As can be learned via the New York Times' interactive reportage utility, "Documents: Federal Officials Quietly Question Shale Gas":
Documents: Federal Officials Quietly Question Shale Gas - Interactive Feature - NYTimes.com;
we might not have nearly as much natural gas available to us on a genuinely economical basis as the shale gas industry, and their more uncritical aficionados in our public press, would prefer to have us believe.
That, coupled with
Wheeling Water Warriors Community Rally | www.wtov9.com; By Celina Pompeani; Wheeling, W.Va.; The Wheeling Water Warriors held a community rally today on the annual river sweep day to remind people how important clean water is. The group is trying to bring attention to the GreenHunter-proposed fracking wastewater treatment facility, just a mile and a half upriver from the main water intake for all Wheeling Ohio County water customers. Some of the speakers here today highlighted radiation and chemical concerns";
the growing public awareness that "America's Clean Energy Alternative", isn't, really, all that clean, or much of an alternative to anything, leads to the conclusion that we might, in fact, need to find a cleaner, more sustainable and more reliable alternative to "America's Clean Energy Alternative".
And, we already have one: Coal.
As we've documented, for just one example, in:
West Virginia Coal Association | Texaco Clean Methane from High-Sulfur Coal | Research & Development; concerning: "US Patent 3,928,000 - Clean Methane ... from High-Sulfur Containing Hydrocarbonaceous Materials; 1975; Assignee: Texaco Incorporated, NYC, NY; Abstract: This is an improved process for converting low-cost high-sulfur containing hydrocarbonaceous materials into a clean methane-rich gas stream which may be burned as a fuel without contaminating the atmosphere. (The) resulting methane-rich gas stream comprises (up to) 95% CH4 (methane). The process ... wherein said sulfur-containing hydrocarbonaceous fuel contains from about 1 to 7% sulfur and is (a slurry) of coal";
we've known for quite some time that we can efficiently make what is, essentially, pure Methane, i.e., substitute natural gas, from Coal.
And, that fact has just been quite recently reconfirmed, with the addition and affirmation of even further economies and intriguing value, by petroleum industry scientists; and, by technical review experts in our United States Government, through their issuance of, as excerpted from the initial link in this dispatch:
"United States Patent 8,461,216 - Process for the Co-Production of Superheated Steam and Methane
Process for the co-production of superheated steam and methane - Shell Oil Company
Date: June 11, 2013
Inventors: Lloyd Anthony Clomburg and Anand Nilekar, Texas
Assignee: Shell Oil Company, Houston
Abstract: A process for the co-production of superheated steam and methane includes reacting a gas containing carbon monoxide and hydrogen in a series of methanation regions to produce a product gas containing methane The gas containing carbon monoxide and hydrogen flows, in passing through the series of methanation regions, successively through at least a first internally cooled methanation region and a second internally cooled methanation region, cooling the first and second internally cooled methanation region with water, which water is vaporized in the first internally cooled methanation region to produce steam and which steam is subsequently superheated in the second internally cooled methanation region to produce superheated steam The internally cooled methanation regions include tubes filled with a methanation catalyst and a space surrounding the tubes The gas containing carbon monoxide and hydrogen and/or product gas flows through the tubes and the water flows through the space surrounding the tubes.
