We did, by the way, resist the urge to title this dispatch "Men In Black Ray Guns Convert Coal into Hydrocarbon Syngas". Our subject herein, the recently-published "United States Patent Application 20130213795 - Heavy Fossil Hydrocarbon Conversion And Upgrading Using Radio-Frequency or Microwave Energy", comes to us from two Federal agencies; agencies which our guess is not too many people living and working in the heart of US Coal Country have heard much, if anything at all, about.
And, the types of energies specified by them to convert Coal, specified to be the "Heavy Fossil Hydrocarbon" of most interest herein, into a hydrocarbon synthesis gas suitable for catalytic condensation into hydrocarbons sound like stuff that could have been reverse-engineered from something that fell to the ground near Roswell, NM.
Even further, even more out of this world, the process disclosed herein can convert not just Coal, but, Coal along with Carbon Dioxide itself and some Carbon-recycling products and wastes, such as biomass and scrap plastic, directly into some hydrocarbons.
As revealed by the Summary, very near the end of the full Disclosure, this invention can process all ranks of Coal and "biomass, plastics, municipal waste, sludge, or other carbon-rich materials".First, an advance excerpt, from the "Government Interests" section of the Disclosure:
"This invention was made with Government support under ARPA Order No. Z075/00, Program Code 9620 issued by DARPA/CMO under Contract HR0011-10-0088. The United States Government has certain rights in the invention."
As it happens, we've cited both "ARPA" and "DARPA" once or twice previously over the past years. But, for a little more info, see:
Defense Advanced Research Projects Agency; "Creating & Preventing Strategic Surprise"; and:
DARPA - Wikipedia, the free encyclopedia; "The Defense Advanced Research Projects Agency (DARPA) is an agency of the United States Department of Defense responsible for the development of new technologies for use by the military. DARPA has been responsible for funding the development of many technologies which have had a major effect on the world, including computer networking ... . DARPA began as the Advanced Research Projects Agency (ARPA) created in 1958 by President Dwight D. Eisenhower for the purpose of forming and executing research and development projects to expand the frontiers of technology and science and able to reach far beyond immediate military requirements. The administration was responding to the Soviet launching of Sputnik 1 in 1957, and ARPA's mission was to ensure U.S. military technology be more sophisticated than that of the nation's potential enemies"; and:
ARPA-E History | ARPA-E; "In 2007, Congress passed and President George W. Bush signed into law "The America COMPETES Act, which officially authorized ARPA-E's creation. In 2009, Congress appropriated and President Barack Obama allocated $400 million to the new Agency, which funded ARPA-E's first projects. ... Since 2009, ARPA-E has funded over 285 potentially transformational energy technology projects. Many of these projects have already demonstrated early indicators of technical success. For example, ARPA-E awardees have (among other things): Engineered microbes that use hydrogen and carbon dioxide to make liquid transportation fuel"; and:ARPA-E - Wikipedia, the free encyclopedia; "ARPA-E, or Advanced Research Projects Agency-Energy is a United States government agency tasked with promoting and funding research and development of advanced energy technologies. It is modeled after the Defense Advanced Research Projects Agency (DARPA)".
