United States Patent Application: 0130150466
We've made a number of reports now on the Carbon Dioxide recycling and utilization technologies developed and being developed by and for the Saudi Arabian company, Saudi Basics Industries Corporation, who, though headquartered in Riyadh, Saudi Arabia, one if the hearts of OPEC, have established a significant outpost in Texas, where some of their CO2-recycling scientists have set up shop.
Our reports on their work so far, clearly demonstrating that Carbon Dioxide is a valuable raw material resource from which we can efficiently synthesize anything we now import from OPEC, have included:
West Virginia Coal Association | Saudi Arabia and Texas CO2 to Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture; 2012; Inventors: Agaddin Mamedov, Texas, and Abdulaziz Al-Jodai, Riyadh, Saudi Arabia; Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, wherein the catalyst substantially consists of chromia/alumina. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be combined with other processes, for example up-stream with other synthesis processes for making products like aliphatic oxygenates, olefins or aromatics. Claims: A process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, consisting essentially of chromium as active substituent, optionally at least one alkali metal or alkaline earth metal as promoter, and alumina as support"; and:
West Virginia Coal Association | Saudi Arabia Converts Even More CO2 into Hydrocarbon Syngas | Research & Development; concerning, in part: "United States Patent Application: 0100190874 - Catalytic Hydrogenation of CO2 into Syngas Mixture; 2010; Inventors: Agaddin Mamedov, et. al.; Texas and Riyadh, Saudi Arabia; Correspondence (and presumed eventual Assignee): SABIC (Saudi Basic Industries Corporation) Americas; Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, which catalyst substantially consists of Mn oxide and an oxide of at least one member selected from the group consisting of Crl Ni, La, Ce, W, and Pt. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be integrated with other processes, both up-stream and/or down-stream; like methane reforming or other synthesis processes for making products like alkanes, aldehydes, or alcohols".
Those are only a few examples, and, you will note that they, and others related to them, all center on the identification and refinement of catalysts that efficiently promote the long-known "reverse water gas shift reaction", or RWGS, wherein Hydrogen reacts with Carbon Dioxide, with the reaction products being Carbon Monoxide and Water; and, which reaction has been recognized and further developed by others, as well, as seen for one example in our report of:
West Virginia Coal Association | France Efficient CO2 to Carbon Monoxide Conversion | Research & Development; concerning: "United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst; 2003; Assignee: Air Liquide (France); 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 carbon dioxide and in hydrogen ... (and) 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".
Again, keep in mind, that, once we have Carbon Monoxide, whether made from Carbon Dioxide or not, we can do a lot of things with it.
For instance, as seen for one example 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";
catalytic technologies exist which promote the reaction of Carbon Monoxide directly with Water, to form various hydrocarbons. However, Carbon Monoxide is most commonly reacted with more Hydrogen, in one variation or another of the long-known Fischer-Tropsch process, which we've made report of and referenced many times, and as is well-described and summarized in:
Fischer–Tropsch process - Wikipedia, the free encyclopedia; "The Fischer–Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. It was first developed by Franz Fischer and Hans Tropsch ... in Germany in 1925. The process ... produces a synthetic lubrication oil and synthetic fuel, typically from coal".
In any case, the accomplished Saudi Arabian scientist, Agaddin Mamedov, lead named inventor of "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture" continues to develop Carbon Dioxide utilization and hydrocarbon synthesis technologies for the Saudi Basic Industries Corporation, of Riyadh, while residing in Texas. There are so many of them now, in fact, that we will simply be unable to make coherent, much less knowledgeable and informed, report on all of them.
