recent report of:
West Virginia Coal Association | Panasonic Sunshine Extracts Even More Hydrogen from H2O | Research & Development; concerning, primarily: "US Patent Application 20130075250 - Hydrogen Production Device";
wherein is disclosed additional technology developed by Japan's Panasonic Corporation to efficiently produce "hydrogen directly from water and sunlight"; and, which report referenced others we've made documenting Panasonic's initial and ongoing improvement of such technology for the generation of Hydrogen from nothing, in essence, but Water and freely-available Sunshine.
We also remind you that we have made a number of reports concerning the invention by France's Paul Sabatier, which invention was rewarded with the 1912 Nobel Prize for Chemistry, whereby Hydrogen, as could be made so efficiently by the Panasonic process of "US Patent Application 20130075250", can be catalytically reacted with Carbon Dioxide, with both the Hydrogen and the Carbon Dioxide being transformed through such reaction into Water and Methane.
It is discussed and summarized in:
Sabatier reaction - Wikipedia, the free encyclopedia; "The Sabatier reaction or Sabatier process involves the reaction of hydrogen with carbon dioxide at elevated temperatures (optimal 300-400 C) and pressures in the presence of a nickel catalyst to produce methane and water. Optionally ruthenium on alumina (aluminum oxide) makes a more efficient catalyst. It is described by the following reaction: CO2 + 4H2 = CH4 + 2H2O".
The Sabatier process was actually an evolution of the longer-known Reverse Water Gas Shift Reaction, as explained in:
Reverse Water-Gas Shift Reaction - Marspedia; "The Reverse Water-Gas Shift Reaction (RWGS reaction) was discovered in the 19th century as a method of producing water from carbon dioxide and hydrogen with carbon monoxide as a side product. In the context of human missions to Mars, it has been proposed as a complement to the Sabatier/water electrolysis (SE) process to produce methane and oxygen from hydrogen and carbon dioxide on the surface. ... (The) carbon monoxide can be used as a ... feedstock to generate higher hydrocarbons (Fischer-Tropsch reaction)".
And, since Carbon Monoxide has a great deal of industrial value and utility, even above and beyond the production of "higher hydrocarbons" via the "Fischer-Tropsch reaction", we herein submit disclosure of a much more advanced version of the nearly-ancient Reverse Water Gas Shift reaction; which might now have even greater relevance in view of technologies like that disclosed by Panasonic, in their above-cited "US Patent Application 20130075250 - Hydrogen Production Device", and others similar, wherein only Water and freely-available environmental energy are needed to generate Hydrogen.
Comment follows excerpts from the initial link in this dispatch to:
"United States Patent Application 20030113244 - Producing Carbon Monoxide by Reverse Conversion
Method for producing carbon monoxide by reverse conversion with an adapted catalyst - Dupont, Rene
Date: June, 2003
Inventors: Rene Dupont, et. al., France
Correspondence (and presumed eventual Assignee of Rights: Air Liquide; Houston, TX
(Home > American Air Liquide; and: Air Liquide - Wikipedia, the free encyclopedia; "L'Air Liquide S.A., or Air Liquide, is a French multinational company which supplies industrial gases and services to various industries including medical, chemical and electronic manufacturers. Founded in 1902, it is the world's largest supplier of industrial gases by revenues, and has operations in over 80 countries.")
Abstract: The invention concerns a method for producing carbon monoxide by reverse conversion, in gas phase, of carbonic acid gas and gaseous hydrogen while minimising the production of methane. The invention is characterised in that the reaction is carried out at a temperature between 300 and 520 C and under pressure between 10 to 40 bars in the presence of an iron-free catalyst based on zinc oxide and chromium oxide. Said method is preferably carried out continuously and comprises preferably the following steps which consist in:
a) preparing a gas mixture rich in CO2 and in hydrogen having a temperature between 300 and 520 C;
b) reacting said gas mixture, forming carbon monoxide and water vapour, by passing said mixture through a catalytic bed based on zinc oxide and chromium oxide maintained under pressure between 10 and 40 bars;
c) cooling the gas flux derived from the catalytic bed so as to cause condensation of all or part of the water vapour formed;
d) separating the condensed water from said gas fluid;
e) optionally, re-treating at least once the resulting gas stream. previously brought to a temperature between 300 and 520 C, by performing steps b) to d) above, so as to increase the proportion of carbon monoxide in the gas stream, each step b) being carried out in a different catalytic bed.
(As we explain in closing comments, the above stipulation that this is a process for producing Carbon Monoxide while "minimising the production of methane" is meaningful and significant. Catalyzed reactions between Carbon Monoxide and Hydrogen tend, "want" is an almost appropriate word, to result in the production of, primarily, Methane. And, if, as herein, Carbon Monoxide is the desired product, then such almost automatic synthesis of Methane has to be suppressed; a function which would reduce the amount of elemental, molecular Hydrogen needed to effect the chemical reduction of the feed Carbon Dioxide.)
