United States Patent Application: 0140288195

As we've reported so many times that it should go without saying, although it apparently instead needs to be repeated rather endlessly, it has been known for a very long time that Coal can be "gasified", that is, partially oxidized, and made to form a gaseous blend of, primarily, Carbon Monoxide and Hydrogen, known as "synthesis gas", or just "syngas", and, which syngas can then be catalytically, chemically condensed into a full range of both gaseous and liquid hydrocarbon fuels and chemicals. 

An example of our reportage outlining to an extent the scope of such technology is accessible via:

Gulf and Chevron Convert Coal to Diesel Fuel and Gasoline | Research & Development | News; and concerns, for a few examples:

"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"; and:

"United States Patent 4,413,064 - Synthesis Gas Conversion for Preparation of Diesel Fuel; 1983; Assignee: Gulf Research and Development Company, Pittsburgh; Abstract: A catalyst useful in the conversion of synthesis gas to diesel fuel ... . Claims: A process for the conversion of synthesis gas to a product high in straight chain paraffins in the diesel fuel 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. The Fischer-Tropsch synthesis involves the production of hydrocarbons of the catalyzed reaction of CO and hydrogen. Commercial plants have operated in Germany, South Africa and other parts of the world"; and:

"United States Patent 4,492,774 - Method for Converting Synthesis Gas; 1985; Assignee: Gulf Research and Development Company, Pittsburgh; Abstract: A process for converting synthesis gas to liquid hydrocarbons ... . Description: Synthesis gas comprising a mixture of hydrogen and carbon monoxide in appropriate proportions can be converted to liquid hydrocarbons ... . Commercial plants have operated in Germany, South Africa and in other countries for the production of liquid fuels from coal-derived synthesis gas".

Further, as seen for just one example in our report of:

Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development | News; concerning:

"United States Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass; 2010; Assignee: ExxonMobil Research and Engineering Company, NJ; Abstract: A process for the co-gasification of carbonaceous solids (coal) and biomass ... The heat required for pyrolyzing the biomass can conveniently be obtained from the heat exchanger used to cool the hot synthesis gas product emerging from the gasifier. The process ... 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";

it is perfectly feasible to produce such "synthesis gas" from a combined feed of Coal and carbon-recycling, renewable "biomass", which practice would help to conserve our reserves of Coal; to mitigate some folks' concerns over the emission of carbon dioxide; and, to make the entire procedure more "sustainable". 

Even further, as seen for just two examples in:

Eastman Chemical Coal to Liquid Fuel, Chemicals and Electricity | Research & Development | News; concerning: "US Patent Application 20070129450 - Process for Producing Variable Syngas Compositions; 2007; Inventors: Scott Barnicki, et. al., TN; Correspondence (and presumed eventual Assignee of Rights): Eastman Chemical Company, TN; Abstract: Disclosed is a process for the production of a variable syngas composition by gasification. Two or more raw syngas streams are produced in a gasification zone having at least 2 gasifiers and a portion the raw syngas is passed to a common water gas shift reaction zone to produce at least one shifted syngas stream having an enriched hydrogen content and at least one unshifted syngas stream. The shifted and the unshifted syngas streams are mixed downstream of the water gas shift zone in varying proportions (to) produce blended and unblended synthesis gas streams in a volume and/or composition that may vary over time in response to at least one downstream syngas requirement. The process is useful for supplying syngas from multiple gasifiers for the variable coproduction of electrical power and chemicals across periods of peak and off-peak power demand"; and:

USDOE Coal to Gasoline, Diesel and Electricity Profitable | Research & Development | News; concerning: "'Baseline Technical and Economic Assessment of a Commercial Scale Fischer-Tropsch Liquids Facility'; DOE/NETL-2007/1260; Final Report for Subtask 41817.401.01.08.001; April 9, 2007; NETL Contact: Michael Reed; Senior Systems Analyst, Office of Systems Analyses and Planning; National Energy Technology Laboratory; Economic and national security concerns related to liquid fuels have revived national interest in alternative liquid fuel sources. Coal to Fischer-Tropsch fuels production has emerged as a major technology option for many states and the Department of Energy. This report summarizes the preliminary results of an NETL study to assess the feasibility of commercial scale, coal-to-liquids production using a high Btu Midwestern Coal. ... Conclusions: The conceptual design evaluated is technically feasible using equipment that has been demonstrated at commercial scale, although no commercial CTL plants are currently operating in the U.S. The conceptual design uses high sulfur bituminous coal to produce distillate and naphtha liquid pools via indirect coal liquefaction (F-T process). With the addition of additives, the distillate can be converted to a saleable diesel fuel. The naphtha liquids can be shipped to a refinery for upgrading into gasoline ... . The plant produces a net power output of 124 MWe which can be exported to the grid";