It might behoove the members of the Coal Country press who are the primary addressees of these reports, however, to pay some heed and take advantage of the fact that the accomplished Agaddin Mamedov, who appears to be spearheading the Saudi development of CO2 utilization technologies, is currently resident in Texas, and might be available for interview, and the concise revelation of information that could - -
(since, as seen for yet another example in:
With U.S. shale gas fields declining, Chesapeake’s McClendon heads out the door - Philadelphia Energy | Examiner.com; "'With U.S. shale gas fields declining, Chesapeake’s McClendon heads out the door'; March 19, 2013; R. Magyar; 30% shale gas production decline in the Texas Barnett formation since 2011 & 2012; 10 days from now Aubrey McClendon, the CEO of Chesapeake Energy, will leave the natural gas company he founded more than 30 years ago. Credited as the man who set off the U.S. shale gas frenzy, he departs in the face of growing evidence of peak production in key shale gas fields along with grim statistics of the massive amounts of capital needed to keep current production in place. ... A new report released by the University of Texas at Austin’s Bureau of Economic Geology (BEG) titled, the “Barnett Shale Assessment Study” analyzed shale gas production reports from the Texas Barnett shale formation through calendar year 2010. While significant amounts of shale gas have been produced and can be produced from the formation, the UT study shows the Barnett began peaking in late 2011 and into 2012 despite the fact the field only began producing large amounts of shale gas in 2007. The report goes on to state output from Barnett formation will decline by more than half over the next 15 years. It also confirmed what geologists such as Arthur Berman had observed back in 2009 when he pointed out that shale gas formations are not uniform as claimed by the industry but rather consist of a handful of production sweet spots in a given shale play. Outside of these sweet spots, the UT report’s economic analysis, as also noted earlier by Berman, confirmed the spending of billions in shareholder capital on marginal non- profitable shale gas wells. Regarding a new report just released by the federal Energy Information Agency (EIA), Allen Brooks, Managing Director of the investment banking firm Parks Paton Hoepfl & Brown, noted the EIA survey shows “Declines in natural gas production from the Lower 48 states for the month of December 2012, the first declines in output since March of that year.” While Brooks pointed out declines in drilling rig activity along with severe winter weather impacting drilling in the western states played a role, he stated, “Additionally, many producers ran out of budget money before the end of the year and were forced to slow activity”. In an eerie echo of the University of Texas (study) Brooks writes, “If nothing else, however, the slowdown in gas output reinforces the phenomenon the industry may soon be confronting, which is the need to ramp up drilling activity to offset the steep decline in existing well production due to the nature of shale gas wells.”With most U.S. shale gas plays now having from 3 to 6 years of actual production records, hard data is finally allowing a realistic comparison between the production data to the shale gas industry hype and media public relations euphoria so much a hallmark of today’s shale gas drilling frenzy"the current object of their editorial ardor might well, rather sooner than later, be withering into a grotesque and empty husk of the swollen, over-hyped dream of energy abundance that has unwarrantedly grown out of what is becoming more and more to seem as a PR scam foisted on the American public for narrow private and corporate short term profit purposes)
- - provide us with an alternative, and domestic, source of needed hydrocarbons; one which would, while using and consuming a supposedly harmful pollutant, make obviously specious all of the CO2-based attacks leveled at our essential use of our genuinely abundant Coal in the generation of truly affordable, truly economical electric power, while at the same time begin to free us from our horrendously unhealthy relationship of co-dependency with OPEC.
We present yet another example of Saudi Arabia's Carbon Dioxide recycling and utilization technologies herein; a variant, it seems to us, of the others cited above, one which specifies somewhat different arrays of catalysts and processing conditions that are effective for promoting the reverse water gas shift reaction between Carbon Dioxide and Hydrogen, as perhaps described better in our above-cited report concerning "United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst", and, of combining the Carbon Monoxide thereby produced from Carbon Dioxide with even more Hydrogen, to form a hydrocarbon synthesis gas suitable for use in the catalytic synthesis of a full array of liquid and gaseous hydrocarbons.
As seen in excerpts from the initial link in this dispatch to the recently-published:
"United States Patent Application 20130150466 - Mixed Oxide Based Catalyst for the Conversion of Carbon Dioxide to Syngas and Method of Preparation and Use
Date: June 13, 2013
Inventors: Aghaddin Mamedov, et. al., Texas
Assignee: Saudi Basic Industries Corporation, Riyadh, Saudi Arabia
Abstract: The invention relates to a catalyst and process for making syngas mixtures including hydrogen, carbon monoxide and carbon dioxide. The process comprises contacting a gaseous feed mixture containing carbon dioxide and hydrogen with the catalyst, where the catalyst comprises Manganese oxide and an auxiliary metal oxide selected from the group consisting of Lanthanum, Calcium, Potassium, Tungsten, Copper, Aluminum and mixtures or combinations thereof.
The process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions.
The process can be ... integrated with ... synthesis processes for making products like alkanes, aldehydes, or alcohols.
Claims: A catalyst composition for making a syngas mixture under isothermal conditions comprising a supported manganese oxide catalyst including one more auxiliary metals selected from the group consisting of La, Ca, K, W, Cu, and Al.
(The above term "isothermal" means, that, with proper design and integration of heat exchangers in the system, we wouldn't really have to add, or to remove, heat energy from the process. It could, in other words, be self-sustaining and, thus, very efficient. The heat generated by exothermic reactions can be used to drive needed endothermic reactions.)
The composition ... wherein the support is selected from the group consisting of Aluminum Oxide, Magnesium Oxide, Silicon Oxide, Titanium Oxide and Zirconium Oxide.
The composition ... wherein the auxiliary metal comprises Copper and the support comprises alumina.
(There is nothing, absolutely nothing, required in any of this that is exotic, rare or hugely expensive.)
A process of making a syngas mixture including hydrogen, carbon monoxide and carbon dioxide under isothermal conditions, comprising a step of contacting a gaseous feed mixture including carbon dioxide and hydrogen in the presence of a catalyst, where the catalyst comprises a supported manganese oxide catalyst including one more auxiliary metals selected from the group consisting of La, Ca, K, W, Cu, and Al.
