Our most recent dispatch, which yet again confirmed the plain truth that Carbon Dioxide, as is co-produced in a small way, in terms of energy units actually produced and distributed versus Carbon Dioxide units emitted - - relative to the CO2 emitted by alternative energy processes such as the combination of mechanized farming, biological fermenting and heat-based distilling activities, all of which, through the combustion of fuel for energy or the biochemical breakdown of carbohydrates and sugars, emit Carbon Dioxide, and which are all demanded by and all go into the production of "clean, green" Corn Ethanol - - by our essential use of Coal in the generation of abundant and truly affordable electric power, is a valuable raw material resource, which can, using only Sunlight to power the process, be converted into hydrocarbons, specifically substitute natural gas Methane, is now accessible via:
West Virginia Coal Association | New York City CO2 to Methane via Artificial Photosynthesis | Research & Development; and concerns:
"US Patent Application 20120208903 - Conversion of Carbon Dioxide to Methane Using Visible Light; Date: August, 2012; Inventor: Harry D. Gafney, NY; Assignee: Research Foundation of City University of New York, NYC; Abstract: The invention relates to a method for converting carbon dioxide to methane".
We do admit that we tend to run on a bit in our compositions, as you will presently see; and, the length of that dispatch was such that a reference we included in our closing remarks, to one of our prior reports, had to be excised, apparently, when the report was posted on the West Virginia Coal Association's web site, so that the report, again we presume, would fit in the available space.
That reference was a link to:
West Virginia Coal Association | More Standard Oil 1944 CO2 + CH4 = Hydrocarbons | Research & Development; concerning: "United States Patent 2.347.682 - Hydrocarbon Synthesis; 1944; Assignee: Standard Oil Company of Indiana; Abstract: This invention relates to an improved method and means for effecting the synthesis of hydrocarbons from carbon monoxide and hydrogen. In practicing my invention I ... prefer to employ... methane (which is) mixed with such proportion of carbon dioxide and steam as to give a gas mixture having an atomic hydrogen:carbon:oxygen ratio of about 4:1:1. (The specified) reforming operation converts the methane-carbon dioxide-steam mixture into a gas consisting chiefly of hydrogen and carbon monoxide ... hereinafter referred to as ... 'synthesis' gas. The reaction products (of the synthesis gas) may be fractionated in any conventional manner ... and may be converted ... into high quality motor fuels";
and, we included it to again demonstrate, that, once we have Methane, as synthesized, perhaps via the process disclosed in that most recent report concerning: "US Patent Application 20120208903 - Conversion of Carbon Dioxide to Methane Using Visible Light", we can react that CO2-derived Methane with even more Carbon Dioxide, and thereby form a "synthesis" "gas consisting chiefly of hydrogen and carbon monoxide"; which gas mixture "may be converted" through known catalytic methods, such as, we submit, the Fischer-Tropsch synthesis, "into high quality motor fuels".
The fact that Methane, as perhaps synthesized from Carbon Dioxide, can be so reacted with even more Carbon Dioxide, with the two being thereby converted into a synthesis gas blend of Carbon Monoxide and Hydrogen suitable for fairly standard catalytic chemical condensation into hydrocarbons, is one we've pretty much beaten to death for you over the past several years.
But, since it was excised from that immediately prior report, again primarily documenting the fact that the Methane can be made, in the first place, from Carbon Dioxide; and, since we've just learned that China has come up with some pretty slick ways of reacting such CO2-derived Methane with even more Carbon Dioxide, which CO2-Methane reforming technologies we will be addressing in future reports, we thought to document for you herein that they also know how to do all of that, have known how to do it for more than a decade, pretty much throughout the entire European Union:
or, at least three nations of it.
Comment follows excerpts from the initial link in this dispatch to:
"United States Patent 5,989,457 - Process for the Production of Synthesis Gas
Date: November, 1999
Inventor: K.I. Seshan, et. al., The Netherlands and Ireland
Assignee: Mannesmann Aktiengessellschaft & K.T.I. Group, Germany
(Note that Mannesmann, once a huge corporation described as a "coal and steel conglomerate", branched out into other arenas of enterprise, and, in the past decade, has been broken up through mergers and acquisitions. More can be learned via:
Welcome to Mannesmann; History of Mannesmann Salzgitter AG; and: Mannesmann - Wikipedia, the free encyclopedia.)
Abstract: A catalyst for the production of synthesis gas (CO and H2) by reaction of CO2 and CH4 and/or other light hydrocarbons, having a support material with at least 80 wt. % ZrO2 of oxides selected from the group of Y, La, Al,
Ca, Ce and Si, as well as of a coating with metals of Group VIII which is applied physically by adsorption.