Note the statement above, that: "ARPA-E awardees have ...: Engineered microbes that use hydrogen and carbon dioxide to make liquid transportation fuel", and see, for one example, our report of:
West Virginia Coal Association | USDOE Hires Massachusetts Bugs to Convert CO2 to Alcohol | Research & Development; concerning: "United States Patent Application 20120288898 - Microbial Production of Multi-Carbon Chemicals and Fuels from Water and Carbon Dioxide Using Electric Current; 2012; Inventors: Derek Lovley and Kelly Nevin, MA; (Presumed eventual Assignee of Rights: University of Massachusetts); Abstract: The invention provides systems and methods for generating organic compounds using carbon dioxide as a source of carbon and electrical current as an energy source. In one embodiment, a reaction cell is provided having a cathode electrode and an anode electrode that are connected to a source of electrical power, and which are separated by a permeable membrane. A biological film is provided on the cathode. The biological film comprises a bacterium that can accept electrons and that can convert carbon dioxide to a carbon-bearing compound and water in a cathode half-reaction. At the anode, water is decomposed to free molecular oxygen and solvated protons in an anode half-reaction. The half-reactions are driven by the application of electrical current from an external source. Compounds that have been produced include acetate, butanol, 2-oxobutyrate, proponal, ethanol, and formate. Government Interests: The U.S. Government has certain rights in this invention pursuant to Cooperative Agreement DE-FCO2-02ER63446 awarded by the (USDOE) and Agreement No. DE-AR0000087 awarded by ARPA-E".And, herein, we see that both DARPA and ARPA-E teamed up in development work performed at one of the USDOE's National Laboratories, perhaps because of Coal's inarguable dominance as far and away our most energy-abundant "Fossil Hydrocarbon" resource, "Heavy" or otherwise, to pioneer a new way to convert Coal into not just a synthesis gas blend of Carbon Monoxide and Hydrogen suitable for catalytic chemical condensation, as via the Fischer-Tropsch process, into a full range of liquid and gaseous hydrocarbons; BUT, a way that, through an innovative approach to applying electrical and thermal energy to the Coal, and blending the Coal with an hydrogenation catalyst, dramatically limits the co-production of unwanted Carbon Dioxide AND results in the direct production of hydrocarbons in the gasification/conversion reactor.
The Coal, and other reactants, such as CO2 and H2O, and are reacted together and converted more or less directly into the desired hydrocarbons.
And, their method of delivering energy into Coal has been presaged by others working to - -
as seen for two examples in our reports of:
West Virginia Coal Association | Exxon CO2 and Methane to Syngas via Microwave Radiation | Research & Development; concerning: "United States Patent 5,266,175 - Conversion of Methane, CO2 and H2O Using Microwave Radiation; 1993; Assignee: Exxon Research and Engineering Company; Abstract: A mixture of methane, water and carbon dioxide can be effectively converted to carbon monoxide and hydrogen by subjecting the mixture to microwave radiation in the presence of at least one plasma initiator that is capable of initiating an electric discharge in an electromagnetic field"; and:
West Virginia Coal Association | Switzerland Recycles CO2 to Fuel | Research & Development; concerning the report: "Hydrogenation of carbon dioxide to methanol with a discharge-activated catalyst; B. Eliasson, et. al.; ABB Corporate Research Ltd., (Switzerland); Abstract: To mitigate greenhouse gas CO2 emissions and recycle its carbon source, one possible approach would be to separate CO2 from the flue gases of power plants and to convert it to a liquid fuel, e.g., methanol. Hydrogenation of CO2 to methanol is investigated in a dielectric-barrier discharge (DBD) with and without the presence of a catalyst";
wherein it was disclosed how microwave radiation, the same stuff you cook your frozen burritos with, can be used to "disassociate" Carbon Dioxide and Water into Carbon Monoxide, Hydrogen and Oxygen, in conjunction with one form or another of a "plasma initiator that is capable of initiating an electric discharge", that is, "a dielectric-barrier discharge", when exposed to microwave radiation;
- - effect the conversion of CO2, as recovered from whatever handy source, and H2O, into a blend of synthesis gas also suitable for catalytic chemical condensation, again as via for one example the Fischer-Tropsch process, into hydrocarbons.
And, intriguingly, though you have to look sharp for it, the process of our subject, though focused on Coal, i.e., the "Heavy Fossil Hydrocarboon", will, as well, process Carbon Dioxide with the Coal, and convert them both into, again, not just hydrocarbon synthesis gas, but, directly into some desirable hydrocarbons, as well.
