United States Patent: 8933135

You know, we - - all of us, each and every American citizen, regardless of our individual thoughts and opinions about the effects of Carbon Dioxide on the environment and about whether or not our economically essential use of Coal in the generation of abundant and affordable electric power contributes meaningful amounts of CO2 to the atmosphere - - are just, simply, being cheated.

Carbon Dioxide, as it is co-produced in a small way - - relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable processes of planetary volcanism - - by that economically essential use of Coal in the generation of abundant and affordable electricity, is a valuable resource.

We could, if we wised up, fashion a club out of Carbon Dioxide to knock OPEC in the head and then chase them out of our house with.

We could, of course, again if we got wise, do the same thing with Coal, too, as seen for just one example in our earlier report of:

ExxonMobil "Coal to Clean Gasoline" | Research & Development | News; concerning: "Coal to Clean Gasoline; ExxonMobil Research and Engineering Company; ExxonMobil's methanol to gasoline technology for the production of clean gasoline from coal. (There is a) commercially proven alternative for converting coal to gasoline, through methanol. ExxonMobil’s methanol-to-gasoline (MTG) process efficiently converts crude methanol to high quality clean gasoline".

There are other ways to convert Coal into Gasoline, aside from such an initial conversion into Methanol, but, since this dispatch is really about King Coal's friendly ghost, Carbon Dioxide, and how it can be efficiently used and consumed in the synthesis of Methanol, we thought that past report to be a good illustration of just how valuable Methanol, whether made from Coal or from Carbon Dioxide, could actually be to us.

By extension of course, that means we don't yet understand, as a nation, just how valuable Coal and Carbon Dioxide, as raw materials can be. And, as might be indicated, again for just one example, in:

NASA 2014 CO2 to Methane | Research & Development | News; concerning: "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2014; Assignee: Precision Combustion, Inc., CT; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen ... so as to produce a product stream comprising water and methane. ... This invention was made with support from the U.S. government under U.S. Contract No. NNX10CF25P sponsored by the National Aeronautics and Space Administration. The U.S. Government holds certain rights in this invention";

that lack of understanding could be especially true of Carbon Dioxide.

Since the production of substitute natural gas Methane from Carbon Dioxide, as via NASA's process of the above "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction" requires the addition of elemental, molecular Hydrogen, we remind you that, as seen in:

Penn State Solar Energy Extracts Hydrogen from H2O | Research & Development | News; concerning: "United States Patent Application 20140251819 - Methods for Hydrogen Gas Production; 2014; Assignee: The Penn State Research Foundation, University Park, PA; Abstract: According to aspects described herein, methods and systems provided by the present invention for hydrogen gas production include a RED stack including one or more RED subunits, and use of a saline material including a heat regenerable salt. The salinity driven energy, provided by the one or more RED subunits, completely eliminates the need for an external power source to produce hydrogen gas (and) wherein the (required) heating comprises heating with waste heat from a second process, heat generated by a solar heater or solar collector or a combination of waste heat from a second process and heat generated by a solar heater or solar collector";

we're getting pretty good at extracting Hydrogen from the abundant water, H2O, molecule in processes which can be driven either by freely-available "solar" thermal energy or by waste "heat from a second process", which "second process" could, actually, be something like the conversion of Carbon Dioxide into Methane, as via NASA's "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction", wherein NASA is actually disclosing how to harvest such waste heat from the Carbon Dioxide-to-Methane "process".

In any case, a reaction process that can be quite similar, although there are several alternative ways to go about it, to the conversion of Carbon Dioxide into substitute natural gas Methane, is the conversion of Carbon Dioxide into fuel alcohol Methanol, which, as via the above-cited ExxonMobil "MTG"(r) process, can then be efficiently converted directly into Gasoline.