(None of the above need be seen as too exotic. The "Y", Yttrium, might be a little scarce; the "La", Lanthanum, perhaps not so much so. Certainly, we should be able to scrape together some "Al", Aluminum, and some "Si", Silicon. The "Ce", Cerium, might be a little problematic; but, the complete list of metals is one presenting options. For instance, "Group VIII", according to European convention - - there have been changes and what appear as resulting geographic inconsistencies in the presentation and interpretation of the Periodic Chart of Elements - - would include three "triads" of elements: Iron, Cobalt and Nickel; Ruthenium, Rhodium and Palladium; and, Osmium, Iridium and Platinum. Any of them, apparently, will work, although there might be variances in efficiency that need worked out and quantified. The "ZrO2" is just what is commonly known as "zirconia", which you've probably heard of, and, it serves as a heat and chemical resistant support structure for the catalysts. There is plenty that around, as well. Further, it's important to note that any and all of that stuff is capital investment; none of it is used up or consumed to any appreciable extent in the process.)
Claims: A process for making CO/H2 -synthesis gas comprising:
contacting a gas containing one of CO2, CH4, hydrocarbons or mixtures thereof with a catalyst at temperatures of between about 400 and about 900 C, and a pressure of between about 1 and about 30 bar, wherein said catalyst comprises:
(a) an oxidic support material and
(b) a coating comprising between about 0.1 and about 7.0 weight percent of at least one of the metals of the group consisting of Platinum, Nickel, Palladium and Cobalt; said support material comprising:
(i) at least 80 weight.percent of ZrO2 (Zirconium Oxide; Zirconia) which has been calcined at a temperature up to about 670 C before the application of said coating;
(ii) 0.5-10 mol % of at least one oxide selected from the group consisting of Y, La, Al, Ca, Ce and Si, wherein said oxide is mixed with said support material so as to thermally stabilize the support material; said coating having been initially formed as a compound in a solvent, and physically impregnated into said support to result in adsorption of said coating substance as a compound, whereupon said solvent was evaporated and the resulting material calcined at a temperature of no greater than 650 C.
The process ... wherein the gas is contacted with the catalyst at temperatures of between about 700 and 800 C (and) wherein the pressure is between about 10 and 20 bar.
The process ... wherein the gas contains CO2 and CH4 (Methane) (and) wherein the molar weight ratio of CO2 to CH4 is between about 0.5 and 4.
(i) at least 80 weight.percent of ZrO2 (Zirconium Oxide; Zirconia) which has been calcined at a temperature up to about 670 C before the application of said coating;
(ii) 0.5-10 mol % of at least one oxide selected from the group consisting of Y, La, Al, Ca, Ce and Si, wherein said oxide is mixed with said support material so as to thermally stabilize the support material; said coating having been initially formed as a compound in a solvent, and physically impregnated into said support to result in adsorption of said coating substance as a compound, whereupon said solvent was evaporated and the resulting material calcined at a temperature of no greater than 650 C.
The process ... wherein the gas is contacted with the catalyst at temperatures of between about 700 and 800 C (and) wherein the pressure is between about 10 and 20 bar.
The process ... wherein the gas contains CO2 and CH4 (Methane) (and) wherein the molar weight ratio of CO2 to CH4 is between about 0.5 and 4.
(In other words, in one way of looking at it, the process could consume four times as much CO2 as it does Methane. As we read it, some of that depends upon the product syngas mix desired, that is, the ratios of Carbon Monoxide to Hydrogen; and, there are tradeoffs in processing efficiency. Again, there is much that would be explained by full documentation associated with the patent; and, much we here are simply unqualified and inadequate to attempt analyzing or explaining for you.)
Background and Field: The present invention relates to a catalyst for the production of synthesis gas in the form of CO and H2 from CO2 and CH4 ... .
Synthesis gas (CO+H2) is used in a number of chemical processes (such as) for the synthesis of methanol, which in its turn can be further converted into other petrochemical products (and) for the Fischer-Tropsch synthesis, which requires an H2 /CO ratio of about 1.7-2.5.
Synthesis gas (CO+H2) is used in a number of chemical processes (such as) for the synthesis of methanol, which in its turn can be further converted into other petrochemical products (and) for the Fischer-Tropsch synthesis, which requires an H2 /CO ratio of about 1.7-2.5.
(Almost gratuitously by now, we must note, that, as in the product "methanol, which in its turn can be further converted into other petrochemical products", one of the "other petrochemical products" into which Methanol can "be further converted" is, as seen in:
West Virginia Coal Association | Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984;
Assignee: Mobil Oil Corporation; Abstract: A process for producing a wide slate of fuel products from coal is provided by integrating a methanol-to-gasoline conversion process with coal liquefaction and coal gasification. The coal liquefaction comprises contacting the coal with a solvent under supercritical conditions whereby a dense-gas phase solvent extracts from the coal a hydrogen-rich extract which can be upgraded to produce a distillate stream. The remaining coal is gasified under oxidation conditions to produce a synthesis gas which is converted to methanol. The methanol is converted to gasoline by contact with a zeolite catalyst. Solvent for coal extraction is process derived from the upgraded distillate fraction or gasoline fraction of the methanol-to-gasoline conversion";
Gasoline. However, various hydrocarbon fuels, including diesel and gasoline blending stock, can be and are produced more or less directly by the "Fischer-Tropsch synthesis".)
