United States Patent: 7678952
Sometimes, in the course of our research and reportage, we just stop, look at each other, and laugh.
Sometimes, though, we almost cry.
Every day, we marvel.
We long ago likened our sense of the situation for you to that of a family sitting around in their living room, with an elephant squatting smack dab in the middle of their living room floor.
The thing is obvious; but, at the same time it is so outrageous, so unbelievable, that, in some process of denial, nobody even mentions it, much less talks about it and openly discusses what to do about it.
In sum, and yet again:
We can efficiently convert our abundant US Coal, along with renewable, sustainable, Carbon-recycling Biomass that we can grow in and on our own American fields, forests and farms, into anything we have, for the past half a century, been pouring our national wealth into the coffers of largely unfriendly, and definitely alien, foreign OPEC powers, and fighting foreign OPEC wars, to keep ourselves supplied with.
The technologies for doing that are now nearly ancient; and, they have been and are being practiced on industrial scales in other nations of the world.
But, our public press, especially, and our public figures, would, apparently, prefer to ignore that fact, that elephant, so that they can, we can here only conjecture, continue playing their roles in an artificial and unnecessary drama that's been running for so long now on the American stage that they, the actors, have memorized their lines, can repeat them, or rewrite them, reflexively and without effort on cue; and, their jobs have thus become so effortless they can almost "mail it in"; and, then devote the bulk of their energies to whatever eccentric and deeply personal sets of things it is that truly interest them - with only the Good Lord in Heaven knowing what, in the world, those sets of things might really be.
Clearly now - - with the absolute public silence that has continued to shroud the now-obvious and indisputable fact that our abundant Coal, and the products of our fields, forests and farms, can be efficiently converted into Gasoline - - our national US prosperity and security; an improving environment; and, full, prosperous employment for our American miners and farmers are not among those things that do truly interest our public press and our public figures.
We, here, would rejoice, absolutely rejoice, in public presentation of any evidence, whatsoever, to the contrary.
Until we can put on our party hats and so rejoice, however, we reckon we'll just keep putting on our helmets, snapping on our cap lamps, and heading down the shaft.
Still got some work to do, some more Coal to mine, apparently.
In any case, herein we see that yet another prominent member of the Big Oil club confirms what, as in:
West Virginia Coal Association | Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development; concerning: "US Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass; 2010; Assignee: ExxonMobil Research and Engineering Company; Abstract: A process for the co-gasification of carbonaceous solids (coal) and biomass ... wherein the solid carbonaceous particles comprise coal (and) wherein the biomass comprises biological matter selected from wood, plant matter, municipal waste, green waste, byproducts of farming or food processing waste, sewage sludge, black liquor from wood pulp, and algae. One established route to the production of hydrocarbon liquids is the gasification of carbonaceous materials followed by the conversion of the produced synthesis gas to form liquids by processes such as Fischer-Tropsch and its variants. In this way, solid fuels such as coal ... may be converted to liquids";
we were told not long ago by one of the petroleum industry's premier representatives:
Coal and Biomass can be consumed together, in a synergistic and more sustainable way, in an efficient process that manufactures, as the end product, liquid hydrocarbon fuels.
First of all, a reminder, a definition of terms, as it were, since the true essence of the thing could get lost in the exposition of the details.
Our subject herein is, in essence, a technology for converting the products of a Fischer-Tropsch reaction into clean Gasoline that is perfectly compatible with the Gasoline we currently refine from petroleum.
And, since our subject is a technology developed by Shell Oil Company, we'll let them explain for you again what the Fischer-Tropsch reaction is, in their own:
"United States Patent: 4499209 - Fischer-Tropsch Catalyst and Preparation of Hydrocarbons from Syngas
(Process for the preparation of a Fischer-Tropsch catalyst and preparation of hydrocarbon from syngas - Shell Oil Company)
Date: February, 1985
Inventors: Arend Hoek, et. al., The Netherlands
Assignee: Shell Oil Company, Houston
Abstract: A Fischer-Tropsch catalyst is ... used in the preparation of hydrocarbons from a H2/CO mixture. A process for the preparation of hydrocarbons by catalytic reaction of carbon monoxide with hydrogen."
