United States Patent: 8212088
The United States Patent we enclose in this dispatch, confirming the fact that, on a practical basis, valuable raw material Carbon Dioxide can be converted into Methanol and the substitute Diesel fuel, Dimethyl Ether, was awarded less than two weeks ago, and, we believe, just, within the past few days, became accessible on the United States Patent and Trademark Office's, the USPTO's, official web site.
First, we have several times noted the problems with reliability and durability of links to published United States Patent Applications on the USPTO's web site; and, sadly, we have been alerted that our posted links to USPTO web site records of awarded patents themselves are starting to prove unreliable.
That said, here is a link to an independent site's record of this newly-published US Patent:
Efficient and selective chemical recycling of carbon dioxide to methanol, dimethyl ether and derived products;
the title of which should be a giveaway that this patent issued from a United States Patent Application about which we earlier reported, as recorded by the West Virginia Coal Association via:
West Virginia Coal Association | California Converts Power Plant CO2 to Methanol | Research & Development; concerning:
"US Patent Application 20060235091 - Efficient and Selective Conversion of Carbon Dioxide to Methanol; Date: October, 2006; Inventors: George Olah and Surya Prakash, CA; 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 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. Claims: An environmentally beneficial method of producing methanol by reductive conversion of an available source of carbon dioxide".
And, following, with comment inserted and appended, are excerpts from the two initial links in this dispatch, wherein our United States Government confirms the claims of Nobel Laureate George Olah, and his fellow University of Southern California genius, G.K. Surya Prakash, that Carbon Dioxide can be efficiently converted into, along with some other useful materials, both Methanol and Dimethyl Ether:
"United States Patent 8,212,088 - Efficient and Selective Conversion of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products
Date: July 3, 2012
Inventors: George Olah and G.K. Surya Prakash
Assignee: University of Southern California, Los Angeles
Abstract: An efficient and environmentally beneficial method of recycling and 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 chemical or electrochemical reduction secondary treatment to produce essentially methanol, dimethyl ether and derived products.
(To get it out of the way:
Methanol, a nicely-performing liquid fuel in it's own right, as seen in our report of:
ExxonMobil Coal to Methanol to Gasoline | Research & Development; which concerned, in part: "United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation; Abstract: The conversion of methanol to gasoline";
can be directly converted into Gasoline.
And, "dimethyl ether", as explained for one instance in our report of:
West Virginia Coal Association | Conoco Converts Coal to Methanol and Dimethyl Ether | Research & Development; concerning: "United States Patent 6,638,892 - Syngas Conversion and Catalyst Employed Therefor; 2003; Assignee: ConocoPhillips Company; Abstract: A process for the conversion of syngas by contact of syngas under conversion conditions with catalyst having as components zinc oxide, copper oxide, aluminum oxide, ... zeolite and clay in ... a one step process for conversion of syngas to dimethyl ether (and) a two step process for conversion of syngas to light olefins ... . Dimethyl ether is a clean and efficient alternative diesel fuel which can be produced by the dehydration of methanol which can be synthesized from syngas. Syngas is obtained using well known processes by the partial combustion or gasification of any organic material such as coal";
can be utilized as an advantageous direct substitute for conventional Diesel fuel.
Further, the concept that Carbon Dioxide can be converted into both Methanol and Dimethyl Ether shouldn't be a new one for you.
As seen in our reports of:
West Virginia Coal Association | Korea CO2 to Methanol & Dimethyl Ether | Research & Development; concerning: "United States Patent 6,248.795 - Dimethyl Ether and Methanol from Carbon Dioxide; 2001; Assignee: Korea Research Institute of Chemical Technology; Abstract: This invention relates to the process of preparing from carbon dioxide a mixture of dimethyl ether and methanol which are useful as clean fuel or raw materials in the chemical industry. More particularly, this invention relates to the process of preparing dimethyl ether and methanol in high yield without by-products such as hydrocarbons by means of chemical conversion of carbon dioxide"; and:
West Virginia Coal Association | Conoco Converts CO2 to Methanol and Dimethyl Ether | Research & Development; "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates; 2003; Inventors: Jinhua Yao and James Kimble, OK; Assignee: ConocoPhillips Company, Houston; Abstract: A catalyst and process for converting carbon dioxide into oxygenates. A catalyst composition for converting carbon dioxide to methanol and dimethyl ether";
some other smart and practical-minded folk have puzzled out the truth of the matter, as well.)
