CO2 Recovered from Air for CO2-to-Gasoline Conversion

United States Patent: 4047894

First, the headline on this dispatch is a bit of an extrapolation on our part.

But, we remind you of an earlier dispatch, now accessible on the West Virginia Coal Association's web site via the link:

August 2011, CO2-to-Gasoline US Patent Awarded | Research & Development; and, wherein is reported:

"United States Patent 7,989,507 - Production of Fuel Materials Utilizing Waste Carbon Dioxide; 2011; Assignee: Siemens Aktiengesellschaft, Germany; Abstract: The present invention is directed to a method for utilizing CO2 waste comprising recovering carbon dioxide from an industrial process that produces a waste stream comprising carbon dioxide in an amount greater than an amount of carbon dioxide present in starting materials for the industrial process. The method further includes producing hydrogen using a renewable energy resource and producing a hydrocarbon material utilizing the produced hydrogen and the recovered carbon dioxide.

The ... present invention provides a novel, efficient, and economical method and system for producing useful fuel materials, i.e. methane, methanol carbon monoxide, syngas, gasoline products, and/or other fuel materials, from carbon dioxide recovered from carbon dioxide-containing waste streams via hydrogen produced by renewable energy resources."

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So, we can assume that any old Carbon Dioxide Siemens AG, as above, might acquire could, via their technology of the above "United States Patent 7,989,507", be converted into "gasoline ... and/or other fuel materials".

You will note in the full Disclosure of USP 7,989.507 that Siemens are careful to reiterate that the Carbon Dioxide they use in the making of "methane, methanol", and etc., is to be recovered from a "waste stream comprising carbon dioxide".

Such "waste stream"s, as it happens, aren't the only source of Carbon Dioxide Siemens are able to utilize.

And, that has valuable implications for West Virginia and the rest of US Coal Country, as we attempt to emphasize, in comments inserted within and following excerpts from the initial link in this dispatch, to a United States Patent that discloses a process for reclaiming Carbon Dioxide from the atmosphere itself, which is putatively to be done for a purpose that seems to us fraught with inherent, perhaps deliberately misdirecting, contradictions in logic.   :

"United States Patent 4,047,894 - Removing Carbon Dioxide from the Air

Date: September, 1977

Inventor: Dieter Kuhl, Germany

Assignee: Siemens Aktiengesellschaft, Munich

Abstract: An improved method and apparatus for removing carbon dioxide from the air in which the air is passed at a slightly elevated pressure over the surfaces of absorption elements impregnated with a carbon dioxide-absorbing liquid. The elements are corrugated plates, and the air flows transverse to the corrugations.

Claims: Apparatus for removing carbon dioxide from air comprising: a housing opened on two opposing sides, said opposing sides forming an inlet and outlet for the air from which carbon dioxide is to be removed; and: 

(A) plurality of corrugated porous sintered plates of polyvinyl chloride impregnated with a carbon dioxide absorbing liquid supported within said housing in parallel spaced relationship to each other with the peaks and valleys of the corrugations also in parallel relationship to define a plurality of spaces, one between each two adjacent plates which spaces are open between said inlet and outlet, the corrugations extending transverse to the direction of flow of air from said inlet to said outlet, whereby the air is conducted through said spaces from said inlet to said outlet between the plates at right angles to the corrugations to result in a longer reaction time and larger surface area to give better material transfer between the air and absorption liquid without appreciable pressure loss. 

A device ... wherein said carbon dioxide absorbing liquid is potassium hydroxide.

Background and Summary: This invention relates to the removing of carbon dioxide from the air in general, and more particularly for an apparatus and method for carrying out such removal, which apparatus and method is particularly useful in removing carbon dioxide from the air used in operating metal-air batteries.

(Therein, above, we begin the divergence into obfuscating speculation. Such "metal-air" batteries were known of, obviously, back in 1977. But, even today, in 2011, the only real commercial use of them we're aware of is in hearing aids. And, those aren't the sorts of batteries Siemens intends herein; since you wouldn't want a type of corrosive lye, i.e., "potassium hydroxide", gurgling around in your ear. The same is roughly true of other applications about which Siemens speculates immediately below.)

Because of the exhaust emissions of hydrocarbon fuels and also because of their recent shortage, there has been a great deal of interest in electric propulsion for motor vehicles. One of the primary problems associated with such propulsion is in the provision of suitable batteries. One type of battery suggested for such a use which type appears to be quite promising, is a metal-air battery. Because these batteries are operated using an alkaline electrolyte, it is necessary to remove the carbon dioxide from the air used before it is supplied to the air electrodes. Otherwise, the electrolytic liquid would become carbonatized. This, in turn, would result in the impairment or destruction of the metal and air electrodes. Similar problems occur in connection with other types of electrochemical cells which are operated with air such as fuel cells. 

