United States Patent Application: 0140243435
Carbon Dioxide, as is co-produced in only a small way, relative to some all-natural and non-political sources of it's emission, such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of truly abundant and genuinely affordable electric power, could and should be treated as a valuable raw material resource.
We can reclaim Carbon Dioxide from whatever source most convenient to us, and then convert that Carbon Dioxide directly into fuel alcohols of nearly immense utility.
We've reported many times over the past years, that - almost totally unacknowledged by the press, including, inexplicably, our Coal Country press - the Eastman Chemical Company has been converting Coal, at a plant in Kingsport, Tennessee, through a process of gasification coupled with subsequent catalytic synthesis, into a range of industrial chemicals, including the immensely-valuable fuel alcohol, Methanol.
For some introductory background, see, for a few examples:
Tennessee Coal to Methanol & Dimethyl Ether | Research & Development | News; which centers on: "United States Patent 5,254,596 - Process for the Manufacture of Methanol and Dimethyl Ether; 1993; Inventors: Gether Irick, Jr., et. al., Tennessee; Assignee: Eastman Kodak Company; Abstract: Disclosed are chemically-mixed, titanium-zinc oxide catalysts and the use of the catalysts in the manufacture of methanol and dimethyl ether (from) synthesis gas ... . Claims: Process ... for the preparation of methanol, dimethyl ether or a mixture thereof which comprises contacting synthesis gas comprising about 8 to 20 volume percent carbon monoxide, about 72 to 92 volume percent hydrogen and up to 20 volume percent carbon dioxide with a catalyst composition essentially free of chromium, copper, and palladium comprising chemically-mixed, titanium-zinc oxide ... .The advantages of including a small amount of carbon dioxide in synthesis gas used in the manufacture of methanol are well documented"; and:
Eastman Chemical Coal Gasification Overview | Research & Development | News; concerning the presentation: "Eastman Gasification Services Company: Eastman Gasification Overview; March 22, 2005; Gasification 101: Just the Basics: C + O2 + H2O = CO + H2; The partial oxidation of carbon to produce a 'synthesis gas'. What Is Gasification? Coal + Water + Oxygen = Carbon Monoxide + Hydrogen. So What Can You Do With CO (Carbon Monoxide) and H2 (Hydrogen)? Syngas = Building Blocks for Chemical Industry + Transportation Fuels + Clean Electricity. Integrated Gasification Combined Cycle: Replace Natural Gas Feed With (Coal-derived) Syngas. Gasification-based Polygeneration: Syngas from Coal (to) Electricity, Chemicals, Synfuels, Fertilizers. Polygeneration Potential of (Coal) Gasification: Fischer-Tropsch Liquids - Car Fuel (and) Diesel; Ethylene and Propylene; Methanol; Power (and more). Benefits of Polygeneration: Higher Overall Value Creation (and) Higher Employment For The Community. Coal needs to return as a key feedstock and energy source in the US!!! Gasification is the technology of choice for converting coal to clean and efficient power, chemicals, fertilizers and fuels".
As indicated in the "Eastman Gasification Overview", it is quite feasible to, as confirmed in:
Eastman Coal to Methanol and Electric Power | Research & Development | News; concerning: "US Patent Application 20060096298 - Method for Satisfying Variable Power Demand; 2006; Inventor: Scott Barnicki, et. al., Kingsport, TN; Assignee: Eastman Chemical Company; Abstract: A process for satisfying variable power demand and a method for maximizing the monetary value of a synthesis gas stream are disclosed. One or more synthesis gas streams are produced by gasification of carbonaceous materials and passed to a power producing zone to produce electrical power during a period of peak power demand or to a chemical producing zone to produce chemicals such as, for example, methanol, during a period of off-peak power demand. The power-producing zone and the chemical-production zone which are operated cyclically and substantially out of phase in which one or more of the combustion turbines are shut down during a period of off-peak power demand and the syngas fuel diverted to the chemical producing zone. This out of phase cyclical operational mode allows for the power producing zone to maximize electricity output with the high thermodynamic efficiency and for the chemical producing zone to maximize chemical production with the high stoichiometric efficiency. The economic potential of the combined power and chemical producing zones is enhanced.";
maximize the value of a Coal-to-chemicals or Coal-to-Methanol operation wherein Coal is first gasified, to produce hydrocarbon synthesis gas, by co-producing, in one integrated process, both valuable chemicals and electrical power.
However, note that all that's needed, really, to produce valuable products like the fuel alcohol Methanol is a blend of the gases "carbon monoxide, ... hydrogen and ... carbon dioxide".