Claims: An environmentally beneficial method of preparing a renewable fuel, which method comprises: obtaining carbon dioxide from a natural or chemical source that would otherwise be present in or discharged into the atmosphere; and producing an energy storage and transportation material or a fuel sufficient to generate energy by hydrogenatively converting the carbon dioxide thus obtained under conditions sufficient to produce methanol as the material or fuel.
The method ... wherein the methanol is produced by reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol.
(Note: The Carbon Dioxide is first being converted into "formaldehyde", along with relatively smaller amounts of "methanol and methane". Subsequent steps convert the Formaldehyde and Methane into, primarily, Methanol and/or Dimethyl Ether. However, there is an alternative potential value that passes without acknowledgement. If we are first converting the Carbon Dioxide into Formaldehyde, that Formaldehyde can itself be utilized in a manner like that explained in:
Urea-formaldehyde - Wikipedia, the free encyclopedia; "Urea-formaldehyde ... is a non-transparent thermosetting resin or plastic, made from urea and formaldehyde ... . These resins are used in adhesives, finishes, MDF (medium density fiberboard), and molded objects",
wherein, to compound the CO2-recycling potentials, the CO2-derived Formaldehyde is made into a plastic resin through reactions with Urea, which, as explained via:
PROCESS FOR THE SYNTHETIC MANUFACTURE OF UREA FROM AMMONIA AND CARBON DIOXIDE
"US Patent 3,607,938 - Process for the Synthetic Manufacture of Urea from Ammonia and Carbon Dioxide; 1971; Assignee: Chemical Construction Corporation, NY; Abstract: A process is provided for the synthetic manufacture of urea from ammonia and carbon dioxide";
is itself can be made, in part, from Carbon Dioxide.
And, any Carbon Dioxide directed, through the synthesis of both Formaldehyde and Urea, and, thence, into the production of Urea-Formaldehyde plastic resin, and the "molded objects" which can be made from that resin, would be forever, and productively, "sequestered".).
The method ... wherein the methanol is produced by generating carbon monoxide from the carbon dioxide through a high temperature reaction with carbon, reacting the carbon monoxide with the previously produced methanol under conditions sufficient to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form additional methanol.
(It's going to start getting complicated here, very complicated. There are, it seems, multiple, and alternative, reaction pathways being, or which can be, exploited, both concurrently and sequentially, to maximize the production of Methanol and/or Dimethyl Ether. One component of this technology is a process that produces Carbon Monoxide from Carbon Dioxide through the reaction of CO2 with hot Carbon, as in our report of:
West Virginia Coal Association | Carbon Dioxide Recycled in the Manufacture of Plastics | Research & Development; which contained separate documentation of:
"United States Patent 4,564,513 - Process for the Production of Carbon Monoxide; 1986; Assignee: Bayer Aktiengesellschaft (AG), Germany; Abstract: Carbon monoxide is produced in an improved process in a carbon-filled, water-cooled generator in the configuration of a truncated cone in the longitudinal section, by the gasification of said carbon with a mixed gas of oxygen and carbon dioxide".
Further, the Carbon Monoxide can be made to react with Water, as in:
United States Patent: 5334759 - "US Patent 5,334,759- Preparation of Formic Acid from Carbon Monoxide and Water; 1994; BASF; Germany; A process for the preparation of formic acid by the reaction of carbon monoxide with water";
to make the Formic Acid. But, there are a lot of things, integrated chemical reactions, going on that demand the attention of someone genuinely knowledgeable to explain and summarize for you, if you are at all really interested. We, here, simply aren't in any way qualified to do that. The upshot is that a suite of products can be made in and extracted from this Carbon Dioxide recycling process, complicated though the process itself might be; or, all of the intermediate products can continue on and be consumed in the process, for the maximum production of Methanol and Dimethyl Ether.)
The method ... wherein the methanol is produced by reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomitant formation of formaldehyde and small amounts of methanol and methane, augmenting the reaction mixture by reacting, without separation of the reaction mixture, the formaldehyde into methanol with some of the formic acid used as a hydrogen source, and reacting some of the formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form methanol.
(We've documented the above reaction for you previously, though we can't at the moment track down the specific report in which it was described. In essence, some of the intermediate product "formic acid" can be and is reacted with some of the product Methanol "to form methyl formate", a substance which is easily hydrogenated back into an increased, multiplied and maximized, actually doubled, volume of Methanol. All of which is summarized in the immediately following claims.)
