United States Patent: 7355088
We've made a number of previous reports on the CO2-recycling accomplishments of the prolific Saudi Arabian chemical genius, Agaddin Mamedov; most recently in:
West Virginia Coal Association | Saudi Arabia and Texas CO2 to Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture; 2012; Inventors: Agaddin Mamedov, Texas, and Abdulaziz Al-Jodai, Riyadh, Saudi Arabia;
Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, wherein the catalyst substantially consists of chromia/alumina. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be combined with other processes, for example up-stream with other synthesis processes for making products like aliphatic oxygenates, olefins or aromatics".
Our study of the venerable Mamedov's body of work has uncovered a number of items which should be worthy of interest to anyone weary of all the Carbon Dioxide emission, and hydrocarbon fuel shortage, baloney sandwiches that have been passed our way over the past few decades; and, we enclose herein another example of his accomplishments, which, if the Coal Country news writers and editors who are, and who always have been, the primary addressees and recipients of these dispatches still prefer to ignore Coal, and Coal people, and the vast potentials for both in the fuller use of Coal and Coal utilization byproducts, should just delete right here and move on to their next email from Publishers Clearing House.
For those of you journalists actually gifted with objective and inquiring minds, and a genuine concern for Coal Country and her people, however, we remind you, that, as we documented most recently in:
West Virginia Coal Association | USDOE Sunlight Converts CO2 into Methane | Research & Development; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; 2013; Inventor: Brian Ingram, et. al.; Assignee: UChicago Argonne, LLC, Chicago; (A) photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen ... . Government Interests: The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory. Claims: A photocatalyst for conversion of carbon dioxide and water into a hydrocarbon ... . A method of converting carbon dioxide and water into a hydrocarbon and oxygen comprising exposing a gaseous mixture of carbon dioxide and water to sun light in the presence of a photocatalyst (as specified). (The) energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane";
it is feasible to, on a practical basis, convert Carbon Dioxide and Water vapor, using nothing but Sunlight to drive the process, into Methane.
And, as we have many times documented from many sources, as, for one example, in:
West Virginia Coal Association | 1940 CO2 + H2O + CH4 = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 2,198,553 - Making a Synthesis Gas Mixture of Carbon Monoxide and Hydrogen; 1940; Assignee: The M.W. Kellogg Company, NY; Abstract: Our invention relates to a method of making synthesis gas and more particularly to a method of making a mixture of hydrogen and carbon monoxide having a controllable ratio of hydrogen with respect to carbon monoxide from 1:1 to 3:1 by volume. Mixtures of carbon monoxide and hydrogen are useful in synthesizing many organic compounds and these mixtures are known to the art as "synthesis gas". Synthesis gas may be made from methane, steam and carbon dioxide ... . Any ratio of carbon monoxide and hydrogen may be obtained (within the defined) limits by varying the relative proportions of carbon dioxide and steam that are reacted with methane";
we have known for quite a long time that Methane, once we have it, whether synthesized from Carbon Dioxide or not, can be reacted with even more Carbon Dioxide, with both the Methane and the Carbon Dioxide being converted through such reaction into a hydrocarbon synthesis gas blend of Carbon Monoxide and Hydrogen, a "syngas" suitable for catalytic chemical condensation, as, for one example, via the:
Fischer–Tropsch process - Wikipedia, the free encyclopedia; "The Fischer–Tropsch process ... is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons";
into a variety of hydrocarbon fuels and chemicals.
And, herein, we learn that Saudi Arabia, too, one of OPEC's crown jewels, via the accomplished Mamedov and a few collaborators, have established their own technology for reacting Methane - - as might be, as via the US Department of Energy process of the above-cited "US Patent Application 20130079577", synthesized from Water, Sunlight and Carbon Dioxide - - with even more Carbon Dioxide, with the result being both useful hydrocarbons and more hydrocarbon synthesis gas.
As seen, with comment appended, in excerpts from the initial link in this dispatch to:
"United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas
Patent US7355088 - Process for producing benzene, ethylene and synthesis gas - Google Patents
Process for producing benzene, ethylene and synthesis gas - Saudi Basic Industries Corporation
Date: April, 2008
Inventors: Agaddin Mamedov, et. al., Saudi Arabia
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;
ii) oxidizing the methane in the reactor at certain reactor conditions optionally using a first catalytic material and/or and additional oxidant; and:
iii) removing a product gas flow comprising benzene, ethylene and synthesis gas from the reactor.