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And, since they define, in the above "United States Patent 4,499,209" that "Syngas", short for "Synthesis Gas", is an "H2/CO", Hydrogen and Carbon Monoxide, "mixture", we'll let Shell also tell us where we can get such an "H2/CO mixture", in an advance excerpt from the full Disclosure of our subject:
"Synthesis gas may be obtained by well known processes like partial oxidation and steam reforming and combinations of these processes starting with a (hydro) carbon feedstock. Examples of possible feedstocks are ... coal ... and biomass, for example wood"
And, actually, we have some even better, even more sustainable and Carbon-recycling options for obtaining such syngas from our abundant Coal, as we'll let Shell Oil themselves explain, via comment concerning another of their technologies appended to our more complete excerpts from the initial link above to:
"United States Patent 7,678,952 - Process to Prepare a Gasoline
(Process to prepare a gasoline - Shell Oil Company)
Date: March, 2010
Inventors: Xander Dupain, et. al., The Netherlands
Assignee: Shell Oil Company, Texas
Abstract: A process to prepare a gasoline fuel by contacting a Fischer-Tropsch product with a catalyst system of an acidic matrix and a large pore molecular sieve wherein the Fischer-Tropsch product has a weight ratio of compounds having at least 60 or more carbon atoms and compounds having at least 30 carbon atoms in the Fischer-Tropsch product ... and wherein at least 30 wt % of compounds in the Fischer-Tropsch product have at least 30 carbon atoms.
(What should be clear is that they are going to explain how to make Gasoline from the crude product generated by the catalytic chemical condensation of Carbon Monoxide and Hydrogen, generated as synthesis gas from Coal and, as we will again see, a few other interesting things.)
Claims: A process to prepare a gasoline fuel comprising: contacting a Fischer-Tropsch product with a catalyst system comprising a catalyst, which catalyst comprises an acidic matrix and a large pore molecular sieve, wherein the Fischer-Tropsch product is a product obtained by a Fischer-Tropsch process catalyzed by a cobalt catalyst, the Fisher-Tropsch product comprises a C20+ fraction (and) has a weight ratio of compounds having at least 60 carbon atoms to compounds having at least 30 carbon atoms of at least 0.2, and at least 30 wt % of compounds in the Fischer-Tropsch product have at least 30 carbon atoms.
(Basically, "the Fischer-Tropsch product" is a crude "oil" containing a lot of long-chain hydrocarbons.)
The process ... wherein contacting occurs at a temperature between 450 and 650C.
The process ... wherein the acidic matrix is alumina.
The process ... wherein the large pore molecular sieve is of the Faujasite type.
(Faujasite - Wikipedia, the free encyclopedia; "Faujasite is a mineral group in the zeolite family of silicate minerals.)
The process ... wherein the catalyst also comprises a medium pore size molecular sieve selected from the group consisting of zeolite beta, Erionite, Ferrierite, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23 and ZSM-57.
(Of the above, "ZSM-5" has proven to be key. And, the development of the use of it in Coal conversion technologies was financed, at least in part, by our tax money; as seen in our report of:
West Virginia Coal Association | USDOE Pays Mobil to Develop Coal Conversion Catalyst | Research & Development; concerning: "United States Patent 4,207,208 - Activity Improvement of Syngas Conversion Catalyst; 1980; Assignee: Mobil Oil Coporation; Abstract: A method is disclosed for the treatment of single particle iron-containing syngas (synthesis gas) conversion catalysts comprising iron, a crystalline acidic aluminosilicate zeolite (as specified). Government Interests: The Government of the United States of America has rights in this invention pursuant to Contract No. E(49-18)2276 awarded by the U.S. Energy Research and Development Administration. A method for treating either a fresh or spent single particle iron-containing syngas conversion catalyst composition prepared by forming a mixture of a water insoluble iron derivative of an organic compound ...and an ... aluminosilicate zeolite ... wherein the zeolite is ZSM-5. Processes for the conversion of coal ... to a gaseous mixture consisting essentially of hydrogen and carbon monoxide and/or dioxide are well known. It is also well known that synthesis gas will undergo conversion to reduction products of carbon monoxide, such as hydrocarbons, ... over a fairly wide variety of catalysts. The Fischer-Tropsch process, for example, which has been most extensively studied, produces a range of liquid hydrocarbons, a portion of which have been used as low octane gasoline. Catalysts that have been studied for this and related processes include those based on iron, cobalt, nickel, (etc.). Recently, it has been discovered that the conversion of synthesis gas into valuable products can be greatly enhanced by employing a special type of crystalline alumino-silicate zeolite exemplified by ZSM-5 in admixture with a conventional Fischer-Tropsch catalyst".)
The process ... wherein contacting is performed in a reactor selected from the group consisting of a fixed bed reactor, a fluidized bed reactor and a riser reactor.