And, in fact, as seen in:
The University of Oxford Converts CO2 into Methanol | Research & Development | News; concerning: "Process For Producing Methanol; Publication No: WO/2011/045605; International Application No: PCT/GB2010/051733; 2010; (University of Oxford, England); Abstract: The present invention relates to a novel process for the production of methanol. The process comprises the heterolytic cleavage of hydrogen by a frustrated Lewis pair comprising a Lewis acid and a Lewis base; and the hydrogenation of CO2 with the heterolytically cleaved hydrogen to form methanol";
it isn't, strictly speaking, necessary to have the Carbon Monoxide as part of the initial reaction mix, since, if enough Hydrogen is available, it can be made to, first , catalytically and chemically "reduce" the Carbon Dioxide, to form Carbon Monoxide, which then reacts with more Hydrogen to form the alcohol.
That - - what is known as "reverse conversion" of CO2 to Carbon Monoxide through reaction with Hydrogen - - is more fully described for one example in our report of:
France Efficient CO2 to Carbon Monoxide Conversion | Research & Development | News; concerning: "United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst; 2003; Assignee: Air Liquide (France); Abstract: The invention concerns a method for producing carbon monoxide by reverse conversion ... of gaseous carbon dioxide and gaseous hydrogen, while minimizing the production of methane".
Thus, if you have Carbon Monoxide, or a blend of Carbon Monoxide and Carbon Dioxide, or, even, just Carbon Dioxide, if enough Hydrogen is available, you can make fuel alcohol Methanol. That fact was confirmed, and even expanded upon, by our United States Department of Energy, who, as in our report of:
USDOE CO2 + Hydrogen = Methanol and Ethanol | Research & Development | News; concerning: "United States Patent 7,858,667 - Alcohol Synthesis from CO or CO2; 2010; Inventors: Jianli Hu, et. al., WA and TX; Assignee: Battelle Memorial Institute, WA; (USDOE Pacific Northwest National Laboratory); Abstract: Methods for producing alcohols from CO or CO2 and H2 utilizing a palladium-zinc (Pd--Zn) on alumina catalyst are described. Methods of synthesizing alcohols over various catalysts in microchannels are also described. Ethanol, higher alcohols, and other C2+ oxygenates can be produced utilizing Rh--Mn (Rhodium and Manganese) or a Fisher-Tropsch catalyst. A portion of this work was funded by the U.S. DOE ... under Contract DE-AC06-76RL01830";
demonstrated that we can efficiently synthesize not just Methanol, but, "Ethanol", as well, from either Carbon Monoxide "or", as recovered from whatever handy source, "CO2".
And, those facts are confirmed herein by the Coal-to-Methanol experts at Eastman Chemical Company. As seen in excerpts from the initial link in this dispatch to the recent publication of:
"United States Patent Application 20140243435 - Production of Methanol and Ethanol from CO or CO2
Production of Methanol and Ethanol from CO or CO2 - EASTMAN CHEMICAL COMPANY
Patent US20140243435 - Production of Methanol and Ethanol from CO or CO2 - Google Patents
Date: August 28, 2014
Inventors: Jan Hendrik Blank, et. al., Qatar, Great Britain and Tennessee
(http://en.wikipedia.org/wiki/Qatar; "Qatar" is a Persian Gulf nation that borders on Saudi Arabia. Do you suppose they're paying attention to these technological developments for converting CO2 into liquid fuels there?)
Assignee: Eastman Chemical Company, Kingsport, Tennessee
Abstract: This invention relates to a process for making methanol and ethanol from carbon dioxide and hydrogen. The process includes contacting a mixture of carbon dioxide and hydrogen with a catalyst system containing a ruthenium compound--and optionally, a chloride or bromide-containing compound--dispersed in a low-melting tetraorganophosphonium chloride or bromide salt under conditions effective to produce methanol and ethanol.
The invention also relates to a process for making methanol and ethanol from carbon monoxide and water using the same catalyst system.