(Hydrogen is required, of course. And, as we have documented for you many times, as for just one example seen in our dispatch of:
West Virginia Coal Association | USDOE Renewable Hydrogen for Coal Liquefaction | Research & Development; concerning the USDOE report: "'Renewable Hydrogen Production for Fossil Fuel Processing'; OSTI ID: 10180379; DOE Contract Number: AC05-84OR21400; 1994; Research Organization: Oak Ridge National Lab., TN; Sponsor: USDOE; Abstract: The objective of this mission-oriented research program is the production of renewable hydrogen for fossil fuel processing. This program will build upon promising results that have been obtained in the Chemical Technology Division of Oak Ridge National Laboratory on the utilization of intact microalgae for photosynthetic water splitting. In this process, specially adapted algae are used to perform the light-activated cleavage of water into its elemental constituents, molecular hydrogen and oxygen"; and, which dispatch, perhaps of interest, also contains linkage to the separate report:"Analysis: US Shale Gas Industry Reserves Are Overstated At Least 100 Percent";we have a number of energy-efficient means available to us for harnessing environmental energy, perhaps, as above, with the assistance of biological intermediaries, to generate the needed Hydrogen from plain old Water, H2O.)
The process (which) is carried out at a temperature between 300 and 600 C, at a pressure between 0.1 MPa and 6 MPa, and with a contact time between 0.5 s and 6 s.
(The needed temperature is high, at least three times the boiling point of water, but, not that high. The pressures, though, aren't demanding; and, the reaction is very fast, with attendant implications for throughput and productivity. Further, we remind you, that, as explained via:
West Virginia Coal Association | NASA Improves CO2 to Methane Conversion | Research & Development; concerning: "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2012; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen in a first reaction zone with a first catalyst bed at a temperature greater than a first designated temperature; feeding the effluent from the first reaction zone into a second reaction zone, and contacting the effluent with a second catalyst bed at a temperature equal to or less than a second designated temperature, so as to produce a product stream comprising water and methane";and, as indicated generally herein by these Saudi scientists, some catalyzed reactions between Carbon Dioxide and Hydrogen are exothermic; and, can provide the necessary heat energy for powering other segments of the overall reaction process. The exothermic heat might well be enough to maintain the above specified temperatures without the need to provide energy from outside the process. And, again, the specified pressures are not very high.)
The process ... wherein the feed mixture contains hydrogen and carbon dioxide in a ratio of from 1 to 5.
The process ... wherein the syngas has a stoichiometric number of from 0.1 to 3.0.
(Again as explained in the full Disclosure, the mix of reactants can be adjusted so as to produce a "syngas" composed of variable ratios of Hydrogen and Carbon Monoxide, and, thus, be made suitable for a variety of subsequent catalytic reactions to synthesize a range of hydrocarbon products.)
The process ... wherein the feed mixture further comprises ... methane.
(If desired, but as we take it not necessary, Methane can be added to the mix of Hydrogen and Carbon Dioxide, in order to adjust or better control the ratio of Hydrogen to Carbon Monoxide in the resultant hydrocarbon synthesis gas. If Methane is desired to add to the H2 and CO2, then, as seen in our
above citation of our report concerning "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction"; and, as confirmed separately in our report of:
West Virginia Coal Association | Penn State May 14, 2013, CO2 to Methane | Research & Development; concerning: "United States Patent 8,440,438 - Electromethanogenic Reactor and Processes for Methane Production; 2013; Inventors: Shaoan Cheng and Bruce Logan, State College, PA; Assignee: The Penn State Research Foundation; Abstract: Biological processes for producing methane gas and capturing carbon from carbon dioxide are provided according to embodiments of the present invention which include providing an electromethanogenic reactor having an anode, a cathode and a plurality of methanogenic microorganisms disposed on the cathode. Electrons and carbon dioxide are provided to the plurality of methanogenic microorganisms disposed on the cathode. The methanogenic microorganisms reduce the carbon dioxide to produce methane gas, even in the absence of hydrogen and/or organic carbon sources";
we have a variety of energy-efficient technologies available to us that enable the synthesis of any desired Methane from, basically, Carbon Dioxide itself.)
The process ... further comprising the step of: using a syngas mixture as an intermediate or as feed material in a subsequent synthesis to form a chemical product or a plurality of chemical products (and) wherein the subsequent synthesis is selected from the group consisting of methanol production, olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins.
(We won't cite references, but, we assure you, the above ranges of reactions in which the resultant, Carbon Dioxide-based synthesis gas can be utilized comprises a full range of alcohol, hydrocarbon fuel and even plastics raw material syntheses.)
