Over the past several years, we've documented for you a number of times the flat reality that, not only can Carbon Dioxide be reclaimed and, on a practical basis, be chemically recycled in the industrial synthesis of hydrocarbons, it is, as seen most recently in our report of:
West Virginia Coal Association | Sweden Makes Public Report of CO2 to Motor Fuel Recycling | Research & Development; concerning the European newspaper article:
"'Iceland As A Green Saudi Arabia'; March 12, 2013; Recently, they shipped the first load to oil company Argos in Holland, for low level blending in gasoline. Vulcanol is just a name for methanol, regular wood spirit. It is the production method which makes this fuel especially interesting. It is made using renewable electricity, water and captured CO2 from the nearby geothermal power plant HS Orka. CRI sees it as a breakthrough for renewable transport fuels which are of non-biological origin. The name Vulcanol refers to the fact that the whole process is driven by geothermal energy, but of course other energy sources could also work well";
being so harvested and utilized in Europe, by the Icelandic-American company "Carbon Recycling International", "CRI":
Carbon Recycling International; "Carbon Recycling International (CRI) captures carbon dioxide from industrial emissions and converts carbon dioxide into Renewable Methanol (RM). RM is a clean fuel that can be blended at different levels with gasoline to meet renewable energy directives. The production process captures carbon dioxide and minimizes emissions from energy intensive industries. CRI's methanol is compatible with existing energy and fuel infrastructure".
More about CRI can be learned via:
Carbon Recycling International - Wikipedia, the free encyclopedia; "Carbon Recycling International Inc. (CRI) is an Icelandic-American renewable methanol company. Its emissions-to-liquid process uses carbon dioxide and water and electricity to create methanol fuel".
As indicated in the above reports, CRI are now converting industrial exhaust gas Carbon Dioxide into commercial quantities of the fuel alcohol, Methanol, likely utilizing technology related to that developed by Nobel laureate George Olah, and colleagues, at the University of Southern California; as disclosed, for just one out of many examples, in our report of:
West Virginia Coal Association | California March 2012 Efficient CO2 to Methanol | Research & Development; concerning: "United States Patent 8,138,380 - Electrolysis of Carbon Dioxide ... for Production of Methanol; 2012; 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 power plants, industrial exhaust gases or the atmosphere itself".
In fact, if you investigate CRI's corporate web site, as accessible via the enclosed link, you will discover that George Olah and Surya Prakash are named as official technical officers or advisors of CRI.
Again, CRI are currently producing Methanol on a commercial basis using industrial exhaust gas CO2 as the basic raw material; and, as we've documented many times, as, for just two examples, in our reports of:
West Virginia Coal Association | ExxonMobil Coal to Methanol to Gasoline | Research & Development; concerning both: "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Assignee: Exxon Research and Engineering Company; This invention provides a process for producing methanol by the substantially thermoneutral reaction of steam with coal"; and: "United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation; Abstract: The conversion of methanol to gasoline"; and:
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, NY; 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";
Methanol, no matter which of our abundant natural resources, whether Coal or CO2, we make it from, can be converted directly into that fuel we're much more familiar with: Gasoline.
However, as we reported last year, via:
West Virginia Coal Association | More Iceland CO2 + H2O = Diesel Fuel, Methanol & Gasoline | Research & Development; concerning: "United States Patent Application: 20070244208 - Liquid Fuels From Carbon Dioxide And Water; 2007; Inventors: Arthur Shulenberger, et. al., Iceland and California; Abstract: A process for producing high octane fuel from carbon dioxide and water is disclosed. The feedstock for the production line is industrial carbon dioxide and water, which may be of lower quality. The end product can be high octane gasoline, high cetane diesel or other liquid hydrocarbon mixtures suitable for driving conventional combustion engines or hydrocarbons suitable for further industrial processing or commercial use";
work, which we believed to have been sponsored by CRI, although the eventual Assignee of rights wasn't named in the records of "United States Patent Application: 20070244208" accessible by us, had been accomplished to effect the conversion of Carbon Dioxide not just into Methanol, but as well more directly into both Gasoline and Diesel fuel.