The method ... wherein the methanol is produced by hydrogenatively converting the carbon dioxide to form a reaction mixture that contains methanol, formic acid and formaldehyde, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde and formic acid to methanol.
The method ... which comprises reacting the formaldehyde with the co-formed formic acid as a hydrogen source, without separation of the reaction mixture, into methanol, including reacting of the formic acid with methanol to form methyl formate, followed by hydrogenating the methyl formate under conditions sufficient to form double the starting amount of methanol.
The method ... wherein the hydrogen needed for the hydrogenation of methyl formate is obtained at least in part from cleavage of the formic acid from the reaction mixture.
The method ... wherein the hydrogen needed for the hydrogenative conversion of carbon dioxide is obtained by the ... by electrolysis of water using an available energy source.
(Some added Hydrogen is, or might be, required; and, as we've documented in a number of reports, such as:
Pittsburgh Hydrogen for Coal Liquefaction | Research & Development; concerning: "United States Patent 3,888,750 - Electrolytic Decomposition of Water; 1975; Assignee: Westinghouse Electric Corporation, Pittsburgh; Abstract: Electrolysis and catalytic thermochemistry are combined to decompose water while minimizing the energy demanded to accomplish the decomposition. The electrolyte is H2SO3 produced by supplying SO2 and the water to be decomposed to the electrolyzer";
and, as we will, off and on, continue to document, there are many, many ways to generate Hydrogen via processes that are not only efficient, but, which can utilize both freely-available environmental energy and, in some cases, otherwise valueless pollutants to make the production of Hydrogen quite economical.)
The method ... which further comprises combusting the fuel to form an exhaust stream that contains carbon dioxide and in a manner that allows collection of the exhaust stream, and recovering the carbon dioxide of the exhaust stream for use as the chemically recyclable source of carbon dioxide for preparing additional fuel (and) wherein the exhaust stream is obtained by combusting the fuel in a fossil fuel burning power or industrial plant.
The method ... which further comprises dehydrating the methanol under conditions sufficient to produce dimethyl ether; using the dimethyl ether as the fuel or as a component of the fuel.
The method ... which further comprises utilizing, as the convenient energy storage and transportation materials, the methanol or dimethyl ether in order to minimize or eliminate the disadvantages or dangers inherent in the use and transportation of hydrogen, LNG or LPG.
(We can, in other words, make a replacement for Liquefied Natural Gas, LNG, out of Carbon Dioxide.)
An environmentally beneficial method of preparing a renewable fuel, which method comprises: obtaining carbon dioxide from a natural or chemical source; and producing an energy storage and transportation material or a fuel sufficient to generate energy by hydrogenatively converting the carbon dioxide thus obtained under conditions sufficient to produce methanol as the material or fuel.
The method ... wherein the natural or chemical source of carbon dioxide is the atmosphere, an exhaust stream from a power or industrial plant, or a source accompanying natural gas.
The method ... wherein the carbon dioxide is captured and obtained from the source and is reduced under conditions sufficient to produce a reaction mixture containing formic acid with concomitant formation of formaldehyde and small amounts of methanol and methane, augmenting the reaction mixture by reacting, without separation of the reaction mixture, the formaldehyde into methanol with some of the formic acid used as a hydrogen source, and reacting some of the formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form methanol.
(As summarized in the above claim, multiple and interrelated reactions are coupled together to maximize the production of Methanol from Carbon Dioxide. It is, again, complicated; but, becomes far more clear if it is drawn out and illustrated schematically, visually, as someone at least modestly knowledgeable was kind enough to attempt for us.)
An environmentally beneficial 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 from a natural or chemical source, which method comprises:
(A) reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomitant formation of formaldehyde and small amounts of methanol and methane, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol; or:
(B) augmenting the reaction mixture of (A) by reacting the formaldehyde with some of the formic acid as a hydrogen source, without separation of the reaction mixture, into methanol, and by reacting some of the formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form methanol; or:
(C) generating carbon monoxide from the carbon dioxide through a high temperature reaction with carbon, reacting the carbon monoxide with methanol produced in (A) under conditions sufficient to form methyl formate, followed by catalytic hydrogenation of the methyl formate under conditions sufficient to form (more, an increased amount of) methanol.
