United States Patent Application: 0130168966
We've provided you now with a number of reports, as for one example seen in:
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";
documenting and establishing the fact, that, not only can Carbon Dioxide be reclaimed from whatever handy source and then be recycled in the synthesis of hydrocarbons, but, that, what some might see as the crown jewel of OPEC is establishing the technology and industry to do just that.
In fact, in another of our reports on those Saudi Arabian Carbon Dioxide developments and potentials:
West Virginia Coal Association | Saudi Arabia and Texas Improve CO2 to Syngas Conversion | Research & Development; concerning: "United States Patent Application 20130150466 - Mixed Oxide Based Catalyst for the Conversion of Carbon Dioxide to Syngas and Method of Preparation and Use; June 13, 2013; Inventors: Aghaddin Mamedov, et. al.; 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";
we included the admonition to everyone in US Coal Country to:.
"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".
Well, guess what? We weren't too far off in our above intimation that a Royal Saudi Arabian tanker full of recycled Carbon Dioxide, in the form of one liquid hydrocarbon fuel or another, might soon be sailing to our shores right under the nose of the Statue of Liberty.
Just this very US Independence Day, this past Fourth of July, a few short weeks ago, Saudi Arabia lit another firecracker, maybe to let us know that we won't for long have to worry about summer vacation gasoline shortages, since more recycled Carbon Dioxide will soon be on it's way in the holds of those Royal Saudi tankers. As seen in excerpts from the initial link above to:
"US Patent Application 20130168966 - Method for Conversion of Carbon Dioxide into Hydrocarbons
Patent US20130168966 - Method for conversion of carbon dioxide into hydrocarbons - Google Patents
METHOD FOR CONVERSION OF CARBON DIOXIDE INTO HYDROCARBONS - KING SAUD UNIVERSITY
Date: July 4, 2013
Inventors: Mazen Abdullah Ba-Abbad, et. al., Riyadh, Saudi Arabia
Assignee: King Saud University, Riyadh
(In passing, we note that King Saud University is seeking international, or "world" rights to this technology, as well, via submission of this US Patent Application to the World Intellectual Property Organization. As can be seen via:
20130168966 METHOD FOR CONVERSION OF CARBON DIOXIDE INTO HYDROCARBONS.
The above WIPO documentation indicates that the original application was actually submitted to the US Patent and Trademark Office late last year. But, for perhaps interesting reasons of their own, the USPTO elected to publish it on this Fourth of July.)
Abstract: The present invention relates to a method for converting carbon dioxide into hydrocarbons by reacting magnesium with carbon dioxide to obtain magnesium oxide and carbon, reacting the carbon with hot water steam to obtain hydrogen (H2) and carbon monoxide, reacting hydrogen and carbon monoxide according to the Fischer-Tropsch method, or reacting the carbon obtained with earth alkaline metal oxide to obtain earth alkaline metal carbide and carbon monoxide, wherein the earth alkaline metal carbide is then reacted with water to obtain acetylene and earth alkaline metal hydroxide.
(We'll interrupt to note several potentials. In "reacting the carbon with hot water steam to obtain hydrogen (H2) and carbon monoxide", that is, a hydrocarbon synthesis gas, the Saudi's are employing technology originally intended, as seen for just one example in our report of:
West Virginia Coal Association | Texaco 1951 Coal + CO2 + H2O + O2 = Syngas | Research & Development; concerning: "United States Patent 2,558,746 - Carbon Monoxide and Other Gases from Carbonaceous Materials; Date: July 3, 1951; Assignee: The Texas Company, NYC; Abstract: This invention relates to a process and apparatus for the generation of gases comprising carbon monoxide from carbonaceous materials. In one of its more specific aspects it relates to a process and apparatus for the generation of a mixture of carbon monoxide and hydrogen, suitable as a feed for the synthesis of hydrocarbons, from powdered coal. ... The present invention is concerned with the generation of a mixture of carbon monoxide and hydrogen (and) is particularly suited to the production of a feed gas for the synthesis of hydrocarbons. Liquid or solid carbonaceous fuels may be used, e.g., ... coal; the method and apparatus is especially useful when powdered coal is used as the feed material. An object of this invention is to provide a process for the generation of carbon monoxide and hydrogen (and) to provide a process particularly suited to the generation of a feed gas for the synthesis of hydrocarbons from coal. In the gasification of carbonaceous material with oxygen, particularly solid fuels, the reaction between oxygen and fuel results in the production of carbon dioxide ... . The oxidation reaction, being highly exothermic, releases large quantities of heat. The carbon dioxide, so produced, in contact with hot carbon, in turn, reacts with the carbon to produce carbon monoxide. Steam also reacts with heated carbon to produce carbon monoxide and hydrogen";
to manufacture such hydrocarbon synthesis gas from Coal.
