Since we just made further report, as seen in:
West Virginia Coal Association | The University of Akron Improves Coal to Gasoline Process | Research & Development; concerning: "'A Novel Synthesis Route for Liquid Fuels from Coal-derived Syngas'; Makarand Gogate, Conrad J. Kulik, and Sunggyu Lee; The University of Akron, Akron, Ohio; Fuel Science Program; Electric Power Research Institute; California; Abstract: Coal-derived syngas can be converted to methanol using Liquid Phase Methanol Synthesis Process. Methanol can be further converted to gasoline using the Mobil Methanol-To-Gasoline (MTG) process. The combination of commercial syngas-to-methanol technology with the MTG Process thus provides a ready synthetic route for liquid hydrocarbon fuels";
on the achievements of the University of Akron, OH, as sponsored by California's Electric Power Research Institute, in the conversion of Coal into both the substitute Diesel fuel, Dimethyl Ether, "DME", and Methanol, and, through either DME or Methanol, into Gasoline, we wanted herein to document for you the United States Patent which issued from the University of Akron's work.
Before proceeding, however, we did want to make note both of one related issue that has arisen and of a technical problem with this dispatch.
First, concerning the technical issue, we have, as is our usual practice, included links to and excerpts from some of our prior dispatches as they are now posted on the West Virginia Coal Association's web site.
For reasons beyond our very limited technical understanding and, absent now the help of knowledgeable computer consultants we once benefited from, uncorrectable, the formatting of those links is effecting the excerpts, and some of our added comments herein, so that they appear "cramped", and might be a little difficult to read.
Our hope is that at least some of our readers will find the subject matter important enough to wade through the inconvenience, and make the effort to squint a little bit to make them out.
Second, we were recently informed by one of the Coal Country, specifically West Virginia, journalists who are among our primary addressee's of these Coal research dispatches, in an exquisitely rare, almost unicorn-like, and gratefully received bit of feedback from those journalists, that, the reason our reportage concerning the facts that both Coal and Carbon Dioxide can be converted into liquid hydrocarbon fuels, direct replacements for anything we now allow our entire nation to be extorted by, and mortgage our grandchildren's future to, the alien nations of OPEC to keep ourselves supplied with in the here and now, isn't being followed up on by the commercial, public press in West Virginia, is because most of our reports have little directly to do with West Virginia; and, that nobody's really doing anything on a commercial basis with Coal conversion.
That, despite some specific reports we've made, such as:
West Virginia Coal Association | WVU and China Coal to $24 per Barrel Oil | Research & Development; concerning: "Coal to Clean Fuel; The Shenhua Investment in Direct Coal Liquefaction; Jerald J. Fletcher, Director and Professor, (and) Qingyun Sun, Research Assistant Professor; Natural Resource Analysis Center; West Virginia University; 3rd US-China Clean Energy Workshop; Morgantown, WV USA; October 18-19, 2004; China National Energy Security Concerns: Goals: Develop coal liquefaction capabilities: DCL: Direct coal liquefaction (and) ICL: Indirect coal liquefaction; Direct Coal Liquefaction plant in Inner Mongolia; Estimated production cost (of Oil products from Coal) $24/bbl"; and:
West Virginia Coal Association | WVU Affirms Coal Liquefaction Viability for US Congress | Research & Development; concerning: "Statement of Richard A. Bajura Director, National Research Center for Coal and Energy West Virginia University; (US Congress) Committee on House Energy and Commerce Subcommittee on Energy and Power; July 10, 2012; 'Chairman Whitfield and Members of the Subcommittee: Mr. Chairman, I thank you and members of your subcommittee for the opportunity to offer testimony on the topic of coal-to- liquids, commonly abbreviated as CTL. ... we could do more with our abundant coal resource than only making electricity. ... Polygeneration is a technology that includes a combination of coal-based electricity generation and liquid fuels production to satisfy our nation's need for power and petroleum";
which most definitely do relate to West Virginia; and, as in:
