EP2014068896 INTEGRATED PROCESS/PLANT FOR STORAGE OF CO2 BY CONVERSION TO SYNTHETIC NATURAL GAS

Carbon Dioxide, as is co-produced in only a small way - - relative to some all-natural and un-taxable sources of it's emission, such as the Earth's inexorable processes of planetary volcanism - - by our economically essential use of Coal in the generation of abundant and affordable electric power, can be seen and treated as a valuable raw material resource.

As seen for example and for instance in our report of:  

Audi is Using Renewable Energy to Convert CO2 into Methane | Research & Development | News; concerning: "(Audi's) e-gas plant, which has the capacity to convert six MW of power, will use renewable electricity for electrolysis. The process splits water molecules into oxygen and hydrogen ... . (The) plant takes the hydrogen and reacts it with CO2 in a methanation unit to generate renewable synthetic methane ... . The CO2 used in the plant is a waste byproduct from a nearby biogas plant renewable electricity for electrolysis";

German car-maker Audi already has one pilot facility up and running, wherein wind-generated electricity is used to extract Hydrogen from the abundant water, H2O, molecule, and that Hydrogen is then reacted with Carbon Dioxide extracted from the exhaust gases of a supposedly environmentally-friendly bio-fuels factory in an updated version of the century-old, Nobel Prize-winning Sabatier CO2-to-Methane process, with the end result being "renewable synthetic" substitute and fracking-free natural shale gas "methane".

That basic CO2-to-Methane technology is well-known among the United States Government and United States corporate communities, as well, as demonstrated for just two examples in our reports of:  

NASA Converts 97% of CO2 to Substitute Natural Gas Methane | Research & Development | News; concerning: "United States Patent Application 20140178270 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2014; Inventors: Christian Junaedi, et. al., CT; Assignee: Precision Combustion, Inc., Hartford, CT; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen in a (series of reaction zones, as described) so as to produce a product stream comprising water and methane. ... Government Interests: This invention was made with support from the U.S. government under U.S. Contract No. NNX10CF25P sponsored by the National Aeronautics and Space Administration. The U.S. Government holds certain rights in this invention. Background and Field: In one aspect, this invention pertains to a process of converting a mixture of carbon dioxide and hydrogen into a product mixture comprising water and methane (hereinafter "the process"). In the art the process is known as the "Sabatier process" or the "Sabatier reaction" or the "carbon dioxide methanation reaction." In another aspect, this invention pertains to an apparatus that finds use as a reactor for an exothermic process, for example, the Sabatier reaction"; and:

Phillips 66 Converts 100% of CO2 to Methane | Research & Development | News; concerning: "United States Patent 8,754,137 - Methanation Reaction Methods Utilizing Enhanced Catalyst Formulations and Methods of Preparing Enhanced Methanation Catalysts; 2014; Inventors: Scott Scholten, et. al., Texas and Oklahoma; Assignee: Phillips 66 Company, Houston; Enhanced mixed metal catalysts are provided which allow high conversions of carbon dioxide to methane, in some cases up to about 100% conversion.  Methods of preparing enhanced mixed metal catalysts comprise a series of steps involving combining nickel and chromium salts with a nucleation promoter in a base environment to form a gel, allowing the gel to digest to form a solid and a mother liquor, isolating the solid, washing the solid, drying the solid, and thermally treating the solid to form a nickel-chromium catalyst. Methanation processes using the catalysts are also provided. The enhanced mixed metal catalysts provide more efficient conversion and lower operating temperatures for carbon dioxide methanation when compared to conventional methanation catalysts. Additionally, these enhanced catalyst formulations allow realization of higher value product from captured carbon dioxide".

As everyone reading this likely knows, some of those genuinely concerned - - whether that concern is actually justified by the facts or not - - about the effects of Carbon Dioxide accumulating in our atmosphere, in for the most part unwitting alliance with other groups of people who's motives are much less noble, have been "pushing" the costly concept of Carbon Dioxide geologic "sequestration", wherein, all at the expense of consumers of Coal-based electric power, Carbon Dioxide would be harvested from power plant exhaust gases and then piped to and pumped down leaky old hydrocarbon extraction wells. In that scheme, the Carbon Dioxide paid for by the consumers of Coal-based electric power would enable the "secondary" recovery of more hydrocarbons from the nearly-depleted natural hydrocarbon geologic reservoirs, with the profit from those hydrocarbons thus recovered going to the gas or oil company that owned the  "sequestration" wells. 

