The US Navy Recycles Yet Even More CO2

United States Patent Application: 0050232833

We have, over the past months and years, made report of what has, now obviously, been an extraordinary research and development effort within the United States Department of Defense to establish comprehensive technology, whereby Carbon Dioxide could be reclaimed from the environment and then be converted into liquid hydrocarbon fuels.

 

Although, as seen, for one example, in our report of:

US Air Force 1965 CO2 to Fuel Conversion | Research & Development; concerning: "Catalytic Reduction of Carbon Dioxide to Methane and Water; Abstract: This report sunmarizes the work accomplished under contract AF 3"(615)-1210, for research on catalytic reduction of carbon dioxide to methane and water. The effort was initiated on 6 January 1964 and completed 31 December 1964";

the United States Air Force was charged, early on, with the development of Carbon Dioxide recycling technology, nearly all of the later work, seemingly begun one quarter of a century ago, as seen, for one example, in:

CO2 to Synfuel Production Ship | Research & Development; concerning: "US Patent 4,568,522 - Synfuel Production Ship; 1986; Assignee: Grumman Aerospace Corporation, NY; Abstract: A vessel, vehicle or aircraft is self-equipped with means for producing and storing synthetic fuel generated from the synthesis of carbon dioxide and hydrogen";

has been done by, or in the support of, the United States Navy. .

Their, and their contractors', efforts have led, in very recent years, to a number of significant achievements in the fields of Carbon Dioxide harvesting and Carbon Dioxide processing, with the end result being the efficient production of liquid hydrocarbon fuels out of Carbon Dioxide extracted from the environment.

Of most note, perhaps, was the recent award of a US Patent on just some of the Navy's CO2-recycling technology, as we reported not long ago in:

US Navy Awarded September, 2011, CO2 Recycling Patent | Research & Development; concerning: "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; September, 2011; Assignee: The United States of America as represented by the Secretary of the Navy; Abstract: A method of: introducing hydrogen and a feed gas containing at least 50 % carbon dioxide into a reactor containing a Fischer-Tropsch catalyst; and heating the hydrogen and carbon dioxide to a temperature of at least about 190 C. to produce hydrocarbons in the reactor. An apparatus having: a reaction vessel for containing a Fischer-Tropsch catalyst, capable of heating gases to at least about 190 C.; a hydrogen delivery system feeding into the reaction vessel; a carbon dioxide delivery system for delivering a feed gas containing at least 50 % carbon dioxide feeding into the reaction vessel; and a trap for collecting hydrocarbons generated in the reaction vessel."

The award of that US Patent followed, by several years, the award of another US Patent for CO2 recycling technology to, essentially, the same team of US Navy scientists, as we reported via:

US Navy 2008 CO2 to Synfuel | Research & Development; concerning: "US Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels; 2008; Assignee: The USA, as represented by the Secretary of the Navy; Abstract: A process for producing synthetic hydrocarbons that reacts carbon dioxide, obtained from seawater or air, and hydrogen obtained from water, with a catalyst in a chemical process such as reverse water gas shift combined with Fischer Tropsch synthesis. The hydrogen is produced by nuclear reactor electricity, nuclear waste heat conversion, ocean thermal energy conversion, or any other source that is fossil fuel-free, such as wind or wave energy. The process can be either land based or sea based."

As we reported, we believed that "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2" was awarded as the result of an application for US patent protection about which we had earlier documented in:

US Navy Seeks CO2 Recycling Patent | Research & Development; concerning: "US Patent Application 2008/0051478A1 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; 2008; Assignee: The Government of the US, as represented by the Secretary of the Navy; Abstract: A method of: introducing hydrogen and a feed gas containing at least 50 volume % carbon dioxide into a reactor containing Fischer-Tropsch catalyst; and heating the hydrogen and carbon dioxide to a temperature of at least 190 C to produce hydrocarbons in the reactor. An apparatus having: a reaction vessel for containing a Fischer-Tropsch catalyst, capable of heating gases to at least about 190 C; a hydrogen delivery system for feeding into the reaction vessel; a carbon dioxide delivery system for delivering a feed gas containing at least 50 volume % carbon dioxide feeding into the reaction vessel; and a trap for collecting hydrocarbons generated in the reaction vessel";

since the wording, as far as we were able to determine, was so closely similar.