Various methods and apparatus have been developed for removing carbon dioxide from the air. In one of these, the air is washed with an alkaline solution in tanks filled with what are referred to as Raschig rings. For the elimination of small amounts of CO2, gel absorbers have also been used. Although these methods are efficient in removing carbon dioxide, they have a serious disadvantage in that the air must be at a fairly high pressure, because relatively high pressure losses occur during the washing process. Furthermore, in order to obtain the increased pressure, compressing means of some nature are required and these means use up a certain amount of energy. This additional energy used in compressing the air can have a particularly unfavorable effect with regard to electro-traction since the energy required for increasing the air pressure would have to be taken from the electrochemical current source being used and this energy would be lost to the main purpose, i.e., the electric propulsion. 

Thus, it can be seen that there is a need for an improved method and apparatus for removing carbon dioxide from the air so that the resulting product may be used in the operation of electrochemical cells, which method and apparatus requires only a small increase of air pressure and an accordingly small amount of energy for operation. 

The present invention solves this problem by passing air at a slightly elevated pressure over the surfaces of absorption elements impregnated with a carbon dioxide absorbing liquid. With the method of the present invention, air with a pressure over atmospheric of about ... 0.1 to 10 mm water column) can be used. It is preferred that air with an excess pressure of approximately ... 1 mm water column be used. In the British system, this is equivalent to only about 0.0014 P.S.I.

(In other words, a little more than one thousandth of one pound over atmospheric pressure is required to operate this Carbon Dioxide air capture process. Thus, the slightest of almost imperceptible breezes could generate the needed pressure.)

As compared to the prior art methods of air cleaning requiring large amounts of energy due to the pressure increase or a lowered temperature, the present invention requires only a small amount of energy to bring out the air to the required pressure.

(With) the present invention, carbon dioxide will be removed if the air has only a small excess pressure (and, this) gives a further advantage to the present invention, since it operates at a very low noise level. 

In accordance with the method of the present invention, potassium hydroxide solution (as specified) can be used to advantage. This concentration of potassium hydroxide exhibits an optimum absorbing action with respect to absorption time. 

Disclosed is a device for carrying out the method of the present invention in which the absorption elements comprise porous sintered plates made of polyvinylchloride (PVC) arranged at a spacing from each other. This type of absorption element made of PVC has a high capacity for the absorption liquid, in particular when potassium hydroxide is used as such liquid. It should be noted, however, that the absorption elements can also consist of other materials such as carbon foam. 

As compared to prior art devices, the device of the present invention has as an additional advantage, a freedom from clogging. Such clogging can result when using the wet scrubbing method due to the formation of carbonate. Furthermore, the device of the present invention is operational even if the absorbing liquid is dried out, which drying out can happen if the moisture in the air is low. 

According to the present invention, a volume porosity of the absorption elements of more than 30% is desired. The size of the pores are selected so that the pores are only large enough so that the absorption liquid adheres well in the porous elements, and only so small that the diffusion processes in the absorption liquid are not affected. 

As illustrated, it is particularly advantageous to make the porous PVC plates corrugated with the plates arranged parallel to each other with the peaks and valleys of the corrugations also always in a parallel relationship. With this arrangement, the air is conducted through the spaces between the plates at right angles to the corrugation. A longer reaction time and larger surface area results to give better material transfer between the air and the absorption liquid. The corrugated plates, preferably are arranged at a mutual spacing which corresponds to the plate thickness. With a plate thickness of about 0.5 mm a small, very compact structural unit is obtained.

(Thus, above, the justification for supposedly using these "small, very compact",  "CO2 air filters", for want of a better label, on, especially in 1977, such futuristic and speculative things as electric "motor vehicles" powered by "metal-air batteries".)

Thus, an improved method and apparatus for removing carbon dioxide from the air has been shown. Although specific embodiments have been illustrated and described, it will be obvious to those skilled in the art that various modifications may be made without departing from the spirit of the invention ...".

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And, which "spirit of the invention" actually extends to the use of variants of this technology in the efficient collection of CO2 at fossil fuel-fired power generation facilities, as Siemens themselves confess in:

http://www.energy.siemens.com/mx/pool/hq/power-generation/power-plants/carbon-capture-solutions/post-combustion-carbon-capture; concerning:

"Siemens: Answers for Energy: Development of an Economic Post-Combustion Carbon Capture Process; Washington D.C.; 2008; Dr. Tobias Jockenhoevel (and) Dr. Ruediger Schneider, Siemens AG, Germany.