The production of oxoalcohols is another important field of use of synthesis gas. In (the specified) production process an H2/CO ratio of about 1 is required. One possibility for producing such a synthesis gas is afforded by the gasification of coal.
The production of oxoalcohols is another important field of use of synthesis gas. In (the specified) production process an H2/CO ratio of about 1 is required. One possibility for producing such a synthesis gas is afforded by the gasification of coal.
Another possibility of producing such a synthesis gas having an H2 /CO ratio of 1 is the reaction of CO2 with CH2.
(The above "CH2" is meant, we were told by someone knowledgeable who believes the explanation correct, to indicate "methylene", a "hydrocarbon radical" split off from Methane which is "extremely reactive and occurs only as an intermediate byproduct in chemical reactions". For more, see:
It is known to effect this reaction at, for instance, 500 C under increased pressure in the presence of a catalyst. ... As suitable catalysts the metals Ni, Pt, Rh and Pd are mentioned, these elements being applied in each case to a support material which consists of AlO3 or SiO2. The effectiveness in principle of such catalysts can easily be shown in a laboratory test. However, they are unsuitable for commercial use. This is due to the fact that undesired side reactions are also promoted by the action of the catalyst ... .
These side reactions are undesired, since they lead to the formation of free carbon which deposits on the catalyst (coking) and reduces the activity thereof more and more (deactivation). The coking can, to be sure, be reduced by a drastic increase in the amount of CO2 beyond the amount stoichiometrically necessary for the amount of CH4 used, but this, of course, results in the need to separate large amounts of excess CO2 from the synthesis gas produced and return it to the process. The economy of such a process is placed in question by the additional expense necessary for this.
These side reactions are undesired, since they lead to the formation of free carbon which deposits on the catalyst (coking) and reduces the activity thereof more and more (deactivation). The coking can, to be sure, be reduced by a drastic increase in the amount of CO2 beyond the amount stoichiometrically necessary for the amount of CH4 used, but this, of course, results in the need to separate large amounts of excess CO2 from the synthesis gas produced and return it to the process. The economy of such a process is placed in question by the additional expense necessary for this.
(Actually, there are other options since catalysts exist which would promote what we can refer to as the Sabatier reaction between Hydrogen and Carbon Dioxide, to form both H2O and more Methane, CH4. That, however, would require supply of additional, economical Hydrogen from an external source; again something that is, as we have documented many times, perfectly feasible. Such options, though feasible, are beyond the necessarily focused scope of this Disclosure.)
In order to reduce the tendency towards coking, it is known to permit the reaction between CO2 and CH4 to take place in the presence of steam.
In order to reduce the tendency towards coking, it is known to permit the reaction between CO2 and CH4 to take place in the presence of steam.
(The above refers to the process of "tri-reforming", such as that seen, for only one example, in our report of:
West Virginia Coal Association | Exxon 2010 CO2 + Methane = Liquid Hydrocarbons | Research & Development; concerning: "United States Patent 7,772,447 - Production of Liquid Hydrocarbons from Methane; 2010; Assignee: ExxonMobil; A process for converting methane to higher hydrocarbons, the process comprising: (a) contacting a feed containing methane and ... H2O (and) CO2 with a (specified) catalyst under conditions effective to convert said methane to aromatic hydrocarbons ...";
wherein a catalyst is integrated into the process to directly convert the product syngas of the reaction between "methane and ... H2O (and) CO2" into "aromatic hydrocarbons".)
Summary: The object of the invention is to find a catalyst which is not only sufficiently active to obtain a high yield of CO and H2 but which, in particular, avoids impermissibly strong coking for sufficiently long periods of time and thus remains sufficiently active for a long period of time, even if the amounts of CO2 and CH4 used are relatively close to the stoichiometric values and the CO2 /CH4 ratio (molecular weights) is therefore equal to about 1. It should be possible to dispense, as far as possible, with the use of steam during the reaction.
(In) experiments, the excellent suitability in particular of Ni and Pt catalysts on the base of thermally stabilized ZrO2 matrix material could be noted. These catalysts not only gave satisfactory activity values but at the same time they were characterized also by long-term resistance to deactivation by coking, without the use of steam being necessary.
(In) experiments, the excellent suitability in particular of Ni and Pt catalysts on the base of thermally stabilized ZrO2 matrix material could be noted. These catalysts not only gave satisfactory activity values but at the same time they were characterized also by long-term resistance to deactivation by coking, without the use of steam being necessary.
