We've made a number of reports so far concerning the very major Coal Country corporate citizen, Bayer Corporation, who, as we've noted once or twice previously, do take their status as such a "citizen" pretty seriously, and make it a company priority to try and be a good one.
We don't know what the correct legal label to apply would be, but, anyone familiar at all with Bayer Corporation in the United States, with their corporate headquarters in Pittsburgh and with a couple of manufacturing sites in West Virginia, among quite a few other places, knows that they are a subsidiary, or operating branch, of the international giant Bayer AG, headquartered in Germany.
There's a lot of ground to cover herein, and we can't dwell on the details of their global operations overmuch, although we will be filling in some more details in future dispatches.
In any case, we remind of a few previous reports we've made concerning Bayer, as in:
West Virginia Coal Association | Bayer Improves Coal + CO2 = Carbon Monoxide | Research & Development; concerning: "United States Patent 7,473,286 - Carbon Monoxide Generator; 2009; Bayer Material Science, AG, Germany; Abstract and Claims: A generator (as described) further comprising a desulfurizing device. The present invention relates to a novel generator for the reaction of carbon-containing raw materials and also to an improved process for the production of carbon monoxide gas (CO gas) having a high degree of purity using such a generator. Carbon monoxide gas is frequently produced in the art by means of a continuous process in which carbon-containing raw materials are reacted with oxygen and carbon dioxide ... . An object of the present invention (is) to provide a continuous process for the production of CO gas by the gasification of coal"; and:
West Virginia Coal Association | Bayer's CO2 Recycling Dream Comes True | Research & Development; concerning the Bayer corporate publication: "'A Dream Comes True'; 2010; Crude oil is the raw material used to produce most plastics. What if one could conserve this limited resource and use carbon dioxide instead, which is available in abundance? For decades, chemists have considered this alternative a “dream reaction”, but now it is close to reality. CO2 is to be integrated into the molecular structure of plastics and thus reduce the use of crude oil in the production of these indispensable engineering materials";
wherein Bayer discloses and explains that Carbon Dioxide can be reclaimed from whatever source and, then, via one or another direct or indirect chemical route, be used in certain chemical syntheses for the production of various organic chemicals, including, through intermediate products, "plastics".
Note in the excerpts from Bayer's "A Dream Comes True" that, currently, "Crude oil is the raw material used to produce most plastics".
Bayer has developed technical processes wherein Carbon Dioxide, and/or Carbon Monoxide, produced we conjecture via the process of "United States Patent 7,473,286 - Carbon Monoxide Generator" from Carbon Dioxide, is utilized and consumed in the direct synthesis of some polymers and polymer intermediaries, that is, "plastics", wherein any CO2 consumed directly or indirectly as a raw material would remain permanently, chemically and productively, "sequestered".
We'll be addressing some more of those specific Bayer processes in a few reports to follow, but, we remind you that there exists now almost ancient technology, i.e., the Fischer-Tropsch synthesis, which was developed in Germany in the 1920's, and which is a method for the conversion of Coal into various hydrocarbons via an indirect process of first gasifying Coal, to produce primarily Carbon Monoxide and Hydrogen - - "synthesis gas" or "syngas" - - and, then, catalytically and chemically condensing that syngas into various hydrocarbon compounds, which range from substitute natural gas methane all the way to solid hydrocarbons, referred to as "Fischer-Tropsch Wax".
A great deal of effort has been directed to the study of that Fischer-Tropsch Coal conversion product mix, relative to the catalysts and processing conditions employed to condense the syngas, as exemplified by one international project reported in:
http://www.aidic.it/cet/13/32/
And, other efforts have been undertaken to deal with, treat and further refine some of the specific products arising from typical Fischer-Tropsch syntheses, as exemplified for one instance in our report of:
West Virginia Coal Association | USDOE Pays Mobil Oil to Refine CoalTL Wax | Research & Development; concerning: "United States Patent 4,684,756 - Process for Upgrading Wax from Fischer-Tropsch Synthesis; 1987; Mobil Oil Corporation, NY; Abstract: The waxy liquid phase of an oil suspension of Fischer-Tropsch catalyst containing dissolved wax is separated out and the wax is converted by hydrocracking, dewaxing or by catalytic cracking with a low activity catalyst to provide a highly olefinic product which may be further converted to premium quality gasoline and/or distillate fuel. Government Interests: The Government of the United States of America has rights in this invention pursuant to Contract No. DE-AC22-83PC60019 awarded by the U.S. Department of Energy".
