US Navy Reclaims CO2 for Hydrocarbon Synthesis

As is now incontrovertible, our United States Navy, and other components of our United States defense establishment, have in hand multiple technologies which enable the productive recycling of Carbon Dioxide in the synthesis of liquid hydrocarbon fuels.
In testament of that fact, we refer you, for just two examples, to our reports of:
"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";
and:
"United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; 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 .... produce hydrocarbons in the reactor".
There is even more, in fact, wherein corporate contractors of the US Navy and the United States Department of Defense have participated in such developments, as seen, for one instance, in:
"United States 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. Claims: A ship for producing gasoline while sailing, comprising: a plurality of absorption ... towers ... to capture air ... . (And) causing CO2 in the air to be absorbed by (a specified chemical) solution which results in a carbonate solution of sodium bicarbonate/hypo carbonate ... . (And) means for ... stripping CO2 as a first byproduct from the carbonate solution ...;  (And) means connected to the stripping means for transferring the CO2 to a methanol converter; (And) electrolysis means for disassociating H2 and O2 from water provided to it; (And) means connected to the electrolysis means for transferring the H2 to the methanol converter; (And) a hydrocarbon synthesizer connected to an outlet of the methanol converter for converting methanol to gasoline."
Note, in the above excerpts from "US Patent 4,568,522 - Synfuel Production Ship", that the Carbon Dioxide is captured from the environment and made available for recycling into hydrocarbons by "causing CO2 in the air to be absorbed by (a specified chemical) solution which results in a carbonate solution of sodium bicarbonate/hypo carbonate ... . (And) means for ... stripping CO2 as a first byproduct from the carbonate solution".
The United States Navy itself, as it happens, has made improvements on just such a system for capturing Carbon Dioxide, presumably for use in a process like that disclosed in the above-cited "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2"; a process that utilizes both the  "carbonate solution"s identified in the above "US Patent 4,568,522 - Synfuel Production Ship" and/or the freely available water of the oceans.
As seen in excerpts from the initial link in this dispatch to:
"US Patent Application 20100028242 - Recovery of CO2 from Seawater/Aqueous Bicarbonate Systems
Date: February, 2010
Inventors: Heather Willauer, Dennis Hardy, et. al., VA and MD
Correspondence (and presumed ultimate Assignee): Naval Research Laboratory, DC
(Note that Dennis Hardy is one of the co-inventors named in the full Disclosure of: "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; 2011; Assignee: The United
States of America as represented by the Secretary of the Navy"; as cited above.)
Abstract: The present invention is generally directed to a system for recovering CO2 from seawater or aqueous bicarbonate solutions using a gas permeable membrane with multiple layers. At elevated pressures, gaseous CO2 and bound CO2 in the ionic form of bicarbonate and carbonate diffuse from the seawater or bicarbonate solution through the multiple layers of the membrane. Also disclosed is the related method of recovering CO2 from seawater or aqueous bicarbonate solutions.
(As we will emphasize further on, this technology is one for efficiently extracting Carbon Dioxide, so that it can be utilized and consumed in a subsequent hydrocarbon synthesis, from either "seawater", where it exists naturally in useable concentrations, or "bicarbonate solutions", which can be made by scrubbing either industrial flue gas or, even, the air itself with appropriate chemicals.)
Claims: A system to recover CO2 from seawater and/or aqueous bicarbonate systems, comprising: a gas permeable membrane comprising multiple layers; and a solution comprising seawater, aqueous bicarbonate, or both, wherein the solution is under a pressure greater than 100 psi; wherein gaseous CO2 and bound CO2 in the ionic form of bicarbonate and carbonate diffuse from the solution through the membrane. 

The system ... wherein the gas permeable membrane is a microporous polypropylene membrane. 

The system ... wherein the gas permeable membrane has seven layers. 

The system ... wherein the pressure is about 500 psi. 

A method for recovering CO2 from seawater and/or aqueous bicarbonate systems, comprising the steps of: pressurizing a solution comprising seawater, aqueous bicarbonate, or both to greater than 100 psi; and contacting the pressurized solution with a gas permeable membrane comprising multiple layers; wherein gaseous CO2 and bound CO2 in the ionic form of bicarbonate and carbonate diffuse from the pressurized solution through the membrane.
Description and Background: The present invention relates generally to CO2 extraction and, more specifically, to recovery of CO2 from seawater and/or aqueous bicarbonate systems using a multi-layer gas permeable membrane. 