(First of all, lest you wonder where we might get the needed "gas containing carbon monoxide and hydrogen", Shell themselves have already addressed that, as, for one example, in our report of:
West Virginia Coal Association | Shell Oil Coal + CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 7,829,601 - Partial Oxidation Process of a Solid Carbonaceous Feed; 2010; Inventors: Johannes Ploeg, et. al., Netherlands; Assignee: Shell Oil Company, Texas; Abstract: The invention is directed to a process for preparing a mixture comprising CO and H2 by operating a partial oxidation process of a solid carbonaceous feed, which process comprises the steps of:(Supplying) the solid carbonaceous feed and an oxygen-containing stream to a burner, wherein a CO2 containing transport gas is used to transport the solid carbonaceous feed to the burner; (And) partially oxidizing the carbonaceous feed in the burner wherein a gaseous stream comprising CO and H2 is being discharged from said burner into a reaction zone ... . (And) wherein the solid carbonaceous feed is coal";
wherein it was seen that Carbon Dioxide, as reclaimed from whatever source, can be consumed and utilized in a Coal gasification process. Further, the technology for such Coal gasification has, as seen in:
West Virginia Coal Association | Celanese Co-Gasifies Coal and CO2-Recycling Algae | Research & Development; concerning: "United States Patent Application 20130144087 - Co-Gasification of Aquatic Biomass and Coal; 2013; Assignee: Celanese International Corporation; Abstract: The invention also relates to co-gasification processes for forming syngas from aquatic biomass and a fossil fuel. In one aspect, the invention is to a process for producing syngas, comprising: introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide; and feeding aquatic biomass with carbon dioxide derived from the syngas. In other aspects, the invention relates to integrated processes for producing industrial chemicals, such as alcohols, carboxylic acids, esters, aldehydes, olefins and polymers from such syngas. A process for producing syngas, comprising: (a) introducing aquatic biomass, a fossil fuel, water and oxygen to a gasifier and forming syngas comprising hydrogen, carbon monoxide and carbon dioxide; and: (b) feeding aquatic biomass with carbon dioxide derived from the syngas (and) wherein the fossil fuel comprises coal";
continued to improve, with the potentials for CO2 utilization and consumption, through indirect means, further enhanced; with additional benefits appending related to Coal conservation and sustainability.)
Claims: A process for the co-production of superheated steam and methane comprising: reacting a gas containing carbon monoxide and hydrogen in a series of methanation regions to produce a product gas containing methane, wherein the gas containing carbon monoxide and hydrogen flows, in passing through the series of methanation regions, successively through at least a first internally cooled methanation region and a second internally cooled methanation region; and cooling the first and second internally cooled methanation region with water, which water is vaporized in the first internally cooled methanation region to produce steam and which steam is subsequently superheated in the second internally cooled methanation region to produce superheated steam, wherein the internally cooled methanation regions comprise tubes filled with a methanation catalyst and a space surrounding the tubes; and wherein the gas containing carbon monoxide and hydrogen and/or product gas flows through the tubes and the water flows through the space surrounding the tubes.The process ... wherein the gas containing carbon monoxide and hydrogen and/or product gas flow through the internally cooled methanation regions in a direction counter-currently to the direction in which the water flows through the internally cooled methanation regions (and) wherein the series of methanation regions consists of a sequence of a first internally cooled methanation region, a second internally cooled methanation region and a third internally cooled methanation region.
The process ... wherein the internally cooled methanation regions comprise a nickel containing methanation catalyst.
(We've previously noted the utility of Nickel, as above, as a methanation catalyst for Carbon oxides. Keep in mind that, as seen in:
West Virginia Coal Association | CO2 Solution Wins Nobel Prize - in 1912 | Research & Development; concerning: "Paul Sabatier; The Nobel Prize in Chemistry 1912; Nobel Lecture, December 11, 1912; 'The Method of Direct Hydrogenation by Catalysis'; During the period 1901 to 1905, together with Senderens, I showed that nickel is very suitable for the direct hydrogenation of nitriles into amines and, no less important, of aldehydes and acetones into corresponding alcohols. Carbon monoxide and carbon dioxide are both changed immediately into methane, which can therefore be synthesized with the greatest ease";its been known for more than a century that Nickel is able to catalyze the reactions between Hydrogen and both Carbon Monoxide and Carbon Dioxide to synthesize Methane; which reactions, as seen in:
West Virginia Coal Association | NASA Improves CO2 to Methane Conversion | Research & Development; concerning: "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2012; Inventors: Christian Junaedi, et. al., Connecticut; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen in a first reaction zone with a first catalyst bed at a temperature greater than a first designated temperature; feeding the effluent from the first reaction zone into a second reaction zone, and contacting the effluent with a second catalyst bed at a temperature equal to or less than a second designated temperature, 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";are exothermic enough that provision needs made, as Shell Oil is also indicating herein, for the extraction and recovery of the generated heat, thermochemical, energy.)
The process ... further comprising storing steam produced in the first internally cooled methanation region in a steam separation vessel and retrieving the produced steam from the steam separation vessel to produce superheated steam in the second internally cooled methanation region.
