United States Patent: 8754137

Europe is now establishing a continent-wide industry that will supply the European Union's needs for natural gas by synthesizing substitute natural gas Methane from Carbon Dioxide, as can be harvested as a valuable byproduct from the exhaust gases of Coal-based generators of reliable and affordable electric power.

That fact is made clear via the web site of Project Helmeth:

http://www.helmeth.eu/; "Integrated High-Temperature ELectrolysis and METHanation for Effective Power to Gas Conversion".

 

You have to dig a bit on their site to get to an English translation and find out what the "METHanation" process actually is. But, noted as one of the initial projects is that seen in our report of:

Audi is Using Renewable Energy to Convert CO2 into Methane | Research & Development | News; wherein it's related, in part: "'Audi E-Gas Plant Uses CO2, Renewables to Make Fuel'; Audi is building an industrial plant in Werlte, Germany, which will use renewable energy and carbon dioxide to make synthetic methane fuel. The plant will use power-to-gas technology to make so-called e-gas for vehicles, such as the new Audi A3 Sportback TCNG. E-gas made at the plant can be distributed to compressed natural gas stations via Germany’s natural gas network and will power vehicles starting next year, Audi said. The 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 "HELMETH" initiative is founded on the century-old, Nobel Prize-winning Sabatier process more fully explained, for one example, in our report of: 

NASA 2014 CO2 to Methane | Research & Development | News; concerning: "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2014; Inventors: Christian Junaedi, et. al., CT; Assignee: Precision Combustion, Inc., CT; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen ... so as to produce a product stream comprising water and methane. ... Government Support: 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".

We know that such processes for manufacturing substitute natural gas might not at this time be of special interest to much of the United States public, who have been propagandized into thinking that the United States of America is, due to the shale natural gas "miracle", now self-sufficient in her supply of natural gas, will remain so for many years, and, even produces enough that it can be exported without impacting United States energy security.

All of those presumptions are false.

The United States is now, and is expected to remain, a net importer of natural gas. That fact is borne out in statistics and projections published by the USDOE's Energy Information Administration, which show that the United States, even though it exports some natural gas, is actually a net importer, with most of it coming in via pipeline from Canada and Mexico. And, even those statistics don't fully educate about the situation. More sober analysis is available via: 

Shale Bubble; "The Reality is that the government’s long-term forecasts - - the ones everyone is relying on to guide our energy policy and planning - - are overly optimistic. An exhaustive county-by-county analysis of the 12 major shale plays in the U.S. (accounting for 89% of current tight oil and 88% of current shale gas production) concludes that both oil and natural gas production will peak this decade and decline to a small fraction of current production by 2040. Shale plays suffer from high decline rates and declining well quality as the “sweet spots” run out, meaning that ever more wells will have to be drilled just to keep production flat - - until even that is no longer achievable. Continued drilling requires massive amounts of capital, which can only be supported by high levels of debt or higher prices"; and:

The Coming Bust of the U.S. Shale Oil & Gas Ponzi; which says, in part: "Also, shale gas fields, just like shale oil fields, have only so many sweet spots and a finite number of drilling locations. So at some point in time (much sooner than later), these shale gas fields will peak and decline. And wouldn't you know it... that's exactly what's happening right now. ... The facts are starting to show that declines for the older shale plays such as the Barnett, Haynesville, Fayetteville and Woodford are very serious. ... (Evidence is provided) revealing just how dire the future energy predicament will be for the United States. ... Very few Americans are aware that the production from these shale oil and gas fields will not continue to grow and last for several decades. When we look at all the data presented here, it is clear to see that the shale energy industry in the United States is behaving more like a Ponzi scheme rather than a long-term viable economic energy system. Shale oil and gas companies have to spend more money each year to increase production or it will fall off a cliff".

In any case, just as the Europeans are making arrangements, via "HELMETH", to keep themselves supplied with substitute natural gas Methane through the productive recycling of Carbon Dioxide, the major petroleum companies are doing the same thing. They are establishing improved technologies for synthesizing Methane from Carbon Dioxide.