Further, if "acetylene" is, as in the Abstract, produced from the metal carbide, in a process well-known to anyone familiar with the old-style Coal miner's open-flame cap lamp, then, as can be learned for one example in:
"United States Patent: 5118893 - Zeolite Catalyzed Conversion of Acetylene; June, 1992; The University of Texas System; Abstract: The invention relates to an efficient process for the production of higher hydrocarbon from the catalyzed conversion of acetylene. This invention describes the use of a nickel or cobalt-containing zeolite catalyst, coupled with the addition of a hydrogen donor co-reactant to the acetylene feed, to obtain continuous and complete conversion of acetylene to other hydrocarbons. The catalyst/reactant feed process described eliminates rapid catalyst deactivation";
Acetylene can serve as the starting point for making a broad range of other, and higher, hydrocarbons, including those in the gasoline range and others which can be utilized in polymer syntheses. In the above "United States Patent 5,118,893", by the way, the specified "hydrogen donor co-reactant" can be either a simple alcohol or just plain old H2O. Further, as we will see in reports to follow, Acetylene, as synthesized herein by Saudi Arabia from Carbon Dioxide, can be put to great good use in some processes for the indirect conversion of Coal into hydrocarbons.)
Claims: Method for converting carbon dioxide into hydrocarbons, comprising the steps:
a) compressing air, optionally under removal of condensed water vapor, to a pressure of above 50 atmospheres, cooling the compressed air, preferably to about ambient temperature, separating carbon dioxide (CO2) from oxygen (O2) and nitrogen (N2), storing carbon dioxide in a storage tank and preferably storing the heat generated during compression and/or cooling in a heat storage medium;
b) electrolyzing water to produce hydrogen (H2) and oxygen (O2), compressing the gases obtained and storing the heat generated during compression;
c) releasing carbon dioxide from the storage tank and reacting it with magnesium metal to produce magnesium oxide and carbon according to the following equation
2Mg + CO2 = 2MgO + C; and either burning oxygen and hydrogen obtained in step b) in a hydrogen torch to obtain hot steam of a temperature of about 2.000-2.400 C, cooling the hot steam to a temperature of about 600-1.000 C and then reacting the steam with carbon obtained in step c) according to the following equation:
H2O + C = H2 + CO
(followed by a) Fischer-Tropsch reaction of CO and H2 obtained (to form hydrocarbons);
and/or reacting the carbon obtained ... with earth alkaline metal oxide MeO, preferably Ca or Mg, at a temperature of about 1,800-2,200 C according to the following equation MeO + 3C =.MeC2 + CO
(and) reacting the earth alkaline carbide obtained ... with water to produce acetylene and/or acetylene derivatives;
and/or ... reacting the carbon obtained ... with alumina according to the following equation:
2Al2O3 + 9C = Al4C3 + 6CO;
(and) reacting the aluminum carbide with water according to the following equation:
Al4C3 +12H2O = 4Al(OH)3 + 3CH4;
(Note, in the above reaction formulae, that both Carbon Monoxide, "CO", and Methane, "CH4" can be the products of this CO2-based reaction sequence, apparently when Aluminum is used to form the intermediate metal carbide; and, we remind you, that, as seen for only one example in our report of:
West Virginia Coal Association | Saudia Arabia CO2 + Methane = Hydrocarbons + Syngas | Research & Development; concerning: "United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas; 2008; Inventors: Agaddin Mamedov, et. al., Saudi Arabia; Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: Process for producing benzene, ethylene and synthesis gas, comprising the steps of: i) introducing a starting gas flow comprising methane and carbon dioxide into a reactor; ii) oxidizing the methane in the reactor at certain reactor conditions optionally using a first catalytic material and/or and additional oxidant; and: iii) removing a product gas flow comprising benzene, ethylene and synthesis gas from the reactor";
Saudi Arabia, as above, like many others, knows how to react such CO2-based Methane with even more Carbon Dioxide, to make both various hydrocarbons and more hydrocarbon synthesis gas.)
Method ... wherein ... the energy for compressing the air is provided from renewable energy sources.
(And) wherein ... the air is compressed in multiple stages, wherein preferably at all stages of compression the compressed air/gases is/are cooled to ambient temperature (and) wherein heat released when cooling the compressed air ... is stored in form of hot oil or molten salt.
(And) wherein a cooling effect obtained when releasing CO2 from its storage ... is used to cool the compressed air.