One of the issues with the Fischer-Tropsch synthesis is that the general reaction is exothermic; that is, as hydrocarbons are catalytically condensed out of the syngas, heat is also generated, a significant amount of it, and, which heat, if allowed to build up in the reactor, influences the types of hydrocarbons produced, with higher temperatures generally leading to the production of smaller molecules, typically gases like Methane.
Consequently, a lot of effort has been directed to the control of temperature in Fischer-Tropsch processes, as one means, in addition to the type of catalyst employed, of exerting control over the types of hydrocarbons produced.
Some of those efforts, as we've previously noted and as we will more fully document in the future, have given rise to the design of Fischer-Tropsch reactors with heat exchange capacity, wherein the exothermic heat of reaction is captured in one fashion or another, removed from the reaction zone, and, in some cases, used for other purposes, such as in the generation of supplemental electricity.
And, herein we learn that Bayer AG, in Germany, with the participation of Bayer's organization in the United States, have designed a Fischer-Tropsch reactor and process for, by controlling and limiting the exothermic heat of the Fischer-Tropsch reaction, converting synthesis gas - - with the Carbon Monoxide component perhaps supplied by the process of Bayer's above-cited "US Patent 7,473,286 - Carbon Monoxide Generator", and thus made from Coal and Carbon Dioxide - - into, basically, a substitute for crude petroleum, from which all other hydrocarbons, including those Bayer might require, as in our above reference to the Bayer publication "A Dream Comes True", which tells us that "Crude oil is the raw material used to produce most plastics", for their multi-national polymer production industry.
Comment follows excerpts from the initial link in this dispatch to the very recent:
"US Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis
(Adiabatic Processes; "An adiabatic process is one in which no heat is gained or lost by the system". The design of this Bayer process is such, that, the exothermic heat of reaction is managed in such a way by the design of the reactor and of the reaction process that no heat energy has to be added and no heat energy has to be extracted in order to maintain the process in what we could term a "steady state" with the result being hydrocarbon products of intrinsically broader and higher potential value - i.e., a synthetic crude petroleum from which all else can be derived and refined.)
October 15, 2013
Inventors: Ralph Schellen, et. al., Germany and Texas
Assignee: Bayer Intellectual Property GmbH, Germany
Abstract: The present invention relates to a multistage adiabatic process for performing the Fischer-Tropsch synthesis at low temperatures, in which the synthesis is performed in 5 to 40 series-connected reaction zones under adiabatic conditions.
(Again, the "low temperatures" will favor the synthesis of longer-chain hydrocarbons, as is desired, as long as formation of wax can be avoided; although, again, as in the above-cited USDOE-Mobil Oil process of "United States Patent 4,684,756 - Process for Upgrading Wax from Fischer-Tropsch Synthesis", the wax, too, can be reprocessed and refined.)
Claims: Process for preparing liquid hydrocarbons from the process gases carbon monoxide and hydrogen, comprising a Fischer-Tropsch synthesis in the presence of heterogeneous catalysts, which is performed in 5 to 40 series-connected reaction zones in which the heterogeneous catalysts are present under adiabatic conditions at temperatures of 220 C to 300 C, wherein downstream of each reaction zone is at least one heat exchange zone through which at least the process gases are passed and around each reaction zone is a thermal insulation zone.
Process ... wherein the conversion is accomplished in 7 to 30 series-connected reaction zones (and) wherein the inlet temperature of the process gas entering the first reaction zone is from 10 to 260 C (and)wherein the absolute pressure at the inlet to the first reaction zone is between 10 and 70 bar (and) wherein the residence time of the process gas in all reaction zones together is between 10 and 700 s.
Process ... wherein the catalysts are present in fixed bed arrangement (and) in the form of monoliths (and) wherein the monolith comprises channels having a diameter of 0.1 to 3 mm.
Process ... wherein the process gases, optionally together with the liquid hydrocarbons, are passed through the at least one heat exchange zone.
(Note the above specification of a "heat exchange zone", which, as Bayer explains further on in the full Disclosure, would enable the collection and possible productive use of the exothermic heat produced by the hydrocarbon synthesis reactions.)
Process ... wherein as the process gases and/or liquid hydrocarbons are cooled in the heat exchange zones by the heat exchanger, steam is raised.
Process ... wherein in the first reaction zone a catalyst is used, which has under otherwise identical conditions a less activity for the reaction of carbon monoxide with hydrogen compared to the catalysts used in the other reaction zones (and/or) wherein the same catalysts are used in each reaction zone.
Description: The present invention relates to a multistage adiabatic process for performing the Fischer-Tropsch synthesis at low temperatures, in which the synthesis is performed in 5 to 40 series-connected reaction zones under adiabatic conditions.