All as explained in excerpts from the initial link in this dispatch to:
"United States Patent Application 20130213795 - Heavy Fossil Hydrocarbon Conversion and Upgrading Using Radio-Frequency or Microwave Energy
Date: August 22, 2013
Inventors: James Strohm, et. al., WA
Assignee: Battelle Memorial Institute, Richland, WA
(The development work leading up to this US Patent Application was performed at the USDOE's Pacific Northwest National Laboratory. And, as we have explained previously, for reasons unfathomable to us, our United States Government has seen fit to farm out management of our critical USDOE National Laboratories, which are essential to our ongoing national security, to non-governmental entities, usually consortiums of private and public institutions of one sort or another and private and public business corporations. "Battelle Memorial Institute", as we have documented in a few previous reports, is, to put it in somewhat vague terms, a strange animal. They are described pretty well via:
Battelle Memorial Institute - Wikipedia, the free encyclopedia; "Battelle Memorial Institute is a private nonprofit applied science and technology development company headquartered in Columbus, Ohio. Battelle is a charitable trust organized as a nonprofit corporation under the laws of the State of Ohio and is exempt from taxation under Section 501(c)(3) of the Internal Revenue Code because it is organized for charitable, scientific and education purposes. The institute opened in 1929 but traces its origins to the 1923 will of Ohio industrialist Gordon Battelle which provided for its creation. Originally focusing on contract research and development work in the areas of metals and material science, Battelle is now an international science and technology enterprise that explores emerging areas of science, develops and commercializes technology, and manages laboratories for customers. In addition to operating three of its own research facilities, as of 2010, Battelle manages or co-manages on behalf of the United States Department of Energy (six) national laboratories (including the) Pacific Northwest National Laboratory". And, more can be learned via:
Battelle: Product Development, Research & Commercialization, Energy, Health & Life Sciences, National Security, Laboratory (La; "Making the World a Better Place: Battelle is the world's largest, independent research and development organization, working to advance scientific discovery and application. ... We partner with government, industry and communities to enhance quality of life for people everywhere".
And, if you really look into all of their areas of interest, if we really do have Men In Black, their payroll checks might well be imprinted with the Battelle logo.)
Abstract: Conversion of heavy fossil hydrocarbons (HFH) to a variety of value-added chemicals and/or fuels can be enhanced using microwave (MW) and/or radio-frequency (RF) energy.
Variations of reactants, process parameters, and reactor design can significantly influence the relative distribution of chemicals and fuels generated as the product.
In one example, a system for flash microwave conversion of HFH includes a source concentrating microwave or RF energy in a reaction zone having a pressure greater than 0.9 atm, a continuous feed having HFH and a process gas passing through the reaction zone, a HFH-to-liquids catalyst contacting the HFH in at least the reaction zone, and dielectric discharges within the reaction zone. The HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds. In some instances, a plasma can form in or near the reaction zone.
Government Interests: This invention was made with Government support under ARPA Order No. Z075/00, Program Code 9620 issued by DARPA/CMO under Contract HR0011-10-0088. The US Government has certain rights in the invention.
Claims: A method for continuous flash conversion of heavy fossil hydrocarbons (HFH), the method comprising: flowing a continuous feed comprising HFH and a process gas through a reaction zone having a pressure greater than 0.9 atm; contacting the HFH and a HFH-to-liquids catalyst in at least the reaction zone; concentrating microwave or RF energy in the reaction zone using a microwave or RF energy source; and generating dielectric discharges within the reaction zone; wherein the HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds.
(Note that this is a fast, high-production process which can be conducted in a reactor that might not be too demanding to construct. keeping in mind that the reaction takes place just at "a pressure greater than 0.9 atm", which could well be "1.0 atm", or, just at atmospheric pressure. Sealed, high-pressure reactor vessels might not be absolutely required, although higher pressures are stipulated as being allowable, further on in the Disclosure.)
The method ... wherein the process gas comprises a hydrogen-containing gas (and) catalyst comprises iron (and) wherein the catalyst comprises char (and) wherein the catalyst comprises a promoter of dielectric discharge.