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

"United States Patent 8,754,137 - Methanation Reaction Methods Utilizing Enhanced Catalyst Formulations and Methods of Preparing Enhanced Methanation Catalysts

Methanation reaction methods utilizing enhanced catalyst formulations and methods of preparing enhanced methanation catalysts

Patent US8754137 - Methanation reaction methods utilizing enhanced catalyst formulations and ... - Google Patents

June 17, 2014

Inventors: Scott Scholten, et. al., Texas and Oklahoma

Assignee: Phillips 66 Company, Houston 

(http://www.phillips66.com/EN/about/history/Pages/index.aspx; "In May 2012, Phillips 66 debuted as an independent downstream energy company with refining, marketing, midstream and chemicals businesses operating across the globe. The name Phillips 66 reflects the company’s rich history and has strong brand recognition and value as it has been one of the leading fuel brand names in the United States for decades. Phillips 66 enjoys a rich and complex history through its many predecessor companies, most notably Conoco and Phillips Petroleum Company. These two companies had long and successful businesses before merging in 2002 to form ConocoPhillips. In 2012, ConocoPhillips repositioned into two stand-alone publicly traded companies, one of which is the Phillips 66 of today".

Recall that ConocoPhillips, from which Phillips 66 sprung, has an established technological base for the productive recycling of Carbon Dioxide, as seen for one example in our report of:

ConocoPhillips Recycles Even More CO2 | Research & Development | News; concerning: "United States Patent 7,273,893 - Process for Converting Carbon Dioxide to Oxygenates; 2007; Inventors: Jinhua Yao and James Kimble, OK; Assignee: ConocoPhillips Company, Houston; Abstract: A catalyst and process for converting carbon dioxide into oxygenates. ... The present invention relates generally to the conversion of carbon dioxide to oxygenates. In another aspect, the invention concerns a catalyst for converting a feed comprising carbon dioxide and hydrogen into methanol and dimethyl ether".)

Abstract: 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. 

Claims: A methanation reaction process comprising the steps of: preparing a nickel-chromium catalyst, wherein the step of preparing comprises the steps of: (a) combining a nickel(II) salt and a chromium(III) salt with a nucleation promoter and ammonium hydroxide to form a gel, the gel comprising a solid and a liquid; (b) allowing the gel to digest to form a mother liquor and an isolatable solid; (c) isolating the solid from the mother liquor; (d) washing the solid; (e) drying the solid; (f) thermally treating the solid to form the nickel-chromium catalyst; wherein steps (a)-(f) result in a nickel/chromium ratio of about 98:2 to about 50:50 in the nickel-chromium catalyst; providing a single reactor vessel; continuously introducing carbon dioxide and hydrogen gas into the single reactor vessel over a fixed bed, the fixed bed comprising the nickel-chromium catalyst; allowing the carbon dioxide and hydrogen gas to react in the single reactor vessel at a conversion rate in the presence of the nickel-chromium catalyst at a reaction temperature; maintaining the reaction temperature in the single reactor vessel at about 205 C to about 220 C by controlling a flow rate of one of the carbon dioxide and the hydrogen gas fed to the single reactor vessel; and wherein the conversion rate to methane is ... about 97 to about 100 percent. 

The process of claim 1 wherein the combining of step (a) further comprises the steps of: (i) combining the nickel(II) salt, the chromium(III) salt, and the colloidal silica in an aqueous solution; (ii) adding the ammonium hydroxide and the aqueous solution to a quantity of water to form a resulting solution and modulating the addition of the ammonium hydroxide at a flow rate sufficient to maintain a target pH of the resulting solution of about 7.5 to about 10; ... wherein the target pH is about 9.

(The claims go on into considerable detail about how the catalyst is to be manufactured. It is all pretty straightforward drying, heat-treating, and etc. And, there is nothing overly exotic or expensive in the catalyst composition. It's all "real world" stuff.)

The process ... wherein the conversion rate to methane is about 100 percent.