Siemens develops an improved CO2 capture process with minimized energy demand, optimized for integration in conventional coal-fired power plants (and) permitting an economic ... capture process."

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In essence, their "coal-fired power plant" CO2 capture scheme is founded on the basic technology of our subject, "United States Patent 4,047,894 - Removing Carbon Dioxide from the Air", as it is modified with the addition of certain amino acids to help increase the CO2-collecting power of the core absorbent, as in United States Patent 4,047,894, "potassium hydroxide".

Furthermore, both those basic technologies disclosed by Siemens have, by others, been taken a step further, as we've previously reported, in:

Efficient Capture of Atmospheric CO2 | Research & Development; concerning: "United States Patent 7,993,432 - Air Collector ... for Capturing Ambient CO2; 2011; August, 2011; Assignee: Kilimanjaro Energy, Inc.; Abstract: An apparatus for capture of CO2 from the atmosphere comprising an anion exchange material formed in a matrix exposed to a flow of the air.Claims: A process for removing CO2 from atmospheric air at a location remote from where the CO2 was generated";

and used, since the above "United States Patent 7,993,432" specifically cites the process of our subject herein, Siemens' "United States Patent 4,047,894", as the basis of a technology wherein Carbon Dioxide can be extracted from the atmosphere itself, wherever, we surmise, a source of environmental energy, i.e., wind, hydro, solar or geothermal, might exist in enough abundance to power the atmospheric Carbon Dioxide collection process.

Finally, we'll note again that regeneration of the CO2 absorbents used in both the above "United States Patent 7,993,432" and "United States Patent 4,047,894" results in the production of a concentrated stream of Carbon Dioxide, which could then be directed into a process, as suggested above, like that of Siemens' own "United States Patent 7,989,507 - Production of Fuel Materials Utilizing Waste Carbon Dioxide", and be thereby converted into, among other things, "gasoline products".

Or, the Carbon Dioxide recovered by Siemens' technology could be directed into a competing process, such as that described in our report of:

Conoco Converts CO2 to Methanol and Dimethyl Ether | Research & Development; concerning: "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates; 2003; Assignee: ConocoPhillips Company; Abstract: A catalyst and process for converting carbon dioxide into ... methanol and dimethyl ether";

and be converted thereby into valuable Alcohols and a substitute Diesel fuel.

Any way you want to cut it, it all sounds a lot more attractive than the Cap and Trade taxation of our vital Coal-use industries and/or their economic enslavement into Big Oil's secondary petroleum scrounging in nearly-depleted natural reservoirs, through the mandated "Geologic Sequestration" of Carbon Dioxide in leaky old oil wells.

All of which is to be performed at the expense of our vital Coal-use industries and their customers.

And, since we can efficiently extract Carbon Dioxide from the atmosphere in an "economic ... capture process", and, then, convert that Carbon Dioxide into "methanol and dimethyl ether", and, "gasoline products"; it all sounds a whole lot smarter than our continued economic debilitation, through ongoing commercial and political enslavement to the inimical nations of OPEC.

Canada Improves CO2 + Methane = Syngas Catalysis

United States Patent: 7985710

We've documented many times and from many sources that Carbon Dioxide can be efficiently recycled through conversion into Methane gas.

The apparent originator of the concept of, and technology for, converting Carbon Dioxide into Methane was one Paul Sabatier, of France, who, as seen in our report:

CO2 Solution Wins Nobel Prize - in 1912 | Research & Development, concerning the award of the 1912 Nobel Prize in Chemistry to Sabatier, and the presentation speech of which includes the statement: "carbon dioxide (is) changed immediately into methane, which can therefore be synthesized with the greatest ease";

Coal Fly Ash Improves Brick Mortar

United States Patent: 4268316

In an earlier dispatch, now accessible via:

Coal Fly Ash Bricks are Greener and Stronger | Research & Development; concerning, primarily: "United States Patent 7,998,268 - Method to Produce Durable Non-vitrified Fly Ash Bricks and Blocks; 2011; Assignee: Ecological Tech Company, Inc.; MO; Abstract: A method of making durable, non-vitrified masonry units comprising fly ash";

we documented the practical use of Coal power plant Fly Ash in the making of, essentially, concrete blocks, and, other masonry units that could substitute for vitrified bricks, all of which meet the applicable American Society for Testing and Materials (ASTM) standards for such products.