(In other words, if we have elemental, molecular Hydrogen, perhaps as efficiently extracted from the abundant water, H2O, molecule in a process that is driven by freely-available environmental energy, like that seen in our report of:
North Carolina Sunshine Extracts Hydrogen from H2O for USDOE | Research & Development | News; concerning: "United States Patent 8,524,903 - Ruthenium or Osmium Complexes and Their Uses as Catalysts for Water Oxidation; 2013; Inventors: Javier Jesus Concepcion Corbea, et. al., North Carolina; Assignee: The University of North Carolina at Chapel Hill; Abstract: The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules. Government Interests: This invention was made, in-part, with United States government support under grants numbered DE-FG02-06ER15788 and DE-SC0001011 from the Department of Energy. The U.S. Government has certain rights to this invention. The present invention generally relates to catalysts for water oxidation. Hydrogen is one of the most promising alternative energy sources. It can be obtained by electrolysis of water, which is environmentally friendly and efficient. However, the electrolysis of water is an energy intensive process, which is very expensive. On the other hand, photolysis, the splitting of water by light, presents an attractive alternative method of obtaining hydrogen. Additionally, light driven reduction of carbon dioxide by water to provide hydrocarbons or methanol may be another promising alternative to alternate energy sources. For both types of reactions, coupled water oxidation to oxygen is required. In order to facilitate the photolysis of water by light in either type of reaction, a catalyst is required for the reaction. Therefore, there is a need in the industry for an efficient catalyst for the electrolysis or photo electrolysis of water to obtain hydrogen or water reduction of carbon dioxide to obtain affordable and sustainable alternative source of energy";
where scientists contracted by our USDOE showed how sunlight could extract Hydrogen from H2O, perhaps even in conjunction with processes that used that used that Hydrogen to chemically reduce "carbon dioxide", specifically for the purposes, as disclosed by our subject herein, of creating "affordable and sustainable source(s) of energy".
However, if we can also make "methanol and ethanol from carbon monoxide and water", as Eastman states, much as seen in our report of:
USDOE Carbon Monoxide + H2O = Alcohol | Research & Development | News; concerning: "United States Patent 4,656,152 - Catalyst for Producing Lower Alcohols; 1987; Assignee: The United States of America, as represented by the Secretary of the USDOE; Abstract: A process and system for the production of the lower alcohols such as methanol, ethanol and propanol involves the reaction of carbon monoxide and water in the presence of a lead salt and an alkali metal formate catalyst combination. ... The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the U.S. Department of Energy and Argonne National Laboratory. A catalyst combination for the reaction of carbon monoxide and water to produce lower alcohols";
it might make more energy sense to operate the process of our subject, "United States Patent Application 20140243435 - Production of Methanol and Ethanol from CO or CO2", by starting with a blend of water and Carbon Monoxide, which Carbon Monoxide, as seen most recently in our report of:
US Gov Hires Delaware to Convert CO2 into Carbon Monoxide | Research & Development | News; concerning: "United States Patent Application 20140262792 - System and Process for Electrochemical Conversion of Carbon Dioxide to Carbon Monoxide; 2014; Inventors: Joel Rosenthal, et. al.; Assignee: University of Delaware, Newark; Abstract: The invention provides a system and a process that allow for the selective electrochemical conversion of carbon dioxide to carbon monoxide with high energy efficiency, using a cathode comprised of bismuth in combination with an anode such as an anode comprised of platinum. The electrolysis system may be comprised of a single or two compartment cell and may employ an organic electrolyte or an ionic liquid electrolyte. The invention permits the storage of solar, wind or conventional electric energy by converting carbon dioxide to carbon monoxide and liquid fuels";
can be made - in a process driven by "solar" or "wind"-generated electricity - from Carbon Dioxide.)
Claims: A process for preparing methanol and ethanol, comprising: contacting a mixture of carbon dioxide and hydrogen with a catalyst system comprising a ruthenium compound dispersed in a low-melting tetraorganophosphonium chloride or bromide salt under conditions effective to produce methanol and ethanol.
The process ... wherein the mixture further comprises carbon monoxide.
The process ... wherein the conditions effective to produce methanol and ethanol comprise a total pressure of 7 MPa to 25 MPa and a temperature of 150 to 220 C (and) wherein the ruthenium compound is selected from the group consisting of ruthenium oxide, ruthenium chloride, ruthenium bromide, anhydrous ruthenium(IV) dioxide, ruthenium(IV) dioxide hydrate (and, others).
The process ... wherein the catalyst system further comprises a chloride or bromide-containing compound (and) wherein the chloride or bromide-containing compound is hydrogen chloride or hydrogen bromide.
(Eastman goes into considerable detail concerning the chemical compositions, detail which is beyond the scope of our presentation herein. The point is that it is known and understood chemistry, and stuff like "hydrogen chloride", aka hydrochloric acid, isn't hard to come by. Other chemicals needed, as specified in additional claims, are organic compounds of phosphous, which again wouldn't be expensive.)
The process ... wherein the volumetric ratio of carbon monoxide to carbon dioxide is from 0.01:1 to 100:1 (and) wherein the volumetric ratio of carbon dioxide to hydrogen is from 0.1:1 to 1:1.
(As above, "carbon monoxide" isn't really needed, since, as above, CO2 can comprise, doing the math, 99.99 percent of the starting mix of carbon-containing gases).
A process for preparing methanol and ethanol, comprising: contacting a mixture of carbon monoxide and water with a catalyst system (specified).
(The above alternative route is as in our earlier comments concerning the precedent art of "United States Patent 4,656,152 - Catalyst for Producing Lower Alcohols").
