As we documented most recently via:
West Virginia Coal Association | USDOE Sunlight Converts CO2 into Methane | Research & Development; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; 2013; Inventor: Brian Ingram, et. al., IL and TN; Assignee: UChicago Argonne, LLC, Chicago; Government Interests: The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory. Abstract: In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen. ... This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane and other hydrocarbon fuels, particularly promoted by sunlight";
our own United States Government, as embodied in the United States Department of Energy and in the USDOE's National Energy Technology Laboratories, recently confirmed, that, in processes which might be termed "artificial photosynthesis", the energy of sunlight can be harnessed to drive catalyzed reactions between that freely-available natural resource, Carbon Dioxide, and plain old Water, H2O, with the result being the production of both Oxygen and substitute natural gas Methane.
In passing, we note that we made report of that US Patent Application very shortly after it was published; and, the links to it we were able to include in that report have proven unreliable and have malfunctioned, as they are posted on the West Virginia Coal Association's web site. We assure you that the Application, with it's exposition of technology that can use simple sunlight to drive the conversion of CO2 and H2O into Methane is quite real; and, following are three fresh links to that Application which, at the time of this transmission, function properly:
United States Patent Application: 0130079577
AUTOGENIC REACTION SYNTHESIS OF PHOTOCATALYSTS FOR SOLAR FUEL GENERATION - UCHICAGO ARGONNE, LLC .
That said, we remind you that, as seen for one example in our report of:
West Virginia Coal Association | 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. Now, the object of my present invention is to develop an improved method and means for producing a gas suitable for the synthesis of hydrocarbons ... from methane ... without using carbon from other sources, for instance, coal ... . The process according to the invention consists in ... heating up the methane ... in the presence of carbon dioxide or carbon dioxide and steam (and) for adding an adjustable quantity of the carbon dioxide to the gas heater while introducing the methane ... . In order to obtain a gas in the proportion of one volume carbon monoxide to one volume hydrogen, the methane according to the present invention is converted ... by the use of carbon dioxide principally in accordance with the ... reaction: CH4 + CO2 = 2CO + H2. The reactions between methane and carbon dioxide or methane and a mixture consisting of carbonic acid and steam, as adopted for the process according to the present invention are already known, but heretofore these reactions have not yet been used on an industrial scale, mainly due to the fact that up to now no suitable source for the carbon dioxide ... was available";we have known for a very long time, that, once we have Methane, perhaps as synthesized, as in "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation", from Carbon Dioxide, we can react that Methane with even more Carbon Dioxide, in processes known variously as "bi-reforming" and "tri-reforming", or just "reforming", and thereby generate a mixture of "hydrogen and carbon monoxide", that is, "a gas suitable for the synthesis of hydrocarbons".
We note, with some irony, the concluding statement in our above excerpt, indicating that such technology was not being more broadly employed since "no suitable source for the carbon dioxide ... was available".
In any case, we reported most recently on such "CH4 + CO2 = 2CO + H2" potentials in our dispatch concerning yet another CO2 utilization process devised by the University of Southern California's Nobel Prize-winning genius, George Olah, 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; Date: June 11, 2013; Inventors: George Olah and G.K. Surya Prakash, CA; 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 ... methane ... 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".
And, herein, via excerpts from the initial link in this dispatch, we see that the above Olah and Prakash, almost coincident with their exposition of the above "United States Patent 8,461,215", devised yet another way to react Carbon Dioxide with Methane in the synthesis of, specifically, Methanol:
"United States Patent 8,440,729 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane
Date: May 14, 2013
Inventors: George Olah and G.K. Surya Prakash, CA
Assignee: University of Southern California, Los Angeles
Abstract: The invention provides for a method of forming methanol by combining a mixture of methane, water and carbon dioxide under specific reaction conditions sufficient to form a mixture of hydrogen and carbon monoxide which are then reacted under conditions sufficient to form methanol. The molar ratio of hydrogen to carbon monoxide is at least two moles of hydrogen to one mole of carbon monoxide and the overall molar ratio between methane, water and carbon dioxide is about 3:2:1. Methane, carbon dioxide and water are bi-reformed over a catalyst. The catalyst includes a single metal, a metal oxide, a mixed catalyst of a metal and a metal oxide or a mixed catalyst of at least two metal oxides.