West Virginia Coal Association | Penn State Solar CO2 + H2O = Methane | Research & Development; concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; Oomman K. Varghese, Maggie Paulose, Thomas J. LaTempa, and Craig A. Grimes; The Pennsylvania State University; 2009; Efficient solar conversion of carbon dioxide and water vapor to methane and other hydrocarbons is achieved"; and:
West Virginia Coal Association | Pittsburgh USBM 1949 Coal Liquefaction | Research & Development; concerning: "United States Patent 2,464,271 - Coal Liquefaction by Hydrogenation; 1949; Inventors: Henry Storch and Lester Hirst, Pittsburgh; Assignee: The United States of America; The invention described herein may be manufactured and used by and for the Government of the United States of America for governmental purposes. Abstract: This invention relates to ... a low pressure process for the production of liquid hydrocarbons from coals ... . It is ... an object of the present invention ... to provide a continuous process for the preparation of fuel oil from coal", and: "United States Patent 2,476,999 - Solvation and Depolymerization of Coal; 1949; Inventor: Milton Orchin, Pittsburgh, PA; Assignee: The United States of America; The invention herein described and claimed may be manufactured by or for the Government of the United States of America. Abstract: This invention relates to the conversion of ... bituminous and subbituminous coals ... to liquid products of enhanced values and utility";
still others that relate to West Virginia's Coal Country roommates.
Now, if you're just a regular old West Virginia, or Pennsylvania, or Ohio, coal miner, reading this, maybe sipping some coffee while you do a little web surfing before heading off to afternoon shift at your mine, the one you've been worried about shutting down because of lack of demand for Coal or because of Cap and Trade CO2 restrictions at the power plant your mine supplies, and you're also worried about the money it costs you to drive back and forth to work, and the fact that most of that money is headed to OPEC, and maybe you've got a son or daughter, or niece or nephew, serving our country in uniform who you're worried might have to go off to Iraq or Afghanistan to fight in another of our endless stream of oil wars, maybe it's time you tried to make the effort to effect a little attitude adjustment among your Coal Country press corps.
Letters to the Editor don't hurt. But, maybe more effective is something we've suggested before:
Get a few of your Coal-mining buddies together, and go around, in a friendly way, to your local businesses who purchase those big ads in the Sunday newspaper. Ask them how they feel about the fact that more local people could be working in higher paying jobs, and purchasing more of their goods and services, if only more were being made known, and more was thus being done, about the fact that our abundant domestic Coal can, as seen in:
West Virginia Coal Association | China Makes "Huge Profits" from Coal Liquefaction | Research & Development; concerning: "'China Coal Producer Reaps Huge Profits From CTL Project'; Shenhua Group, China's largest coal producer, has made huge profits from its pilot coal-to-liquid (CTL) project in north China in the first three months of this year, a company executive said Saturday"; and, separately, via:Sasol - Wikipedia, the free encyclopedia; "Sasol Limited is an integrated energy and chemical company that began in Sasolburg, South Africa in 1950. It develops and commercialises technologies and builds and operates world-scale facilities to produce a range of product streams including liquid fuels, chemicals and electricity. In particular, Sasol produces petrol and diesel profitably from coal";
be profitably converted, via processes that have been in use elsewhere in the world for more than half a century, into both Gasoline and Diesel fuel, into anything we buy more toe rings for Arab sheik harem girls, and take Christmas presents away from our children, every time we pull into a gas station and fill 'er up.
Seriously, it's far past time every last one of us who actually cares anything at all about the future of Coal Country, about the future of the USA, got off our dead cans and started to insist that our Coal Country journalists got off their dead cans and started doing what we all are, indirectly at least, paying them to do:
Inform.
With our diatribe out of the way, allow us now to return to the University of Akron, and the process they developed for California's Electric Power Research Institute, as described in our above-cited report concerning "'A Novel Synthesis Route for Liquid Fuels from Coal-derived Syngas'.