Background and Field: The invention generally relates to processes for making methanol and ethanol. In particular, in one aspect, the invention relates to the catalyzed hydrogenation of carbon dioxide to form methanol and ethanol. In another aspect, the invention relates to the catalyzed reaction of carbon monoxide with water to form methanol and ethanol.
The conversion of either carbon monoxide or carbon dioxide into derivatives with a C--C bond is an important first step in developing technology for producing organic chemicals from these C1 feedstocks. Due to its low reactivity, carbon dioxide poses a particular challenge, yet an important one, to achieve efficient utilization of many carbon feedstocks in large-scale fuel or commodity chemical production. An emphasis on carbon dioxide utilization has inspired development of CO2-to-methanol technologies.
Summary: Briefly, the present invention provides processes for preparing methanol and ethanol. In one embodiment, the process comprises contacting a mixture of carbon dioxide and hydrogen with a catalyst system comprising a ruthenium compound (and optionally, a chloride or bromide-containing compound) dispersed in a low-melting tetraorganophosphonium chloride or bromide salt under conditions effective to produce methanol and ethanol.
In another embodiment, the process comprises contacting a mixture of carbon monoxide and water with a catalyst system comprising a ruthenium compound and a chloride or bromide-containing compound dispersed in a low-melting tetraorganophosphonium chloride or bromide salt under conditions effective to produce methanol and ethanol".
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We'll close there.
In brief, the technology now exists to convert Carbon Dioxide - - either directly through reactions with Hydrogen, or somewhat indirectly through an initial conversion of CO2 into Carbon Monoxide, a step which can be integrated into the total process - - into the fuel alcohols Methanol and Ethanol.
Methanol and Ethanol have a growing utility in the synthesis of polymers, which we've touched on briefly in prior reports, and which we might address in more detail further on. But, for now, keep in mind, that, as seen for one example in our report of:
Mobil Oil 1977 Coal-Derived Alcohols to Gasoline | Research & Development | News; concerning: "US Patent 4,025,575 - Process for Manufacturing Olefins; 1977; Assignee: Mobil Oil Corporation, NY; Abstract: A lower alcohol and/or ether feed is selectively converted to a mixture of light olefins, including ethylene and propylene, by catalytic contact of the feed, for example methanol or dimethyl ether, ... with certain crystalline aluminosilicate zeolite catalysts exemplified by HZSM-5. Claims: (A) method for converting a feed to light olefins, said feed comprising one or more compounds selected from the group consisting of the lower monohydric alcohols with up to four carbon atoms and their simple and mixed ether derivatives. (And) wherein said feed comprises methanol or dimethyl ether (a methanol derivative, and) wherein said feed comprises ethanol. ... This invention is concerned with the manufacture of light olefin hydrocarbons from lower alcohols or their ethers. It is particularly concerned with the catalytic conversion of such alcohols and ethers selectively to mixtures of olefins having up to five carbon atoms. A remarkable growth in the production of synthetic fibers, plastics and rubber has taken place in recent decades. This growth, to a very large extent, has been supported and encouraged by an expanding supply of inexpensive petrochemical raw materials such as ethylene, propylene, and other, four and five carbon olefins. Side by side with this remarkable development, there has been an increasing demand for alkylate, made by reacting olefins with isobutane, for use as a high octane gasoline component. Burgeoning demand for olefins, particularly ethylene, propylene and butenes, has of course led to periods of shortage, either due to short supply of suitable feedstocks or to limited processing capacity. In any case, it would appear desirable to provide efficient means for converting raw materials other than petroleum to olefins. Brief Summary: In a preferred embodiment of the present invention, a feed comprising one or more compounds, selected from the lower monohydric alcohols with up to four carbon atoms and their simple or mixed ether derivatives, is substantially completely converted, to a mixture comprising a major fraction of light olefins ... . The alcohols may be manufactured from synthesis gas, i.e. a mixture of CO and H2 made from coal";
both Methanol and Ethanol, as can be produced - - via the process of our subject, Eastman Chemical's "United States Patent Application 20140243435 - Production of Methanol and Ethanol from CO or CO2" - - from Carbon Dioxide, can be directly converted into hydrocarbons, specifically "light olefins", such as "ethylene and propylene". And, those "petrochemical raw materials" can then be converted into components of "high octane gasoline" and/or serve "in the production of synthetic fibers, plastics and rubber", wherein the Carbon Dioxide consumed in the initial synthesis of the "Methanol and Ethanol" would be forever, but productively, with the creation of industries and jobs, "sequestered".
Forgive us the repetition, but: Carbon Dioxide, as is co-produced in only a small way, relative to some all-natural and non-political sources of it's emission, such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of truly abundant and genuinely affordable electric power, could and should be treated as a valuable raw material resource.