Claims: A process for the production of carbon monoxide by reverse conversion, in the gas phase, of gaseous carbon dioxide and gaseous hydrogen, while minimizing the production of methane, characterized in that the reaction is carried out at a temperature of 300 to 520 C and at a pressure of 10 to 40 bar in the presence of a catalyst based on zinc oxide and chromium oxide and not containing iron.
(The temperatures and pressures would require the expenditure of some energy. The "300" degrees Centigrade, or Celsius, is three times the boiling point of water. But, the minimum pressure of "10 ... bar" is really only about 150 psi; and, anyone who's worked with compressed gases, such as oxy-acetylene torches or scuba diving gear, will know that's not really too high a pressure. It's readily do-able on an industrial scale; and, as we intend to document separately in future dispatches related to this and other Carbon conversion technologies, various forms of freely-available environmental energy, and waste heat from established industrial facilities, can be harnessed in order to help things along. And, as far as the pressure goes, how much would we have to compress Carbon Dioxide, in the first place, to pipe it all to Texas and pump it down a leaky old oil well, to help Big Oil out with secondary scrounging of dregs from natural petroleum reservoirs, if nonsense like the mandated Geologic Sequestration of CO2, all done at the expense of consumers of Coal-based electricity, somehow became law?)
The process ... characterized in that said catalyst includes no more than 2.5% by weight of nickel (and wherein) the weight ratio of zinc oxide to chromium oxide is ... preferably between 1.5 and 2.5.
The process ... characterized in that it is carried out continuously and in that it comprises the step consisting in making a gas mixture rich in hydrogen and CO2 pass at a temperature of 300 to 520 C through a catalyst bed furnished with said catalyst.
The process ... characterized in that the molar ratio of hydrogen to carbon dioxide in said gas mixture is between 0.5 and 15.
(We could, in sum, need a lot of Hydrogen. A "0.5" to "15" ratio, relative to the Carbon Dioxide, is a pretty broad spread. We suspect it was written that way to encompass all possibilities, and to thus exclude competing, similar and related, patent claims from others. If you study the Sabatier process, via the references included above, you'll see that not anywhere near "15" times the Hydrogen, relative to the CO2, is needed to effect the chemical reduction of Carbon Dioxide and synthesize Methane.)
The process as claimed in any one of the preceding claims, characterized in that it furthermore includes the step consisting in separating the steam contained in the gas mixture, produced during the reaction, by condensation (and) characterized in that the steam formed is separated from the mixture progressively as it is formed.
The process ... characterized in that it is carried out continuously and in that it comprises the steps consisting in:
a) preparing a gas mixture rich in hydrogen and in carbon dioxide, having a temperature of between 300 and 520 C.;
b) in making sail gas mixture react, with formation of carbon monoxide and steam, by passing said gas mixture through a catalyst bed furnished with a catalyst based on zinc oxide and chromium oxide and maintained at a pressure of 10 to 40 bar;
c) cooling the gas stream leaving said catalyst bed so as to condense the steam formed;
d) separating the condensed water from said gas stream; and:
e) if necessary, re-treating, at least once, the resulting gas stream ... by implementing the preceding steps b) to d), so as to increase the proportion of carbon monoxide in the gas stream (and further) characterized in that ... the gas stream is re-treated from one to four times.
The process ... characterized in that the catalyst bed is heated by an external heat source in such a way that the temperature of the outgoing gas stream is not less than the temperature of the incoming gas mixture (and) characterized in that, before the steam is separated, the outgoing gas stream reheated beforehand to a temperature between 300 and 500 C, is made to pass again through a second catalyst bed furnished with said catalyst.
A reactor for implementing the process as claimed ..., consisting of a closed vessel of vertical axis closed by an external shell and comprising:
(i) a cylindrical reaction chamber furnished with a catalyst based on zinc oxide and chromium oxide and not containing iron, placed within said reactor along its vertical axis and bounded over its entire lateral surface by a layer of thermally insulating steam-permeable material and at its two ends, top and bottom, by two grids, a free annular space being provided between the external shell and said layer of thermally insulating material;
(ii) a cooling means wound around the external shell of the reactor;
(iii) a heat exchanger placed along the vertical axis of the reactor within the reaction chamber and passing right through the reactor;
(iv) a gas feedstock pipe
(v) a pipe for discharging the outgoing gas stream; and:
(vi) a water discharge pipe.
(The full patent application document, which is not accessed via the initial link to the USPTO in this dispatch, contains the diagrams and schematics to which the claims make specific reference. Those schematics can be accessed via the second backup link enclosed above.)
