United States Patent: 7629288
Our main thesis, over the course of our long reportage, has been that Coal, and, secondarily, both Carbon Dioxide itself and CO2-recycling botanical matter can be converted into anything, quite literally anything, we now allow ourselves to be fooled into mortgaging our grandchildren's future to the noble, democratic, magnanimous and peace-loving nations of OPEC to keep ourselves supplied with in the here and now.
Most people, upon reading that statement, would automatically think in terms of, as in:
USDOE Converts CO2 to Gasoline | Research & Development; concerning what should be the rather startling: "United States Patent 4,197,421 - Synthetic Carbonaceous Fuels and Feedstocks; 1980; Inventor: Meyer Steinberg; Assignee: The United States of America; Abstract: This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous sodium carbonate/bicarbonate solution, obtained from scrubbing atmospheric carbon dioxide";
"gasoline"; and, as in:
West Virginia Coal Association | Mobil 1984 Improved Diesel Fuel from Coal | Research & Development; concerning: "United States Patent 4,447,312 - Improving the Diesel Fuel Quality of Coal Derived Liquids; 1984; Assignee: Mobil Oil Corporation; Abstract: A process for preparing diesel fuel from coal-derived light fuel oils by alkylating said coal-derived light fuel oils ... derived by the direct liquefaction of coal";
"diesel fuel".
But, the modern-day plastics upon which our society depends are also, by and large, derived from OPEC hydrocarbons, although, as seen, for one instance, in:
West Virginia Coal Association | Bayer Is Converting Coal Power Plant CO2 Into Plastics | Research & Development; concerning the: "Bayer Material Science CO2-to-Plastics Pilot Plant, Germany; In February 2011, Bayer MaterialScience started a new pilot plant (in the) North Rhine-Westphalia state of Germany for producing plastics from carbon dioxide (CO2). It will be used to develop polyurethanes from the waste gas released during power generation. Bayer aims to use CO2 as an alternative to production of polymer materials from fossil fuels";
one admirable titan of international chemical industry, with significant roots in US Coal Country, is, unbeknownst to anyone in US Coal Country, forging a path to a saner, more secure future.
Herein, we demonstrate again that Coal, too, can serve as the source of raw materials from which we can make the various plastics and polymers which have become essential to our modern way of life, and to our future.
First, as in some few other processes and inventions we've documented for you, the dirty, four-letter word "Coal" isn't mentioned, not even once, in the full Disclosure of the United States Patent, issued to the ConocoPhillips Company, which we present to you herein.
However, we'll let ConocoPhillips themselves tell you, right up front, where we might get the "fluid containing hydrogen and carbon monoxide", the "synthesis gas, a mixture of carbon monoxide and hydrogen" they do specify as their raw material herein, as in our report of:
West Virginia Coal Association | Conoco Converts Coal to Methanol and Dimethyl Ether | Research & Development; concerning: "United States Patent 6,638,892 - Syngas Conversion and Catalyst Employed Therefor; 2003; ConocoPhillips Company; Abstract: A process for the conversion of syngas by contact of syngas under conversion conditions with catalyst having as components zinc oxide, copper oxide, aluminum oxide, ... zeolite and clay in ... a one step process for conversion of syngas to dimethyl ether (and) a two step process for conversion of syngas to light olefins ... . Syngas is obtained using well known processes by the partial combustion or gasification of any organic material such as coal".