As it happens, and as, for reasons we can't explain, went undiscovered by us, almost coincident with our above report of "United States Patent Application: 20070244208", that application was approved, deemed to be exposition of an innovative and practical technology, by the technical experts in our United States Patent and Trademark Office, resulting in, as accessible via the initial link in this dispatch, issuance of:
"United States Patent 8,198,338 - Process for Producing Liquid Fuel from Carbon Dioxide and Water
Patent US8198338 - Process for producing liquid fuel from carbon dioxide and water - Google Patents
Process for producing liquid fuel from carbon dioxide and water - CRI EHF
Date: June 12, 2012
Inventors: Arthur Shulenberger, et. al., Iceland and California
Assignee: CRI (Carbon Recycling International) Ehf, Iceland
Abstract: A process for producing high octane fuel from carbon dioxide and water is disclosed. The feedstock for the production line is industrial carbon dioxide and water, which may be of lower quality. The end product can be high octane gasoline, high cetane diesel or other liquid hydrocarbon mixtures suitable for driving conventional combustion engines or hydrocarbons suitable for further industrial processing or commercial use. Products, such as dimethyl ether or methanol may also be withdrawn from the production line. The process is emission free and reprocesses all hydrocarbons not suitable for liquid fuel to form high octane products. The heat generated by exothermic reactions in the process is fully utilizes as is the heat produced in the reprocessing of hydrocarbons not suitable for liquid fuel.Claims: A process for production of a liquid fuel from carbon dioxide and water using electricity, comprising:
(a) capturing carbon dioxide from a concentrated carbon dioxide stream within a mixed industrial gas stream;
(b) purifying said concentrated carbon dioxide by separating other constituents from said mixed industrial gas stream;
(The above collection of CO2 from an "industrial gas stream" might be accomplished via a process like that seen in our report of:
West Virginia Coal Association | WVU March 28, 2013, Economical Harvesting of Flue Gas CO2 | Research & Development; concerning: "United States Patent Application 20130078172 - Layered Solid Sorbents for Carbon Dioxide Capture; 2013; Assignee: West Virginia University Research Corporation; Abstract: A solid sorbent for the capture and the transport of carbon dioxide gas ... . Government Interests: Certain embodiments of this invention were made with Government support in conjunction with the National Energy Technology Laboratory, Pittsburgh, Pa., under RES contract number DE-FE0004000 awarded by the U.S. Department of Energy. The Government may have certain rights in the invention".)
(c) providing water and electricity and electrolyzing the water into hydrogen and oxygen;
(Numerous technologies and concepts for the above production of Hydrogen from Water, which rely on environmental energy to drive the processes, have been developed. As, for one example, seen in:
West Virginia Coal Association | Japan Maximizes Hydrogen Production from Wind Power | Research & Development; concerning: "United States Patent 7,667,343 - Hydrogen Production System Using Wind Turbine Generator; 2010; Assignee: Hitachi, Ltd., Tokyo; Abstract: A wind turbine-driven hydrogen production system controlling a power converter system such that the wind turbine stays in its operable range for a longer time and thus the hydrogen production system produces hydrogen for a longer time".)
(d) reacting a mixture of purified carbon dioxide from step (b) and hydrogen in the presence of a catalyst to produce methanol, carbon monoxide, water, and at least one hydrocarbon byproduct wherein heat is generated and controlled by increasing the relative amount of said carbon monoxide to increase said heat and/or by adding said carbon dioxide to decrease said heat;
(A number of catalytic processes exist for the, as above, direct synthesis of Methanol from Hydrogen and Carbon Dioxide, as seen for one example in:
West Virginia Coal Association | Monsanto Recycles CO2 to Methanol | Research & Development; concerning, in part: "United States Patent 4,181,675 - Process for Methanol Production; 1980; Assignee: Monsanto Company, St. Louis; Abstract: An improved methanol synthesis process is provided wherein synthesis gas containing hydrogen and carbon dioxide is passed over a methanol synthesis catalyst".
And, as indicated, the reaction of Hydrogen with CO2 can also yield Carbon Monoxide in a long-known reaction called the "Reverse Water Gas Shift", or, more simply, "Reverse Conversion", as exemplified in our report of:
West Virginia Coal Association | France Uses Hydrogen to Convert CO2 to Carbon Monoxide | Research & Development; concerning: "United States Patent Application 20030113244 - Producing Carbon Monoxide by Reverse Conversion; 2003; Correspondence (and presumed eventual Assignee of Rights: Air Liquide; Houston, TX; The invention concerns a method for producing carbon monoxide by reverse conversion (and) 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 (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".)
