United States Patent Application: 0140323600

Although we've made previous mention of the British company "Air Fuel Synthesis", and their pilot operations for harvesting Carbon Dioxide from the atmosphere and then converting that harvested CO2 into fuel alcohol Methanol, it seems timely now to provide some more complete information concerning them.

By way of introduction and explanation, a decent article about Air Fuel Synthesis, and their initial prototype, small proof-of-concept facility, was published by the United Kingdom's Daily Telegraph back on October 18, of 2012:

British engineers produce amazing 'petrol from air' technology - Telegraph; "A small company in the north of England has developed the “air capture” technology to create synthetic petrol using only air and electricity. Experts tonight hailed the astonishing breakthrough as a potential “game-changer” in the battle against climate change and a saviour for the world’s energy crisis. The technology, presented to a London engineering conference this week, removes carbon dioxide from the atmosphere.The “petrol from air” technology involves taking sodium hydroxide and mixing it with carbon dioxide before "electrolysing"  the sodium carbonate that it produces to form pure carbon dioxide.Hydrogen is then produced by electrolysing water vapour captured with a dehumidifier.The company, Air Fuel Synthesis then uses the carbon dioxide and hydrogen to produce methanol which in turn is passed through a gasoline fuel reactor, creating petrol".

First of all, just to remind you, concerning the passage: "methanol ... is passed through a gasoline fuel reactor, creating petrol", as seen for one example in our report of:

ExxonMobil Coal to Methanol to Gasoline | Research & Development | News; concerning both: 

"United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Assignee: Exxon Research and Engineering Company, NJ"; and:

"United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation, NY";

the technology certainly exists to convert Methanol, no matter which of our abundant natural resources, whether Coal or Carbon Dioxide, we make it from, into "petrol", i.e., Gasoline.

And, further, as seen in our reports of:

England Recycles CO2 to Methanol | Research & Development | News; concerning: "United States Patent 3,950,369 - Methanol Production; 1976; Assignee: Imperial Chemical Industries Limited, London; Abstract: In a methanol production process synthesis gas containing carbon dioxide is passed over a methanol synthesis catalyst ... . Claims: (A) process for the production of methanol by passing a gas comprising hydrogen and carbon dioxide over a methanol synthesis catalyst which consists essentially of copper, zinc and a third component which is chromium (or other specified) metal oxide"; and:

Oxford University 2015 CO2 to Methanol | Research & Development | News; concerning: "United States Patent 8,933,135 - Process for Producing Methanol; 2015; Assignee: ISIS Innovation, (Oxford University), Summertown, Great Britain; 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";

the good people at Air Fuel Synthesis aren't the only folks across the pond who have figured out how to synthesize the Methanol from Carbon Dioxide.

What they have done is improve the efficiency of converting Carbon Dioxide and Hydrogen, as we can extract from, water, H2O, into Methanol a bit, via techniques disclosed in, as excerpted from the initial link in this dispatch:

"United States Patent Application 20140323600 - Process for the Conversion of Carbon Dioxide to Methanol

Process for the Conversion of Carbon Dioxide to Methanol - AIR FUEL SYNTHESIS LIMITED

Patent US20140323600 - Process for the Conversion of Carbon Dioxide to Methanol - Google Patents

Date: October 30, 2014

Inventor: James Robert Jennings, Great Britain

Assignee: Air Fuel Synthesis Limited, Darlington, Great Britain

Abstract: Carbon monoxide conversion processes are described for the conversion of carbon monoxide via hydrogenation to methanol. The process utilizes initial carbon monoxide priming before introduction of 3:1 hydrogen/carbon dioxide mixture to the reactor. After the optimum reaction conditions are established the feed of carbon monoxide may be withdrawn and any required carbon monoxide provided via reactor effluent recycle. The process provides for enhanced catalyst performance and life.

(Note, that, as 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)". 

the Carbon Monoxide needed to, so to speak, prime the pump and kick-start the Carbon Dioxide hydrogenation reaction is actually being, or can be, made in the Air Fuel Synthesis "reactor" from CO2.)

Claims: A process for the conversion of carbon dioxide to methanol via hydrogenation, which process comprises introduction of carbon monoxide to the carbon dioxide hydrogen feed to the reactor.

A process ...  which further comprises separation of non converted reactants from the reactor effluent for recycle to the reactor (and) wherein the non-converted reactants comprises one or more of carbon dioxide, hydrogen and carbon monoxide (and) wherein the non-recycle carbon monoxide to the feed is reduced or terminated after recycle of non converted reactants.