The method ... wherein the HFH and the catalyst are admixed.
The method ... further comprising generating a plasma in or near the reaction zone (and) wherein the pressure in the reaction zone is up to 7 atm.
The method ... wherein the residence time is greater than or equal to 5 milliseconds.
The method ... wherein said concentrating comprises emitting microwave or RF energy from a source into the reaction zone in a direction parallel to the continuous feed through the reaction zone.
A system for continuous flash conversion of heavy fossil hydrocarbons (HFH) comprising:
- a reaction zone having a pressure greater than 0.9 atm;
- a source emitting microwave or RF energy concentrated in the reaction zone;
- a source of a continuous feed comprising HFH and a process gas, the continuous feed passing through the reaction zone;
- a HFH-to-liquids catalyst contacting the HFH in at least the reaction zone;
- and dielectric discharges within the reaction zone; wherein, the HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds.
The system ... wherein the process gas comprises a hydrogen-containing gas (and) wherein the process gas is selected from a group consisting of ... carbon dioxide, ... recycle gas, carbon monoxide, ... water, ... and combinations thereof.
(The inclusion of "water", H2O, thus qualifies it as a "hydrogen-containing gas". Other options are identified, as well; but, if "carbon dioxide" and "water" are all we need, why would we want anything else?)
The system ... wherein the (Heavy Fossil Hydrocarbon) HFH concentration in the process gas is between 0.1 wt % and 100 wt % (and) wherein the system comprises a fluidized bed reactor, an entrained flow reactor, a free fall reactor, or a moving bed reactor.
The system ... wherein the catalyst comprises iron (and) char (and) wherein the catalyst is (further) selected from the group consisting of nickel, cobalt, molybdenum, carbon, copper, alumina, silica, oxygen and combinations thereof.
(Nothing too exotic or rare is required, in other words.)
The system ... wherein the catalyst comprises a promoter of hydrogenation (and) wherein the catalyst comprises a promoter of electrical discharge.
(The "iron (,) nickel, cobalt (and) molybdenum" are all well-known "promoter(s) of hydrogenation" and have been specified as such in many Coal liquefaction technologies. The Iron Group metals are also, by the way, excellent "promoter(s) of electrical discharge" when exposed to microwave radiation. If you're one of those people still lucky enough to be able to carry a little cash on you in this day and age, pull a nickel out of your pocket, toss it in the radar range on your kitchen counter, and turn it on high for a few seconds. But, the inclusion of such hydrogenation catalysts is what enables the direct production of some hydrocarbons in the reactor, as opposed to just a hydrocarbon syngas blend of Carbon Monoxide and Hydrogen.)
The system ... wherein the catalyst comprises a promoter of hydrogen formation.
(Finely divided Iron is pretty good at that.)
The system ... wherein the catalyst and the HFH are admixed.
The system ... further comprising a plasma in or near the reaction zone.
(The "plasma" will be generated by the "electrical discharge"; it's not something that has to be added.)
The system ... wherein the pressure in the reaction zone is up to 7 atmospheres.
(So, the pressure can be between "0.9", essentially one, atmosphere, and "7 atmospheres", which still isn't extremely high pressure, maybe around 100 psi.)
The system ... wherein the residence time is greater than or equal to 5 milliseconds.
(The process is extremely fast, in sum, which should allow for high throughput and high productivity in a reactor that might not have to take up that much space in order to process a large amount of raw material and generate a correspondingly large amount of product.)