(The use of "methyl formate" as an intermediate in Carbon Dioxide recycling processes directed towards the production of Methanol is a common feature of CO2-recycling technologies developed by George Olah, and his colleagues, at the University of Southern California. For instance, in our report of:
West Virginia Coal Association | California Recycles More and More Carbon Dioxide | Research & Development; concerning, among other items:
Method for producing methanol, dimethyl ether, derived synthetic hydrocarbons and their products from carbon dioxide and water; "United States Patent 7,459,590 - Method for Producing Methanol, Dimethyl Ether, Derived Synthetic Hydrocarbons and Their Products from Carbon Dioxide and Water (Moisture) of the Air as Sole Source Material; 2008; 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. The method ... further comprises reducing the carbon dioxide under conditions sufficient to form carbon monoxide, reacting the carbon monoxide with methanol under conditions sufficient to obtain methyl formate, and catalytically hydrogenating the methyl formate under conditions sufficient to produce methanol";
it is also utilized as an intermediate product to help maximize the production of Methanol from CO2. And, in fact, additional, related technology has been developed by Olah and his US Patent 7,459,590 co-inventor, Robert Aniszfeld, about which we will report in future dispatches.
And, as confirmed, for just one example, via:
Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 a; "Efficient Hydrogenation of Organic Carbonates, Carbamates and Formates Indicates Alternative Routes to Methanol Based on CO2 and CO; The Weizmann Institute of Science; Israel; Catalytic hydrogenation of organic carbonates, carbamates and formates is of significant interest both conceptually and practically, because these compounds can be produced from CO2 and CO, and their mild hydrogenation can provide alternative, mild approaches to the indirect hydrogenation of CO2 and CO to methanol, an important fuel and synthetic building block";
the use of such "organic formates" is a widely-recognized route for the synthesis of Methanol.)
Background: Hydrocarbons are essential in modern life. Hydrocarbons are used as fuel and raw material in various fields, including the chemical, petrochemical, plastics, and rubber industries. Fossil fuels, such as coal, oil and gas, are composed of hydrocarbons with varying ratios of carbon and hydrogen, and is non-renewably used when combusted, forming carbon dioxide and water. Despite their wide application and high demand, fossil fuels present a number of disadvantages, including the finite reserve, irreversible combustion and contribution to air pollution and global warming. Considering these disadvantages, and the increasing demand for energy, alternative sources of energy are needed.
One such alternative frequently mentioned is hydrogen, and the so-called "hydrogen economy." Hydrogen is beneficial as a clean fuel, producing only water when combusted. Free hydrogen, however, is not a natural energy source, and its generation from hydrocarbons or water is a highly energy-consuming process. As it is extremely volatile and potentially explosive, hydrogen gas requires high-pressure equipment, costly and non-existent infrastructure, special materials to minimize diffusion and leakage, and extensive safety precautions to prevent explosions.
It was suggested that a more practical alternative is methanol.
Methanol is not only a convenient and safe way to store energy, but, together with its derived dimethyl ether (DME), is an excellent fuel. Dimethyl ether is easily obtained from methanol by dehydration and is an effective fuel particularly in diesel engines because of its high cetane number and favorable properties. Methanol and dimethyl ether can be blended with gasoline or diesel and used as fuels, for example in internal combustion engines or electricity generators. One of the most efficient use of methanol is in fuel cells, particularly in direct methanol fuel cell (DMFC), in which methanol is directly oxidized with air to carbon dioxide and water while producing electricity.
Closely related and derived from methanol, and also a desirable alternative fuel is dimethyl ether. Dimethyl ether (DME), the simplest of all ethers, is a colorless, nontoxic, non-corrosive, non-carcinogenic and environmentally friendly chemical that is mainly used today as an aerosol propellant in spray cans, in place of the banned CFC gases. DME has a boiling point of -25C, and is a gas under ambient conditions. DME is, however, easily handled as liquid and stored in pressurized tanks, much like liquefied petroleum gas (LPG). The interest in dimethyl ether as alternative fuel lies in its high cetane rating of 55 to 60, which is much higher than that of methanol and is also higher than the cetane rating of 40 to 55 of conventional diesel fuels. The cetane rating indicates that DME can be effectively used in diesel engines. Advantageously, DME, like methanol, is clean burning, and produces no soot particulates, black smoke or SO2, and only very low amounts of NOx and other emissions even without after-treatment of its exhaust gas.
Our invention relates to various embodiments of an environmentally carbon neutral use of utilizing and recycling carbon dioxide from industrial or natural sources, as well as from the air itself into methanol dimethyl ether and derived products.