(e) reacting methanol and a mixture of said carbon monoxide and unreacted hydrogen from step (d) in at least one step to obtain said liquid fuel;
(The above is known as an "homologation" reaction; and, is exemplified in our report of:
West Virginia Coal Association | Dow Uses Coal Syngas to Convert Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,825,013 - Higher Alcohols from Lower Carbon Number Alcohols; 1989; Assignee: The Dow Chemical Company; Abstract: A process for forming an alcohol fraction boiling in the range of motor gasoline ... comprises contacting a mixture of hydrogen, carbon monoxide and a lower alkanol with a (specified and detailed catalyst) ... under conditions sufficient to convert at least some of the one or more lower alcohols to higher alcohols. A process comprising contacting a mixture of hydrogen, carbon monoxide and one or more lower alcohols with a heterogeneous catalyst ... under conditions sufficient to convert at least some of the one or more lower alcohols to higher alcohols (and) wherein the one or more lower alcohols contain methanol. The hydrogen and carbon monoxide required for this process may be obtained by ... gasification of hydrocarbonaceous materials such as coal".)
(f) reacting oxygen from step (c) and said at least one hydrocarbon byproduct to produce additional carbon monoxide and hydrogen for increased production of said liquid fuel.
(The above "hydrocarbon byproduct", of reacting Hydrogen with Carbon Dioxide, is likely to be Methane formed via the Sabatier process, which, as can be learned via:
West Virginia Coal Association | CO2 Solution Wins Nobel Prize - in 1912 | Research & Development;
is a reaction which has been known for more than a century.
And, the above Claim refers to a partial oxidation, or "reforming", of the "byproduct" Methane, using Oxygen generated during the production, via electrolysis, of the needed Hydrogen from Water. And, as seen for one example in our report of:
West Virginia Coal Association | Amoco CO2 + CH4 = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 5,614,163 - Process for Making Synthesis Gas; 1997; Assignee: Amoco Corporation; Abstract: A process is disclosed for preparing a synthesis gas comprising hydrogen and carbon monoxide by partial oxidation of hydrocarbyl compounds using a source of oxygen comprising molecular oxygen, carbon dioxide, or mixtures thereof in the presence of a catalyst ... . A process for partial oxidation of at least one hydrocarbyl compound ... consisting of methane";
such Methane reforming, to produce additional Carbon Monoxide and Hydrogen hydrocarbon synthesis gas, can also be structured so as to consume even more Carbon Dioxide.)
The process ... further comprising the steps of:
(g) separating hydrocarbon byproducts from said liquid fuel;
(h) reacting said separated hydrocarbon byproducts from step (g) to produce said carbon monoxide and/or said carbon dioxide, said hydrogen, and water; and (i) introducing said carbon monoxide and/or carbon dioxide and said hydrogen produced in step (h) to the reactions of step(s) (d) and/or (e) to produce said liquid fuel.
(In the above, they seem to be suggesting again that lighter, undesirable hydrocarbons can be separated from the mix of products, and, if desired, like the Methane, be reprocessed into more synthesis gas. All of which is reiterated in following claims. They further specify that byproduct H2O be recycled to the Hydrogen production electrolysis step. Further, as we've documented in prior reports, the hydrocarbon synthesis step, which is related at least in general terms to the Fischer-Tropsch synthesis, is exothermic; and, CRI specifies reclaiming that heat of reaction for use elsewhere in the system, again as further explained in additional claims.)
The process ... wherein heat from said liquid fuel synthesis ... is utilized to drive the production of said carbon monoxide and said water ... .
The process ... wherein said mixed industrial gas stream is selected from the group consisting of a geothermal power plant, an aluminum plant, a coal fired power plant, and a cement production plant.
The process ... wherein said liquid fuel synthesis ... comprises a one-step Fisher-Tropsch type process for producing said liquid fuel including gasoline and/or diesel.
(And) wherein said hydrocarbon byproducts (include) methane, ethane, ethene, ethyne, butane, butene, tert-butane, propane and isobutane.
The process ... wherein the reactant mixture ... is optimized to maximize desired products yield.
The process ... wherein total electrical energy consumption of the electrolysis step (c) is lowered by using excess energy from recycling of hydrocarbons not suitable for use as said liquid fuel and/or by using excess energy from exothermic steps in the production process.
The process ... wherein the total electrical energy consumption of the electrolysis step (c) is lowered by using heat energy generated in other step(s) of the process for compression of the electrolysis products.
The process ... wherein the total electrical energy consumption of the electrolysis step (c) is lowered by using heat energy generated in other step(s) of the process converted to electric energy to supply electric power to the electrolysis.
