GB2010051733 PROCESS FOR PRODUCING METHANOL
To get it out of the way, right up front, "The University of Oxford" in our headline is the real deal.
It is, in other words, most definitely not the "Ox Ford" alma mater claimed by someone who might be more familiar to many of our older US Coal Country readers: Jethro Bodine.
That bit of allusion to Americana aside, The University of Oxford was founded in England all the way back around the year 1100; and, it is the oldest university in the English-speaking world. More about it can, almost of course, be learned via:
University of Oxford - Wikipedia, the free encyclopedia.
And, we must thank Oxford Professor Jamie Ferguson for very kind and direct personal assistance in gathering the information and providing the source documents needed for our composition of this dispatch.
Please do note, however, that:
Dr. Ferguson was kind enough to provide the source documents, but did not assist or advise in our study of them, or in our composition of this dispatch.
Any errors in interpretation and/or presentation are ours and ours alone.
But, the point of our message herein is, we are certain, quite clear, and indisputable:
Carbon Dioxide, as it is co-produced in only a small way, relative to natural sources of emission such as Mother Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of abundant and truly affordable electric power, is a valuable raw material resource.
We can reclaim Carbon Dioxide from whatever source convenient to us, even, as confirmed, for only one example with more to follow, in our report of:
West Virginia Coal Association | Efficient Capture of Atmospheric CO2 | Research & Development; concerning: "United States Patent 7,993,432 - Air Collector ... for Capturing Ambient CO2; 2011; Assignee: Kilimanjaro Energy, Inc., WI; 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";
from the atmosphere itself; and, then, efficiently convert that Carbon Dioxide into the nearly-precious, in terms of it's utility, Methanol.
As seen in relatively, due to quite complete and complex chemical formulae and graphics included in the full Disclosure, excerpts from the initial link in this dispatch to:
"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 Britain
Applicants: Isis Innovation Limited, Great Britain
(Isis Innovation - Wikipedia, the free encyclopedia: "Isis Innovation Ltd is a British technology transfer company, wholly owned by the University of Oxford, located in Summertown, Oxford, England.
We remind you that we have previously cited the University of Oxford with regards to the development of CO2-recycling technology, as in our report of:
West Virginia Coal Association | England Turns Carbon Dioxide into Fuel | Research & Development; concerning: "Turning Carbon Dioxide into Fuel"; Philosophical Transactions of the Royal Society, 2010; by: Z. Jiang, et. al.; Department of Chemistry; University of Oxford; Oxford, UK; Here, we provide a brief overview of an alternative mid- to long-term option, namely, the capture and conversion of CO2 to produce sustainable, synthetic hydrocarbon or carbonaceous fuels, most notably for transportation purposes. Basically, the approach centres on the concept of the large-scale re-use of CO2 released by human activity to produce synthetic fuels, and how this challenging approach could assume an important role in tackling the issue of global CO2 emissions. We highlight three possible strategies involving CO2 conversion by physico-chemical approaches: sustainable (or renewable) synthetic methanol, syngas production derived from flue gases from coal-, gas- or oil-fired electric power stations, and photochemical production of synthetic fuels".)
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.
(It does get a tad complicated here. First, we remind you that the synthesis of Methanol from Carbon Dioxide is a technology, that, in general concept, is at least several decades old, as witness our reports of:
West Virginia Coal Association | USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; 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";
and. contemporaneously, via a different chemical processing route, in the United Kingdom:
West Virginia Coal Association | England Recycles CO2 to Methanol | Research & Development; 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 ... . (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".
It would be beyond both our scope herein and our sadly limited capacities to attempt full explanation of what, in terms of the Oxford/Isis-specified catalyst, "a frustrated Lewis pair comprising a Lewis acid and a Lewis base" might be.