A process to prepare gasoline comprising: performing a Fischer-Tropsch reaction using a cobalt catalyst thereby obtaining a Fischer-Tropsch product having (a composition as specified, and) contacting the Fischer-Tropsch product with a catalyst comprising an acidic matrix and a large pore molecular sieve, and isolating a gasoline fraction.
The process ... wherein the contacting of the Fischer-Tropsch product and the catalyst is performed in a riser reactor at a temperature of between 500 and 600C and a contact time of between 2 and 10 seconds.
The process ... wherein the Fischer-Tropsch reaction is performed in a tubular reactor.
Background and Field: The invention relates to a process to prepare a gasoline from a Fischer-Tropsch product.
Preparing a gasoline having an acceptable octane number from a Fischer-Tropsch product is not straightforward. This because the Fischer-Tropsch product, as such, consists for a large portion, of normal paraffins which have a low octane value or contribution.
The invention provides a process to prepare a gasoline fuel by contacting a Fischer-Tropsch product with a catalyst system comprising a catalyst, which catalyst comprises an acidic matrix and a large pore molecular sieve ... .
Applicants found that the combination of a relatively heavy Fischer-Tropsch product and the claimed catalyst can yield a gasoline product having a high content of iso-paraffins and olefins, compounds which greatly contribute to a high octane number. Another advantage is that a distillate fraction, which boils in the gas oil range, is obtained in a high yield and having excellent properties, for example Cetane Number, to be used as a diesel engine fuel or as a blending component for such a fuel.
A further advantage is that no hydroprocessing is required. For example, the Fischer-Tropsch synthesis product can be directly used in the process according to the invention without having to hydrotreat the feed. Another advantage is that use can be made of well-known catalyst and reactors known for fluid catalytic cracking (FCC) processes.
Synthesis gas, which is hydrogen and carbon monoxide, is typically fed to the process at a molar ratio in the range from 0.5 to 2.5.
The Fischer-Tropsch synthesis (of hydrocarbons) may be performed in a slurry reactor or preferably in a fixed bed. Synthesis gas may be obtained by well known processes like partial oxidation and steam reforming and combinations of these processes starting with a (hydro) carbon feedstock. Examples of possible feedstocks are ... coal ... and biomass, for example wood."
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Since we are back to synthesis gas, in closing it might be interesting to share with you a later Shell Oil development for the making of syngas out of "coal ... and" Carbon-recycling, sustainable "biomass".
As seen in our report of:
Shell Oil Coal + CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning:
"United States Patent 7,829,601 - Partial Oxidation Process of a Solid Carbonaceous Feed; 2010; Assignee: Shell Oil Company, Texas; Abstract: The invention is directed to a process for preparing a mixture comprising CO and H2 by operating a partial oxidation process of a solid carbonaceous feed, which process comprises the steps of: (Supplying) the solid carbonaceous feed and an oxygen-containing stream to a burner, wherein a CO2 containing transport gas is used to transport the solid carbonaceous feed to the burner; (And) partially oxidizing the carbonaceous feed in the burner wherein a gaseous stream comprising CO and H2 is being discharged from said burner into a reaction zone ... . (And) wherein the solid carbonaceous feed is coal. In some embodiments the invention provides a process for preparing a mixture comprising CO and H2 by operating a partial oxidation process of a solid carbonaceous feed (which includes) supplying the solid carbonaceous feed and an oxygen-containing stream to a burner (and) wherein a CO2 containing transport gas is used to transport the solid carbonaceous feed to the burner";
Carbon Dioxide, as recovered from whatever handy source, can be utilized as the "transport gas" which conveys the "solid carbonaceous feed", i.e., "coal ... and" Carbon-recycling and sustainable "biomass, for example wood", into the "Partial Oxidation Process", wherein they are all converted into a gas "mixture comprising CO and H2"; that is, "syngas", which can be directed into a process like that disclosed in the above-cited "United States Patent 4,499,209 - Fischer-Tropsch Catalyst and Preparation of Hydrocarbons from Syngas"; and, be converted therein into a crude mix of hydrocarbons; which hydrocarbons, we infer, could then be directed into the process of our subject, "United States Patent 7,678,952 - Process to Prepare a Gasoline", and be refined into, well, "Gasoline".
But, nobody knows about any of it; and, the way things have been progressing in the course of our research since before President Obama was elected, we doubt that anyone beyond the occasional Coal miner surfing the West Virginia Coal Association's web site ever will come to know about any of it.
Like we said: Sometimes we laugh. Sometimes we cry.