The process ... characterized in that the gas mixture, the product of the reaction, which comprises carbon monoxide, carbon dioxide and hydrogen, is treated so as to isolate the carbon monoxide or a carbon monoxide/hydrogen mixture.
(And, again, if you wonder what can be done with a "carbon monoxide/hydrogen mixture", see:
West Virginia Coal Association | Japan Converts More Coal Syngas to Gasoline and Diesel | Research & Development; concerning: "United States Patent 6,410,477 - Hydrogenation catalyst of carbon monoxide; 2002; Assignee: Tohoku University, (Japan); Abstract: Provided is a hydrogenation catalyst of carbon monoxide, which is suited to the manufacture of a hydrogenation product containing target components (e.g., gasoline fuel oil components or diesel fuel oil components) at high selectivity from a gas mixture of hydrogen and carbon monoxide"; and:
West Virginia Coal Association | British Petroleum Coal Syngas to Motor Fuels | Research & Development; concerning: "United States Patent Application 20090298958 - Fischer Tropsch Process; 2009; Assignee: BP Exploration Operating Company Limited, (England); Abstract: The present invention relates to a process for converting synthesis gas to hydrocarbons, in particular to hydrocarbons in the C5-C60 range particularly suitable for use as liquid motor fuels".)
Description and Summary: The invention relates to a process for the production of carbon monoxide by reverse conversion, in the gas phase, of hydrogen and carbon dioxide.
The reaction of hydrogen with carbon dioxide results, under appropriate operating conditions, in a mixture of water and carbon monoxide. This reaction leads to an equilibrium between the various constituents and metal catalysts are generally used to approach this equilibrium in times compatible with an acceptable size of the reactors. To shift the equilibrium towards the formation of carbon monoxide, it is known to operate in the presence of metal catalysts."
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We'll close our excerpts there, since the bulk of the Disclosure is given over to description and illustration of operational examples.
Air Liquide's preferred examples demonstrate that, on a first, or single, pass through their catalytic reactor, roughly 40 percent of feed gas CO2 is converted into product. And, even though this is a process, as they state, "for producing carbon monoxide (and) minimising the production of methane"; at least one, preferred, example they illustrate shows that the product gas actually consists of 40 percent Methane and, roughly, only 20 percent Carbon Monoxide. The remaining 40 percent consists in large part of un-reacted CO2 and Hydrogen, which can be recycled or passed on to a second, downstream reactor for further processing.
And, Methane, being so valuable a product that we're willing to put our groundwater and our health at risk by drilling and fracking for it, might, in fact, through sale or use of that byproduct Methane, make the Carbon Monoxide produced herein, from Carbon Dioxide, essentially free.
That, especially, since, as seen for further confirmation of the fact in our report of:
West Virginia Coal Association | USDOE Hydrogen from Sunlight and Water | Research & Development; concerning: "United States Patent 4,476,105 - Process for Photosynthetically Splitting Water; 1984; Assignee: The United States of America; Abstract: The invention is an improved process for producing gaseous hydrogen and oxygen from water. The process is conducted in a photolytic reactor which contains a water-suspension of a photoactive material containing a hydrogen-liberating catalyst";
we can make the needed Hydrogen from nothing but freely-available Water and Sunlight.
And, that essentially-free Carbon Monoxide, which could be seen really as a byproduct, rather than the primary product, of our subject herein, "United States Patent Application 20030113244 - Producing Carbon Monoxide by Reverse Conversion", as made from Hydrogen and Carbon Dioxide, has a wealth of valuable industrial chemical manufacturing uses, in addition to that, for only one more example, seen in our report of:
West Virginia Coal Association | Exxon Carbon Monoxide + Water = Hydrocarbons | Research & Development; concerning: "United States Patent 4,269,784 - Process for Converting CO and H2O into Hydrocarbons; 1981; Assignee: Exxon Research and Engineering Company; Abstract: A homogeneous process for preparing hydrocarbons from CO and H2O ... employing a soluble ruthenium catalyst. The process comprises contacting CO and H2O ... 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 ... . (The) products are C9 to C60 hydrocarbons".
In even additional reports to follow, we will be further documenting the industrial value of Carbon Monoxide.
And, the process of our subject herein, "United States Patent Application 20030113244 - Producing Carbon Monoxide by Reverse Conversion", wherein both Carbon Monoxide and Methane are specified as being products, should be seen as even further confirmation of the now-plain fact, that, Carbon Dioxide, as arises in only a small way, relative to natural sources of emission, such as the Earth's inexorable, and all-natural, processes of planetary volcanism, from our economically essential use of Coal in the generation of abundant and truly affordable electric power, is a valuable raw material resource.
We can reclaim CO2 from whatever convenient source, and then, as herein, convert it into valuable raw materials, such as Carbon Monoxide, for the synthesis of hydrocarbons and, as we will see, other products of commercial value.