The process ... wherein the product ratio of said carbon monoxide to said methanol is optimized to an extent where the exothermic synthesis of said methanol supplies most or all of the required heat to run the mildly endothermic production of carbon monoxide.
The process ... wherein generated heat in the process is used for compression, preheating of reactant streams, or to drive endothermic reactions in the process.
(As seen in the above several claims, a great deal of attention has been paid to maximizing the efficiency and the economy of the system.)
The process ... wherein a part of the unreacted hydrogen from step (d) is removed by semi-permeable membrane means and recycled in the process.
The process ... wherein said hydrocarbon byproducts are reacted with oxygen in step (f) in a process selected from the group consisting of a partial oxidation process, an auto thermal process, a steam reforming process, and a total oxidation process to produce said carbon monoxide and said hydrogen.
(Again, as exemplified by our above citation of our report concerning "US Patent 5,614,163 - Process for Making Synthesis Gas".)
The process ... wherein the synthesis of said liquid fuel ... comprises the production of any one or combination of dimethyl ether, methanol, gasoline, and diesel.
The process ... wherein the liquid fuel synthesis ... comprises a two-step process of (i) producing dimethyl ether, and (ii) producing gasoline (and/or) producing dimethyl ether, and (ii) producing diesel.
(We won't cite past reports here; but, as we have previously documented, "dimethyl ether", DME, can serve, with modifications of fuel storage/delivery systems, as a direct substitute for both Diesel fuel and LPG. And, like Methanol, it can be directly converted into either Gasoline or Diesel.)
The process ... wherein said liquid fuel synthesis ... comprises at least three sub-steps comprising:
(i) producing methanol,
(ii) producing dimethyl ether, and:
(iii) producing gasoline (or) producing diesel.
Background and Field: The present invention is broadly within the field of energy conversion and relates to processes for producing hydrogen by electrolysis of water, processes for reacting hydrogen with carbon dioxide for producing methanol and/or producing syngas and processes for synthetic liquid fuel production.
It is ... very important to develop processes that allow utilization of alternative energy sources to provide fuel that can immediately substitute the currently used gasoline and diesel distilled from petroleum oil. Such fuel which is compatible with combustion engines as they are today will render the need for major, time consuming, technical developments and infrastructural changes unnecessary.
Currently, two processes have been used on industrial scale to produce synthetic liquid hydrocarbon fuel. One is the SASOL process which is based on classic Fisher-Tropsch chemistry and converts coal to syngas, which is converted to a variety of hydrocarbons via the Fisher-Tropsch synthesis.
(Concerning the above, see, interestingly enough, for one example, our report of:
West Virginia Coal Association | US EPA Recommends Coal Liquefaction as a Clean Alternative | Research & Development; concerning: "'Clean Alternative Fuels: Fischer-Tropsch'; United States Environmental Protection Agency; EPA420-F-00-036; March 2002; A Success Story (!) For the past 50 years, Fischer-Tropsch fuels have powered all of South Africa’s vehicles, from buses to trucks to taxicabs. The fuel is primarily supplied by Sasol, a world leader in Fischer-Tropsch technologies. Sasol’s South African facility produces more than 150,000 barrels of high quality fuel from domestic low-grade coal daily. The popular fuel is cost-competitive with crude oil-based petroleum products".)
The other is the Mobil Methanol-to-Gasoline process (MTG) ... .
(As in our above-cited report concerning: "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Assignee: Exxon Research and Engineering Company" and "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline".)
Syngas or synthesis gas is a term used for gases of varying composition that are generated in coal gasification (and, the) name comes from their use in creating synthetic petroleum for use as a fuel or lubricant via Fischer-Tropsch synthesis.
The Fisher Tropsch process was developed by the German researchers Franz Fisher and Hans Tropsch in the 1920s. It is a well documented process that has been used on industrial scale for production of diesel and other synthetic petroleum products for decades. This process is used by a number of companies today to produced low-sulfur diesel and other petroleum products on large scale. For example, SASOL has implemented this process since 1955 to produce petroleum fuel.
The conversion of methanol to gasoline using the Mobil methanol to gasoline process (MTG) is a viable alternative to the Fisher-Tropsch synthesis when converting syngas to liquid fuel.
It is ... an important challenge to develop a process that allows recycling carbon dioxide to a valuable product such as liquid fuel. It is even more beneficial to develop a process to recycle carbon dioxide to a liquid fuel that is equivalent or even superior to the currently used gasoline and diesel, and can substitute these without any need for technical or infrastructural changes.