We'll have more to offer on that, inserted within and appended to our excerpts from the initial link to:
"United States Patent 7,629,288 - Catalyst Composition Comprising Ruthenium and a Treated Silica Support Component and Processes Therefor and Therewith for Preparing High Molecular Weight Hydrocarbons such as Polymethylene
Patent US7629288 - Catalyst composition comprising ruthenium and a treated silica support ... - Google Patents
Catalyst composition comprising ruthenium and a treated silica support component and processes therefor and therewith for prep
Date: December, 2009
Inventors: James Kimble and Jianhua Yao, OK
Assignee: ConocoPhillips Company, Houston
(Note that we have cited Inventors Kimble and Yao previously, as in our, we would think intriguing, report of:
West Virginia Coal Association | Conoco Recycles More CO2 | Research & Development; concerning: "United States Patent 7,273,893 - Process for Converting Carbon Dioxide to Oxygenates; 2007; Inventors: Jianhua Yao and James Kimble, Oklahoma; Assignee: ConocoPhillips Company; Abstract: A catalyst and process for converting carbon dioxide into oxygenates ... (wherein) said product stream (comprises) less than about 50 carbon mole percent methanol (and/or) at least 60 carbon mole percent dimethyl ether. Oxygenates can be used for a variety of purposes such as, for example, enhancing of motor fuel octane and improving the emissions quality of motor fuel. Methanol and dimethyl ether are two oxygenates which can be of particularly high value. Methanol can be used for a variety of purposes including, for example, as an alternative motor fuel, as an intermediate in the production of high octane ethers, and as a fuel for fuel cell driven vehicles. Dimethyl ether is also useful for a variety of purposes including, for example, as an alternative motor fuel (and) as a starting material towards the synthesis of various hydrocarbons".)
Abstract: A catalyst composition and a process of using a catalyst composition for preparing high molecular weight hydrocarbons, such as polymethylene, from a fluid containing hydrogen and carbon monoxide are disclosed. The catalyst composition contains ruthenium and a treated silica support component. The treated silica support component is prepared by a process including contacting a silica support component, such as silicon dioxide, and a treating agent, such as a silicon-containing compound.
(Note, that, as can be learned via:
Polyethylene - Wikipedia, the free encyclopedia; "Polyethylene (abbreviated PE) or ... poly(methylene)) is the most common plastic. The annual production is approximately 80 million metric tons. Its primary use is within packaging (plastic bag, plastic films, ... containers including bottles, etc.";
the terms "polymethylene" and "polyethylene" are virtually synonymous, as we understand the literature, with all of the rather vast commercial potentials that implies.)
Claims: A process of preparing a catalyst composition comprising contacting a ruthenium component and a treated silica support component; wherein said treated silica support component is prepared by a process comprising contacting a silica support component and a treating agent and further wherein said contacting is selected from the group consisting of impregnation, mixing, and combinations thereof; wherein said catalyst composition comprises a weight ratio of total silicon dioxide to ruthenium in the range of from about 0.01:1 to about 20:1; and wherein said treating agent comprises an organosilicon compound (as specified).
(Note that this is mostly about making the catalyst to convert Syngas into polymethylene, rather than demonstrating that Syngas can be converted into polymethylene. As the full Disclosure reveals, that has already been accomplished; and, this is just a more efficient catalyst and process for so accomplishing that polymethylene synthesis.)
A process ... wherein said ruthenium component is selected from the group consisting of ruthenium bromide, ruthenium bromide hydrate, ruthenium chloride, ruthenium chloride hydrate, ruthenium iodide, ruthenium nitrosyl nitrate, ruthenium oxide, ruthenium oxide hydrate, and combinations thereof (and/or) ruthenium chloride, ruthenium chloride hydrate, or ruthenium nitrosyl nitrate.
(Note that "ruthenium", a Platinum Group metal, is, indeed, exceedingly rare. Canada and South America do have some worthwhile deposits, where it is produced as a byproduct of mining mainly those other Platinum metals. Being exceedingly rare, it is also exceedingly expensive. However, it does serve as a catalyst, and, as such, it isn't used up to any appreciable extent in the process. Obtaining the Ruthenium would be more of a capital than an operational expense.)
A process ... wherein said silica support component is silicon dioxide.
(That's cheap, at least.)
A process ... wherein said silica support component is in a form selected from the group consisting of tablets, pellets, extrudates, spheres, and combinations thereof (and) wherein said silica support component has a particle size in the range of from about 50 micrometers to about 10 millimeters.
(It would look like the guts inside an automobile's catalytic converter, for all you gear heads curious enough to have torched one open.)