A system for continuous flash conversion of heavy fossil hydrocarbons (HFH) comprising: a reaction zone having a pressure greater than 0.9 atm; an energy source configured to emit microwave or radio frequency energy concentrated in the reaction zone; and one or more sources configured to pass a HFH-to-liquids catalyst and a continuous feed comprising HFH and a process gas to the reaction zone; wherein, the HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds and dielectric discharges are generated in the reaction zone when the system is operated.Background: Traditional liquefaction methods for coal, and other heavy fossil hydrocarbons (HFH), can be divided into two general categories. The first is indirect liquefaction, where the coal is first gasified to synthesis gas that is then used for chemical and fuel production. The second method is direct liquefaction, where the coal chemicals and fuels are either extracted/refined from the coal or the coal undergoes a series of thermochemical reactions. Most of these traditional methods of coal liquefaction have significant energy requirements and environmental impact. Conventional techniques for direct coal liquefaction will generally result in lower CO2 emissions compared to indirect techniques, but will typically require relatively higher temperatures and higher pressure hydrogen to obtain significant product yield and quality. Operation at high temperature and high pressure results in high energy requirements, water consumption, and capital costs.
Therefore, alternative methods for conversion of HFH to value-added chemicals and fuels are required to reduce the capital costs, the operating costs, and the environmental impact of HFH liquefaction and in order to make facilities such as coal-to-liquids (CTL) plants feasible.
Summary: This document describes a system that utilizes microwave (MW) and/or radio-frequency (RF) energies to convert HFH to a variety of value-added chemicals and/or fuels.
(The) direct generation of acetylene, olefins, naphtha, naphthalenes, benzene, toluene, xylene (BTX), polyaromatics, paraffins, and fuel precursors from flash conversion of coal in inert atmospheres has been observed. Addition of hydrogen and/or methane can further increase direct fuel production and hydrogenation of HFH-derived liquids even when operating at atmospheric pressure and at modest temperatures.Variations of reactants, process parameters, and reactor design, within the scope of the present invention, can significantly influence the relative distribution of chemicals and fuels generated as the product.
One embodiment is a system for the continuous flash conversion of HFH using microwave and/or radio-frequency energy. The system comprises a source emitting microwave or RF energy that is concentrated in and/or through a reaction zone having a pressure greater than 0.9 atm, a continuous feed comprising HFH and a process gas flowing through the reaction zone, a HFH-to-liquids (HFHTL) catalyst contacting the HFH in at least the reaction zone, and dielectric discharges within the reaction zone. Contact between the HFH and the catalyst can include physical contact between separate particles (or the liquid) entrained in the gas, particles comprising a mix of the HFH and catalyst in close proximity within the process gas, and/or HFH with catalytically active species directly impregnated on the HFH particles and/or within the pores of the HFH. For example, the catalyst or catalyst precursors, which can include various metal/metal oxide salts, organometallic species, or nano-metal/metal oxide particles, can be impregnated in the HFH using aqueous or organic solvents. The HFH and the catalyst have a residence time in the reaction zone of less than 5 minutes. Preferably, the residence time is less than 30 seconds, and can be approximately tens of microseconds. In some instances, a plasma can form in or near the reaction zone.
Another embodiment includes a method for continuous flash conversion of HFH. The method comprises the steps of flowing a continuous feed comprising HFH and a process gas through a reaction zone. The pressure in the reaction zone is greater than 0.9 atm. The HFH and an HFHTL catalyst are contacted in at least the reaction zone. The method further comprises concentrating microwave or RF energy in the reaction zone and generating dielectric discharges within the reaction zone. The HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds.
As used herein, continuous refers to systems and methods in which reactants are continuously fed through the reaction zone and continuously emerge as products and/or waste in a flowing stream.
Examples of suitable process gases include, but are not limited to ... carbon dioxide, ... water vapor, oxygen, and combinations thereof. Preferably, the process gas comprises a hydrogen-containing gas.