The Fischer-Tropsch synthesis is a chemical synthesis route which has become common knowledge and allows the preparation of hydrocarbons from carbon monoxide and hydrogen. Especially in recent times, increasing significance is being ascribed to this synthesis route, since global resources of natural hydrocarbons in the form of mineral oils or waxes are becoming increasingly scarce.
Carbon monoxide and hydrogen are, however, available in a relatively large amount, or are obtained as by-products in connection with other processes or can be prepared selectively, without necessarily needing to resort to the aforementioned natural resources.
(As noted, the "Carbon monoxide ... can be prepared selectively" via Bayer's own process, as cited above, of "US Patent 7,473,286 - Carbon Monoxide Generator", from Coal and Carbon Dioxide. Many technologies now exist and are available, as for just one example in our report of:
West Virginia Coal Association | USDOE and Delaware Sunshine Extracts Hydrogen from Water | Research & Development; concerning: "United States Patent Application 20130175180 - Devices and Methods for Increasing Solar Hydrogen Conversion Efficiency in Photovoltaic Electrolysis; 2013; University of Delaware; Abstract: Devices and methods for photovoltaic electrolysis are disclosed ... . Government Interests: This invention was made with Government support ... by the Department of Energy. Claims: A device for photovoltaic electrolysis (using) solar energy This invention relates generally to electrolysis, and more particularly to devices and methods for increasing solar hydrogen conversion efficiency in photovoltaic electrolysis";
for the extraction of the needed "hydrogen" from water, H2O, which use environmental energy, like "solar energy", to split the water molecule.
And, we'll note, in passing, that, if we are making Hydrogen efficiently from Water,using Solar energy, then we could, as well, as seen in our report of:
West Virginia Coal Association | France Efficient CO2 to Carbon Monoxide Conversion | Research & Development; concerning: "United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst; 2003; Assignee: Air Liquide (France); 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";
use extra Hydrogen to convert Carbon Dioxide into the needed Carbon Monoxide, thereby conserving some of our precious Coal, relative to the Bayer process of "United States Patent 7,473,286 - Carbon Monoxide Generator"; for essential use in the generation of truly abundant and truly affordable electric power.)
A distinction is nowadays generally drawn between two basic subgroups of the Fischer-Tropsch synthesis. One is the low-temperature process variant, and the other the high-temperature process variant. The present invention relates, as already described, to the low-temperature process variant.
The low-temperature process variant is generally advantageous in that the shorter-chain hydrocarbons of the high-temperature process variant can also be obtained from the longer-chain hydrocarbons by the process of "cracking" which is common knowledge to those skilled in the art, but the longer-chain hydrocarbons at the same time constitute starting materials for higher-value products such as waxes.
A fundamental problem in both process variants of the Fischer-Tropsch synthesis is the strongly exothermic character of the synthesis, such that, in terms of process technology, high demands are made on the removal of the heat from the synthesis when the desire is to control the synthesis exactly. As already described above, the temperature has a strong influence on the product properties from the Fischer-Tropsch synthesis. When the desire is thus to obtain a specific fraction of the hydrocarbons with a defined chain length, the temperatures under which the process is performed should be established and controlled particularly exactly.
In addition, there is the general problem that, in the event of a locally excessive temperature ("hot spot"), the formation of methane as an undesired by-product is favored.
(It) would therefore be advantageous to provide a process for preparing liquid hydrocarbons from carbon monoxide and hydrogen, which can be performed in simple reaction apparatus and which enables exact, simple temperature control, such that it allows high conversions at maximum purities of the product.
It is therefore an object of the invention to provide a process for preparing liquid hydrocarbons from carbon monoxide and hydrogen, which is performable with exact temperature control in simple reaction apparatus and which, as a result, allows high conversions at high purities of the product, the heat of reaction being utilizable either for the benefit of the reaction or in another way.
It has been found that, surprisingly, a process for preparing liquid hydrocarbons from the process gases carbon monoxide and hydrogen, comprising a Fischer-Tropsch synthesis in the presence of heterogeneous catalysts, characterized in that it is performed in 5 to 40 series-connected reaction zones in which the heterogeneous catalysts are present under adiabatic conditions at temperatures of 220 C to 300 C, achieves this object.
In the context of the present invention, carbon monoxide refers to a process gas which comprises essentially carbon monoxide (;and,) hydrogen refers to a process gas which comprises essentially hydrogen.