More Nobel Prize-Winning Coal Liquefaction

Process of hydrogenating carbon compounds under high pressure and elevated temperature

We've previously documented some of the Coal Liquefaction technology developed early in the last century by the German scientist, Friedrich Bergius.

Our reports have included one concerning a United States Patent awarded to him for Coal conversion technology, as in:

Bergius 1928 Coal Liquefaction | Research & Development; concerning: "US Patent 1,669,439 - Process for Distilling and Liquefying Coal; 1928; Friedrich Bergius, Germany; Abstract: This invention relates to improvements in a correlated process for distilling and liquefying coal";

and, another concerning the subsequent award of the Nobel Prize in Chemistry to him, as in:

CoalTL Wins Nobel Prize - in 1931 | Research & Development; which dispatch includes confirmation of the fact that the Bergius process could convert "no less than 80%" of Coal into "oils", and, that the technology could be employed to do the same thing with Carbon-recycling, renewable "timber".

As we noted for you in our comments in the above dispatch concerning the 1931 Nobel Prize, we were somewhat puzzled that the label applied by the Nobel Committee to the Bergius process, as being one of two worthy "High Pressure Techniques", didn't seem consistent with the technology disclosed by Bergius in his 1928 "US Patent 1,669,439 - Process for Distilling and Liquefying Coal".

As it happens, the Nobel Prize wasn't awarded to Bergius for that particular, patented Coal conversion process, but, for another he had developed nearly a decade earlier, with an intriguing twist or two, as seen in excerpts, with comment inserted and appended, from the initial link in this dispatch to:

"United States Patent 1,391,664 - Hydrogenating Carbon Compounds Under High Pressure

Date: September, 1921

Inventor: Friedrich Bergius, Germany

Assignee: The Chemical Foundation, Inc., Delaware

(Now, here is one of the intriguing, let's call it discouraging, "twists":

This United States Patent might not have been applied for by Bergius, himself. It might have been a United States Patent that was a direct, translated copy of a German patent already issued, and then, subsequent to WWI, simply seized by the United States as a portion of the war booty that was taken from Germany subsequent to the Treaty of Versailles.

More about it can be learned via:

The Chemical Foundation, Inc - Journal of Industrial & Engineering Chemistry (ACS Publications); and:

UNITED STATES v. CHEMICAL FOUNDATION, Inc. | Supreme Court | LII / Legal Information Institute;

wherein it's revealed that "The Chemical Foundation" was actually set up by the United States Government to assume ownership of many thousands of Germany-originated patents from the Custodian of Alien property, and, that, the Bergius patent was likely one of those "seized pursuant to the Trading with the Enemy Act of October 6, 1917 ... and the Act of November 4, 1918"; and, that, "the Chemical Foundation was incorporated under the laws of Delaware. The certificate of incorporation discloses that it was created and empowered to purchase enemy-owned patents seized by the Custodian and to hold the 'property and rights so acquired in a fiduciary capacity for the Americanization of such industries".

According to those, and other, sources, many thousands of German patents were so acquired, and, the "Chemical Foundation", composed of and directed by representatives from American industries, managed them so tyrannically and corruptly that the United States Government was compelled to bring an anti-trust suit against that company, which the Government itself had set up, for violating laws prohibiting monopolies.

So, it is little wonder that we never heard of the Bergius process for converting Coal into liquid hydrocarbon fuels.)

Abstract: This invention is an improvement in the process of hydrogenating, under high pressure and at an elevated temperature, natural coal or other products of carbonization of wood and other vegetable matter (which) are carbonized by the heat of the process. By such process, these carbonaceous materials are transformed into liquids.

(That is, renewable and Carbon-recycling botanical materials are, in essence, converted into Charcoal in the process itself, and, then, hydrogenated and liquefied right along with Coal. It is, thus, similar in concept, and in some aspects of technology, to other processes we have documented for you, as in:

Mobil Co-Liquefies Coal & CO2-Recycling Wastes | Research & Development; concerning: "United States Patent 4,089,773 - Liquefaction of Solid Carbonaceous Materials; 1978; Mobil Oil Corporation; Abstract: This invention provides an improved process for solubilizing coal and other solid carbonaceous materials (and is a) process for dissolution of solid carbonaceous material ... wherein the solid carbonaceous material is coal (and/or) partly municipal refuse (and/or) sewage sludge (and/or) cellulosic waste.")

In order to secure these effects according to the invention care is taken to continuously circulate the atmosphere in contact with the carbon compound to be reacted on. Such circulation whereby a part of the gaseous atmosphere in contact with the raw material is continuously drawn out of the reaction space and again returned offers an opportunity to effect heat exchange which is necessary to secure the reaction temperature within the reaction vessel, and it affords at the same time an opportunity to separate the reaction products from the reaction gas.