(Note that not a lot of Carbon Dioxide is needed in this particular version of tri-reforming, relative to the Methane and Water. But, if the Methane itself has been synthesized, as seen for yet another example in:
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; Government Interests: This invention was made with support from the U.S. government under U.S. Contract No. NNX10CF25P sponsored by the National Aeronautics and Space Administration. The U.S. Government holds certain rights in this invention. Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen in a first reaction zone with a first catalyst bed ... so as to produce a product stream comprising water and methane";
from Carbon Dioxide, this still represents, in essence, an intensive, recycling of Carbon Dioxide. But, further, we must note, that, as seen for one example 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, CA; Assignee: University of Southern California, Los Angeles; 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. Converting carbon dioxide by an electrochemical reduction of carbon dioxide in a divided electrochemical cell";
such "Reforming" reactions with Methane, with the subsequent formation of an intermediate blend of Carbon Monoxide and Hydrogen, are not the only means by which CO2 can be converted into Methanol.
And even further, as seen in our report of:
West Virginia Coal Association | California Awarded March, 2011, CO2-to-Methanol US Patent | Research & Development; concerning: "United States Patent 7,906,559 - Conversion of CO2 to Methanol and/or Dimethyl Ether using Bi-Reforming of Methane or Natural Gas; 2011; Inventors: George Olah and G.K. Surya Prakash, CA; Assignee: University of Southern California, Los Angeles; Abstract: The invention discloses a method of converting carbon dioxide to methanol and/or dimethyl ether using any methane source or natural gas consisting of a combination of steam and dry reforming, in a specific ratio to produce a 2:1 molar ratio of hydrogen and carbon monoxide with subsequent conversion of the CO and H2 mixture exclusively to methanol and/or dimethyl ether";
the process of our subject herein, "United States Patent 8,440,729 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane", is only one of the latest examples of such "Reforming" CO2 utilization technologies to emerge from George Olah's USC laboratory.)
Claims: A method of preparing methanol from carbon dioxide, water and a methane source which comprises: conducting a bi-reforming reaction, wherein the only reactants are methane, carbon dioxide and water in a mole ratio of about 3:1:2 as follows:
3CH4 + 2H2O + CO2 by:
conducting wet reforming of methane from the methane source with water to form carbon monoxide and hydrogen as follows:
2CH4 + 2H2O = 2CO + 6H2;
conducting dry reforming of methane from the methane source with carbon dioxide to form carbon monoxide and hydrogen as follows:
CH4 + CO2 = 2CO + 2H2
combining effluents consisting of the carbon monoxide and hydrogen from the wet and dry reforming reactions without separation of components of the reforming reactions or their effluents to produce a mixture of hydrogen and carbon monoxide having a molar ratio of hydrogen to carbon monoxide that is 2:1 to 2.1:1; and converting the molar mixture of hydrogen and carbon monoxide under conditions sufficient to exclusively form methanol, as follows:
4CO + 8H2 = 4CH3OH.
("CH3OH" = Methanol. And, here seems a good place to remind you, that, as seen for only one example out of many in our report of:
West Virginia Coal Association | ExxonMobil "Clean Gasoline from Coal" | Research & Development; concerning the ExxonMobil marketing/promotional document: "'Methanol to Gasoline (MTG): Production of Clean Gasoline from Coal; So Advanced, Yet So Simple'; Coal is expected to play a key role as an energy source in the rapidly growing economy in countries such as China, India and even the United States (such as via) the conversion of coal into high quality, clean-burning transportation fuel. "There are two commercially demonstrated routes for converting coal to transportation fuels through gasification ... . The first is the widely known Fischer-Tropsch process, discovered in the 1920’s. It has been commercially practiced in several different forms to produce fuels from either coal or natural gas. Less known, is another commercially proven alternative for converting coal to gasoline through methanol. ExxonMobil Research and Engineering Company’s (EMRE) Methanol-to-Gasoline (MTG) process converts coal to high quality clean gasoline when coupled with commercially proven coal gasification and methanol synthesis technology";Methanol - - once we've synthesized it from one or the other of our abundant resources, Coal or, as via one or the other of the University of Southern California technologies developed by Nobel Laureate Olah, Carbon Dioxide - - can be directly converted into that stuff we're mortgaging our grandchildren's future to the tender loving nations of OPEC to keep ourselves supplied with in the here and now, i.e.: Gasoline.)