(Note, in the above, that, as indicated, some Carbon Monoxide might be needed to initiate the reaction, but, subsequently, any needed Carbon Monoxide can be recovered from the reactor effluent, as it's being made from Carbon Dioxide. All as explained further in additional claims.)

A process ... wherein the carbon monoxide is introduced at the level for optimum methanol production (and) wherein the process conditions are selected to provide the required level of carbon monoxide in the recycle to achieve carbon monoxide equilibrium without the need for continued introduction of fresh non reactor carbon monoxide to the reactor.

A process ... wherein the carbon dioxide feed is provided from recovery of carbon dioxide from a carbon dioxide source such as the atmosphere, the oceans and/or the effluent streams of industrial processes (and) wherein the feed is provided via a two stage process comprising caustic scrubbing of carbon dioxide from the carbon dioxide source followed by electrolysis of the caustic/sodium carbonate mixture to release carbon dioxide.

A process ... wherein the hydrogen is provided from the electrolysis of water (and) wherein the water electrolysis is carried out using a carbon neutral or renewable sources of electricity.

(Concerning the above "hydrogen is provided from the electrolysis of water ... using a carbon neutral or renewable sources of electricity", see, for just one example, our report of:

USDOE Renewable Hydrogen for Coal-to-Oil and CO2-to-Alcohol | Research & Development | News; concerning: "United States Patent 9,011,651 - Apparatus and Method for the Electrolysis of Water; 2015; Assignee: UT-Battelle, LLC, Oak Ridge (USDOE Oak Ridge, Tennessee, National Laboratory). Abstract: An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen ... . Government Interests: This invention was made with government support under Contract Number DE-AC05-000R22725 between the United States Department of Energy and UT-Battelle, LLC. The U.S. government has certain rights in this invention. An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen (and) wherein said electrolyzer is powered by a renewable energy source (and) wherein said renewable energy source comprises solar energy (or) wind energy".

And, as far as "the feed is provided via a two stage process comprising caustic scrubbing of carbon dioxide from the carbon dioxide source followed by electrolysis of the caustic/sodium carbonate mixture to release carbon dioxide", see, in our report of:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development | News; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Inventor: Meyer Steinberg, NY; Assignee: The USA as represented by the USDOE; Abstract: A method and system for synthesizing methanol from the CO2 in air using electric power.; The CO2 is absorbed by a solution of KOH to form K2CO3 which is electrolyzed to produce methanol, a liquid hydrocarbon fuel.; Summary: In accordance with a preferred embodiment of this invention, a solution of KOH is employed to absorb CO2 from air forming an aqueous solution of K2CO3, the solution is then electrolyzed to produce CH3OH (i.e., Methanol) and reform KOH in solution, the CH3OH is then removed, and make-up water is then added prior to repeating the aforementioned steps. Other products ... are also formed which can be separated and recovered as valuable products. By the process described above, it is seen that any source of electrical power may be employed, such as coal-fired power plants. However, from an environmental point of view ... solar energy generated power, would be preferred";

how our own US Government developed closely similar technology four decades ago using an electrolytic Potassium Carbonate/Potassium Hydroxide cycle, with Potassium and Sodium being very much alike in terms of chemical reactivity and behavior.)

A process ... wherein the hydrogenation reaction is undertaken at ... most preferably 300 C or less (and at) a pressure of ... most preferably 10 MPa (100 atm) or less.

A process ... wherein the hydrogen and carbon dioxide is introduced to the reactor in a 3:1 molar ratio (and)wherein the hydrogenation catalyst comprises Cu (Copper) and ZnO (Zinc Oxide) on alumina.

A process for the manufacture of gasoline from methanol, which process uses methanol as produced by the process.

(For more background on/confirmation of the above claim, see, for example:

Japan CO2 to Methanol to Gasoline | Research & Development | News; concerning, in part: "United States Patent Application 0130014430 - Method for Generating Electricity and for Producing Gasoline from Methanol and System Therefore; 2013; Inventor: Masaki Iijima, Japan; Assignee: Mitsubishi Heavy Industries, Ltd., Tokyo".)

Background and Field: This invention relates to a process for the conversion of carbon dioxide into methanol via the hydrogenation of carbon dioxide.

The conventional industrial processes for the production of methanol have used a means to convert synthesis gas (a mixture of carbon monoxide, carbon dioxide, and hydrogen) into methanol.

Synthesis gas may (also) be produced from coal.

The hydrogenation of carbon dioxide is said to be faster than that of carbon monoxide and according to academic literature carbon dioxide should be considered as the primary source of carbon in methanol synthesis ... .