(First, note that this process for reacting Methane with CO2 results in the co-production of "synthesis gas":
Syngas - Wikipedia, the free encyclopedia; "Syngas, or synthesis gas, is a ... mixture consisting primarily of hydrogen, carbon monoxide, and very often some carbon dioxide. The name comes from its use as intermediates in creating synthetic natural gas (SNG) and for producing ammonia or methanol. Syngas is also used as an intermediate in producing synthetic petroleum ... via the Fischer-Tropsch process";
as well as some valuable hydrocarbons, i.e.:
Benzene - Wikipedia, the free encyclopedia; "Benzene is used mainly as an intermediate to make other chemicals. ... Its most widely produced derivative is ethylbenzene, precursor to styrene, which is used to make polymers and plastics"; and:
Ethylene - Wikipedia, the free encyclopedia; "Ethylene is widely used in chemical industry, and its worldwide production (over 109 million tonnes in 2006) exceeds that of any other organic compound".
And, which "ethylene", we must note, as seen in:
West Virginia Coal Association | Columbia University Converts CO2 to Ethylene | Research & Development; concerning: "United States Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2; 2013; Assignee: The Trustees of Columbia University in the City of New York; Abstract: An electrolytic cell system to convert carbon dioxide to a hydrocarbon (and) wherein the hydrocarbon (produced) is ethylene";
can be made from Carbon Dioxide via some other technologies, as well; and, also, as seen in our report:
West Virginia Coal Association | Ethane Cracker Realities | Research & Development; which included a separate reference to: "United States Patent Application 0100145125 - Producing Light Olefins Through the Conversion of Methanol and Ethanol; 2010; Assignee: China Petroleum and Chemical Corporation, Beijing
Abstract: The present invention discloses a process of producing light olefins through the conversion of methanol and ethanol. The process comprises: ... contacting the feed with the catalyst and allowing it to react, to give a stream containing ethylene and propylene. Background: An important approach for producing light olefins from non-petroleum feedstock is the conversion of oxygenates, for example, lower alcohols (methanol, ethanol), ethers (dimethyl ether, methyl ethyl ether), esters (dimethyl carbonate, methyl formate) and the like to olefins, especially the conversion of lower alcohols to light olefins. The production of light olefins from methanol is a promising process, because methanol can be produced in large scale from coal";
indirectly, through Methanol, from Coal.)
Claims: A process for producing benzene, ethylene and synthesis gas, comprising the steps of:
- introducing a feed gas comprising methane and carbon dioxide in a molar ratio in the range from 40:60 to 70:30 into a reactor defined by at least one reactor wall;
- oxidizing the feed gas in the reactor in the presence of a non-zeolite catalyst material consisting essentially of Mn(NO3)2; and:
- recovering a product comprising benzene, ethylene and synthesis gas from the reactor.
(The above "Mn(NO3)2" is formally known as "Manganese (II) Nitrate"; and, it is inexpensive and easy to make.)
The process ... wherein said reactor wall has an interior surface which is treated with said catalyst material.
The process ... wherein said catalyst material, mixed with SiO2 sol-gel.
(The above "SiO2 sol-gel" is what's known as "silica sol-gel"; and, we're advised that what might actually be meant is what's known as a silica "xerogel" or "aerogel". That's not the way it's stated, but one consultant advises that it would be hard to conceive of a catalytic reaction occurring within what might be thought of as a "sol-gel", unless it's intended that the sol-gel, or "solid" gel, is just a carrier for the catalyst, so that it can be coated onto the "interior surface" of the reactor. Either way, it would be a readily-available commercial product; and, more can be learned via:
Aerogel - Wikipedia, the free encyclopedia.
The term "sol-gel", in any case, as we were instructed, actually refers more to a process than a product or material. See:
Sol Gel; "The sol-gel process is a versatile solution process for making advanced materials, including ceramics and organic-inorganic hybrids".)
The process ... wherein a second oxidant comprising air or oxygen is mixed with the feed gas in the reactor during the oxidation of said feed gas (and) wherein the concentration of the second oxidant relative to the feed gas is not more than 2% by volume.
The process ... wherein said reactor has a reactor inlet and a reactor outlet and wherein the feed gas oxidation is carried out at a temperature profile which is in the range of from about 1500 C to about 1000 C at the reactor inlet and from about 700 C to about 600 C at the reactor outlet.
(Those are actually fairly high temperatures; and some provision should be made, one would think, to provide them via the engagement of some sort of environmental energy, like a small, dedicated hydroelectric or wind energy installation.)
The process ... wherein the feed gas is introduced into the reactor at a temperature of about 965 C and the product is recovered from the reactor at a temperature of about 715 C.
(It seems like some residual waste heat could be recovered from the product gas and recycled to help get the feed gas part-ways up to temperature.)
The process ... wherein said reactor has a reactor inlet and a reactor outlet and wherein there is a second catalyst material comprised of a basic oxide in the reactor at the reactor inlet (and) wherein said second catalyst material comprises (Tungsten Oxide, Strontium Oxide, Lanthanum Oxide, Manganese Oxide, etc.).