Method according to any of the preceding claims ... comprising the additional steps:
- hydrating the magnesium oxide obtained ... to its hydroxide according to the equation:
MgO + H2O = Mg(OH)2;
- preparing hydrochloric acid by reacting chlorine gas with hydrogen gas: H2 + Cl2 =.2HCl;
- preparing magnesium chloride according to the following equation:
Mg(OH)2 + 2HCl = MgCl2 +2H2O
- heating the magnesium chloride obtained to its melting point and electrolyzing thereof:
MgCl2. = Mg + Cl2;
- transferring the Mg obtained into (the Carbon Dioxide reduction/reaction) step ... and preferably recycling the Cl2 obtained into the step of preparing hydrochloric acid.
(Once the Chlorine is obtained, in other words, not much more of it would be needed, since it is recycled in the system. We'll note as well that King Saud University proposes a great deal of internal heat recycling, where heat energy from exothermic reactions is used to help drive needed endothermic reactions. Our abbreviated summary doesn't fully reproduce those details of potential economies, but one is exemplified in the following claim.)
Method ... wherein the chlorine gas obtained is heat exchanged with the compressed air ... which is then expanded into a turbine to produce electricity.
Description: The present invention relates to a method for conversion of carbon dioxide into hydrocarbons. Several methods are known in the art to convert carbon dioxide into several hydrocarbon materials.
U.S. Pat. No. 7,605,293 discloses a method of reducing the carbon dioxide content of the atmosphere by recycling carbon dioxide and producing methanol using a reductive conversion of an available source of carbon dioxide that is present in or would otherwise be discharged into the atmosphere.
(Concerning the above reference to "U.S. Pat. No. 7,605,293", see our report of:
West Virginia Coal Association | Even More California 2009 CO2 to Methanol | Research & Development; concerning: "United States Patent 7,605,293 - Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products; 2009; Inventors: George Olah and G.K. Surya Prakash;
Assignee: University of Southern California; Abstract: An environmentally beneficial method of producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by electrochemical reduction produces formic acid and some formaldehyde and methanol mixtures. The formic acid can be used as source of carbon as well as hydrogen to produce methanol, dimethyl ether and other products".)
U.S. Pat. No. 7,459,590 B2 discloses a method for producing methanol and dimethyl ether using the air as the sole source of materials. The method is related to producing methanol by removing water from atmospheric air, obtaining hydrogen from the removed water, obtaining carbon dioxide from atmospheric air; and converting the carbon dioxide under conditions sufficient to produce methanol.
(Concerning the above, see our report of:
West Virginia Coal Association | California Recycles More and More Carbon Dioxide | Research & Development; concerning, in part: "United States Patent 7,459,590 - Producing Methanol ... from Carbon Dioxide and Water; 2008; Inventors: George Olah and Robert Aniszfeld; Assignee: University of Southern California; Abstract: A method for producing methanol and dimethyl ether using the air as the sole source of materials is disclosed. The invention relates to a method for producing methanol by removing water from atmospheric air, obtaining hydrogen from the removed water, obtaining carbon dioxide from atmospheric air; and converting the carbon dioxide under conditions sufficient to produce methanol. Thereafter, the methanol can be dehydrated to produce dimethyl ether or further processed to produce synthetic hydrocarbons, polymers, and products derived from them".)
One disadvantage of the methods known in the art is that, if renewable energy, such as solar or wind energy, is utilized, the methods may not work efficiently, especially if solar wind energy is fluctuating or interrupted. Also, the known methods do not have forms of process energy recovery, i.e. thermal or photonic. Additionally, these methods may consume large amounts of fresh water, which is not widely available in many parts of the world. Also, the prior art methods may require complicated process controls and very expensive process equipment.
It is therefore an object of the present invention to provide a method for conversion of carbon dioxide into hydrocarbons which overcomes the difficulties and disadvantages of the prior art.
This object is achieved by a method for converting carbon dioxide into hydrocarbons (as detailed by the included formulae and equations).
(The full Disclosure reiterates both the reaction formula and restates the potentials for energy economies, as well as pointing out that the air separation of Carbon Dioxide leads to the potential for economically recovering other components of the atmosphere, which, when treated as industrial products or commodities, can lead to further reductions in the overall effective cost of converting the reclaimed CO2 into hydrocarbons. We include one passage illustrating those potentials following.)
A combination of a method for converting nitrogen into ammonia and/or nitrate with the inventive method for converting carbon dioxide (adds) benefits, for example improved flexibility, easy control to produce a variety of valuable hydrocarbon products as well as fertilizers. Further, especially when combining the method for converting carbon dioxide into hydrocarbons with production of ammonia and/or nitrate allows that the net reactions do not consume all of the oxygen gas, so that the system actually produces oxygen. In case that the compressed air contains suitable amounts of a moisture so that the water vapor is sufficient to form the hydrocarbons, the combined system then only needs CO2, but will produce O2.