Other work has shown that the production of methanol from a synthesis gas that contains carbon dioxide, occurs mainly from the carbon dioxide component, at least in the initial stages of the reaction.

The present invention is concerned with processes for the conversion of carbon dioxide to methanol, which utilize carbon monoxide in the early stages of the process to improve the initial or start-up operating conditions of the process and the subsequent life and activity of the catalysts used. In many of these processes (as described above for the conversion of carbon dioxide and hydrogen to methanol) the process conditions will result in a proportion of reverse water gas shift reaction, producing small quantities of carbon monoxide in the reactor effluent. The initial reactor conditions are set to keep the equilibrium carbon monoxide levels as low as possible as it is not desirable to produce large quantities of carbon monoxide as a waste product from the process. 

With reference to the present invention it has been found that if a quantity of carbon monoxide is added to the carbon dioxide/hydrogen 1:3 mixture subsequent to activation of the catalyst by reduction in a hydrogen/nitrogen mixture, then this allows the subsequent process to be operated immediately under conditions closer to those pertaining to conventional methanol synthesis with a positive impact on operating conditions, selectivity and catalyst life. In the process of the present invention the reaction effluent is processed to recover methanol and to enable a mixture of hydrogen carbon dioxide and carbon monoxide to be recycled into the reaction, thus mimicking the normal process.

Once the process has been initiated and recycle has commenced, the amount of introduced carbon monoxide may be reduced and eventually terminated, as the required carbon monoxide levels are generated within the reactor due to the reverse water gas shift.

In essence the initial carbon dioxide hydrogen feed has carbon monoxide introduced to the feed to create a synthetic syngas mixture, which is subsequently maintained in the process due to carbon monoxide recycle as the initial carbon monoxide feed is removed. At this point the only feeds into the reactor are carbon dioxide (preferably from carbon dioxide capture from the atmosphere), hydrogen (preferably from the electrolysis of water using carbon neutral electricity) and reactor recycle. If the process needs to be shut down for any reason, it may be necessary to start up again with a temporary addition of carbon monoxide to the reactor feed.

Thus the present invention provides a process for the conversion of carbon dioxide to methanol via hydrogenation.

It is preferred that the carbon dioxide is provided from recovery of carbon dioxide from the atmosphere, the oceans and/or the effluent streams of industrial or fermentation processes.

[0033] In a preferred embodiment, the process of the present invention is integrated into downstream processes for utilization of the methanol produced by the process. One preferred integrated process is the methanol to gasoline process (MTG)".

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We'll close our excerpts there, but will note that this technology is very derivative of others about which we have previously reported. For instance, the specification of  "Cu (Copper) and ZnO (Zinc Oxide)" as Carbon Dioxide "hydrogenation catalysts" is similar to that, for one example, disclosed in our report of: 

Conoco Converts CO2 to Methanol and Dimethyl Ether | Research & Development | News; concerning: "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates; 2003; Assignee: ConocoPhillips Company, Houston; Abstract: A catalyst and process for converting carbon dioxide into oxygenates. The catalyst comprises copper, zinc, aluminum, gallium, and a solid acid. Claims: A catalyst composition comprising: copper; zinc; aluminum; gallium; and a solid acid (wherein) said solid acid (comprises) a zeolite (specified as) ZSM-5. A catalyst composition for converting carbon dioxide to methanol and dimethyl ether".

And, the complete Disclosure of our subject, "United States Patent Application 20140323600 - Process for the Conversion of Carbon Dioxide to Methanol", contains a commendable of amount of documentation concerning other, similar technology, some of which we have previously reported on, but which we haven't, for the sake of concision, made reference to.

One key feature somewhat unique to "Application 20140323600", though, in addition to using Carbon Monoxide to help initiate the Carbon Dioxide hydrogenation reaction, is the seeming integration of the Methanol-to-Gasoline process step, or at least it's prominent specification as the intended use of the Methanol synthesized from Carbon Dioxide.

And, the implications should be clear:

Carbon Dioxide can be seen and treated as a valuable, and natural, raw material resource.

We can harvest Carbon Dioxide from the environment, from "the atmosphere, the oceans and/or the effluent streams of industrial processes", and then efficiently convert that Carbon Dioxide into Methanol and, through the Methanol, in one, integrated process, into non-OPEC Gasoline.  

The implications for increased employment, a much-improved domestic economy, and a national security impervious to threats levied one way and another against us through OPEC oil, again, should be obvious.


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