Our continuing research has uncovered further documents relating to Carbon Dioxide recycling technology developed by the same core team of scientists in the employ of the United States Navy. And, we must confess that our sadly limited capacities, and diminished core of advisors, have left us unable to do an adequate job of sorting and organizing the rather impressive trail of records left by the Navy, in their development of what should be seen as absolute National Treasure: A complete body of technology that would enable us to, on an industrial basis, extract Carbon Dioxide from the environment and then convert that Carbon Dioxide into liquid hydrocarbon fuels.

Herein, as another bit of evidence attesting to the plain fact that Carbon Dioxide can be so harvested and utilized, we submit record of another United States Patent Application made by the key Navy scientists behind the technologies identified in our above references.

There is more, quite a lot more, to follow in coming reports.

And, given that we are, simply, even unable to print out the full documents so that we can compare them word-for-word, we suggest that the focus of our dispatch herein might, in fact, be the Patent Application that led to issuance, as in our previous report noted above, in 2008, of  ""US Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels".

However, since there will be more to follow, and our wish is to be as thorough, as impeccable, as we can be; and, since the subject matter so fraught with misinformation and controversy, we present herein even further evidence that, not only can Carbon Dioxide be productively reclaimed from the environment and then, on a practical basis, be converted into liquid hydrocarbon fuels, but, that, multiple branches of our own United States Government know full-well that to be true.

Comment follows excerpts from the initial link in this dispatch to:

"US Patent Application 20050232833 - Process for Producing Synthetic Liquid Hydrocarbon Fuels

Date: October, 2005

Inventors: Dennis Hardy and Timothy Coffey, VA

Correspondence (and presumed Assignee): Naval Research Laboratory (i.e. US Navy), Washington, DC

Abstract: A process for producing synthetic hydrocarbons that reacts carbon dioxide, obtained from seawater of air, and hydrogen obtained from water, with a catalyst in a chemical process such as reverse water gas shift combined with Fischer Tropsch synthesis. The hydrogen is produced by nuclear reactor electricity, nuclear waste heat conversion, ocean thermal energy conversion, or any other source that is fossil fuel-free, such as wind or wave energy. The process can be either land based or sea based.

Claims: A system for producing synthetic hydrocarbons, comprising: (a) a unit for recovering carbon dioxide from seawater, air, or a combination thereof; (b) a unit for producing hydrogen from water; and (c) a Fischer Tropsch synthesis unit wherein a reverse water gas shift reaction for intermediary carbon monoxide production or a Carnol or Lurgi process for intermediary methanol production is combined with Fischer Tropsch synthesis to produce said hydrocarbons from said carbon dioxide and said hydrogen.

(Note mention of the "Carnol" technology, above. That, too, is a US Government-owned Carbon Dioxide recycling process, about which we have previously reported, for one instance, in:

CO2 Recycling: "Carnol" Process Converts CO2 into Ethanol | Research & Development; concerning: "The Carnol Process for CO2 Mitigation from Power Plants and the Transportation Sector; Meyer Steinberg; Brookhaven National Laboratory (USDOE); A CO2 mitigation process is developed which converts waste CO2, primarily recovered from coal-fired power plant stack gases with natural gas, to produce methanol as a liquid fuel and coproduct carbon as a materials commodity".

And, we take the Carnol process to be similar to other, so-called "reforming" processes which require Methane, i.e., "natural gas", as a co-reactant for the Carbon Dioxide; as seen for just one out of many examples, in:

Texaco 1948 CO2 + CH4 = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,448,290 - Process for the Production of Synthesis Gas; 1948; Assignee: The Texas Company, NYC (i.e., Texaco); Abstract: This invention relates to a continuous method of manufacturing water gas involving the reaction of a gaseous hydrocarbon with carbon dioxide and steam so as to produce carbon monoxide and hydrogen";

wherein the resulting "Synthesis Gas" blend of "carbon monoxide and hydrogen" is quite suitable, as is the product gas blend of our subject invention herein, for use in a "Fischer Tropsch synthesis to produce said hydrocarbons".

And, since Methane is a required co-reactant for Carbon Dioxide in such processes, we remind you that we have known since award of the 1912 Nobel Prize in Chemistry to Paul Sabatier that we can synthesize Methane from Carbon Dioxide itself, as in our above citation of the United States Air Force, and their process for the "Catalytic Reduction of Carbon Dioxide to Methane and Water".