it also perfectly feasible to, in a process wherein Coal is being gasified to form hydrocarbon synthesis gas, and wherein that synthesis gas is being catalytically condensed into hydrocarbon fuels, to also co-produce genuinely commercial amounts of electric power, which power can, via one route, be derived from heat energy arising from exothermic chemical processes within the total reaction sequence, including excess heat in the syngas resulting from the partial combustion/gasification process. That aside from, as varying demand warrants, combusting a portion of the syngas to produce more heat energy for power generation.

All of those above factors, and others, have been recently integrated by an agency of the government of France, they have been combined into a complete process for the efficient generation of a CO2-free hydrocarbon synthesis gas from a combined feedstock of Coal and renewable Biomass.

As seen in excerpts from the initial link in this dispatch to:

"United States Patent Application 20140288195 - Processes for the Thermochemical Conversion of a Carbon-Based Feedstock to Synthesis Gas Containing Predominantly H2 and CO

Patent US20140288195 - Process for the thermochemical conversion of a carbon-based feedstock to ... - Google Patents

PROCESS FOR THE THERMOCHEMICAL CONVERSION OF A CARBON-BASED FEEDSTOCK TO SYNTHESIS GAS CONTAINING PREDOMINANTLY H2 AND CO - CO

September 25, 2014

Inventors: Pierre Castelli, et. al., France

Assignee: Commissariat A L'Energie Atomique Et Aux Energies Alternatives

(Commissariat à l'énergie atomique et aux énergies alternatives - Wikipedia, the free encyclopedia; "(English: Atomic Energy and Alternative Energies Commission) or CEA, is a French public government-funded research organisation in the areas of energy, defense and security, information technologies and health technologies. The CEA maintains a cross-disciplinary culture of engineers and researchers, building on the synergies between fundamental and technological research.)

Abstract: The invention relates to a novel process for the thermochemical conversion of a carbon-based feedstock to synthesis gas containing predominantly hydrogen (H2) and carbon monoxide (CO). The process comprises (a) oxycombustion of the carbon-based feedstock to create a cogeneration of electricity and of heat; (b) high-temperature electrolysis (HTE) of water using at least the heat produced according to step (a); and (c) reverse water gas shift (RWGS) reaction starting from the carbon dioxide (CO2) produced according to step (a) and the hydrogen (H2) produced according to step (b).

(What they're proposing, in sum, is using some of the heat energy generated by the "oxycombustion" of Coal in a power plant to effect the "high-temperature electrolysis of water" in a more efficient water splitting reaction performed to extract elemental, molecular Hydrogen from the H2O molecule perhaps like that disclosed in our report of: 

USDOE Efficient Hydrogen for Liquid Fuel Synthesis | Research & Development | News; ; concerning: "United States Patent Application 20120149789 - Apparatus and Methods for the Electrolysis of Water; 2012; Assignee: UT-Battelle, LLC (a limited liability partnership between the University of Tennessee and Battelle Memorial Institute that manages the Oak Ridge National Laboratory for the United States Department of Energy); Abstract: An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen ... . This invention was made with government support under Contract Number DE-AC05-000R22725 between the United States Department of Energy and UT-Battelle, LLC. The U.S. government has certain rights in this invention. Claims: An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen (and) further comprising means for collecting evolved hydrogen and oxygen gas (and) wherein said electrolyzer is powered by a renewable energy source (and) wherein said said electrolysis method is coupled to a process that utilizes hydrogen (and) wherein said process is a Fischer-Tropsch process for the synthesis of liquid hydrocarbons".