Based on the information above concerning Audi, NASA, and the Phillips 66 company, we should be saying "nuts" to all of that CO2 geologic "sequestration", or "storage", nonsense, and, instead, focusing on the creation of new jobs and new industries in United States Coal Country based on the conversion of Carbon Dioxide, in processes powered if desired, as Audi's factory is, by renewable energy, into such synthetic and fracking-free Methane; in essence "storing" Carbon Dioxide, profitably, as synthetic natural gas.

That, in fact, is the basic concept and core technology recently disclosed by a major center of science and engineering development in the fastidiously neutral, and immensely practical, nation of Switzerland.

As explained in excerpts from the initial and following links in this dispatch to:

"International Application Number: PCT/EP2014/068896; Publication Number: WO/2015/055349

INTEGRATED PROCESS/PLANT FOR STORAGE OF CO2 BY CONVERSION TO SYNTHETIC NATURAL GAS

(Note: The links take you to the European Union publication of this document. The official World Intellectual Property Organization, "WIPO", version is not yet accessible on the web. When it becomes available, we might make separate report of it. Our assumption is that a United States Patent Application has also been filed, and, based on past experience, the US Government publication of it, if any, will follow that of WIPO. In any case, it seems possible, perhaps likely, that web links now available, the ones we're using here, might soon be changed and cease to function. One perhaps more durable link we're providing as an alternative is:

https://patentscope.wipo.int/search/en/detail.jsf?docId=WO2015055349&recNum=2&maxRec=26603&office=&prevFilter=&sortOption=Pub+Date+Desc&queryString=FP%3AMethane&tab=PCT+Biblio.)

Applicant: Paul Scherrer Institut, Villigen, Switzerland

Inventors: Tilman J. Schildhauer, et. al., Switzerland and Germany

(Yeah, we know, you've never heard of the Paul Scherrer Institute, or Institut. As can be learned via:

Paul Scherrer Institut (PSI) :: Paul Scherrer Institute; "The Paul Scherrer Institute, PSI, is the largest research centre for natural and engineering sciences within Switzerland. We perform world-class research in three main subject areas: Matter and Material; Energy and the Environment; and Human Health"; and:

Paul Scherrer Institute - Wikipedia, the free encyclopedia; "The Paul Scherrer Institute (PSI) is a multi-disciplinary research institute which belongs to the Swiss Federal Institutes of Technology Domain ... . It was established in 1988 by merging (the) Federal Institute for Reactor Research) and (the) Swiss Institute for Nuclear Physics. The PSI is a multi-disciplinary research centre for natural sciences and technology. In national and international collaboration with universities, other research institutes and industry, PSI is active in solid state physics, materials sciences, elementary particle physics, life sciences, nuclear and non-nuclear energy research, and energy-related ecology. It is the largest Swiss national research institute with about 1,400 (year 2011) members of staff, and is the only one of its kind in Switzerland";

it is, actually, a very substantial center of research and development with ties to the Swiss government.) 

Abstract: It is the goal of the present invention to provide a method and a plant for a most efficient operation of the industrial operation thereby storing the CO2 generated by this industrial operation in a way that further processes benefit from the energy stored into the CO2 separated from the industrial operation (wherein the CO2 can be subjected to a conversion into another product, such as SNG (Synthetic Natural Gas). This goal is achieved according to the present invention by a method and a plant for storing CO2 stemming from an industrial process as synthetic or substitute natural gas, comprising :

a) an industrial operation plant generating CO2 comprised in a flue gas; said industrial operation plant performing an industrial combustion or calcination process or metallurgical process;

b) a CO2 separating unit for separating a CO2 containing gas mixture from the flue gas;

c) an electrolysis unit for splitting water by electrolysis to produce H2 and O2;

d) a methanation unit for converting the CO2 containing gas mixture and the H2 by a methanation reaction to a methane rich gas which can be used as or upgraded to synthetic natural gas. Therefore, the present invention forms an integrated process to combine the four steps (combustion and/or calcination of cement; CO2 separation; electrolysis to produce H2 and O2; methanation) in a synergetic way to solve both problems described above with a significantly higher efficiency than possible in non-integrated plants.