Furthermore, since, as, for one example, seen in:

Penn State Solar CO2 + H2O = Methane | Research & Development; concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; The Pennsylvania State University; 2009; Abstract: Efficient solar conversion of carbon dioxide and water vapor to methane";

we now have technologies in hand that enable us to use freely-available environmental energy to drive the conversion of Carbon Dioxide into Methane, the use if Methane in a process that consumes more Carbon Dioxide should be seen as big plus.)

The system ... wherein said carbon dioxide recovery unit is selected from the group consisting of: (a) a partial vacuum degassing process used during the pumping of seawater from any depth; (b) an extraction process for recovering carbon dioxide from seawater; (c) an absorption process for recovering carbon dioxide from air; and (d) any other process for recovering carbon dioxide from air or water; or (e) any combination thereof.

(See, for example, our report of:

CO2 Recovered from Air for CO2-to-Gasoline Conversion | Research & Development; concerning, in part: "United States Patent 4,047,894 - Removing Carbon Dioxide from the Air; 1977; Assignee: Siemens Aktiengesellschaft; Abstract: An improved method and apparatus for removing carbon dioxide from the air";

with additional reports of similar and related technologies to follow.)

The system ... wherein said hydrogen production unit is selected from the group consisting of: (a) an electrolysis process; (b) a thermolysis process; (c) a thermochemical process; and (d) any combination thereof.

(See, for example, our report of:

NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,045,315 - Solar Photolysis of Water; 1977; NASA; Abstract: Hydrogen is produced by the solar photolysis of water";

also with additional reports of similar and related technologies to follow.)

The system ... wherein the energy required for said hydrogen production unit is provided by ...  any other non fossil fuel source such as waves, tide, wind, or ocean current energy; or combinations thereof.

(See, for example:

http://hydropower.inel.gov/resourceassessment/pdfs/states/wv.pdf; concerning: "U.S. Hydropower Resource Assessment for West Virginia; 1998; U.S. Department of Energy"; and:

Wind Powering America: West Virginia 50-Meter Wind Resource Map; concerning: "West Virginia 50-Meter Wind Resource Map; The Department of Energy's Wind Program and the National Renewable Energy Laboratory (NREL) published a wind resource map for the state of West Virginia. This resource map shows wind speed estimates at 50 meters above the ground and depicts the resource that could be used for utility-scale wind development".)

The system ... wherein said Fischer Tropsch synthesis unit uses a catalyst selected from the group consisting of: (a) metals selected from the group consisting of iron, cobalt, and nickel, and combinations thereof; (b) metal oxides selected from the group consisting of iron oxide, cobalt oxide, nickel oxide, ruthenium oxide, and combinations thereof; (c) support type material selected from the group consisting of as alumina or zeolites; (d) supported metals, metal oxides, mixed metals, or mixed metal oxides; and (e) any combination thereof. 

A process for producing synthetic hydrocarbons, comprising: (a) recovering carbon dioxide from seawater, air, or a combination thereof; (b) producing hydrogen from water; and (c) reacting said carbon dioxide and said hydrogen with a catalyst in a chemical process using: (1) a reverse water gas shift for intermediary carbon monoxide production or a Carnol or Lurgi process for intermediary methanol production; and (2) a Fischer Tropsch synthesis to produce said hydrocarbons from said hydrogen and said intermediary carbon monoxide or methanol.

Background and Field: The present invention relates to hydrocarbon production and, more specifically, to a process to make synthetic liquid hydrocarbons from carbon dioxide ... without the use of fossil fuels in any step of the process.

Summary: (In) the present invention ... desired synthetic hydrocarbons are produced by reacting carbon dioxide, obtained from seawater or air, and hydrogen from water with a catalyst in a chemical process such as reverse water gas shift combined with Fischer Tropsch synthesis. The reverse water gas shift (CO2+H2=.CO+H2O) produces carbon monoxide, which is reacted with hydrogen in the Fischer Tropsch synthesis to produce synthetic liquid hydrocarbons and water.

In a preferred embodiment, carbon dioxide is recovered ... from seawater (or) absorption from air ... .

Hydrogen is produced by standard electrolysis of water using electrodes, thermolysis of water ... and any combination of the above methods. Energy for the hydrogen production can be provided by ... (a) source of fossil fuel free electricity such as ocean waves, wind, tides or currents; or any combination (thereof). 