The process ... wherein at least part of the produced steam and/or at least part of the produced superheated steam is added to the gas containing carbon monoxide and hydrogen upstream of the first reactor (and) wherein at least part of the produced steam and/or at least part of the produced superheated strain is used as a moderator in a gasification reaction to produce synthesis gas.
The process ... further comprising the use of the product gas containing methane as a substitute for natural gas.
The process ... wherein the gas containing carbon monoxide and hydrogen is synthesis gas obtained by reacting a carbonaceous feed and an oxidant in a gasification reaction.
The process ... wherein the carbonaceous feed comprises coal ... .
The process ... wherein the superheated steam is subsequently used to generate power.
(Which by-product "power", we submit, could be employed in a separate process, such as that seen in our report of:
West Virginia Coal Association | USDOE Converts CO2 into Methane via "Syntrolysis" | Research & Development; concerning: "'Results of Recent High Temperature Co-Electrolysis Studies at the Idaho National Laboratory'; 2007; Idaho National Laboratory, and ... Ceramatec, Inc.; For the past several years, the Idaho National Laboratory (INL) and subcontractor Ceramatec, Inc. have been studying the ... high temperature coelectrolysis of steam/CO2 mixtures to produce syngas: the raw material for synthetic fuels production. ... An inline methanation reactor has also been tested to study direct methane production from coelectrolysis products. (High) temperature coelectrolysis can provide a carbon neutral means of producing syngas while consuming CO2. Summary: The Idaho National Laboratory has demonstrated the feasibility of using high temperature solid oxide cells to coelectrolyze H2O and CO2 simultaneously to produce syngas (and, the) concept of directing coelectrolysis products through a methanation reactor was tested, with yields of 40-50 volume % methane being produced";
to generate, through co-electrolysis, more of the desired Carbon Monoxide and Hydrogen, for catalytic conversion into Methane, from H2O and Carbon Dioxide.)
Background and Field: The invention relates to a process for the co-production of superheated steam and methane.
A methanation reaction comprises a catalytic reaction of hydrogen with carbon monoxide to produce methane. This methane is sometimes also referred to as synthetic natural gas (SNG) and can be used as substitute gas for natural gas. In areas where there is little natural gas available, other sources of energy, such as coal ... may be partially oxidized in a gasification process to produce a gas comprising hydrogen and carbon monoxide. Such a gas comprising hydrogen and carbon monoxide is sometimes also referred to as synthesis gas. The synthesis gas can subsequently be used to produce synthetic natural gas (SNG) in a methanation process.
The methanation reaction proceeds, in the presence of a suitable methanation catalyst, in accordance with the following equations:
CO + 3H2 = CH4 + H2O + heat (and) CO2 + 4H2 = CH4 + 2H2O + heat.
Summary: Accordingly, the present invention provides a process for the co-production of superheated steam and methane comprisingreacting a gas containing carbon monoxide and hydrogen in a series of methanation regions to produce a product gas containing methane, wherein the gas containing carbon monoxide and hydrogen flows, in passing through the series of methanation regions, successively through at least a first internally cooled methanation region and a second internally cooled methanation region, cooling the first and second internally cooled methanation region with water, which water is vaporized in the first internally cooled methanation region to produce steam and which steam is subsequently superheated in the second internally cooled methanation region to produce superheated steam, wherein the internally cooled methanation regions comprise tubes filled with a methanation catalyst and a space surrounding the tubes; and wherein the gas containing carbon monoxide and hydrogen and/or product gas flows through the tubes and the water flows through the space surrounding the tubes.
The process according to the invention allows the co-production of methane and superheated steam without the necessity of adiabatic reactors, whilst the costs for the construction material of the methanation regions can be kept low. In the first internally cooled methanation region, the temperature of the tube walls can be similar to the temperature of the boiling water, which boiling water may have a temperature of for example around 300 C. In the second internally cooled methanation region, the temperature of the catalyst may already be lower than the temperature of the catalyst in the first internally cooled methanation region. The temperature of the tube walls in the second internally cooled methanation region can be similar to the temperature of the steam, which steam may have a temperature of for example around 450-500 C. The process of the invention has the advantage that the temperature of the metal of the tube walls can be reduced and that cheaper construction materials (for example cheaper metal) may be used in the methanation regions.