(Concerning the above "electrolysis unit for splitting water by electrolysis to produce H2 and O2", keep in mind that, as seen for one recent example in:

USDOE Renewable Hydrogen for Coal-to-Oil and CO2-to-Alcohol | Research & Development | News; concerning: "United States Patent 9,011,651 - Apparatus and Method for the Electrolysis of Water; 2015; Inventor: Elias Greenbaum, Knoxville, TN; Assignee: UT-Battelle, LLC, Oak Ridge; (Again: UT-Battelle, LLC is 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.) Government Interests: 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 (as disclosed and described). ... A method for producing hydrogen and oxygen gases from the electrolytic splitting of water, the method comprising charging an electrolyzer with an aqueous electrolyte, and electrically powering said electrolyzer to produce hydrogen and oxygen gases ... . The method ... wherein said electrolyzer is powered by a renewable energy source (and) wherein said renewable energy source comprises solar energy (or) wind energy. The method ... wherein said electrolysis method is coupled to a process that utilizes hydrogen or oxygen gas (and) wherein said process is a Fischer-Tropsch process for the synthesis of liquid hydrocarbons (or)  wherein said process is a hydrogenation process";

the technologies for accomplishing such "electrolysis to produce H2 and O2" from the abundant water molecule are becoming ever more efficient, to the point where they can be powered by various forms of freely-available, so-called "renewable", energy. Further, this European patent application disclosure is, as we take it, much more of a "design" patent for a large industrial process to convert Carbon Dioxide into substitute natural gas Methane than a disclosure of genuinely new or proprietary technology. We'll explain that a bit further in concluding remarks.)

EP2014068896 INTEGRATED PROCESS/PLANT FOR STORAGE OF CO2 BY CONVERSION TO SYNTHETIC NATURAL GAS

The present invention relates to a method and a plant for storing CO2 stemming from an industrial process

as synthetic or substitute natural gas.

Power to Gas applications, excess electricity is used to produce a storable gas; most often hydrogen production by electrolysis is considered. This hydrogen could either be used directly in industrial applications or for running fuel cells, e.g. in fuel cell vehicles. Due to the wider applicability and large storage capacity, direct injection of hydrogen into the natural gas grid (up to 10%) or conversion into synthetic natural gas by methanation and subsequent injection in the gas grid is discussed. Methanation has the advantage to maintain the high heating value of the gas and to avoid adaptation in the gas grid equipment necessary for higher hydrogen contents. As carbon source for the methanation, carbon oxides, e.g. CO2 from biogas, is considered. Therefore, the amount of electricity, which can be stored at one site, depends on the CO2 stream available. As biogas plants are often of limited size, there is a need for further larger CO2 sources.

(In other words, as we read it, using the CO2 co-produced by "biogas plants", as Audi is doing in Werlte, Germany, to synthesize substitute natural gas Methane, unnecessarily limits the amount of Methane which can be synthesized. Thus, "larger CO2 sources" are actually desirable. Anyone know where we might find a few to work with, and thereby create a few more industries and a few more jobs?)

It is therefore the goal of the present invention to provide a method and a plant for a most efficient operation of the industrial operation thereby storing the CO2 generated by this industrial operation in a way that further processes benefit from the energy stored into the CO2 separated from the industrial operation (wherein the CO2 can be subjected to a conversion into another product, such as methane, SNG or the like).

With respect to the present invention (the above is accomplished by):

a) separating a CO2 containing gas mixture from a flue gas stemming from an industrial combustion or calcination step or a metallurgical process;

b) splitting water by electrolysis to produce H2 and O2;

c) converting the CO2 containing gas mixture and the H2 by a methanation reaction to a methane rich gas which can be used as or upgraded to synthetic natural gas.

In order to take advantage of the exothermic methanation reaction, the CO2-separation can be conducted in a scrubber unit and the heat of the methanation reaction can be at least partly used to regenerate a scrubbing liquid used in the scrubber unit. Alternatively, the CO2-separation is conducted in a temperature swing adsorption reactor and the heat of the methanation reaction is at least partly used to regenerate the sorbents used in the temperature swing adsorption reactor.

In a further preferred embodiment of the present invention the oxygen stream from the water electrolysis and/or the heat from the methanation reaction may be at least partly used in the industrial combustion or calcination process to increase the thermal efficiency and/or to increase the CO2 partial pressure which facilitates CO2 separation and/or to regenerate the chemical looping material.

In order to further establish energy saving circumstances, a high pressure electrolysis may be applied, and the expansion of the hydrogen and/or oxygen from the electrolysis pressure down to the conditions in the combustion/calcination or the methanation unit is used to generate mechanical energy, which is used for gas compression (e.g. of the flue gas or the CO2 rich gas stream) and/or for electricity production in terms of turbine expansion).