However, as can be learned via:
Frustrated Lewis pair - Wikipedia, the free encyclopedia; "In chemistry, a frustrated Lewis pair is a compound or mixture containing a Lewis acid and a Lewis base that ... are very reactive and are able to split the hydrogen molecule"; and:
Lewis acids and bases - Wikipedia, the free encyclopedia;
they are in known, understood and not horribly exotic. And, the specification of rather complicated catalysts in such and related CO2 processing and recycling technologies, as in our report of:
West Virginia Coal Association | Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development; concerning: "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company; Abstract: A process for the electrocatalytic reduction of carbon dioxide comprises immersing a transition metal complex with square planar geometry into an aqueous or nonaqueous solution which has been acidified to a (specified) hydrogen ion concentration ... , adding the carbon dioxide, applying an electrical potential of from about -0.8 volts to about -1.5 volts ... , and reducing the carbon dioxide to carbon monoxide.The process ... wherein said square planar geometry is provided for by a salen complex (or) a cyclam-type complex";
now seems sort of "standard"; and, the benefits they offer in terms of efficiency in Carbon Dioxide chemical reduction reactions would seem to make exerting the effort to learn about and understand them well worth the while.)
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).
Background: It is now imperative that new reactions and processes are discovered that can either efficiently store or utilise the abundant and renewable CO2 resource ... .
(What a refreshing way to think about it: CO2 as an "abundant and renewable ... resource".)
(A) desirable outcome would be the low temperature conversion of CO2 into alternative chemicals useful for both energy production and as chemical feedstocks. Simultaneously this would have the additional benefit of reducing our requirements on fossil fuel reserves. Homogenous and heterogeneous processes have been developed that utilise CO2 to produce CO, formic acid and its derivatives.
(Concerning the above suggested synthesis of "formic acid" from CO2, see, for another example:
West Virginia Coal Association | United Technologies Converts CO2 to Formic Acid | Research & Development; concerning: "United States Patent 4,921,585 - Electrolysis Cell and Method of Use; 1990; Assignee: United Technologies Corporation; Abstract: The present invention discloses an improved solid polymer electrolysis cell for the reduction of carbon dioxide. The improvement being the use of a cathode having a metal phthalocyanine catalyst which results in the suppression of the formation of hydrogen during the reduction process and the subsequent improved conversion efficiency for carbon dioxide.(and) an improved electrolysis cell useful in the production of oxygen and the reduction of carbon dioxide. (I)t is intended as a primary use that the electrolysis cell be used with water as the fuel. This would permit the electrolytic decomposition of water to form oxygen ... while supplying the hydrogen ions for the carbon dioxide reduction. The improvement comprises the selection of the cathode material (which) will improve the conversion efficiency of carbon dioxide in the presence of hydrogen ions to organic compounds. The most prevalent reaction is the reduction of carbon dioxide to formic acid".)
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); a substitute for traditional fossil fuels; and in the generation of electricity in fuel cells.
(And, yet again, as seen, for only one example out of now many, in our report of:
West Virginia Coal Association | Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984; Assignee: Mobil Oil Corporation; Abstract: A process for producing a wide slate of fuel products from coal is provided by integrating a methanol-to-gasoline conversion process with coal liquefaction and coal gasification. (Coal)is gasified under oxidation conditions to produce a synthesis gas which is converted to methanol. The methanol is converted to gasoline by contact with a zeolite catalyst";
Methanol, no matter which of our precious natural resources, whether Coal or, as herein, Carbon Dioxide, we make if from, can also be converted rather directly into, can serve as a "precursor" for, Gasoline.)
CO2 hydrogenation has been extensively developed using solid oxide catalysts ... . However, these systems tend to give distributions of Ci products, namely CO, CH3OH and CH4 (and) the transition metal oxide catalysts used in these hydrogenation reactions can be expensive ... .
(Not that "CO", Carbon Monoxide, or "CH4", Methane, are bad things to have, mind you. As we've documented in other of our reports, they both, as products of CO2 and Coal conversion processes, can have great utility and value. But, the technology herein is specific for the production of Methanol.)
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 by-products);
(ii) be operated at relatively low temperatures and pressures; and:
(iii) avoid the use of transition metal catalysts.
Brief Summary of the Disclosure:
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 C by-products are formed).
Definitions: Frustrated Lewis pair: The term "frustrated Lewis pair" is used herein to refer to a compound or mixture of compounds containing a Lewis acid and a Lewis base which, because of steric hindrance, cannot combine to form a strongly bound adduct, or may not in fact form any adduct at all. The frustrated Lewis pairs of the present invention must be capable of heterolytically cleaving hydrogen.
(Concerning the above, refer to our included references, earlier on.)