The invention has shown that, in particular, Pt and Ni catalysts on a thermally stabilized support material consisting predominantly of ZrO2 ... not only give good activity values but, at the same time, also show excellent resistance to deactivation by coking.
The production of CO/H2 -synthesis gas with the use of a catalyst in accordance with the invention is effected at temperatures of between ... preferably between about 700 and 800 C The pressure upon the reaction ... is preferably between about 10 and 20 bar. The amounts of CO2 and CH4 used should be so adapted to each other that the molar weight ratio of CO2 to CH4 is generally between about 0.5 and 4, more specifically between 0.5 and 1.5, and particularly preferred the value 1.
The use of steam for reducing the tendency to coking is not necessary."
------------------------
Our concluding excerpted statement seems indicative of one, perhaps important, economy; and, perhaps represents the main thrust of this invention. But, there remain what, for us, seem to be rather immense complexities in the full details provided concerning the allowable, or prefered, variances in the ratio of Carbon Dioxide relative to Methane in the feed gas mixture, and the resulting Carbon Monoxide to Hydrogen ratios in the product synthesis gas, which would influence the choice of directing the syngas to the specified "synthesis of methanol" or, as alternatively specified, "the Fischer-Tropsch synthesis", which would result in the more direct production of hydrocarbons.
In the best case illustrated, 55% of the initial Carbon Dioxide is converted 100% to Carbon Monoxide, without formation of other Carbon-containing products or of elemental Carbon deposited, via "coking", on the catalyst surfaces.
First instinct would be that the un-reacted CO2 could be recycled into the system for reaction with more Methane; but, we submit that un-reacted CO2 might better serve to go into, be added to, a basic stream of raw material Carbon Dioxide collected from other sources being directed into, alternatively, a separate process like that described in our report of:
West Virginia Coal Association | Chicago Bugs Convert CO2 into Methane | Research & Development; "United States Patent Application 20090130734 - The Production of Methane from CO2; 2009; Inventor: Lauren Mets; (Presumed Assignee: The University of Chicago); Abstract: A method of converting CO2 gas produced during industrial processes comprising contacting methanogenic archaea with the CO2 gas under suitable conditions to produce methane"; or of:
West Virginia Coal Association | Pittsburgh USDOE Converts CO2 to Methane & Methanol | Research & Development; concerning: "Visible Light Photoreduction of CO2; 2009; National Energy Technology Laboratory, USDOE, Pittsburgh, PA; Abstract: A series of ... Titanium Dioxide (catalysts) have been synthesized, characterized, and tested for the photocatalytic reduction of CO2 in the presence of H2O.Our results show that these ... materials are capable of catalyzing the photoreduction of CO2 using visible light illumination ... . The ... analysis shows that the primary reaction product is CH4";
and be simply converted into more Methane, "CH4", for direction back into the process of our subject, "United States Patent 5,989,457 - Process for the Production of Synthesis Gas", for reaction with even more Carbon Dioxide, as recovered from whatever convenient source; and, the subsequent production of more hydrocarbon synthesis gas.
In closing, there is one final thing that needs pointed out:
Although the product Carbon Monoxide and Hydrogen "syngas" seems specified to be used in the production of fuels via the Methanol or, especially, the Fischer-Tropsch syntheses; the combustion of which fuels would simply return any Carbon Dioxide consumed directly and, via the initial synthesis of Methane, as via the process, for one example, of the above-cited "United States Patent Application 20090130734 - The Production of Methane from CO2", indirectly, in the process of our subject, "Process for the Production of Synthesis Gas"; to the atmosphere, there are alternatives.
As we have documented in prior reports and as we will document further in reports to follow, any Methanol synthesized directly and or indirectly via the process of our subject from Carbon Dioxide can be used in the synthesis of certain types of plastic, wherein any CO2 consumed as an initial raw material would be forever "sequestered". And, as can be seen in:
http://www.plastics.ca/_files/
"'Synthesis Gas Utilization; The Fischer-Tropsch Process'; Julius Pretorius, PhD; Environment and Carbon Management; Edmonton Waste Management Centre. Alberta Plastics Recycling Association, The Canadian Plastics Industry Association, and the American Chemistry Council in conjunction with the annual conference of the Recycling Council of Alberta";
with special attention paid to: "Slide 4: Syngas as building block";
it is also perfectly feasible to, via "The Fischer-Tropsch Process", directly synthesize, from Carbon Monoxide and Hydrogen, as could be made from Carbon Dioxide and Methane, almost any conceivable hydrocarbon raw material needed for the subsequent synthesis of most types of commercial plastics, wherein, again, the CO2 consumed directly and indirectly in the production of the synthesis gas would be permanently, and productively, "sequestered".