A methanation reaction method comprising the steps of: (a) providing a nickel-chromium catalyst, the nickel-chromium catalyst having a nickel/chromium ratio of about 98:2 to about 50:50; (b) providing a single reactor vessel; (c) introducing carbon dioxide and hydrogen gas into the single reactor vessel; (d) allowing the carbon dioxide and hydrogen gas to react at a conversion rate in the presence of the nickel-chromium catalyst in the single reactor vessel at a reaction temperature; (e) maintaining the reaction temperature in the single reactor vessel at about 205 C to about 220 C; and (f) wherein the conversion rate to methane is about 100 percent. 

The method ... wherein the nickel/chromium ratio in (the catalyst) is about 80:20.

The method (which) further comprises continuously introducing carbon dioxide and hydrogen gas into the single reactor vessel and wherein the nickel-chromium catalyst is supported in a fixed-bed arrangement (and) wherein the step of maintaining the reaction temperature in step (e) is achieved by controlling a flow rate of one of the carbon dioxide and the hydrogen gas fed to the single reactor vessel.

Background: (One) way of taking advantage of carbon dioxide production is by converting the carbon dioxide to a higher value product.

Methanation reactions are one example of a reaction process for converting carbon dioxide to a more desirable product, in this case, methane.

Methanation is typically accomplished through the conversion of carbon monoxide over a conventional nickel catalyst to methane as described by the following chemical reaction: CO + 3H2 = CH4 + H2O

The chemical reaction of carbon dioxide to methane is: CO2 + 4H2 = CH4 + 2H2O

Achieving desirable reaction in methanation reactions typically requires temperatures exceeding approximately 230 C using conventional catalysts. This high temperature means that reaction vessels for these reactions must be fabricated out of metallurgies able to withstand the high temperatures or alternatively, one must stage the reaction over multiple reactors in series. In other words, the high temperatures required to achieve economically satisfactory completion of the methanation reactions essentially require either higher capital costs or higher operating costs. The high capital costs are due to having to use reactor metallurgies capable of withstanding the higher temperatures involved or having to stage multiple reactors in series. Where such higher temperatures are avoided by additional cooling equipment, higher operating costs are necessarily incurred.

Another disadvantage of conventional catalysts is the higher coke formation inherent in the use of these conventional catalysts. Catalyst deactivation via coke deposition occurs with any carbon-containing source when oxygen is not present in the stream. The rate of coke deposition is strongly dependent on reaction temperature with higher deposition rates at higher temperatures. Operation at lower temperatures favors slower deposition rates, hence, less deactivation.

Description and Summary: The present invention relates to improved methanation reaction methods utilizing enhanced catalyst formulations and methods of preparing enhanced methanation catalysts.

One example of a methanation reaction method comprises the steps of: (a) providing a nickel-chromium catalyst, the nickel-chromium catalyst having a nickel/chromium ratio of about 98:2 to about 50:50; (b) providing a single reactor vessel; (c) introducing carbon dioxide and hydrogen gas into the single reactor vessel; (d) allowing the carbon dioxide and hydrogen gas to react at a conversion rate in the presence of the nickel-chromium catalyst in the single reactor vessel at a reaction temperature; (e) maintaining the reaction temperature in the single reactor vessel at about 205 to about 220 C; and (f) wherein the conversion rate to methane is about 100 percent.

The present invention relates to improved methanation reaction methods utilizing enhanced catalyst formulations and methods of preparing enhanced methanation catalysts. Methanation of carbon dioxide is typically accomplished over a nickel catalyst to methane as described in the following chemical reaction: CO2 + 4H2 = CH4 + 2H2O

One conventional catalyst used to achieve this methanation reaction is the Haldor-Topsoe methanation catalyst PK-7R. This conventional catalyst is advertised as a low-temperature carbon monoxide methanation catalyst with operation temperatures down to 190 C while maintaining 100% conversion. When the PK-7R catalyst is employed in carbon dioxide methanation (as opposed to carbon monoxide methanation), testing performance of the PK-7R catalyst reveals that 100% conversion is only achieved at temperatures exceeding approximately 230 C Testing of other nickel oxide methanation catalysts achieved similar results. Accordingly, conventional methanation catalysts only achieve 100% carbon dioxide conversions at unacceptably high temperatures.