The method ... wherein the single bi-reforming step is conducted at a temperature of about 800 to 1100 C.
The method ... wherein the reacting of methane, water and carbon dioxide is conducted without any significant coke formation (and) in the presence of a combination of metal and metal oxide catalysts (and) wherein the catalyst combination is Ni and V2O5; Ni2O3 and V2O5; or Ni2V2O7 and Ni3V2O8.
(The Nickel, Ni, and Vanadium, V, serving as catalysts rather than reactants, aren't used up or consumed to any appreciable extent in this process. Once we have them, we're good to go. But, our good friends in Canada, if needed, can supply us with plenty of Nickel. And, even though Russia, China and South Africa are the top producers of Vanadium in the world, we used to, and could again, produce some from deposits in Colorado. And, there are major deposits in northern Quebec and northern Manitoba, again in Canada, which could be developed if overseas sources for some reason became unavailable.)
The method ... wherein the catalyst combination is supported on a high surface (area) support (and) wherein the support comprises silica, alumina, a metal oxide or a metal.
Description and 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 natural gas, are composed of hydrocarbons with varying ratios of carbon to hydrogen. Despite their wide application and high demand, fossil fuels also have limitations and disadvantages, particularly due to their finite reserve ... .
One alternative frequently mentioned non-carbon fuel is hydrogen, and its use in the so-called "hydrogen economy." Hydrogen is thought to be beneficial as a clean fuel, producing only water when combusted. Free hydrogen, however ... hydrogen is difficult and costly to handle, transport and distribute. As it is extremely light, volatile and potentially explosive, it requires high-pressure equipment. The needed non-existent infrastructure also necessitates special materials to minimize diffusion and leakage, and extensive safety precautions to prevent explosions.
Methanol (however) is a convenient safe liquid easily obtained from ... coal ... via methods developed and practiced since the 1920's.
Methanol not only represent a convenient and safe way to store and transport energy, but together with its derived product dimethyl ether (DME), is an excellent fuel. Dimethyl ether is easily obtained from methanol by dehydration or from methane ... with CO2 via a bi-reforming process. It is a particularly effective fuel for diesel engines because of its high cetane number and favorable combustion properties. Methanol and dimethyl ether exceedingly blend well with gasoline or diesel oil to be used as fuels in internal combustion engines or electricity generators.
Contrary to gasoline, which is a complex mixture of many different hydrocarbons and additives, methanol is a single simple chemical compound. It contains about half the energy density of gasoline, meaning that two liters of methanol provide the same energy as a liter of gasoline. Even though the energy content of methanol is lower, it has a higher octane rating of 100 (average of the research octane number (RON) of 107 and motor octane number (MON) of 92), which means that the fuel/air mixture can be compressed to a smaller volume before being ignited. This allows the engine to run at a higher compression ratio of 10-11 to 1 more efficiently than the 8-9 to 1 ratio of a gasoline-powered engine. Efficiency is also increased by methanol's (oxygenates') higher "flame speed," which enables faster, more complete fuel combustion in the engines. These factors explain the high efficiency of methanol despite its lower energy density than gasoline. Further, to render methanol more ignitable even under the most frigid conditions, methanol is mixed with gasoline, and other volatile components or with a device to vaporize or atomize methanol. For example, an effective automotive fuel comprised by adding methanol to gasoline with the fuel having a minimum gasoline content of at least 15% by volume (M85 fuel) so that the engine can readily start even in low temperature environments were commercially used in the US in the 1980's. M20fuel (with 20 volume % methanol) is also being introduced.