Surprisingly it was found, that the present invention provides a new method to convert atmospheric carbon dioxide into useful hydrocarbons that can be used as fuel (gasoline and diesel) or valuable petrochemicals consuming only energy which can come preferably from renewable resources.
The inventive method is much more economic with renewable energy forms that are fluctuating and require energy storage, for example solar and wind energy. Additionally, this method works best when utilized to absorb carbon dioxide from exhaust flue gases that are rich in carbon dioxide, for example from power plants, biological digesters or ammonia manufacturing plants. The inventive method provides higher efficiency than other methods, as most of the process heat, photonic emissions and cooling effects (decompression cooling) can be recovered and recycled into the system. Also this method has a net effect of producing oxygen. All this is done in a simple way.
The inventive method simply comprises renewable energy collection and conversion systems with waste heat recovery; an energy storage subsystem (in the form of compressed air), which serves also as a simple carbon dioxide capturing system. Water vapor exists in considerable quantities in the exhaust gases of oil or gas fired power plants, so this water vapor can be condensed and utilized. Another energy storage unit is the water splitting unit that preferably uses renewable energy electricity to electrolyze water and produce hydrogen and oxygen. During air, oxygen, hydrogen gases compression, the heat generated is preferably extracted and stored in hot fluid medium to be used later to pre-heat the gases in processes and into turbine expansion to generate electricity; and chemical reactors that are coupled with energy recovery subsystems for thermal and photonic recovery.
The only core method inputs are carbon dioxide, water and heat (at suitable temperatures for each method step) and electricity.
Magnesium (Mg), water, magnesium or calcium hydroxide and chlorine gas are substances utilized in the method which can be fully recycled.
The inventive method is very flexible and can be easily controlled to produce a variety of valuable hydrocarbon products.
Further, it shall be highlighted that there are no harmful rejects to the environment."
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This is an early version of this United States Patent Application; and, in coming months, as we understand the patent application process, it will undergo revision and editing in response to critique, inquiry, requests for clarification and challenges from the USPTO.
It will likely evolve into a more concise and understandable document. But, the key technical components are in place:
In a process driven by environmental energy and process-derived exothermic reaction heat, Carbon Dioxide is first recovered from the atmosphere, using well-established technology that also produces commercial byproducts like Oxygen and Nitrogen, as well as, potentially, H2O, from which Hydrogen is extracted, perhaps, as specified, via reactions with hot carbon extracted from the CO2, as per the specified: "reacting the steam with carbon" according to the equation: "H2O + C = H2 + CO".
We'll note that King Saud University also proposes "electrolyzing water to produce hydrogen (H2)", since additional Hydrogen does have use in the complete technology; and, since the Arabian peninsula has abundant sunshine, we remind you that, as seen, for one example, in our report of:
West Virginia Coal Association | NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,045,315 - Solar Photolysis of Water; 1977; NASA; Abstract: Hydrogen is produced by the solar photolysis of water";
they might have some other possibilities available to them on their desert peninsula for that Hydrogen production, as well.
In any case, Saudi Arabia, as herein, knows how to, starting with that Carbon Dioxide extracted from the atmosphere as the basic and primary raw material, and using various metal/metal oxide intermediaries, in a process driven in large part by environmental energy, make such seemingly-desirable stuff as "H2 + CO" synthesis gas which can be converted "into hydrocarbons ... according to the Fischer-Tropsch method", as well as "acetylene" and substitute natural gas Methane, "CH4".
Saudi Arabia, through this 4th of July declaration, are announcing their pending independence from inevitably dwindling supplies of natural petroleum and natural gas.
And, just as our own government did, as seen in our report of:
West Virginia Coal Association | USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; May, 1976; Inventor: Meyer Steinberg, NY; Assignee: The USA; Abstract: A method and system for synthesizing methanol from the CO2 in air using electric power";
in the bicentennial year of our own 4th of July Declaration, Saudi Arabia are as well herein confirming a key fact that just about everyone, it seems, has done their best to keep hidden from We the People, i.e.:
Carbon Dioxide, as it arises in only a small way, relative to the earth's inexorable and all-natural processes of planetary volcanism, from our economically essential use of Coal in the generation of truly abundant and truly affordable electric power, is a valuable raw material resource.
We can, as confirmed by King Saud University, reclaim Carbon Dioxide from our environment, and, then, in an energy-efficient process, we can convert that Carbon Dioxide into various gaseous hydrocarbons, such as Acetylene and Methane, and into hydrocarbon synthesis gas which can itself be converted, via for one example the Saudi-specified "Fischer-Tropsch method", into virtually all forms of liquid hydrocarbons.
Do you really suppose that the US citizens of US Coal Country really want to wait on the Camel Express mail carriers, ferried over on the decks of tankers hauling petroleum products synthesized from Carbon Dioxide, to bring them the news of that?