(Concerning the above, and in other words: There are already known and commercial catalysts that will convert Carbon Dioxide into substitute natural gas Methane.) 

Conventional methanation catalysts have been optimized to convert feeds containing primarily carbon monoxide. To date, no conventional catalysts have been optimized for methanation feeds primarily composed of carbon dioxide to the inventor's knowledge.

The methods disclosed herein provide an enhanced mixed metal catalyst which may lead to energy savings by lowering the operating temperature of carbon dioxide methanation.

In particular, the addition of chromium may promote the reverse water gas shift reaction which is described by the following chemical reaction: CO2 + H2 = CO + H2O

In certain embodiments, the enhanced mixed metal methanation catalyst disclosed herein demonstrates methanation of carbon dioxide with 100% conversion at approximately 210 C, which represents a 20 C improvement over other conventional commercial catalysts tested. At lower reaction conversions, the enhanced mixed metal methanation catalyst provides even lower reaction temperatures, resulting in further economic savings. These lower reaction temperatures translate into reduced operating costs and/or lower equipment capital costs depending on reactor design".

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In sum, this Phillips 66 innovation can achieve an efficient, 100% conversion of Carbon Dioxide into substitute natural gas Methane through direct reaction with elemental, molecular Hydrogen.

And, as we've seen in a number of reports, one example being:

USDOE 2014 Sunshine Extracts Hydrogen from Water | Research & Development | News; concerning: "United States Patent 8,729,798 - Anti-reflective Nanoporous Silicon for Efficient Hydrogen Production; 2014; Inventors: Jihun Oh and Howard Branz, CO; Assignee: Alliance for Sustainable Energy, LLC, Golden, CO; Abstract: Exemplary embodiments are disclosed of anti-reflective nanoporous silicon for efficient hydrogen production by photoelectrolysis of water. A nanoporous black Si is disclosed as an efficient photocathode for H2 production from water splitting half-reaction. Government Interests: The United States Government has rights in this invention under Contract No. DE-AC36-08GO28308 between the United States Department of Energy and the Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory";

we're getting pretty good at using freely-available environmental energy to extract Hydrogen from the abundant water, H2O, molecule.

As a further note, and as has been emphasized in expositions of other, related, CO2-to-Methane processes, some efficiencies and temperature control is achieved, as in the above passage:

"The methods disclosed herein provide an enhanced mixed metal catalyst which may lead to energy savings by lowering the operating temperature of carbon dioxide methanation. In particular, the addition of chromium may promote the reverse water gas shift reaction which is described by the following chemical reaction: CO2 + H2 = CO + H2O";

by conducting the CO2-to-Methane process via an initial reaction that converts the Carbon Dioxide into Carbon Monoxide, as in our report of:

France Efficient CO2 to Carbon Monoxide Conversion | Research & Development | News; concerning: "United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst; 2003; Inventor: Rene Dupont, et. al., France; Assignee: Air Liquide; 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. The invention is characterised in that the reaction is carried out at a temperature between 300 and 520 C and under pressure between 10 to 40 bars in the presence of an iron-free catalyst based on zinc oxide and chromium oxide. Said method is preferably carried out continuously and comprises preferably the following steps which consist in: a) preparing a gas mixture rich in carbon dioxide and in hydrogen ... between 300 and 520 C; b) 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 maintained under pressure between 10 and 40 bars";

and, then reacting the Carbon Monoxide made from Carbon Dioxide with more Hydrogen to synthesize the desired product Methane.

In any case, the technology without doubt exists to start treating the Carbon Dioxide co-generated by our economically essential use of Coal in the production of abundant and affordable electric power as a valuable raw material resource.

Carbon Dioxide can be efficiently converted, as herein, into substitute natural gas Methane.


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