The reaction zone can exist within a reactor having a variety of configurations including, but not limited to, a fluidized bed reactor, an entrained flow reactor, a free fall reactor, or a moving bed reactor. The pressure in the reaction zone is, preferably, less than 7 atmospheres. The residence time of reactants in the reaction zone is, preferably, greater than or equal to 5 milliseconds and under 30 seconds. The source can be arranged to emit microwave or RF energy at any angle from parallel to perpendicular to the flow direction in the reaction zone. Furthermore, the energy can pass through the reactor walls defining, in part, the reaction zone. Alternatively, the energy can be emitted directly from or into the reaction zone by proper placement of the source, or by proper placement of an antenna or waveguide at or within the reaction zone. Emission directly into the reaction zone improves efficiency and eliminates the need to transmit through reactor walls.
As used herein, HFH can refer to ... coal of any rank (and) can also refer to biomass, plastics, municipal waste, sludge, or other carbon-rich materials."
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We'll close our excerpts there, as the bulk of the Disclosure is given over to examples and experimental results. In brief, there are numerous possible variations on the process, with corresponding variances in the types of products generated, and in the product distribution. Our cursory analysis suggests that there exists associated with "United States Patent Application 20130213795 - Heavy Fossil Hydrocarbon Conversion and Upgrading Using Radio-Frequency or Microwave Energy" a rather extensive body of research results which would indicate what blends of raw materials, what power applied to the microwave generator, how the microwaves are applied and what catalysts are used would result in what specific product mixes.
Further, should you examine the experimental results available in the full Application and it's supporting documentation, be wary of what appear to be results indicating that only a portion of the Coal, and "biomass", etc., is converted into product, with a relatively large portion of residual carbonaceous "char" remaining.
A close read will reveal that the "char" is to be further processed, as in the following excerpt taken from the full Summary:
"(In) some embodiments, at least a portion of the residual char is further reacted with a reactive plasma, such as hydrogen, to yield acetylene and other chemicals that could be used to increase distillate fuels production and/or help offset production costs through production of value-added chemicals (such as acetylene, BTX, styrene, ethyl-benzene, aromatics, olefins, and LPG) from the char".
And, that product mix is essentially equivalent to the product mix noted above, i.e., "acetylene, olefins, naphtha, naphthalenes, benzene, toluene, xylene (BTX), polyaromatics, paraffins, and fuel precursors" generated directly "from flash conversion of coal".
The "BTX", we remind you, is Benzene, Toluene and Xylene, the basic blending stock for Gasoline; and, "naphtha", as well, is a basic compound that can be used in Gasoline manufacture. The "paraffins", we believe, make a good starting material from which to manufacture, via hydro-treating, Diesel fuel.
Even further, it is disclosed via experimental results that Methane or Hydrogen can be added to the reactive mix of gases to be treated, with the Coal and Biomass, etc., with resulting direct influence on the product mix and conversion efficiency.
Both gases are, or can be, generated within the process itself, and recycled from the product mix; or, both could be, perhaps need to be to achieve the amounts needed, imported. Without citing past reports, we remind you that both can be, if needed or wanted, generated, in processes driven by one sort of environmental energy or another, from Water and Carbon Dioxide.
Finally, some electricity is required to power the microwave generator(s), and that might represent an opportunity for employing one or another site-specific environmental energy, such as wind or hydro, to generate the limited amount of juice needed for that microwave generation.
There's a lot more to this technology than is accessible, or made clear, via the currently-published version of "Application 20130213795"; and, we suspect that revisions will follow wherein the technology will be more clearly explicated and summarized. We'll make follow-up report on them as they become available.
But, in sum, two departments of our United States Government have collaborated in the development of a technology that, perhaps relying on environmental energy to generate the microwaves needed to drive the process, will convert all ranks of Coal, along with "biomass, plastics, municipal waste, sludge, or other carbon-rich materials", and "carbon dioxide", into, at least "acetylene, olefins, naphtha, naphthalenes, benzene, toluene, xylene (BTX), polyaromatics, paraffins, and fuel precursors".
"We The People" paid to have this advanced Coal utilization technology developed. Do you suppose that "We" will ever be deemed privileged enough to be told all about it, much less be empowered to utilize it?