Summary: The present invention provides a integrated, emission-free process for conversion of carbon dioxide and water to liquid fuel, such as high octane gasoline or diesel, suitable to drive combustion engines.
The process may also be used to produce other hydrocarbons or hydrocarbon mixtures suitable for driving conventional combustion engines or hydrocarbons suitable for further industrial processing or other commercial use. Intermediate products such as methanol or dimethy lether may also be generated by the production process of the invention. The overall process comprises in a preferred embodiment the conversion of water and carbon dioxide to C5+ hydrocarbons (i.e., with five or more carbon atoms), preferably C5-C10 hydrocarbons.
The overall process may also encompass the conversion of water and carbon dioxide to high cetane diesel or other liquid hydrocarbon mixtures suitable for driving conventional diesel combustion engines.
Accordingly, the present invention provides in one aspect a process for production of liquid fuel from carbon dioxide and water using electricity, comprising: providing water and electricity and electrolyzing the water into hydrogen and oxygen, providing carbon dioxide and reacting it with the obtained hydrogen to produce methanol and/or carbon monoxide and water, where said methanol can comprise the desired final product or be reacted further to liquid hydrocarbon fuel, or, in the case of carbon monoxide intermediate production, reacting the obtained carbon monoxide with hydrogen in one or more steps to produce liquid fuel, which can be methanol or other liquid fuel such as liquid hydrocarbon fuel.
Another aspect of the invention provides a process for production of liquid fuel from carbon dioxide and water using electricity, comprising: providing water and electricity and electrolyzing the water into hydrogen and oxygen, and providing carbon dioxide and reacting with the obtained hydrogen to produce in a one step process liquid fuel."
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Presuming you to have followed our over-long excerpts, you will know that not only can we, on a practical basis, convert Carbon Dioxide into Gasoline and Diesel, we can also, along the way, convert Carbon Dioxide into some other useful things, like Methanol and Methane; all in one, integrated process that can be driven by environmental energy, waste industrial process heat and energy derived from exothermic chemical reactions that are components of the CO2-recycling and conversion process itself.
Usually, we summarize and close our expositions of technology like that embodied in our subject herein,
"United States Patent 8,198,338 - Process for Producing Liquid Fuel from Carbon Dioxide and Water", with maybe snide comments about our apparent national subconscious wish to fail, in light of our ongoing public silence about the facts that Coal and, as herein, Carbon Dioxide, can be efficiently converted into anything, quite literally anything, we now rely on natural petroleum and gas deposits for our supply of; with that obstinate silence continuing in the face of our growing indebtedness to OPEC and looming, exploitive duplicities like Cap and Trade taxation.
We won't do that here, but, will remind you that the technology resident now in Iceland for recycling Carbon Dioxide, and for synthesizing all conceivable sorts of hydrocarbons from Carbon Dioxide, continues, as seen in our report of:
West Virginia Coal Association | Iceland, August 2012, CO2 to Gasoline and Diesel | Research & Development; concerning:"US Patent Application 20120201717 - Process and System for Producing Liquid Fuel from CO2 and Water; August 9, 2012; Shwetank Singh, et. al., Iceland; Assignee: CRI, Iceland' Abstract: A process and system for producing high octane fuel from carbon dioxide and water is disclosed. The feedstock for the production line is industrial carbon dioxide and water, which may be of lower quality. The end product can be high octane gasoline, high cetane diesel or other liquid hydrocarbon mixtures suitable for driving conventional combustion engines or hydrocarbons suitable for further industrial processing or commercial use. Products, such as dimethyl ether or methanol may also be withdrawn from the production line. The process is emission free and reprocesses all hydrocarbons not suitable for liquid fuel to form high octane products. The heat generated by exothermic reactions in the process is fully utilized";
to be advanced and improved.
In any case, as confirmed herein by our United States Government, through their allowance of "United States Patent 8,198,338 - Process for Producing Liquid Fuel from Carbon Dioxide and Water", we can, on a thoroughly practical basis, recover Carbon Dioxide from whatever convenient source, and, then, in an energy efficient process that can in large part be powered by environmental energy, we can convert that Carbon Dioxide into, at least, "high octane gasoline or diesel".Time for the newspaper, with that headline, to be delivered, ain't it?
No tips or Christmas cookies for the Coal Country paper boy, or paper girl, until it is.