Background and Field: Embodiments of the present invention relate to catalyst compositions, to processes for making the catalyst compositions of this invention, to catalytic processes for producing a synthesis gas (syngas) mixture under isothermal conditions from carbon dioxide and hydrogen using a catalyst of this invention and to processes for using the syngas mixtures to produce various chemical products.
More specifically, embodiments of the present invention relate to catalyst compositions, to processes for making the catalyst compositions of this invention, to catalytic processes for producing a syngas mixture under isotherm'al conditions from carbon dioxide and hydrogen, where the syngas mixture includes hydrogen, carbon monoxide and carbon dioxide and the processes include contacting a gaseous feed mixture including carbon dioxide and hydrogen with a metal oxide catalyst to produce the syngas mixture. Embodiments of the invention also relate to processes for making the catalyst compositions and processes for utilizing a syngas mixture in the production of various chemical products.
Summary: Embodiments of this invention provide processes of making synthesis gas (syngas) mixtures containing hydrogen, carbon monoxide and carbon dioxide under isothermal conditions. The processes comprise contacting a gaseous feed mixture including carbon dioxide and hydrogen with a catalyst comprising a supported manganese oxide catalyst including at least one auxiliary metal selected from the group (of metals specified above), where one of the elements may be used as a support while other elements are used to modify the activity of the manganese oxide, resulting in the hydrogenation of carbon dioxide to a desired syngas mixture.
Embodiments of this invention provide processes for making a chemical product using a syngas mixture of this invention as an intermediate material or as feed material. The processes first comprise converting carbon dioxide and hydrogen in a carbon dioxide hydrogenation step to a syngas mixture, and second the processes comprise converting the syngas mixture alone or in combination with other compounds into the chemical products. In certain embodiments, the syngas mixtures may be used in methanol production, olefin synthesis, production of aromatics, hydroformylation of olefins, carbonylation of methanol, and/or carbonylation of olefins."
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In the bluntest terms possible:
Saudi Arabia is aggressively developing perfectly valid technology that, starting with Carbon Dioxide as the basic, essential raw material, will synthetically and efficiently produce anything and everything they now pump up from beneath their desert sand, and which we now squander our national, domestic United States wealth to buy from them by the tanker ship full.
That, while the United States of America squanders her time and her attention, her seeming fascination, on a relatively very small Carbon resource like shale gas, and, cripples utilization of her by far largest Carbon resource, Coal, by implementation of policies that limit co-production of the, as herein, precious raw material resource, Carbon Dioxide.
Our way has been lost; and, it has been lost because those upon whom we rely, and trust, to inform, guide and lead us, have abrogated their responsibilities to do any of that fully, completely and honestly.
Keep that in mind, you Coal miners and you Coal-fired power plant workers, when, finally laid-off and idle because of the mindless, uncritical stampede of the herd in alternative energy resources like shale gas, and the imposition of Cap and Trade CO2 taxes on Coal-based electricity, you sit watching TV, if you can afford the electric bill, while your spouse is out making minimum wage clerking at the local convenience store, so that you'll at least have the gas money to get back and forth to the food bank, and, on CNN, you see the first Royal Saudi Arabian tanker full of recycled Carbon Dioxide, sloshing around in the ship's holds as one liquid hydrocarbon or another, sail portentously into New York harbor, past the Statue of Liberty, and begin to offload it's shipment; a shipment that, after travel through the distribution system, you will be paying for the privilege, perhaps at the gas pump at the convenience store where your spouse works, of putting into the gasoline tank of your car.
That, when, as seen for only the most recent out of many related of our reports in:
West Virginia Coal Association | US Gov Confirms Coal Can Be A CO2-Neutral Source Of Power | Research & Development; concerning: "United States Patent 8,461,215 - Rendering Coal As An Environmentally Carbon Dioxide Neutral Fuel And A Regenerative Carbon Source; 2013; Inventors: George Olah and G.K. Surya Prakash; Assignee: The University of Southern California; Abstract: The invention provides a method for rendering coal as an environmentally essentially carbon dioxide-neutral fuel. Carbon dioxide produced from coal combustion is captured, purified, combined with coalbed methane or any other natural methane or natural gas source, or with hydrogen, and reacted under reaction conditions sufficient to form methanol and/or dimethyl ether, which can be used as fuel or feedstock for derived synthetic hydrocarbons and products";
we have available to us in the United States of America, our own technologies for the recycling of Carbon Dioxide as is co-produced during our production of genuinely economical electricity from Coal, and the synthesis, from that Carbon Dioxide, of the same sorts of hydrocarbons being made from Carbon Dioxide by the Saudi Arabian oil sheiks.
If you can still afford the postage, be sure to let the editors of your Coal Country news outlets know how you feel about those facts, and the facts that you weren't by them informed or forewarned.