So "novel" was that process for converting Coal into both a substitute Diesel fuel, DME, and, through DME, into Gasoline, that the University of Akron scientists who developed the process were awarded a United States Patent for it, as
seen, with comment inserted and appended, in excerpts from the initial link in this dispatch to:
"United States Patent 5,459,166 - Catalytic Process for Production of Gasoline from Synthesis Gas
Patent US5459166 - Catalytic process for production of gasoline from synthesis gas - Google Patents
Date: October, 1995
Inventors: Sunggyu Lee, Makarand Gogate, et. al., OH and CA
(Note, that, Dr. Lee is now at Ohio University, where, as can be learned via:
Professor Sunggyu Lee's Research Program; his "research specialties are in the areas of transportation and alternative fuels, advanced coal technology, chemical process engineering, polymer synthesis and processing, polymer and blends composites. To be specific, they include C1 Chemistry, hydrogen generation, fuel reforming, carbon dioxide conversion, gas cleanup and purification, clean coal technology, methanol and DME synthesis, synthesis of gasoline and oxygenates (and) Fischer-Tropsch".)
Assignee: Electric Power Research Institute, Palo Alto, CA
Abstract: A process is provided whereby syngas is converted to gasoline via a liquid-phase process producing dimethyl ether as an intermediate.
Claims: A process for the liquid-phase production of gasoline from a syngas comprising carbon oxides and hydrogen, comprising the steps of: contacting said gas with a catalyst slurry at a temperature in the range of about 200 to 285 C and pressure in the range of about 700 to 1600 psig to produce a liquid product comprising dimethyl ether as a major component thereof, wherein said slurry comprises a mixture of a first catalytic component comprising copper and zinc oxide, supported on alumina, zirconia and/or titania; and a second catalytic component comprising a dehydration catalyst ... under such conditions as to produce a product having an organic portion which is predominantly liquid hydrocarbons boiling in the C5 to 400 F range.
A process ... wherein said syngas is hydrogen-rich (or) carbon monoxide rich.
The process ... wherein said dehydration catalyst comprises .gamma.-alumina.
(The above-specified "dehydration catalyst ... .gamma-alumina" is commercial stuff, already being used, by the way. Have a look at:
http://iopscience.iop.org/
Background and Field: The present invention relates to the production of gasoline from synthesis gas (syngas) through dimethyl ether as an intermediate.
There are methods known in the art for producing gasoline from synthesis gas such as the method disclosed in U.S. Pat. No. 3,894,102, however there is a need for improvement in the productivity, heat transfer, reactor size and other significant parameters which can lead to cost efficiency.
("United States Patent: 3894102 - Conversion of Synthesis Gas to Gasoline; 1975; Inventors: Clarence Chang and Anthony Silvestri; Assignee: Mobil Oil Corporation: Abstract: Contacting snythesis gas (mixed carbon monoxide and hydrogen) with a mixture of a carbon monoxide hydrogenation catalyst and an acid dehydration catalyst to produce a first stage product comprising dimethyl ether and contacting this first stage product, preferably in its entirety, with a crystalline aluminosilicate having a silica to alumina ratio of at least about 12 and a constraint index of about 1 to 12 to convert it to high octane gasoline".