One process for the conversion of Carbon Dioxide into Methanol was disclosed in our report of:

The University of Oxford Converts CO2 into Methanol | Research & Development | News; which centered on Oxford University's international patent application:


"Process For Producing Methanol; Publication No: WO/2011/045605; International Application No: PCT/GB2010/051733; International Filing Date: October 14, 2010; Inventors: Dermot O'hare and Andrew Ashley, Great BritainApplicants: Isis Innovation Limited, Great Britain (Isis Innovation is wholly owned by the University of Oxford, England); Abstract: The present invention relates to a novel process for the production of methanol. The process comprises the heterolytic cleavage of hydrogen ... and the hydrogenation of CO2 with the heterolytically cleaved hydrogen to form methanol";

but, which also contained a link to the United States Patent Application for the same technology:

"United States Patent Application 0120283340 - Process for Producing Methanol; November 8, 2012;
Inventors: Dermot Ohare and Andrew Ashley; 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".

And, herein we learn, that, just a month ago, technical experts employed by our United States Government confirmed that the University of Oxford, in England, as represented by their technology transfer company, the now-unfortunately named "ISIS Innovation", have, indeed, devised an innovative and efficient means for transforming Carbon Dioxide into fuel alcohol Methanol.

Comment follows and is inserted within excerpts from the initial link in this dispatch to:

"United States Patent 8,933,135 - Process for Producing Methanol

Process for producing methanol - ISIS Innovation Limited

Date: January 13, 2015

Inventors: Dermot O'Hare and Andrew Ashley, Great Britain

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.

(We refer you to our earlier report concerning "Process For Producing Methanol; Publication No: WO/2011/045605; International Application No: PCT/GB2010/051733", for explanation, with reference links, of what "a frustrated Lewis pair", and "a Lewis acid", etc., actually are. In sum, they are well-known types of chemical reagents, and not terribly exotic or expensive ones at that, which are familiar to chemists. The label "Lewis" connotes how, in theory, those specific compounds exchange, or share, electrons in chemical reactions. They do offer special properties of use in Oxford University's/ISIS Innovation's Carbon Dioxide utilization technology disclosed herein.)

Claims: A process for the preparation of methanol comprising the steps of:

(i) heterolytic cleavage of hydrogen by a frustrated Lewis pair comprising a Lewis acid and a Lewis base; and:

 (ii) hydrogenation of CO2 with the heterolytically cleaved hydrogen formed in step (i) to form methanol.

A process ... wherein the Lewis acid and the Lewis base are separate molecules that together form the frustrated Lewis pair.

(The Claims go into explicit detail about the formulation of the "Lewis pair". Though complicated, too complicated for inclusion herein, the chemistry doesn't entail the use of anything too exotic or expensive. It is just a complicated chemical sequence in which the Lewis compounds serve to "cleave" the Hydrogen molecule, H2, so as to make available the more reactive Hydrogen atoms, which more easily, readily combine with the Carbon Dioxide. The "Lewis" compounds serve to replace catalysts, as used in the NASA process of "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction", which catalysts facilitate reaction between Hydrogen molecules and Carbon Dioxide. With Hydrogen atoms "cleaved" from Hydrogen molecules, such a catalyst isn't needed since the Hydrogen atoms will, as we take it, react almost spontaneously with the Carbon Dioxide. They entrain the available Oxygen into the reaction, as well. Thus, the end product is what is known as an "oxygenated" hydrocarbon, an alcohol, Methanol, as opposed to a simple hydrocarbon, such as Methane. That, at least, is as we understand one explanation provided to us.)

A method of heterolytically cleaving hydrogen, said method comprising the step of contacting hydrogen with a frustrated Lewis pair comprising a Lewis acid and a Lewis base, wherein the contacting step heterolytically cleaves the hydrogen, and wherein the hydrogen is subsequently used for the production of methanol.

Description and Background: This invention relates to a novel process for the production of methanol. More specifically, the present invention relates to a process of producing methanol by the hydrogenation of carbon dioxide (CO2).

There is particular interest in the reduction of CO2 by H2 to give renewable sources such as methanol. Methanol is considered to be a valuable product because it can be safely stored and transported. In addition, world demand for methanol is currently increasing enormously because of its role as a precursor to many useful organic chemicals (e.g., formaldehyde, acetic acid) ... .

CO2 hydrogenation has been extensively developed using solid oxide catalysts, but was only first reported in homogeneous solution (and) these systems tend to give distributions of C1 products, namely CO, CH3OH and CH4.