In addition to the essential hydrogen component of the process gas, it may also comprise secondary components. Non-exclusive examples of secondary components which may be present in the process gas are, for instance, argon, nitrogen and/or carbon dioxide. The same applies in the case of the carbon monoxide process gas.
The two process gases, hydrogen and carbon monoxide, together with their particular components, are also referred to collectively in the context of the present invention as the process gas.
In general, in the context of the present invention, the process gas is thus understood to mean a gas mixture which comprises hydrogen, carbon monoxide and secondary components.
In the context of the present invention, liquid hydrocarbons refer to aliphatic hydrocarbons which are present in the liquid phase in the reaction zones under the conditions of the process. Typically, these are aliphatic hydrocarbons comprising at least nine carbon atoms, preferably comprising at least 12 carbon atoms.
According to the invention, the performance of the process under adiabatic conditions means that essentially no heat is supplied actively to, nor heat is withdrawn from, the reaction zone from the outside.
One advantage of the inventive adiabatic method with 5 to 40 series-connected reaction zones over a non-adiabatic method is that there is no need to provide any means of heat removal in the reaction zones, which implies a considerable simplification of the construction. This gives rise more particularly to simplifications in the manufacture of the reactor and in the scalability of the process, and an enhancement of the reaction conversions. Moreover, the heat generated in the course of progression of the exothermic reaction can be utilized in a controlled manner to enhance the conversion in the individual reaction zone.
A further advantage of the process according to the invention is the possibility of very exact temperature control through the close graduation of adiabatic reaction zones. It is thus possible to establish and control a temperature which is advantageous in the progression of the reaction in each reaction zone.
Catalyst materials (could include) oxides of aluminium, titanium, zirconium and/or silicon, and/or oxides of lanthanoids. These materials are usually supports of the catalyst materials, to which the active constituents of the catalyst are applied.
Suitable active constituents of the catalysts are, for instance, cobalt compounds as already known to the person skilled in the art and/or compounds which comprise nickel, platinum and/or palladium. In preferred embodiments, they may also be doped with magnesium oxide as a promoter.
In a preferred embodiment of the process according to the invention, the conversion is effected in 7 to 30 and more preferably 10 to 20 series-connected reaction zones (and, the) process gas and the liquid hydrocarbons (produced) are preferably passed through at least one heat exchange zone connected downstream (as further described).
In a particular embodiment of the process, as the process gas and/or liquid hydrocarbon is cooled in the heat exchange zones by the heat exchanger, steam is raised.
A conversion of carbon monoxide of 99% is obtained. The selectivity obtained for liquid hydrocarbons comprising at least nine carbon atoms, based on carbon monoxide, is 40%.
It can thus be shown that, by virtue of the very closely graduated temperature control by means of the process according to the invention, the full reaction of carbon monoxide with pure hydrogen in the manner of a multiphase Fischer-Tropsch synthesis in the presence of a heterogeneous catalyst can be operated safely, and that, at the same time, very advantageous conversions and selectivities, and also a very advantageous space-time yield, can be achieved. In addition, closer graduation of an increased number of smaller adiabatic reaction zones with downstream heat exchange zone makes an even higher space-time yield achievable."
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In sum, Bayer has designed a process of Fischer-Tropsch synthesis which enables the essentially complete conversion, by a process that requires no input, or extraction, of heat energy, of Carbon Monoxide, and Hydrogen, into a well-controlled and specifiable range of liquid hydrocarbons, which blend of hydrocarbons lends itself to further processing for the production of desired end products.
Although we focused our presentation herein on the use of Carbon Monoxide, as might be made separately via one technique or another from Carbon Dioxide, blended with Hydrogen, as might be extracted separately from Water, to form the mix of gases required by the hydrocarbon synthesis process of our subject herein, Bayer's "United States Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis", we remind you that, as seen for only one example in our report of:
West Virginia Coal Association | Pittsburgh 1942 Coal Gasification Utilizes CO2 | Research & Development; concerning: "United States Patent 2,302,156 - Process and Apparatus for the Production of Useful Fuel Gas; Date: November, 1942; Assignee: Koppers Company, Pittsburgh, PA; Abstract: This invention relates to the production of fuel gas or high heating power out of dusty of finely granular fuels, such as black or brown coal, or coke or semi-coke made therefrom, the fuel being converted at a high temperature with air (oxygen), steam and carbon dioxide whereby a gas is produced which is rich in hydrogen and carbon monoxide";
it has been known for a long time that such a blend of Carbon Monoxide and Hydrogen can also be efficiently produced together via the gasification, using Steam and Carbon Dioxide, of Coal.