The above is similar and closely related to another, similar Mobil Oil Coal conversion invention, made by the same team of Mobil scientists, about which we've earlier reported, as in:
West Virginia Coal Association | Mobil Converts Coal to High Quality Gasoline | Research & Development; concerning: "United States Patent 4,076,761 - Process for the Manufacture of Gasoline; 1978; Inventors: Clarence Chang and Anthony Silvestri; Assignee: Mobil Oil Corporation; Abstract: Synthesis gas comprising a mixture of carbon monoxide and hydrogen is derived from fossil fuels and catalytically converted in a first reaction zone to a mixture of methanol and dimethyl ether which in turn is converted in a separate reaction zone ... into a high octane gasoline fraction, a light hydrocarbon gas fraction which may be liquefied and a hydrogen-rich gaseous by-product which is recycled to the conversion of fossil fuels to synthesis gas or may be otherwise used. Claims: (The) process for manufacture of liquid hydrocarbon fuels boiling in the gasoline boiling range from coal which comprises converting the coal to a gaseous mixture of hydrogen and carbon oxides and converting said gaseous mixture to normally liquid hydrocarbons and oxygen-substituted hydrocarbons comprising methanol (with the) additional step of contacting ... said methanol with a catalytically active aluminosilicate zeolite ... (and recovering) liquid hydrocarbons".And, note in the above "United States Patent 4,076,761 - Process for the Manufacture of Gasoline", the similarity with our subject herein, "United States Patent 5,459,166 - Catalytic Process for Production of Gasoline from Synthesis Gas", in the intermediate production of "dimethyl ether" or mixture of "methanol and dimethyl ether" as intermediate to the final synthesis of "gasoline".)
One of the disadvantages of the process of U.S. Pat. No. 3,894,102 is that it is economically justified only if the syngas feed stock is hydrogen-rich.
(The full Disclosure of "U.S. Pat. No. 3,894,102" specifies that "hydrogen" from an external source, "may be added". As we've documented, for only one example in:
West Virginia Coal Association | General Motors Uses Sunshine to Make Hydrogen | Research & Development; concerning: "United States Patent 7,459,065 - Hydrogen Generator Photovoltaic Electrolysis Reactor System; 2008; Assignee: General Motors Corporation; Abstract: An apparatus for creating hydrogen from the disassociation of water using sunlight (photoelectrolysis) is provided. The system utilizes an aqueous fluid filled container which functions both to hold the water to be disassociated and as a light collecting lens. A photovoltaic module is positioned at a point to most efficiently accept the refracted light from the fluid filled container. A pair of electrodes which are coupled to the photovoltaic module are disposed within the fluid and configured to split the water into hydrogen and oxygen"; and: "United States Patent 7,510,640 - Method and Apparatus for Hydrogen Generation; 2009; Assignee: General Motors Corporation;
Abstract: A method for configuring a solar hydrogen generation system and the system optimization are disclosed";
there are now some options available for the economical generation of supplemental Hydrogen.)
A more versatile process is desirable. Furthermore, in the prior art process, in the first stage of conversion of the syngas to methanol, a significant amount of water is produced which must be separated from the mixture prior to proceeding to the gasoline synthesis stage. Other processes related to syngas-to-gasoline conversion include U.S. Pat. No. 4,882,360 describing a process for producing an alcohol fraction comprising methanol, ethanol and some propanol from a syngas using a catalyst consisting of three components: molybdenum sulfide, iron sulfide and a suitable promoter. This does not appear to be a process wherein syngas is made to produce dimethyl ether which is in turn converted to gasoline.("United States Patent: 4882360 - Process for Producing Alcohols from Synthesis Gas; 1989; Inventor: Rex Stevens, MI; Assignee: The Dow Chemical Company; A process for making alcohols comprising contacting a mixture of hydrogen and carbon monoxide with a catalyst (as specified). to form an alcohol fraction boiling in the range of motor gasoline ... . The hydrogen and carbon monoxide required for this process can be obtained by methods known in the art. Examples are gasification of hydrocarbonaceous materials such as coal".)
U.S. Pat. No. 4,814,536 discloses an improvement on the process of converting methanol to gasoline by selectively programming a feed weight hourly space velocity (WHSV) to a fixed bed catalytic conversion reactor so as to increase cycle average gasoline yield and increase useful life in the conversion catalyst.
("United States Patent: 4814536 - Conversion of Oxygenates to Gasoline; 1989; Inventor: Sergei Yurchak; Assignee: Mobil Oil Corporation; Abstract: An improved MTG (methanol-to-gasoline) process for converting lower aliphatic C1 - C4 oxygenates, such as methanol, to gasoline boiling range hydrocarbons is disclosed which is capable of obtaining improved cycle average gasoline yields and improved catalyst life ... . The methanol, in turn, may be readily obtained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes.")