(Again, as noted above in our reference to ExxonMobil's "Methanol to Gasoline (MTG): Production of Clean Gasoline from Coal; So Advanced, Yet So Simple", Methanol can be converted into Gasoline.)
Similarly, dimethyl ether (DME) mixed with diesel oil or in household use as a substitute of natural gas or LPG is of commercial interest. These mixtures are not only efficient fuels but conserve or replace decreasing oil resources. The amount of methanol or dimethyl ether added can be determined depending upon the specific condition and needs.As mentioned, the closely related derivative of methanol, which is a highly desirable alternative fuel, is dimethyl ether. Dimethyl ether (CH3OCH3), 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. Dimethyl ether has a boiling point of -25 C, and is a gas under ambient conditions. Dimethyl ether is, however, easily handled as a 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 dimethyl ether is effectively used in diesel engines. Advantageously, dimethyl ether, 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.
Another methanol derivative is dimethyl carbonate (DMC), which can be obtained by converting methanol with phosgene or by oxidative carbonylation of methanol. DMC has a high cetane rating, and can be blended into diesel fuel in a concentration up to 10%, reducing fuel viscosity and improving emissions.
Methanol and its derivatives, e.g., dimethyl ether, DMC ... have significant and expanding uses. They can be used, for example, as a substitute for gasoline and diesel fuel in ICE(Internal Combustion Engine)-powered cars with only minor modifications to the existing engines and fuel systems. Methanol can also be used in fuel cells, for fuel cell vehicles (FCVs), which are considered to be the best alternatives to ICEs in the transportation field. DME is also starting to be used in admixture to LNG and LPG in domestic and industrial fuel uses.
In addition to use as fuels, methanol, dimethyl ether and derived chemicals have significant applications in the chemical industry. Today, methanol is one of the most important feedstock in the chemical industry. The majority of the some 35 million tons of the annually produced methanol are used to manufacture a large variety of chemical products and materials, including basic chemicals such as formaldehyde, acetic acid, MTBE (although it is increasingly phased out for environmental reasons), as well as various polymers, paints, adhesives, construction materials, and others.
Methanol is also a feedstock for chloromethanes, methylamines, methyl methacrylate, and dimethyl terephthalate, among others. These chemical intermediates are then processed to manufacture products such as paints, resins, adhesives, antifreeze, and plastics.
(In which "paints, resins, adhesives ... and plastics", we submit, any Carbon Dioxide consumed, via the process of our subject herein, "United States Patent 8,440,729 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane", in the synthesis of the Methanol, would be chemically and permanently, and productively and profitably, "sequestered". )
Formaldehyde, produced in large quantities from methanol, is mainly used to prepare phenol-, urea- and melamine-formaldehyde and polyacetal resins as well as butanediol and methylene bis(4-phenyl isocyanate) MDI foam, which is used as insulation in refrigerators, doors, and in car dashboards and bumpers. Formaldehyde resins are predominantly used as adhesives in a wide variety of applications, e.g., manufacture of particle boards, plywood and other wood panels.
The presently existing methods of producing methanol involve syngas. Syngas is a mixture of hydrogen, carbon monoxide and carbon dioxide, and produces methanol over a heterogeneous catalyst according to the following reactions:
CO + 2H2 = CH3OH + (heat)
CO2 + 3H2 = CH3OH + H2O + (heat)
CO2 + H2 =.CO + H2O
The first two reactions are exothermic (while the) third equation describes the endothermic reverse water gas shift reaction (RWGSR). Carbon monoxide produced in the third reaction can further react with hydrogen to produce methanol.
Synthesis gas for methanol production can be obtained by reforming or partial oxidation of any carbonaceous material, such as coal ... .
In a preferred embodiment, the method comprises: conducting wet reforming of methane from the methane source with water to form carbon monoxide and hydrogen as follows:
2CH4 + 2H2O = 2CO + 6H2;
conducting dry reforming of methane from the methane source with carbon dioxide to form carbon monoxide and hydrogen as follows:
CH4 + CO2 = 2CO + 2H2;
combining the carbon monoxide and hydrogen from the wet and dry reforming without separation of components to produce a molar mixture of hydrogen and carbon monoxide wherein the hydrogen is present in an amount such that the ratio of hydrogen to carbon monoxide is at least 2:1; and: converting molar mixture of hydrogen and carbon monoxide under conditions sufficient to exclusively form methanol, as follows:
4CO + 8H2 = 4CH3OH."
