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US Navy Recovers 92% of Environmental CO2 for Fuel Synthesis

United States Patent Application: 0130039837

As is now irrefutable - - - as should some time ago have been headline news in every Coal Country newspaper serving US citizens whose way of life sprang from, and remains reliant on, the Coal mining and power generation industries, and whose way of life is being threatened by nonsense like Cap & Trade Carbon Dioxide taxation; indeed, as should have been headline news in every newspaper in the United States of America serving all US citizens whose way of life is threatened, has for a long time been crippled, by imported oil OPEC extortions - - - the United States Navy, as seen for one example in:

West Virginia Coal Association | US Navy 2008 CO2 to Synfuel | Research & Development; concerning: "United States 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 ... 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";

knows how to convert, how to recycle, Carbon Dioxide into liquid hydrocarbon fuels. And, so assured is that Carbon Dioxide recycling technology, the Navy has further, as seen in:

West Virginia Coal Association | US Navy Recovers Environmental CO2 for Hydrocarbon Synthesis | Research & Development; concerning: "United States Patent 8,313,557 - Recovery of CO2 from Seawater/Aqueous Bicarbonate Systems; 2012; Inventors: Heather Willauer, et. al., VA and MD;

Assignee: The United States of America as Represented by the Secretary of the Navy; Abstract: The present invention is generally directed to a system for recovering CO2 from seawater";

devoted effort to establishing efficient means to recover Carbon Dioxide from the environment in which they operate with which to synthesize those hydrocarbon fuels.

And, that effort by the Navy to establish even more efficient means of recovering environmental Carbon Dioxide continues, as seen in excerpts from the initial link in this dispatch to what should have been seen as a Valentine's Day card sent just a few weeks ago by the US Navy to the heart of US Coal Country:

"US Patent Application 20130039837 - Continuous Recovery of CO2 from Acidified Seawater

Method for the Continuous Recovery of Carbon Dioxide from Acidified Seawater - Patent application

Method for the Continuous Recovery of Carbon Dioxide from Acidified Seawater - Willauer, Heather D.

Date: February 14, 2013

Inventors: Heather Willauer, et. al., VA, WV, CT and MD

(Note that Willauer is, of course, the lead named inventor of the Navy's earlier "United States Patent 8,313,557", as cited above. And, if you make the effort to open the links we send along in our dispatches and examine the full documents, you will know that she is working with a core team of scientists that is for the most part coherent and consistent throughout the development of the Navy's Carbon Dioxide recovery and recycling technologies. The Navy, pretty obviously, deliberately selected and put together an elite team of scientists some years ago, tasked them with developing a complete system for efficiently recovering CO2 and chemically recycling it into liquid hydrocarbon fuels, and, told that elite team to stick together until the task was accomplished.

We are making the assumption that the United States Navy is the sponsor of the research that led to this patent application, and will be the "Assignee" of rights eventually named. As is usual in early published versions of US Patent Applications, the Assignee, and presumed sponsor of the technical innovation disclosed by the applications, is not named or specified. In this case, it will, without doubt, be the United States Navy. As can be further learned via:

http://www.dtic.mil/cgi-bin/GetTRDoc?AD=ADA483621; concerning: "Recovery of CO2 from Aqueous Bicarbonate using a Gas Permeable Membrane; Navy Technology Center for Safety and Survivability, Chemistry Division; June 25, 2008"; and;

Fueling the Fleet, Navy Looks to the Seas - U.S. Naval Research Laboratory; concerning the news release: "Fueling the Fleet, Navy Looks to the Seas; 2012; Scientists at the U.S. Naval Research Laboratory are developing a process to extract carbon dioxide (CO2) and produce hydrogen gas (H2) from seawater, subsequently catalytically converting the CO2 and H2 into jet fuel by a gas-to-liquids process";

most, if not all, of the inventors named in the full "US Patent Application 20130039837" document are employed by the US Naval Research Laboratory.)

Abstract: A method for recovering carbon dioxide from acidified seawater using a membrane contactor and passing seawater with a pH less than or equal to 6 over the outside of a hollow fiber membrane tube while applying vacuum or a hydrogen sweep gas to the inside of the hollow fiber membrane tube, wherein up to 92% of the re-equilibrated CO2 is removed from the natural seawater.