EP2014068896 INTEGRATED PROCESS/PLANT FOR STORAGE OF CO2 BY CONVERSION TO SYNTHETIC NATURAL GAS

Claims:

A method for storing CO2 stemming from an industrial process as synthetic or substitute natural gas, comprising the steps of:

a) separating a CO2 containing gas mixture from a flue gas stemming from an industrial combustion or calcination step or a metallurgical process;

b) splitting water by electrolysis to produce H2 and O2;

c) converting the CO2 containing gas mixture and the H2 by a methanation reaction to a methane rich gas which can be used as or upgraded to synthetic natural gas.

The method ... wherein the CO2-separation is conducted in a scrubber unit and the heat of the methanation reaction is at least partly used to regenerate a scrubbing liquid used in the scrubber.

The method ...  wherein the heat of the methanation reaction is at least partly used to increase the efficiency of the water electrolysis.

The method ... wherein the oxygen stream from the water electrolysis and/or the heat from the methanation reaction are at least partly used in the industrial combustion or calcination step to increase the thermal efficiency and/or to increase the CO2 partial pressure which facilitates CO2 separation and/or to regenerate the chemical looping material.

The plant according to any of the preceding claims ...  wherein a high pressure electrolysis is applied, and the expansion of the hydrogen and/or oxygen from the electrolysis pressure down to the conditions in the combustion/calcination or the methanation unit is used to generate mechanical energy, which is used for gas compression (e.g. of the flue gas or the CO2 rich gas stream) and/or for electricity production in terms of turbine expansion".

----------------------- 

As we've noted in previous reports concerning such CO2-to-Methane process technologies, including our above-cited report concerning NASA's "United States Patent Application 20140178270 - Sabatier Process and Apparatus for Controlling Exothermic Reaction", and as the Paul Scherrer Institute makes clear in multiple claims and specifications herein, the exothermic CO2-to-Methane reaction generates enough heat to be worth collecting, especially since it needs to be removed from the reaction in any case to prevent catalyst deactivation and to maximize Methane production, and to use in other processes, such as, as is made clear herein, to facilitate the extraction of the needed Hydrogen from water and/or the harvesting of Carbon Dioxide from industrial exhaust gases.

Further, even the pressure generated by the water electrolysis can be utilized, for example "to generate mechanical energy". And, the Oxygen co-produced with the Hydrogen by the water electrolysis could be used to support "an industrial combustion" source of the Carbon Dioxide.  

We suspect that the United States Patent Application for this technology, which we expect will eventually be forthcoming, will be, for us, a much clearer exposition of the technology and concept embodied herein: that is, a rather complete industrial facility for utilizing renewable energy, and thermal energy recovered from steps within the overall process itself, to extract Hydrogen from water; to harvest Carbon Dioxide from one "industrial" process or another, such as "combustion", as in a thermal power plant, or "calcination", as in a cement production kiln; and, to then combine the Hydrogen and the Carbon Dioxide in a "methanation unit" that produces both useable thermal energy and a substitute for natural shale gas, synthetic Methane.

West Virginia Coal Association Senior Vice President Chris Hamilton served as the keynote speaker for the April 2 meeting of the Kanawha Valley Mining Institute in South Charleston. Hamilton praised the work of the new legislative leadership as he gave an overview of the recently concluded 2015 session of the West Virginia Legislature and important coal and business-related legislation that was passed. 

United States Patent Application: 0150064105

There are without doubt many good people, honest United States citizens, even brave patriots who have served, or would serve if called, in uniform, who have become convinced that Carbon Dioxide is accumulating in the atmosphere due to our use of fossil fuels; that such CO2 accumulation results in dangerous "global warming"; and, that to prevent calamitous climate change we must somehow limit our use of fossil fuels, with most fingers pointing at Coal as the CO2-emitting culprit-in-chief.

United States Patent: 9011651

To be blunt:

Only our blind and obstinate clinging to the mythologies and - - we, here, have become convinced - - to the blind and narrow politics of oil and energy shortages prevents us all from embarking on a new era of United States of America hydrocarbon fuel self-sufficiency, and of United States Coal Country full employment and economic prosperity.

US2014058961 ELECTROCHEMICAL REDUCTION OF CO2 AT COPPER NANOFOAMS

The international, or "world", patent application, for an electrochemical process that converts Carbon Dioxide, as recovered from whatever convenient source, into the polymer, or plastics, raw material "propylene", we report on herein, is actually a republication of a United States Patent Application originating from the state of Rhode Island, from Brown University specifically - - a United States Patent Application submitted last year by Brown University which hasn't yet been published on the web by the United States Government.


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