Because of its economic and long range availability advantages, methanol is considered a potential prime feedstock for processes currently utilizing more expensive feedstock such as ethylene and propylene, to produce chemicals including acetic acid, acetaldehyde, ethanol, ethylene glycol, styrene, and ethylbenzene, and various synthetic hydrocarbon products. For example, direct conversion of methanol to ethanol can be achieved using a rhodium-based catalyst, which has been found to promote the reductive carbonylation of methanol to acetaldehyde with selectivity close to 90%, and a ruthenium catalyst, which further reduces acetaldehyde to ethanol.
Producing ethylene glycol via methanol oxidative coupling instead of using ethylene as feedstock is also pursued, and significant advances for synthesizing ethylene glycol from dimethyl ether, obtained by methanol dehydration, have also been made.
Conversion of methanol to olefins such as ethylene and propylene, also known as methanol to olefin (MTO) technology, is particularly promising considering the high demand for olefins, especially in polyolefin and synthetic hydrocarbon products production.
There is also a methanol to gasoline (MTG) process, in which medium-pore zeolites with considerable acidity, e.g., ZSM-5, are used as catalysts. In this process, methanol is first dehydrated to an equilibrium mixture of dimethyl ether, methanol and water over a catalyst, and this mixture is then converted to light olefins, primarily ethylene and propylene. The light olefins can undergo further transformations to higher olefins, C3-C6 alkanes, and C6-C10 aromatics such as toluene, xylenes, and trimethylbenzene.
Summary: The invention now provides novel methods for converting methane and carbon dioxide to methanol without any release of carbon dioxide to the atmosphere or without by-product formation or the use of hydrogen to form water.
In one embodiment, the invention provides for a method of forming methanol, by combining methane, water and carbon dioxide, preferably in a mixture, in single or multiple steps under reaction conditions sufficient to form a molar mixture of hydrogen and carbon monoxide in a specific ratio of at least two moles of hydrogen to one mole of carbon monoxide, and reacting the mixture of hydrogen and carbon monoxide under conditions sufficient to exclusively form methanol."
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The full Disclosure is even more detailed than what we know to be our tediously-long excerpts. But, the value of Methanol as a basic raw material for the industrial synthesis of all kinds and sorts of hydrocarbons cannot be overstated.
It deserves emphasis - as does the fact that Methanol can be synthesized from Carbon Dioxide.
Again, unlike processes represented by our earlier citation of our report concerning: "United States Patent 8,138,380 - Electrolysis of Carbon Dioxide ... for Production of Methanol", which require only Water and Electricity to convert CO2 into Methanol, the process of our subject, "US Patent 8,440,729 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane" requires Methane for catalyzed, thermally-driven reaction with Carbon Dioxide to form the blend of Hydrogen and Carbon Monoxide synthesis gas, which is then catalytically, chemically condensed into Methanol.
And, we again emphasize, that, as seen for yet another example 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; Assignee: The Penn State Research Foundation, University Park, PA; 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 (wherein) methanogenic microorganisms reduce the carbon dioxide to produce methane gas";
a variety of technologies exist which enable the synthesis of that necessary Methane from Carbon Dioxide; thus making the process of "US Patent 8,440,729 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane" a potentially very intensive Carbon Dioxide recycling technology; one which, we insist, should make clear the truth of the matter:
Carbon Dioxide, as fortuitously arises as a co-product from our economically essential use of Coal in the generation of reliable, truly abundant and truly affordable electric power, is a valuable raw material resource, a resource which can be productively utilized and consumed in the synthesis of Methanol, and, through Methanol, all sorts of other alcohols, such as Ethanol; all sorts of liquid hydrocarbon fuels, including Gasoline and Diesel; and, a wide variety of plastics and polymers, wherein the Carbon Dioxide consumed in their syntheses would remain permanently, and profitably, sequestered.