Claims: A method for the recovery of re-equilibrated CO2 from acidified natural seawater, comprising: passing natural seawater with a pH less than or equal to 6 over the outside of a hollow fiber membrane tube in a membrane contactor; and simultaneously applying vacuum to the inside of the hollow fiber membrane tube; wherein up to 92% of the re-equilibrated CO2 is removed from the natural seawater (and) wherein the vacuum applied is up to 30 inches of (Mercury) and wherein the seawater has a pH less than or equal to 4.

(Note: We consulted with a few knowledgeable folk on the above numbers. First, in theory, on the surface of the plant earth, according to an air conditioning technician who makes frequent use of vacuum pumps in his repair work, a vacuum of "30 inches" of mercury would be in very slight excess of a "perfect vacuum" and is, strictly speaking, not achievable. However, vacuums of 29 inches of mercury can be pulled by available vacuum pumps. And, since the specification of "up to 30 inches" figures in, we just don't know, and it isn't specified in the full Disclosure, how much below the theoretical perfect vacuum would be acceptable. It would take quite a lot of energy to maintain a near-perfect vacuum on a large scale. Further, the "pH less than or equal to 4" can be related to commercial vinegar, which has a pH ranging between 2.5 to 3.5, and lemon juice, according to one web-based reference which might be suspect, with a pH of 2 to 2.5. And, a pH of less than 5 has, in the past, qualified mine drainage as being "acid". So, even though the ocean has a vast buffering capability and discharging process water from a ship with a pH of 4, or less, might not be a problem, a truly large, shore-based facility drawing and then discharging untreated water from and into the sea to operate this process might cause localized problems at the point of discharge, and be objectionable to the environmentally-concerned - - which we all should in any case try to be. The upshot is, that, for a large, shore-based facility operating this process, we might have to start quarrying more limestone - - which, unlike liquid hydrocarbons, we do have plenty of in the US - - to create buffering filters for the discharge. Such acid buffering would, though, generate more CO2, so the net environmental CO2 reduction effected by this process would, to a greater or lesser extent, be negated. We hesitated to introduce those negative notes; but, all things in this world must be considered. The issues aren't insoluble.)

A method for the recovery of re-equilibrated CO2 from acidified natural seawater, comprising: passing seawater with a pH less than or equal to 6 over the outside of a hollow fiber membrane tube in a membrane contactor; and simultaneously using hydrogen as a sweep gas on the inside of the hollow fiber membrane tube; wherein up to 92% of the carbon dioxide is removed from the natural seawater. 

The method ...  wherein the hydrogen sweep gas has a flow rate up to 1500 mL/min (and) wherein the seawater has a pH less than or equal to 4.

(Note: It isn't entirely clear, but, in lieu of an exceedingly low vacuum, a "hydrogen sweep gas" might be used to help scavenge the CO2 from the processed seawater. That's fine, since the CO2 must be blended with Hydrogen in any case to effect the hydrocarbon synthesis specified, as in our introductory citation, by "United States Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels". And, we might as well take the opportunity to remind you, that, as seen, for only one example, in:

West Virginia Coal Association | More NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,051,005 - Photolytic Production of Hydrogen; 1977; Assignee: United Technologies Corporation; Government Interests: The invention described herein was made in the course of a contract with the National Aeronautics and Space Administration; Abstract: Hydrogen and oxygen are produced from water in a process involving the photo-dissociation of molecular bromine with radiant energy at wavelengths within the visible light region. (And) wherein the source of radiation is sunlight";

we have some options available to use environmental energy to effect the production of Hydrogen.)

Description and Background: The present invention relates generally to CO2 extraction and, more specifically, to recovery of CO2 from acidified natural seawater. 

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. This dissolved bicarbonate and carbonate is essentially bound CO2 ... .

The acidification of natural seawater offers an indirect approach to recovery of CO2 from its bicarbonate and carbonate form from the equilibrium conditions of CO2 in seawater (as described).