Some of that Hydrogen is then reacted with the Carbon Dioxide, co-produced by the specified "oxycombustion of the carbon-based feedstock", in a "reverse water gas shift (RWGS) reaction" like that disclosed for example in:

France Uses Hydrogen to Convert CO2 to Carbon Monoxide | Research & Development | News; concerning: "United States Patent Application 20030113244 - Producing Carbon Monoxide by Reverse Conversion; 2003; Inventors: Rene Dupont, et. al., France; Correspondence (and presumed eventual Assignee of Rights: Air Liquide; Houston, TX; Abstract: The invention concerns a method for producing carbon monoxide by reverse conversion, in gas phase, of carbonic acid gas and gaseous hydrogen while minimising the production of methane. ... Said method is preferably carried out continuously and comprises preferably the following steps which consist in: preparing a gas mixture rich in CO2 and in hydrogen having a temperature between 300 and 520 C (and) reacting said gas mixture, forming carbon monoxide and water vapour, by passing said mixture through a catalytic bed based on zinc oxide and chromium oxide".

The resulting Carbon Monoxide is then blended with additional Hydrogen to form the product "Synthesis Gas Containing Predominantly H2 and CO".)

Claims: Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas containing predominantly hydrogen (H2) and carbon monoxide (CO), comprising the following steps: (a) oxycombustion of the carbon-based feedstock to create a cogeneration of electricity and of heat; (b) high-temperature electrolysis (HTE) of water using at least the heat produced according to step (a); (c) reverse water gas shift (RWGS) reaction starting from the carbon dioxide (CO2) produced according to step (a) and the hydrogen (H2) produced according to step (b). 

Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas ... wherein the high-temperature electrolysis (HTE) of water of step (b) is also carried out using the electricity produced according to step (a) (and) wherein all the oxygen produced by the electrolysis (HTE) according to step (b) is used as oxidising agent of the oxycombustion step (a).

Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas ... wherein only part of the oxygen produced by the electrolysis (HTE) according to step (b) is used as oxidising agent of the oxycombustion step (a), the other part being recovered.

(In other words, some of the Oxygen co-produced when the water is electrolyzed to produce Hydrogen is directed to the "oxycombustion" process to support and improve combustion of the Coal.)

Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas ... wherein the water (H2O) produced by the RWGS reaction according to step (c) recycled and injected as input product of the HTE electrolysis according to step (b).

Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas ... further comprising a step (d) of cleaning of the gas obtained according to step (c) so as to extract hydrogen (H2) and carbon monoxide (CO). 

Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas ... wherein the carbon dioxide (CO2) cleaned according to step (d) is injected as input product for the RGWS reaction according to step (c). 

Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas ...  wherein the carbon monoxide (CO) and the hydrogen (H2) derived from the cleaning according to step (d) are injected as input products of a step (e) according to which a Fischer Tropsch (FT) synthesis is carried out to obtain a liquid fuel.

(Keep in mind that this a process directed primarily to the generation of hydrocarbon synthesis gas from Coal, for use in the "Fischer Tropsch (FT) synthesis ... to obtain a liquid fuel", as seen for example in: 

Bayer Improves Fischer-Tropsch Hydrocarbon Synthesis | Research & Development | News; concerning: "United States Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis; 2013; Inventors: Ralph Schellen, et. al., Germany and Texas; Assignee: Bayer Intellectual Property GmbH, Germany".

But, as claimed herein by the government of France, and as confirmed by our own US Government in:

USDOE Coal to Gasoline, Diesel and Electricity Profitable | Research & Development | News; concerning: "'Baseline Technical and Economic Assessment of a Commercial Scale Fischer-Tropsch Liquids Facility'; DOE/NETL-2007/1260; Final Report for Subtask 41817.401.01.08.001; April 9, 2007; Coal to Fischer-Tropsch fuels production has emerged as a major technology option for many states and the Department of Energy. This report summarizes the preliminary results of an NETL study to assess the feasibility of commercial scale, coal-to-liquids production using a high Btu Midwestern Coal. The conceptual design evaluated is technically feasible using equipment that has been demonstrated at commercial scale, although no commercial CTL plants are currently operating in the U.S. The conceptual design uses high sulfur bituminous coal to produce distillate and naphtha liquid pools via indirect coal liquefaction (F-T process). With the addition of additives, the distillate can be converted to a saleable diesel fuel. The naphtha liquids can be shipped to a refinery for upgrading into gasoline ... . This plant produces 22,173 bbls/day of liquid naphtha that is shipped to a refinery for further upgrading to commercial grade products or for use as a chemical feedstock. The plant also produces 27,819 bbls/day of diesel product. The total coal input requirements are 24,533 tons/day of Illinois #6 coal. All production figures are calculated at 100% of design capacity. The plant produces a net power output of 124 MWe which can be exported to the grid";

a worthwhile amount of electrical power can be co-produced in such indirect Coal-to-Liquid Fuel processes.)


Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas (wherein) the water (H2O) derived from the Fischer Tropsch FT synthesis according to step (e) is recycled and injected as input product of the HTE electrolysis according to step (b) (and) wherein the overhead gas of the FT synthesis according to step (e) is injected as input product of the oxycombustion according to step (a).

(Concerning the above, the "Fischer-Tropsch synthesis" of hydrocarbons from syngas, even though the desired product is liquid hydrocarbon fuels, will co-generate a certain amount of byproduct hydrocarbon gases, such as Methane, which can be recycled for use as fuel or as the raw material for more synthesis gas within the total system.)

Description and Field: The invention relates to a novel process for the thermochemical conversion of a carbon-based (carbonaceous) feedstock to synthesis gas containing predominantly hydrogen (H2) and carbon monoxide (CO), with a view to producing liquid (Fischer-Tropsch "FT" diesel, dimethyl ether "DME", methanol or gaseous (synthetic natural gas (SNG) fuels, or other synthetic chemicals ... .

The main intended application of the invention is that for which the carbon-based feedstock is biomass (but) "carbon-based feedstock" designates any combustible material constituted of carbon-containing compounds (and, it) It may thus be biomass, in other words any inhomogeneous material of plant origin containing carbon, such as lignocellulosic biomass, forest or farming (straw) waste, which may be quasi-dry or soaked with water, such as household wastes.

It may also be ... coal.

(France doesn't have a lot of mine-able Coal left. And, in fact, without going into the history of it, much of the Coal they did have was difficult to mine, even though they did mine a lot of it through the 1800's and earlier 1900's. Coal mining has, actually, a long and proud tradition in France, as it does in Germany. But, they no longer mine any Coal in France, having closed their last mine not that long ago. That doesn't mean that France has turned totally away from Coal; it's just a lot cheaper for them to import it. But, they're not as fond of importing energy products as we in the US sadly seem to be, and are turning to things they can produce in France, like "forest or farming ... waste". A rather decent review of the circumstances is accessible via:

http://www.independent.co.uk/news/world/europe/france-ends-coal-mining-with-tears-but-not-a-single-protest-561039.html.

As a consequence, even though the French Government does include Coal as one of the feed materials, as above, the bulk of the Disclosure herein makes reference primarily to "biomass" as the starting raw material. Which is okay, considering that Coal is just fossilized Biomass.)

It may also be combustible wastes of industrial origin containing carbon, such as plastic materials or tyres. 

It may also be a combination of biomass and of fossil fuels.

Current processes being studied or at the industrial pilot scale, making it possible to convert by a thermochemical route biomass into liquid fuel by a chemical synthesis according to the process widely known by the name "Fischer Tropsch process", necessarily comprise a step of gasification ... to obtain a synthetic gas containing predominantly carbon monoxide (CO) and hydrogen (H2). The Fischer Tropsch process then makes it possible, starting from CO and H2, to obtain (hydrocarbon) chains similar to that of diesel ... .


The actual step of gasification is carried out continuously ... in a chemical reactor (gasification reactor), either of the fluidised bed type or of the entrained flow type operating under pressure.

Fluidised bed type reactors are less efficient on account of the reaction temperature comprised generally between 800 and 1000 C, which leads to ... the generation among others of methane (CH4).


Entrained flow reactors have for their part excellent conversion efficiency of the biomass into CO and H2 synthesis gas, and are thus entirely suitable for the production of fuels or synthetic chemicals ... .

The input of heat of currently known processes is achieved in general by the combustion of part of the biomass itself (raw biomass, gas, solid residues, tars, etc.). These processes are known as "autothermic". In autothermic processes, part of the carbon stemming from the biomass is thus not converted into liquid fuel. 