A process ... wherein said treating agent is selected from the group consisting of tetraalkyl orthosilicates, poly(alkylaryl)siloxanes, and combinations thereof (and/or) tetraethyl orthosilicate, poly(methylphenyl)siloxane, and combinations thereof (and) wherein said treating agent is present in a solution selected from the group consisting of an aqueous solution, an alcohol-containing solution, and a hydrocarbon solution (and) wherein said alcohol is methyl alcohol.
(Which "methyl alcohol", i.e., "methanol", we can make, via the above-cited Conoco process of "United States Patent 7,273,893 - Process for Converting Carbon Dioxide to Oxygenates", out of CO2. The bulk of the Claims are devoted to component specification and preparation of the catalyst; and, Conoco explains in the "Summary" section that the treating agents they specify are commercially available.)
Background: The present invention relates to a process of preparing high molecular weight hydrocarbons, such as polymethylene, in the presence of a catalyst composition.
It is known that reacting synthesis gas, a mixture of carbon monoxide and hydrogen, at very high pressures, for example greater than 15,000 pounds per square inch ..., and at temperatures of from about 100 C to about 500 C in the presence of supported catalysts can provide high molecular weight hydrocarbons such as polymethylene. However, the pressures required to produce such products from synthesis gas are difficult to achieve, require specific equipment, involve many safety issues, and have a negative impact on the economics of the process. Thus, production of high molecular weight hydrocarbons, such as polymethylene, utilizing moderate reaction conditions that do not require high pressures and related equipment needed to handle the high pressures would be a significant contribution to the art and to the economy.
It is also known that a serious problem associated with synthesis gas operations has been the non-selectivity of the product distribution since high activity catalysts generally yield a liquid product containing numerous hydrocarbon materials such as methanol and branched chain higher alcohols. Thus, complicated recovery schemes are necessary to separate the desired products and the overall yield of the valuable organic products is low. Thus, a process which can produce high molecular weight hydrocarbons, such as polymethylene, from synthesis gas to provide a high degree of selectivity to polymethylene would also be of significant contribution to the art and to the economy.
It is also known that supported ruthenium catalyst compositions have been used at high pressure reaction conditions for producing polymethylene from synthesis gas. However, such catalyst compositions require the use of high pressures and are not useful for obtaining a high yield of polymethylene from synthesis gas conversion at moderate reaction conditions. Thus, a supported ruthenium catalyst composition, a process of making such catalyst composition, and a process for using such catalyst composition for producing polymethylene from synthesis gas that provides a high yield of polymethylene at moderate reaction conditions compared to supported ruthenium catalyst compositions utilized at high pressure conditions would also be of significant contribution to the art and to the economy.
Summary and Description: It is an object of the present invention to provide a process for contacting, under reaction conditions, a catalyst composition, comprising ruthenium and a treated silica support component, and a fluid comprising hydrogen and carbon monoxide to provide high molecular weight hydrocarbons, such as polymethylene, where moderate reaction conditions can be utilized.
(The "moderate reaction conditions", that is, relatively low temperature and low pressure, i.e., relatively low energy and low expense, are what make this attractive.)
Another object of the present invention is to provide novel catalyst compositions and processes of producing such catalyst compositions that can be utilized in the production of high molecular weight hydrocarbons, such as polymethylene, from the conversion of fluids comprising hydrogen and carbon monoxide.
An embodiment of the present invention comprises a process comprising contacting, under reaction conditions, a catalyst composition and a fluid comprising hydrogen and carbon monoxide. The catalyst composition comprises ruthenium and a treated silica support component. Such a process utilizes moderate reaction conditions.
It has been discovered that a novel catalyst composition comprising ruthenium and a treated silica support component can be contacted with a fluid comprising hydrogen and carbon monoxide to provide for high molecular weight hydrocarbons such as polymethylene that can be utilized under moderate reaction conditions. Further, such catalyst composition provides for higher yields of such high molecular weight hydrocarbons compared to currently used catalyst compositions such as ruthenium on a silica support component that has not been treated according to a process of the present invention.
The polymethylene material comprises a mixture of various molecular weights.