(Carbon monoxide, formic acid, methane, etc., are unwanted. Much more of the available Hydrogen and Carbon Dioxide are going into the thus more efficient synthesis of the desired Methanol.)

Furthermore, the transition metal oxide catalysts used in these hydrogenation reactions can be expensive, and their toxicity can also give rise to potential environmental and/or disposal problems.

Accordingly, there is a need for improved processes for the manufacture methanol from CO2 which can:

(i) provide the methanol in a pure form (i.e. without other C1 by-products);

(ii) be operated at relatively low temperatures and pressures; and:

(iii) avoid the use of transition metal catalysts.

Summary: In a first aspect, the present invention provides a process for the preparation of methanol comprising: (i) the heterolytic cleavage of hydrogen by a frustrated Lewis pair comprising a Lewis acid and a Lewis base; and (ii) the hydrogenation of CO2 with the heterolytically cleaved hydrogen formed in step (i) to form methanol.

In addition to the obvious advantages associated with a process that utilises the abundant CO2 resource available, the process of the present invention also avoids the use of metallic catalysts. Furthermore, the reaction can proceed at relatively low temperatures and pressures, and it is also specific for the production of methanol (i.e. no other C1 by-products are formed)".

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Carbon Dioxide and Hydrogen are the only real inputs, along with the recyclable Lewis compounds and a relatively small amount, "low temperatures and pressures", of energy, needed to synthesize, primarily, the immensely valuable raw material and fuel alcohol Methanol.

We remind you that, as in: 

Iceland Recycles Even More CO2 | Research & Development | News; "Carbon Recycling International (CRI) , Iceland0 captures carbon dioxide from industrial emissions and converts carbon dioxide into Renewable Methanol (RM)"; and:

: Saudi Arabia and CO2: The Rich Get Richer | Research & Development | News; wherein we learn, in part, that:"'SABIC (Saudi Arabia Basic Industries Corporation) Unit Plans World’s Largest CO2 Purification Plant'; United Jubail Petrochemical Company, an affiliate of Saudi’s SABIC, has awarded a construction contract for the plant to Germany’s Linde Group. By Aarti Nagraj, August 21, 2013; An affiliate of Saudi Basic Industries Corporation (SABIC) announced that it has awarded a construction contract to build the world’s largest carbon dioxide (CO2) purification and liquefaction plant in the Kingdom. United Jubail Petrochemical Company (United), a manufacturing unit of SABIC, has given the engineering, procurement and construction contract for the project to Germany’s The Linde Group, it said in a statement. ... The plant will be designed to compress and purify about 1,500 tons per day of raw carbon dioxide coming from ethylene glycol plants. The purified gaseous CO2 will then be supplied through pipes to three SABIC-affiliated companies for enhanced methanol and urea production";

industrial facilities for the consumption and use of Carbon Dioxide in the synthesis of Methanol are currently operating and being constructed in various places around the world, and, as in:

Morgantown and Pittsburgh Improve CO2-to-Methanol Catalysis | Research & Development | News; concerning: "Adsorption and Deactivation Characteristics of Cu/ZnO-Based Catalysts for Methanol Synthesis from Carbon Dioxide; Date: December 31, 2013; Authors: Sittichai Natesakhawat, et. al.; DOE Contract Number: DE-FE0004000; Research Organization: National Energy Technology Laboratory - In-house Research; National Energy Technology Laboratory (NETL), Pittsburgh, PA, and Morgantown, WV; Sponsoring Organization: United States Department of Energy Office of Fossil Energy; Abstract: The adsorption and deactivation characteristics of coprecipitated Cu/ZnO-based catalysts were examined and correlated to their performance in methanol synthesis from Carbon Dioxide hydrogenation. The addition of Ga{2}O{3} and Y{2}O{3} promoters is shown to increase the Cu surface area and CO2/H2 adsorption capacities of the catalysts and enhance methanol synthesis activity"; and:

Princeton University March, 2014, CO2 to Methanol | Research & Development | News; concerning: "United States Patent 8,663,447 - Conversion of Carbon Dioxide to Organic Products; March 4, 2014; Inventors: Andrew Bocarsly, NJ, and Emily Barton Cole, TX; Assignee: Princeton University, NJ; Abstract: The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product. Government Interests: This invention was made with United States government support from National Science Foundation Grant No. CHE-0616475. The United States Government has certain rights in this invention. Claims: An environmentally beneficial method of producing methanol by electrochemical reduction of any available source of carbon dioxide";

technology in the United States of America, whereby Carbon Dioxide can be consumed in the synthesis of, primarily, Methanol, continue to be developed and improved upon.