The catalyst for the Fischer Tropsch reaction can be a metal such as iron, cobalt, nickel, and combinations thereof; a metal oxide such as iron oxide, cobalt oxide, nickel oxide, ruthenium oxide, and combinations thereof; support type material such as alumina or zeolites; supported metals, mixed metals, metal oxides, mixed metal oxides; and any combination of the above. 

Unique benefits of liquid hydrocarbons produced according to this invention include: they have no sulfur content, they have no nitrogen content, they have no aromatics content, they have high volumetric and gravimetric energy density, they have an excellent resistance to thermal oxidation processes, they are fire safe (i.e., they are hard to ignite), they have good low temperature properties, they ... are produced without using fossil fuels, the process is carbon neutral when combusted, the starting materials are cost free, and in situ production of stored energy requires no large storage volumes or long distance transport ... .

Additionally, an equal volume of fresh water is produced as a useful byproduct.

The preferred embodiment will produce synthetic liquid hydrocarbons at a rate and daily production that is dependent upon the limitations described (concerning amounts of available environmental energy).

A typical production of about 100,000 gallons per day (about 4,000 gallons per hour) ... is possible for ocean-based embodiments with fossil fuel free electricity of about 100 mega watts. A land-based embodiment would typically be a multiple of this."

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In other words, to be clear: One ship, at sea, using environmental energy, can make "100,000 gallons" of liquid hydrocarbon fuel "per day" out of reclaimed Carbon Dioxide.

The constraints, as spelled out in some detail by the US Navy, are the practical size of the ship and the energy that one practically-sized ship can extract from either the wind or from ocean currents.

"A land-based embodiment would typically be a multiple of this."

How many gallons, what "multiple", do you suppose, of that liquid hydrocarbon fuel production, per day, could a plant spread along a space as big as ten football fields on the bottom lands along the Ohio River, and powered by something like the installation described in:

New Martinsville | American Municipal Power; concerning the fact, that: "New Martinsville owns and operates the New Martinsville Hydroelectric Plant at the Hannibal Locks and Dam. New Martinsville is one of only two municipal electric systems in West Virginia. At the time of its construction in 1988, its twin bulb turbine generators were among the largest in the world. Each is capable of creating 18 MW of hydroelectric power, enough to power seven cities the size of New Martinsville";

realize, presuming we have as much Carbon Dioxide floating around, as the now-suspect "environmentalists" say we do, in the Ohio River Valley air, from all of the Coal-fired power plants strung along that critical artery; Coal-fired power plants that, in the process of keeping everyone's lights on and everyone's homes heated, keep thousands of Coal miners and power plant workers, and their families, supported with some of the most productive and best paying jobs in America?

Nuts: If we finally get our heads screwed on straight about all of this, and quit eating all of the Baloney Sandwiches we've been fed for so long, maybe we could wind up some day selling the extremely high-quality

"liquid hydrocarbons produced according to this invention", as disclosed by our subject herein, "US Patent Application 20050232833 - Process for Producing Synthetic Liquid Hydrocarbon Fuels", by the barge full to the rich potentates of OPEC, when their sands start to run dry.

And, man, if that thought don't give you the warm willies, you really should be honest and act honest:

Renounce your US Coal Country citizenship, move to some third-world country, live in a hand-built mud hut, and start getting skinny eating all of your organically home-grown vegetables and whatever you can forage from the surrounding woods.

We have the opportunity here to make ourselves energy independent, and maybe even affluent, and to give the sandal-wearing environmental sign-wavers a reason to move on to truly noxious and dangerous environmental disasters-in-waiting, like off-shore drilling platforms and nuclear power plants.

As with the very real, very practical technologies that would, if reduced to genuine commercial and industrial practice in the United States of America, as they are in the now somewhat more technologically advanced nation of South Africa, enable us to start, on a practical and profitable basis, converting some of our abundant Coal into liquid hydrocarbon fuels, the technology developed herein by our own US Navy, and, through our own government, in theory, owned by us, that would enable us to convert our, some say too abundant, Carbon Dioxide into liquid hydrocarbon fuels, none of it will do any of us any good unless all of us are afforded the opportunities to, first, at least be informed that they exist, and, then, to use them.

All the rest of it: The public media silence, the willful and seemingly-deliberate ignorance, is just more of that big, steaming pile of Baloney Sandwiches.