Furthermore, it is widely known to incinerate household wastes to produce cogeneration of electricity and of heat. Moreover, it has already been envisaged to carry out an oxycombustion of household wastes: 

The goal of the invention is to provide a novel process for the thermochemical conversion of a carbon-based feedstock to synthesis gas containing predominantly hydrogen (H2) and carbon monoxide (CO), with a view to producing liquid fuels or other synthetic chemicals, which has better energy and/or mass efficiency than that of currently known processes.

Generally, oxycombustion produces essentially, or even uniquely, CO2 as gas, without CO. Generally, all the carbon of the carbon-based feedstock is transformed into CO2. 

According to an advantageous embodiment, the high temperature electrolysis (HTE) of water of step b/ is also carried out using the electricity produced according to step a/. The efficiency of the process is further increased because less external energy needs to be input into the process.

The invention is a combination of elementary processes known individually and already proven but which had never been all three coupled together with a view to producing synthesis gas containing predominantly hydrogen and carbon monoxide.

(The) cleaned CO+H2 synthesis gas serves as basic reaction intermediate for the production of synthetic products (liquid (FT diesel, "DME", methanol) or gaseous (SNG) fuels, or synthetic chemicals such as methanol for example). For example, it makes it possible to obtain a liquid fuel by Fisher Tropsch synthesis".

-----------------------------

Again, if you open the link and read the full Disclosure, France's Atomic Energy and Alternative Energies Commission refers primarily to the use of "biomass", although, as in some of our highlighted excerpts above, they do make clear that they consider Coal to be included in the "biomass", albeit as a fossilized biomass.

We'll note, further, that this is far from the only strategy for converting Coal into a CO2-free hydrocarbon synthesis gas. Other ways of going about that have been disclosed, for example, in our reports of:

Mobil Oil 1986 Coal to CO2-free Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent 4,583,993 - Carbon Monoxide and Hydrogen from Carbonaceous Material; 1986; Inventor: Nai Chen, New Jersey; Assignee: Mobil Oil Corporation, New York; Abstract: Hydrogen and carbon monoxide are produced from coal, char or other carbonaceous material in a processing combination comprising a catalytic CO generator employing as reactant materials, fluid carbon material and CO2 product of the reaction of steam with CO to produce hydrogen and CO2. CO2 produced in the process is relied upon as the primary endothermic heat source in the fluid CO generator"; and:

Texaco 1951 Coal + CO2 + H2O + O2 = Syngas | Research & Development | News; concerning: "United States Patent 2,558,746 - Carbon Monoxide and Other Gases from Carbonaceous Materials; 1951; Assignee: The Texas Company; Abstract: This invention relates to a process and apparatus for the generation of gases comprising carbon monoxide from carbonaceous materials. In one of its more specific aspects it relates to a process and apparatus for the generation of a mixture of carbon monoxide and hydrogen, suitable as a feed for the synthesis of hydrocarbons, from powdered coal. An object of this invention is to provide a process for the generation of carbon monoxide and hydrogen (and) to provide a process particularly suited to the generation of a feed gas for the synthesis of hydrocarbons from coal. In the gasification of carbonaceous material with oxygen, particularly solid fuels, the reaction between oxygen and fuel results in the production of carbon dioxide ... . The oxidation reaction, being highly exothermic, releases large quantities of heat. The carbon dioxide, so produced, in contact with hot carbon, in turn, reacts with the carbon to produce carbon monoxide. Steam also reacts with heated carbon to produce carbon monoxide and hydrogen".

The full Disclosure also more fully emphasizes that nearly all of the energy required by the total process can be extracted as heat from the gasification process and, as explained in our prior report, as linked above, concerning Bayer Corporation's "US Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis", from the exothermic Fischer-Tropsch synthesis of hydrocarbons, as well.

In sum, sophisticated technologies are being developed around the world, as in the French Government's process of "United States Patent Application 20140288195 - Processes for the Thermochemical Conversion of a Carbon-Based Feedstock to Synthesis Gas Containing Predominantly H2 and CO", which would enable us to begin converting our abundant Coal, in combination with the renewable products of our farms and forests, into anything and everything we now squander our national treasure and impoverish our children's futures, and put our young men and women in uniform in harm's way, to continue buying from OPEC.

Although the evidence for us now is slim and perishing, we, here, have to continue believing that someone, somewhere out there, actually cares about that. 


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