There is interest in producing synthetic fuel from renewable sources on sea-based vessels to avoid the risks in procuring fuel from foreign sources and/or in maintaining long supply lines. The procurement and transportation risk can be reduced by producing synthetic fuel from hydrogen and carbon generated near the point of fuel use.
Although there are current technologies to synthesize hydrocarbon fuel on land given sufficient primary energy resources such as coal, these technologies are not practical for sea-based generation.
The ocean is a possible resource for carbon dioxide. The total carbon content of the world's oceans is roughly 38,000 GtC (gigaton of carbon). Over 95% of this carbon is in the form of dissolved bicarbonate ion (HCO3-). This ion along with carbonate is responsible for buffering and maintaining the ocean's pH, which is relatively constant below the first 100 meters. In addition, the bicarbonate/carbonate system maintains the pH of the ocean below 100 m. This dissolved bicarbonate and carbonate is essentially bound Carbon Dioxide and ...  the sum of these species along with gaseous CO2 represents the total carbon dioxide concentration of seawater.
In the atmosphere, the concentration of CO2 approximately is 370 ppm (v/v), which is 0.7 mg/L (w/v) or 780 GtC. Comparing this value on a w/v basis, it is apparent that CO2 in seawater is about 140 times greater than air. Thus if carbon dioxide could be economically and efficiently extracted from the ocean, then marine engineering processes such as OTEC (ocean thermal energy conversion) ... could be proposed to utilize this carbon as a chemical feedstock in processes such as catalytic polymerization with hydrogen.
(The above is as in our introductory citation of  "US Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels", wherein it is posited that, in a process "for producing synthetic hydrocarbons that reacts carbon dioxide ... and hydrogen", the "hydrogen is produced by", among other things, "ocean thermal energy conversion". And, as we will document in at least one report to follow, the US Navy contracted, three decades ago, a major university to initiate the design of just such an "OTEC", that is, "ocean thermal energy conversion"-powered process, and even, in a way similar to that disclosed in the above-cited "US Patent 4,568,522 - Synfuel Production Ship", a ship operating that "OTEC" process, to reclaim, and to recycle into hydrocarbon fuels, environmental Carbon Dioxide.)
Seawater is a very complex buffered system that is in equilibrium with the atmosphere above it. Thus under equilibrium conditions, the dissolved CO2 ... is actually hydrated with one mole of water in the form known as carbonic acid ... . The dissolved bicarbonate and carbonate are in equilibrium with this dissolved carbonic acid species.
Summary: The ... present invention ... provides a system for recovering CO2 from seawater and/or aqueous bicarbonate solutions using a gas permeable membrane with multiple layers. At elevated
pressures, gaseous CO2 and bound CO2 in the ionic form of bicarbonate and carbonate diffuse from the seawater through the multiple layers of the membrane. Also disclosed is the related method of recovering CO2 from seawater or aqueous bicarbonate systems.
(Note that this is not just a process for recovering Carbon Dioxide from seawater. The specification of "aqueous bicarbonate systems" can well be those exemplified, for one instance, in our report of:

"United States Patent 3,865,924 - Process for Regenerative Sorption of CO2; 1975; Assignee: Institute of Gas Technology, Chicago; Abstract: A process and apparatus for the removal of carbon dioxide from a gaseous stream, wherein the CO2 content ranges from trace amounts up to 50 mole percent, and for subsequent transfer to another gas stream by thermal regeneration. A special composition comprising a finely ground mixture of potassium carbonate and alumina, which has synergistic properties, is used as the absorbent. A method of removing CO2 from a gaseous stream (by) passing a CO2 -containing inlet gas stream into contact with a synergistic sorbent composition of finely divided, particulate alkali metal carbonate and alumina, said alumina and carbonate being separate discrete particles and having been ground together to provide such sorbent, to sorb CO2 thereinto and convert said carbonate to bicarbonate, maintaining said sorbent composition in hydrated form, thereby to remove CO2 from said gases stream; and: regenerating said sorbent composition by supplying heat to reconvert said bicarbonate to said carbonate form while evolving CO2 therefrom, without forming a crust over said sorbent. A particularly suitable use of the invention is removal of CO2 from air".

Which systems, as above, can be made to be so efficient that they can be productively utilized for the  extraction of CO2 from the atmosphere itself.)

CO2 in the ionic form of bicarbonate, undergoes a phase transition as it disproportionates to carbon dioxide and carbonate. This happens when gaseous carbon dioxide is removed from water by diffusion through multiple gas permeable membrane layers at elevated bulk water pressures (100 psi). The multiple layers can be used to minimize water permeability especially at pressures near or above the bubble point of a single layer membrane.
The ... present invention which provides a system for recovering CO2 from seawater and/or aqueous bicarbonate solutions using a gas permeable membrane with multiple layers. At elevated pressures, gaseous CO2 and bound CO2 in the ionic form of bicarbonate and carbonate diffuse from the seawater through the multiple layers of the membrane."
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Again, this is a process, or, in combination with another process, such as that disclosed in the above-cited "United States Patent 3,865,924 - Process for Regenerative Sorption of CO2", for efficiently "recovering CO2 from seawater and/or aqueous bicarbonate solutions", that is, from the environment itself, so that such recovered Carbon Dioxide can then be directed into a process like that disclosed, for yet another United States Government-sponsored example, in our report of:
"Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas; 2007; Idaho National Laboratory, USDOE; and Ceramatec, Inc.; Abstract: An experimental study has been completed to assess the performance of single-oxide electrolysis cells ... simultaneously electrolyzing steam and carbon dioxide for the direct production of syngas ... a mixture of hydrogen and carbon monoxide (which) can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes".
And, there is even quite a lot more to the US Navy's involvement, and accomplishments, in the reclamation of Carbon Dioxide from the environment, and, the subsequent efficient conversion of that reclaimed Carbon Dioxide into liquid hydrocarbon fuels, as we will further document in future reports.
The point of it all is, that:
Carbon Dioxide, as it arises in only a small way, relative to natural sources of emission, such as volcanoes, from our essential and vital use of Coal in the generation of affordable electric power, is a valuable raw material resource.
We can, as demonstrated herein, efficiently reclaim Carbon Dioxide, even from the environment itself, and, then convert that reclaimed Carbon Dioxide into anything, quite literally anything, we now allow ourselves to be financially extorted by OPEC and Big Oil for the supply of.
It's far, far past time that truth was made publicly known in the heart of United States Coal Country, and some wooden stakes thus driven into the hearts of economic vampires like the Cap & Trade taxation scheme and the CO2 geologic sequestration scam.