U.S. Pat. No. 4,898,717 discloses a multistage process for converting C1 - C4 aliphatic oxygenares to heavy hydrocarbons in the diesel fuel boiling range. In the first stage the feed is converted to lower olefins and in the second stage the ethane-free lower olefins are converted to diesel fuel boiling range hydrocarbons.
("United States Patent: 4898717 - Converting Oxygenates to Distillate Hydrocarbons; 1990; Chung Hsia, et. al.; Assignee: Mobil Oil Corporation; An integrated process is provided for converting methanol, dimethylether or the like to heavy hydrocarbon products, especially distillate range hydrocarbons. Distillate range hydrocarbons are useful as diesel fuel or the like.")
U.S. Pat. No. 4,444,652 is directed to the production and upgrading of low grade gasoline derived from syngas over an iron or cobalt catalyst. Low grade gasoline is upgraded with a C3 to C4 aliphatic hydrocarbon stream over a gallium-impregnated zeolite catalyst.
U.S. Pat. No. 4,399,234 is directed to production of gasoline via Fischer-Tropsch synthesis over cobalt/alumina catalysts.
(West Virginia Coal Association | Gulf and Chevron Convert Coal to Diesel Fuel and Gasoline | Research & Development; concerning, in part: "United States Patent 4,399,234 - Preparing Gasoline Range Hydrocarbons from Synthesis Gas; 1983; Assignee: Gulf Research and Development Company, Pittsburgh; Abstract: Synthesis gas is converted to a gasoline boiling range product high in branched chain paraffins and olefins utilizing a catalyst consisting essentially of silicalite and cobalt ... . Claims: A process for the conversion of synthesis gas consisting essentially of CO and hydrogen to a product high in branched chain paraffins and olefins in the gasoline boiling range. Background: The growing importance of alternative energy sources has brought a renewed interest in the Fischer-Tropsch synthesis as one of the more attractive direct and environmentally acceptable paths to high quality transportation fuels".)
U.S. Pat. No. 4,263,141 is directed to the production of gasoline from syngas using a conventional methanol-to-gasoline route in two stages. In the first stage syngas is converted to methanol over a copper based catalyst. Then the entire product stream is fed to a gasoline reactor the product of which is cooled and the C.sub.5 and higher gasoline fraction is collected as a product.
(West Virginia Coal Association | Germany Makes Gasoline from Coal Syngas Via Methanol | Research & Development; concerning: "United States Patent 4,263,141 - Process of Producing Gasoline from Synthesis Gas; Inventor: Friedrich Moller, et. al.; 1981; Abstract: A process for the catalytic production of gasoline hydrocarbons from synthesis gas comprising carbon oxides and hydrogen is disclosed wherein the synthesis gas is fed initially to a methanol synthesis and thereafter effluent from the methanol synthesis is converted to gasoline hydrocarbons in a gasoline synthesis stage".)
It is therefore an object of the present invention to provide a method for converting syngas, either hydrogen-rich or carbon monoxide-rich, to gasoline through an intermediate which comprises as a major portion dimethyl ether, which improves the reaction chemistry, productivity and heat transfer as compared to processes which utilize methanol as an intermediate.
It is a further object of the present invention to provide an improved process for converting syngas to gasoline whereby the lowering of the energy requirements is by about 15% or more as compared to a process utilizing methanol as an intermediate.
Summary: A process is provided for the liquid-phase production of gasoline from a gas comprising carbon oxides and hydrogen, comprising the step of contacting the gas with a catalyst slurry at a temperature in the range of about 200 to 285C, at a pressure in the range of about 700 to 1600 psig, wherein the slurry comprises a mixture of a first catalytic component comprising copper and zinc oxide supported on alumina, zirconia and/or titania; and a second catalytic component comprising .gamma.-alumina ... and then contacting the resulting product which comprises as a major component thereof dimethyl ether, with a zeolite catalyst in a temperature range from about 650 to 1000 F under such a combination of conditions as to produce a product which comprises an organic portion which is predominantly liquid hydrocarbons boiling in the range C5 to 400 F range.