As previously stated, the present invention provides a process for the preparation of methanol comprising:
(i) the heterolytic cleavage of hydrogen by a frustrated Lewis pair; and
(ii) the hydrogenation of CO2 with the heterolytically cleaved hydrogen formed in step (i) to yield the methanol product.
Frustrated Lewis pair: Any suitable frustrated Lewis pair that can heterolytically cleave hydrogen can be used in the process of the present invention.
(The Disclosure goes on at great and detailed length describing the chemical formulations and catalytuc operations of the "Lewis pair". Again: They are understood and accessible; and, they don't seem to us to require anything hugely exotic or expensive in their composition.)
Methanol synthesis: The process of the present invention is carried out in the presence of a suitable solvent. Suitable solvents include solvents that do not co-ordinate (i.e. they are non-polar). Examples include aromatic solvents such as toluene, alkanes such as hexane, and cycloalkanes.
The reaction may be conducted at any suitable temperature ranging from room temperature upwards. Temperatures of 150 C or greater are generally preferred.
(The process is also conducted at relatively low pressures. "1 to 2 atmospheres" is suggested.)
The process may be performed as a series of discrete steps in which intermediates formed during the process are individually formed and isolated or, more preferably, the reaction may be conducted in a single step.
The methanol product formed by the process of the invention can conveniently collected by distillation."
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Our excerpts from "International Application No: PCT/GB2010/051733 - Process For Producing Methanol" do not, of course, do real justice to the elegance of, nor fully explain, the invention.
And, absent now the advice of the more technically astute consultants who used to assist us, we want to be conservative, and avoid error, in attempting any explanation of chemical technicalities.
In brief sum, our take on it is that economies and efficiencies are achieved by the employment of innovative Lewis Pair catalysts that, first, provide great chemical leverage in freeing Hydrogen from Water; and, then, facilitate the recombination of that Hydrogen with Carbon Dioxide to form Methanol; with the upshot being that even "room temperature" is adequate for the process to operate; and, for perhaps greater efficiencies, only half again the boiling temperature of Water, "150 C", is really needed.
And, it can be conducted at relatively low, "1 to 2 atmospheres", pressure.
Further, it seems to be a consolidated and integrated process that wouldn't require the capital outlay needed for separate and individual chemical processing trains.
The final, and perhaps definitive, benefit we see, and as Oxford/Isis do explain, is that this process is almost exclusive for the relatively high productivity synthesis of Methanol, with fewer co-products like Formic Acid, as we take it, for one example; with even further efficiencies and economies to be had in product separation and purification, which, again as specified, consists of a relatively straightforward distillation.
In closing, we note that a United States Patent for this process has been applied for; with that application having been only recently published, as accessible via:
"United States Patent Application: 0120283340 - Process for Producing Methanol
PROCESS FOR PRODUCING METHANOL - ISIS INNOVATION LIMITED
Date: 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".
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We elected to anchor our dispatch herein on the British and European version since our perception, perhaps incorrect, has been that the full technical exposition and documentation of inventive processes is more easily accessed in British, other European and World Intellectual Property Organization patent publications than in online United States Patent and Trademark Office records, as we believe we have earlier noted for you.
Further, we did want to give some pride of place to the nation who, herein, again confirms what we have now been documenting for you for the past more than several years:
Carbon Dioxide is a valuable raw material resource.
We can, according to highly-accomplished scientists at the prestigious University of Oxford, and at Oxford's technology commercialization partner, Isis Innovations, efficiently and economically convert Carbon Dioxide, as recovered from whatever convenient source, into Methanol, an alcohol which has a multitude of applications, being able to serve both as a basis for the direct synthesis of Gasoline and as a raw material for the synthesis of a variety of plastics, wherein the Carbon Dioxide consumed in the synthesis of the Methanol would be forever, chemically and profitably, "sequestered".
We are absolutely nuts if we allow misguided, and now suspect, initiatives like Cap and Trade taxation and the mandated sequestration of CO2, an "abundant and renewable resource", done at the expense of consumers of Coal-based electricity, in leaky old oil wells to facilitate Big Oil's no-cost scrounging of dregs from nearly-depleted petroleum reservoirs, to lurch one further step closer to manifestation.