The carbon dioxide obtained from such sources is typically converted to methanol by catalytic, photochemical or electrochemical hydrogenation. The conversion to methanol, however, forms a reaction mixture also containing formic acid and formaldehyde. These can be, without separation of the reaction mixture, in a subsequent treatment step conducted under conditions sufficient to produce formaldehyde and formic acid themselves, converted to methanol using modifications of the so-called Canizzaro-Tischenko reactions.
(If you're really interested, see:
Tishchenko reaction - Wikipedia, the free encyclopedia; and:
Cannizzaro reaction - Wikipedia, the free encyclopedia.
Olah and Prakash are reducing some pretty esoteric stuff to concrete practice herein, all of which combine to make for a very efficient, at least as relative to prior art, conversion of Carbon Dioxide into Methanol, and, through Methanol, into a variety of other fuels and industrially-valuable chemicals, including DME.)
Converting the formaldehyde with co-formed formic acid as a hydrogen source is also feasible, without separation of the reaction mixture, into methanol, and by reacting some of the formic acid with methanol to form methyl formate, followed by hydrogenating the methyl formate under conditions sufficient to form methanol. The hydrogen needed for the hydrogenation of methyl formate can be obtained from electrolysis of water, by decomposing at least some of the formic acid from the reaction mixture or by the reaction of methane with carbon dioxide (dry reforming).
(We'll have more on obtaining Hydrogen via the "electrolysis of water" as in our above citation of "United States Patent 3,888,750 - Electrolytic Decomposition of Water", in some future reports; and, we have documented the rather intriguing potentials of "dry reforming" in some earlier reports, such as:
Pittsburgh 1941 CO2 + Methane = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,266,989 - Manufacture of a Gas from CO2 and Methane; 1941; Assignee: Koppers Company, Pittsburgh, PA; Abstract: The present invention relates to the manufacture of gases suitable for the synthesis of higher hydrocarbons or the like, said gases containing definite volumes of carbon monoxide and hydrogen in a certain proportion, by reacting on methane ... with carbon dioxide or a mixture of carbon dioxide and steam, so that the methane ... is decomposed into hydrogen and carbon monoxide";
wherein the "carbon monoxide" could be extracted and utilized separately in a process like that seen in:
Pittsburgh 1951 Carbon Monoxide + Water = Hydrocarbons | Research & Development; concerning: "United States Patent 2,579,663 - Process of Synthesizing Hydrocarbons; 1951; Assignee: Gulf Research and Development Company, Pittsburgh; Abstract: This invention relates to a process for synthesizing hydrocarbons; more particularly the invention relates to a process for synthesizing normally liquid hydrocarbons from carbon monoxide and steam";
thus leaving the "hydrogen" available for addition to the CO2-recycling process of our subject, "United States Patent 8,212,088 - Efficient and Selective Conversion of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products".)
The available source of carbon dioxide is preferably an exhaust stream from a fossil fuel burning power or other industrial plants, or a natural source accompanying natural gas. These available sources would otherwise be released into the atmosphere. The utilization of the exhaust stream as a source for chemical recycling avoids emitting the carbon dioxide into the atmosphere. The available source of carbon dioxide may also the air of our atmosphere with the carbon dioxide obtained by absorbing atmospheric carbon dioxide onto a suitable adsorbent followed by treating the adsorbent to release the adsorbed carbon dioxide therefrom. By removing and recycling carbon dioxide from the atmosphere provides a source that is inexhaustible. Suitably, the adsorbent is treated by sufficient heating or is subjected to sufficient reduced pressure to release the adsorbed carbon dioxide."
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We, too, think the collection of our valuable Carbon Dioxide resource from the atmosphere, for a number of reasons, is a better way to go about it, as we reported, for one example, in:
West Virginia Coal Association | Capture of CO2 from Ambient Air | Research & Development; concerning: "'Capture of CO2 from Ambient Air: A Specific Approach'; Klaus Lackner; Columbia University; Abstract: We describe a technology for capturing CO2 directly from ambient air (air capture) at collection rates that far exceed those of trees or other photosynthesizing organisms and at costs that would allow the widespread use of air capture in managing the anthropogenic carbon cycle and combating climate change";
especially since CO2 collection facilities could be installed at sites where available environmental energy, i.e., solar, wind or hydro, could be more easily harnessed to drive the process of Carbon Dioxide collection, thus avoiding parasitic loads on our Coal-fired power plants; and, subsequently, via the process of our subject herein, "United States Patent 8,212,088 - Efficient and Selective Conversion of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products", for just one example, the conversion of that Carbon Dioxide, through an "environmentally beneficial method", into "a renewable fuel".