The water that is produced in situ in the catalyst ... reacts rapidly with the carbon monoxide present in the syngas feed, resulting in formation of carbon dioxide and hydrogen, both of which are reactants for the main synthesis reaction.
(Note that co-product "carbon dioxide" is, or can be, one of the "reactants for the main synthesis reaction". There is no need for an indirect Coal-to-Gasoline process to emit CO2.)
(The) overall thermodynamic equilibrium of conversion of syngas is (thus) improved.
The catalysts comprising the catalysts for converting the syngas to dimethyl ether in the first stage will be those known in the art which usually comprise copper, zinc oxide and alumina, zirconia and/or titania supports. Such catalysts are disclosed, for example, in U.S. Pat. No. 4,417,000.
(United States Patent: 4417000 - Dimethyl Ether Process; 1983; Shell Oil Company; Texas; Abstract: Dimethyl ether is produced from syngas in high yield utilizing a physical mixture of two catalyst components: a first component comprising copper-zinc and alkali metal supported on alumina, and a second component comprising tungsten oxide supported on silica-alumina.)
The co-catalyst which is used to convert the methanol to dimethyl ether will be a dehydration catalyst such as .gamma.-alumina, zeolite, or aluminum silicate.
The organic intermediates comprising essentially dimethyl ether formed in the first stage are then fed into the second stage, preferably with a minimum of interstage cooling. In the second stage the catalysts are zeolites which are useful for converting hydrocarbons to gasoline (as specified in the above reference to United States Patent 3,894,102).
The .gamma.-aluminas which are useful in the present invention are readily available commercially.
Generally, given identical temperatures and pressures, the higher the ratio of the methanol catalyst to dehydration catalyst, the more efficient and the greater the yield is of dimethyl ether as compared to methanol.
The particular advantages of the present process are that the total reaction time of conversion of the syngas to gasoline is reduced and the space velocity which may be utilized with a catalyst is increased. Furthermore, if desired the reactor size may be much smaller than utilized in systems in which methanol is a primary product since volumetrically one mole of dimethyl ether is approximately equivalent of 2 moles of methanol in hydrocarbon value.
Production of water in the first stage of the present invention is low, which is also an advantage in that the small amount of water can be handled by reaction with carbon monoxide to produce more reactants, that is carbon dioxide and hydrogen ... .
(Again, "carbon dioxide" is identified as one of the "reactants”.)
Furthermore, according to the present invention the equilibrium conversion of dimethyl ether to gasoline is higher than the conversion to gasoline when there is a mixed feed of substantial amounts of dimethyl ether, methanol and water. Moreover, since the intermediate in the present invention is primarily dimethyl ether, the necessity of separating methanol and water intermediate products, made according to the prior art, is eliminated therefore saving on the thermal usage of the overall process.
Finally, the versatility of the catalysts ... is such that the hydrogen-rich or carbon monoxide-rich source of syngas may be utilized, which is a significant advantage over the prior art in which economic operation is limited to the use of hydrogen-rich syngas sources."
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And, we'll close our excerpts there, since Coal would most definitely be a "carbon monoxide-rich source of syngas", for this University of Akron process, developed for the Electric Power Research Institute, as in our introductory citation of our report concerning: "'A Novel Synthesis Route for Liquid Fuels from Coal-derived Syngas'; Makarand Gogate, Conrad J. Kulik, and Sunggyu Lee; The University of Akron", which efficiently converts our abundant Coal into the valuable alcohol, Methanol, the substitute Diesel fuel, Dimethyl Ether; and, through either or both of those, into Gasoline.
Now, Akron, OH, might be on the western frontier of US Appalachian Coal Country. But, since one among our number here actually mined Coal in Ohio, while living in West Virginia, we sort of feel that its all somehow "connected".
Too danged bad the paid journalists living in West Virginia, and Pennsylvania, don't feel the same way.