Without wishing to be bound to any kind of theory, it is believed that by cooling the first methanation region, where the temperature of the catalyst and feed may be highest, with water that is still to be vaporized, a more efficient cooling can be achieved. The water, that is still to be vaporized, is capable of absorbing more heat than steam that is being superheated. As a result the overall metal temperature in the first methanation region can be lower and less expensive material is needed for construction of the first methanation region. In the second methanation region, the temperature of the catalyst and feed may be lower and less cooling is required. The overall metal temperature in the second methanation region can avoid the use of special material for the tube walls.
The gas containing carbon monoxide and hydrogen, may be any gas comprising carbon monoxide and hydrogen. An example of a gas comprising carbon monoxide and hydrogen is synthesis gas. Herein synthesis gas is understood to be a gas comprising at least hydrogen and carbon monoxide. In addition, the synthesis gas may comprise other compounds such as carbon dioxide, water, nitrogen, argon and/or sulphur containing compounds. Examples of sulphur containing compounds that may be present in synthesis gas include hydrogen sulphide and carbonyl sulphide.
The synthesis gas may be obtained by reacting a carbonaceous feed and an oxidant in a gasification reaction.
By a carbonaceous feed is understood a feed comprising carbon in some form. The carbonaceous feed may be any carbonaceous feed known by the skilled person to be suitable for the generation of synthesis gas.
The carbonaceous feed may ... include coal, such as lignite (brown coal), bituminous coal, sub-bituminous coal, anthracite, ... peat, biomass, ... or combinations thereof.
In a preferred embodiment, the synthesis gas is obtained by gasification of a solid carbonaceous feed that comprises coal ... .
By an oxidant is understood a compound capable of oxidizing another compound. The oxidant may be any compound known by the skilled person to be capable of oxidizing a carbonaceous feed. The oxidant may for example comprise oxygen, ... carbon dioxide (in a reaction to generate carbon monoxide) or mixtures thereof. If an oxygen-containing gas is used as oxidant, the oxygen-containing gas used may be pure oxygen, mixtures of oxygen and steam, mixtures of oxygen and carbon dioxide, mixtures of oxygen and air or mixtures of pure oxygen, air and steam."
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We can, thus, generate a gas blend of Carbon Monoxide and Hydrogen from "bituminous coal (or) biomass, ... or combinations thereof" in a gasification process using an "oxidant (that) may for example comprise oxygen (and) carbon dioxide" ; and, which "carbon monoxide and hydrogen" can then be passed into "a series of methanation regions to produce a product gas containing methane", along with "superheated steam", which, as we noted above through reference to the work accomplished at the USDOE's Idaho National Laboratory, has, through the suggestion that the steam can be "subsequently used to generate power", some intriguing potentials for the generation of even more Carbon Monoxide and Hydrogen, and, thus, more Methane.And, aside from it's obvious utility as, as Shell Oil herein suggests, "synthetic natural gas", a "substitute gas for natural gas", we remind you, that, as seen for only one example in:
West Virginia Coal Association | Saudia Arabia CO2 + Methane = Hydrocarbons + Syngas | Research & Development; concerning: "United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas; 2008; Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: Process for producing benzene, ethylene and synthesis gas, comprising the steps of: i) introducing a starting gas flow comprising methane and carbon dioxide into a reactor (and) removing a product gas flow comprising benzene, ethylene and synthesis gas from the reactor";the Methane co-product of our subject herein, "US Patent 8,461,216 - Process for the Co-Production of Superheated Steam and Methane", as made so efficiently along with power-producing "Superheated Steam", from such raw materials as "bituminous coal (and) biomass", via the intermediate production of "a gas comprising hydrogen and carbon monoxide ... also referred to as synthesis gas", can be reacted directly with Carbon Dioxide, as recovered from whatever handy source, and be made through such reactions to form a number of valuable and needed hydrocarbons, along with even more "synthesis gas", likely suitable for adding to the synthesis "gas containing carbon monoxide and hydrogen" of our subject herein, and the subsequent synthesis of even more "superheated steam" and even more Methane, "as a substitute for natural gas".