The University of Oxford and their now ugly-sounding ISIS Innovations technology transfer company herein more lately describe a technology wherein once the starting materials, Carbon Dioxide and Hydrogen, have been obtained, the Methanol synthesis might proceed with a lower energy input, and generate a more pure Methanol product, than apparently competing technologies developed here in the United States.

But, we do remind you, that, as in our report of:

US Navy Captures CO2 and Hydrogen for Hydrocarbon Synthesis | Research & Development | News; concerning: "United States Patent Application 20140238869 - Electrochemical Module Configuration for the Continuous Acidification of Alkaline Water Sources and Recovery of CO2 with Continuous Hydrogen Gas Production; 2014; Inventors: Felice DiMascio, Heather Willauer, et. al., CT, VA, MD & PA; (Presumed Assignee of Rights: The United States of America as represented by the Secretary of the Navy); Abstract: An electrochemical cell for the continuous acidification of alkaline water sources and recovery of carbon dioxide with simultaneous continuous hydrogen gas production ...  Also disclosed is the related method for continuously acidifying alkaline water sources and recovering carbon dioxide with continuous hydrogen gas production. Claims: An electrochemical cell for the continuous acidification of alkaline water sources and recovery of carbon dioxide with continuous hydrogen gas production ... . The electrochemical cell ...  wherein when current is applied to the electrochemical cell to generate hydrogen gas, this current produces the protons at the mesh anode that lower the pH of the alkaline water to produce carbon dioxide with no additional current or power. An electrochemical cell for the continuous acidification of alkaline water sources and recovery of carbon dioxide with continuous hydrogen gas production ... The method ... wherein when current is applied to the electrochemical cell to generate hydrogen gas, this current produces the protons at the mesh anode that lower the pH of the alkaline water to produce carbon dioxide with no additional current or power. ... The present invention provides an electrochemical cell for the continuous acidification of alkaline water sources and recovery of carbon dioxide with continuous hydrogen gas production";

we are, in the United States of America, developing very efficient technologies for the recovery of both the needed Carbon Dioxide and the Hydrogen.

And, the sum of it all is this:

We can efficiently reclaim Carbon Dioxide, even from the environment, and we can efficiently extract elemental, molecular Hydrogen, H2, from the abundant water, H2O, molecule.

Once we have the CO2 and the H2, we can combine them in the process developed herein by Oxford University, as disclosed by our subject, the recently-issued "United States Patent 8,933,135 - Process for Producing Methanol", and, with very little added energy needed, we can convert that Carbon Dioxide and that Hydrogen into, primarily, an essentially pure Methanol, which can, as in our above-cited report concerning:

"Coal to Clean Gasoline; ExxonMobil Research and Engineering Company; ExxonMobil's methanol to gasoline technology for the production of clean gasoline from coal";

convert directly and efficiently into Gasoline.

To be honest, our incredulity here has burned out. We, in the United States, remain reliant on OPEC oil, to our great harm, and we remain seemingly entrenched in patterns of denial and simple offense when it comes to the CO2-based attacks on our economically-essential Coal-fired power generation industries by those presenting themselves as being concerned with the environment and by those who obviously have vested interest in representing competing means of generating electricity.

We have, herein, the means to turn all of that on its head, while we put a lot more of our fellow Coal Country citizens to work - in factories making Methanol, and products like Gasoline derived from Methanol, out of the Carbon Dioxide by-product of our Coal-fired power plants.

Is there some reason we don't want to openly talk about and promote such options?

Is there some reason we would wish to remain silent, and idle, while OPEC and Coal's competitors continue to press their advantage?

It's time we got to work. We, here, pray that the willingness to actually do some work, the character trait of "Industry", isn't one of the many virtues that have, as we here perceive things, been lost, like Truth and Honor seem to have been among many people we know, over recent years. 


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