An electrochemical method to acidify seawater and recover CO2 simultaneously with hydrogen gas from alkaline water sources such as seawater has been developed at the Naval Research Laboratory. (U.S. patent application 12/958,963 filed on Nov. 17, 2011 by Felice DiMascio, the entire contents of which are incorporated herein by reference.)

(We believe that initial US Patent Application has matured into the formal, published Application discussed in our report of:

West Virginia Coal Association | US Navy Reclaims More CO2 for Hydrocarbon Synthesis | Research & Development; concerning: "United States Patent Application 20110281959 - Extraction of Carbon Dioxide and Hydrogen from Seawater and Hydrocarbon Production There from; Date: November 17, 2011; Inventor: Feice DiMascio, et. al. CT, MD, VA and PA; Assignee: The Government of the USA as represented by the Secretary of the Navy; Abstract: Apparatus for seawater acidification including an ion exchange, cathode and anode electrode compartments and cation-permeable membranes that separate the electrode compartments from the ion exchange compartment. Means is provided for feeding seawater through the ion exchange compartment and for feeding a dissociable liquid media through the anode and cathode electrode compartments. A cathode is located in the cathode electrode compartment and an anode is located in the anode electrode compartment and a means for application of current to the cathode and anode is provided. A method for the acidification of seawater by subjecting the seawater to an ion exchange reaction to exchange H+ ions for Na+ ions. Carbon dioxide may be extracted from the acidified seawater. Optionally, the ion exchange reaction can be conducted under conditions which produce hydrogen as well as carbon dioxide. The carbon dioxide and hydrogen may be used to produce hydrocarbons".

As noted in our introductory comments, and as detailed in the above background discussion, our subject invention herein represents an improvement on technology for Carbon Dioxide recovery already established by the Navy.)

(An included figure) illustrates the percent removal of CO2 plotted as a function of pH for effluent seawater samples taken from the electrochemical acidification cell during a 40 minute constant polarity cycle. This figure indicates that approximately 50% of the CO2 is spontaneously degassed from the effluent natural seawater at pH less than or equal to 4.

To complement this technology, the Naval Research Laboratory has developed the present invention to enhance re-equilibrated CO2 recovery up to 92% from seawater ... .

Summary: The present invention provides a method for recovering re-equilibrated CO2 from acidified natural seawater using a membrane contactor and passing seawater with a pH less than or equal to 6 over the outside of the hollow fiber membrane tube while applying vacuum or a hydrogen sweep gas to the inside of the membrane tube, wherein up to 92% of the re-equilibrated CO2 is removed from the natural seawater. 

The method of the present invention requires only vacuum or a sweep gas to recover low concentrations of CO2 from acidified seawater. In the case of vacuum, CO2 can be concentrated in proportions needed for feedstock. In the case of hydrogen as a sweep gas, no additional energy penalty is required to recover the CO2.

The hydrogen/CO2 mixture produced in the acidification of the seawater can be used directly as a feedstock."

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As we noted in our inserted comments, if Hydrogen, in lieu of some of the vacuum, is used as a "sweep gas" to recover the Carbon Dioxide, then it might be feasible to use the blend of gases "directly as a feedstock", perhaps for another US Navy process, as we reported in:

West Virginia Coal Association | 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; 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".

Now, our tax money, tax money extracted from each and every one of us, most ironically from those of us living and working in United States Coal Country, paid for these United States government-owned technologies, which, first, extract Carbon Dioxide from the environment; and, then, convert that Carbon Dioxide into liquid hydrocarbon fuels.

And, our government is considering asking us consumers of Coal-based electric power to pay more taxes in the form of Cap and Trade Carbon Dioxide penalties?

And, our government is spending more of our tax money to protect the Persian Gulf shipping lanes, so that OPEC and Big Oil can continue to extract more exorbitant profits from us?

Shouldn't our United States government, instead, be spending our tax money on the construction of factories and facilities operating the processes defined and disclosed by, among others, our subject herein, "United States Patent Application 20130039837 - Continuous Recovery of CO2 from Acidified Seawater"; and: "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2"?

Does anyone out there know why they are not?

Isn't any Coal Country journalist out there motivated enough to get off his or her dead can and find out?