The process ... wherein the mole ratio of methane to carbon dioxide in the feed gas is about 50:50.
The process ... wherein the interior wall of the reactor is cylindrical and with an interior diameter of about 2 to 1000 mm.
(If we're reading that right, the reactor could be better than a yard - "1000 mm", i.e., one meter - wide. That could pass, and process, a lot of gas.)
The process ... wherein the reactor has a length and the length to diameter ratio of the reactor is from about 200 to 1 to about 100 to 50.
(It could, in other words, be pretty big. If it were "1000 mm", call it a yard, in diameter, at a "length to diameter ... ratio (of) 200 to 1" it would be as long as two football fields. The full Disclosure actually details a range of possible sizes and length-to-diameter ratios. It doesn't seem to instruct on how the optimum would be calculated.)
Description and Background: The present invention relates to a process for producing benzene, ethylene and synthesis gas from methane.
The partial oxidation of methane is of great industrial importance either for the production of synthesis gas or the production of higher hydrocarbons and aromatics, such as benzene.
Nowadays, benzene is often produced by methods comprising the production from catalytic reformate, production from gasoline pyrolysis, production by toluene conversion and production by LPG (Liquified Petroleum Gases) aromatization.
It is an object of the present invention to provide a process for producing benzene which overcomes the drawbacks of the prior art, especially to provide a process for simultaneously producing benzene, ethylene and synthesis gas with high conversion of methane and with high selectivity and yield of benzene.
This object is achieved by a 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,
ii) oxidizing the methane in the reactor at certain reactor conditions optionally using a first catalytic material and/or an additional oxidant; and:
iii) removing a product gas flow comprising benzene, ethylene and synthesis gas from the reactor.
Most preferably, the process is carried out in a reactor that is made of quartz, ceramic, alumina alloy, stainless steel or the like. A quartz reactor is preferred, because, for example, in a metallic reactor the benzene yield is low due to the deep decomposition of the methane on the metallic surface.
(The above suggests one potential problem in all of this. A "quartz" reactor a yard wide and as long as a football field could wind up being pretty danged expensive. The possibility of using "ceramic", though, does provide some potentially much more affordable options. The Disclosure goes on to explain how problems of "coking" can occur during the partial oxidation of Methane, and, how the inclusion of CO2 in the feed gas mix helps to overcome those problems and to increase the yield of hydrocarbons and synthesis gas.)
The use of carbon dioxide in the process of the present invention allows to oxidize the coke fragments accumulated during the reaction ...; ... carbon dioxide is a mild oxidant and changes the equilibrium and increases the methane conversion. Carbon dioxide ... decreases the coke formation.
A dilution with carbon dioxide allows to realize a high methane conversion. Further, the presence of carbon dioxide in a mixture with methane provides the formation of active coke fragments and decreases the formation of graphitic forms of coke.
(A) dilution with carbon dioxide decreases the concentration of heavy aromatics, such as toluene, naphthalene, acetonaphthalene, phenantrene and the coke formation reactions.
Carbon dioxide reacts with coke and hydrogen to produce simultaneously the synthesis gas, which is important for methanol synthesis."
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So, the "synthesis gas" co-produced, along with "ethylene", from Methane and Carbon Dioxide, can be used for the "synthesis" of "methanol", which Methanol could, as via our above-cited process of "United States Patent Application 0100145125 - Producing Light Olefins Through the Conversion of Methanol", then be used to make more Ethylene, or, as in our report of:
West Virginia Coal Association | Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984;
Assignee: Mobil Oil Corporation; Abstract: A process for producing a wide slate of fuel products from coal is provided by integrating a methanol-to-gasoline conversion process with coal liquefaction and coal gasification. ... (Coal) is gasified under oxidation conditions to produce a synthesis gas which is converted to methanol. The methanol is converted to gasoline by contact with a zeolite catalyst";
some stuff of perhaps more immediate interest.
And, again, as seen separately in our report of:
West Virginia Coal Association | New York City CO2 to Methane via Artificial Photosynthesis | Research & Development; concerning: "US Patent Application 20120208903 - Conversion of Carbon Dioxide to Methane Using Visible Light; 2012; Assignee: Research Foundation of City University of New York, NYC; Abstract: The invention relates to a method for converting carbon dioxide to methane. The method comprises exposing carbon dioxide adsorbed on a nanoporous silicate matrix to light in the presence of a source of carbon dioxide and a source of hydrogen for a time and under conditions sufficient to convert carbon dioxide to methane (and wherein a) preferred source of hydrogen is water";
we can synthesize the Methane, needed by the process of our subject herein, "United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas", to be reacted with Carbon Dioxide, for the production of various hydrocarbons and hydrocarbon synthesis gas, out of nothing but Sunlight, Water, and more Carbon Dioxide.