A catalyst composition of the present invention can be used in a process of the present invention comprising contacting, under reaction conditions, a catalyst composition with a fluid comprising hydrogen and carbon monoxide. The term "fluid" as referred to herein denotes gas, liquid, vapor, and combinations thereof.
Generally, a mole ratio of hydrogen to carbon monoxide can be any mole ratio that provides for a fluid that can be contacted with a catalyst composition of the present invention to provide high molecular weight hydrocarbons, preferably polymethylene. Generally, the mole ratio of hydrogen to carbon monoxide is in the range of from about 1:1 to about 5:1, preferably in the range of from about 1:1 to about 4:1, more preferably in the range of from about 1:1 to about 3:1, and most preferably the mole ratio is about 2:1.
Reaction conditions of a process of the present invention can be any reaction conditions that suitably provide for the production of polymethylene from a fluid comprising hydrogen and carbon monoxide according to a process of the present invention.
The fluid comprising hydrogen and carbon monoxide can be contacted by any suitable means, method(s), or manner with a catalyst composition of the present invention as described herein contained within a reaction zone. The contacting step can be operated as a batch process step or, preferably, as a continuous process step, preferably in a slurry phase reactor. In the latter operation, a solid catalyst bed, a moving catalyst bed, a fluidized catalyst bed, or a bubble slurry bed can be employed. Any of these operational modes have advantages and disadvantages, and those skilled in the art can select the one most suitable for particular fluid and catalyst composition. The contacting step is preferably carried out within a reaction zone comprising a slurry phase reactor, wherein is contained a catalyst composition of the present invention, and under reaction conditions that suitably promote the production of polymethylene from at least a portion of the fluid."
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In sum, ConocoPhillips devised a process that, efficiently, at moderate conditions of temperature and pressure, converts a "fluid", that is, as they explain, a gas, or vapor, blend of "hydrogen and carbon monoxide" into, predominantly, a widely used commodity plastic ordinarily derived from petrochemicals.
Left unsaid is where we might get such a blend of "hydrogen and carbon monoxide".
Although, as in our above-cited report concerning: "United States Patent 6,638,892 - Syngas Conversion and Catalyst Employed Therefor; 2003; ConocoPhillips Company; Abstract: A process for the conversion of syngas by contact of syngas under conversion conditions with catalyst having as components zinc oxide, copper oxide, aluminum oxide, ... zeolite and clay in ... a one step process for conversion of syngas to dimethyl ether (and) a two step process for conversion of syngas to light olefins ... . Syngas is obtained using well known processes by the partial combustion or gasification of any organic material such as coal";
ConocoPhillips do explain it a bit. And, in another of our reports:
West Virginia Coal Association | Conoco 2011 Coal + CO2 + H2O + O2 = Syngas | Research & Development; concerning: "United States Patent 7,959,829 - Gasification System and Process; 2011; Assignee: ConocoPhillips Company; Abstract: A system and process for gasifying carbonaceous feedstock with staged slurry addition in order to prevent the formation of tar that causes deposition problems. Dry solid carbonaceous material is partially combusted, then pyrolyzed along with a first slurry stream comprising carbonaceous material in two separate reactor sections, thereby producing mixture products comprising synthesis gas. A process for gasification of a carbonaceous material, comprising ... pyrolyzing a first slurry stream comprising a slurry of particulate carbonaceous material in a liquid carrier ... wherein said carrier liquid is selected from group consisting of water, liquid Carbon Dioxide, (or) mixtures thereof (and) wherein said particulate carbonaceous material is ... coal, lignite, ... and mixtures thereof. ... Additional carbonaceous materials are coke from coal, coal char, coal liquefaction residues, particulate carbon, ... biomass, concentrated sewer sludge, bits of garbage, rubber and mixtures thereof";
we see that they explain it even - - from the standpoint of sustainability, economy and environmental sensitivity - - better.
And, the sum of it all is this:
We can manufacture a group of commodity plastics that now require imported petrochemical raw materials, efficiently, from a synthesis gas derived by the gasification of renewable waste botanical and other organic materials, Carbon Dioxide and Coal.
The only thing we have left to figure out is why we haven't started doing it.