The possibility of an efficient temperature control in the above said manner by circulating the gas which is in contact with raw material broadly depends on the fact that the gas is under very high pressure of say 100 atmospheres and that therefore a comparatively small quantity or volume of the gas is adapted to carry considerable quantities of heat. I order to secure the effect aimed at it is necessary to circulate a quantity of gas which is considerably in excess of the quantity of hydrogen which is consumed by the reaction.

(So, we need an excess of Hydrogen to circulate throughout the process; and, as seen in:

USDOE Algae Make Hydrogen for Coal and CO2 Hydrogenation | Research & Development; concerning: "Photosynthetic Hydrogen and Oxygen Production by Green Algae; USDOE; Abstract: Photosynthesis research at Oak Ridge National Laboratory is focused on hydrogen and oxygen production by green algae in the context of its potential as a renewable fuel and chemical feed stock";

one way we can get Hydrogen is by cultivating certain strains Algae, which, in the cyclic course of their photosynthetic business of consuming Carbon Dioxide, can be made to excrete Hydrogen as a byproduct.

Other efficient means of obtaining Hydrogen, as we have otherwise documented, and as we will further report, are available as well.

Further, Bergius seems to stipulate that the free Hydrogen circulates throughout the total process, with only some of it being consumed in the Carbon hydrogenation reactions; and, that, "under very high pressure" the circulating Hydrogen is able to convey "considerable quantities of heat" from an exothermic reaction to a needed endothermic reaction. The implication is that energy economies are thus achieved similar to those described, perhaps more clearly, in related Coal conversion technology disclosed in our report of:

ExxonMobil Self-Powered Coal Conversion | Research & Development; concerning: "United States Patent 3,254,023 - Heat Balancing in Organic Reactions; 1966; Socony Mobil Oil Company; Abstract: This invention relates to a method of carrying out an exothermic chemical reaction and an endothermic reaction in a single reaction zone wherein the heat evolved in the exothermic reaction is utilized to effect the endothermic reaction";

wherein one of ExxonMobil's precedent companies describes how heat can be reclaimed in a Coal conversion technology that was a contemporary of the Bergius invention herein, the Fischer-Tropsch process, which "United States Patent 3,254,023" discloses itself to be a variant of, and be circulated back into the process to help drive some of the needed endothermic chemical Coal conversion reactions.

We'll further note that high pressures are needed in the Bergius process described herein to contain the heated Hydrogen, and, to help, as we would put it, "force" the hydrogenation reaction between that Hydrogen and the Carbon.

Such high pressures might seen undesirable or impractical, but, consider that the Bergius process was one of the technologies reduced to practice by Germany during WWII to help supply her military with liquid fuel.

If they could handle the pressures back then, more than half a century ago, one must presume that modern chemical engineering practices are well-able to efficiently accommodate such pressures now.)

Claims: A process of hydrogenating solid carbon compounds which consists in heating in a retort such compounds in the presence of a hydrogen atmosphere and under high reaction pressure to a high reaction temperature, continuously abstracting a mixture of reaction products and reaction gas, condensing the reaction products, reheating the abstracted reaction gas and returning it to the retort."

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All of which serves to transform Coal and Carbon-recycling "wood and other vegetable matter into liquids".

Again, the needed high pressures could be handled, and were acceptable, even in the chemical processing industry of the early twentieth century; so much so that the process herein was awarded a Nobel prize for chemical technology innovation, and then reduced to industrial practice during World War II.

We'll have a little more to offer on the Bergius process itself in the future; but, we wanted to submit the basic United States Patent on this direct Coal hydrogenation technology at this point, since, in addition to use of the Bergius process during WWII, there have been much later evolutions of the technology, with efficiency improvements, established by our more contemporary petroleum and chemical processing industries; all of those improvements founded, in essence, on the principals of direct Coal hydrogenation and liquefaction established by our subject herein: "United States Patent 1,391,664", issued all the way back in 1921, wherein both Coal and renewable "wood and other vegetable matter" can be together directly transformed into hydrocarbon "liquids".

The US Navy Recycles Even More Co2

United States Patent Application: 0110268617

Following hot on the heels of their receipt of a United States Patent, disclosing an efficient technology for transforming Carbon Dioxide into liquid hydrocarbon fuels, as we reported 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; Date: September 13, 2011; Inventors: Nick Tran, Dennis Hardy, et. al., DC and VA; 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";