Utah Improves Fischer-Tropsch Hydrocarbon Synthesis

United States Patent: 9011788

We've many times documented that Coal can, even in combination with renewable and carbon-recycling organic wastes, like sewage treatment plant sludge and products of agriculture, as for just one example seen in our report of:

Standard Oil Co-Gasifies Coal & Carbon-Recycling Biomass | Research & Development | News; concerning: "United States Patent 2,633,416 - Gasification of Carbonaceous Solids; 1953; Inventor: Edward Gornowski and Karl Nelson, NJ; Assignee: Standard Oil Development Company; Abstract: The present invention relates to the production of gases from non-gaseous carbonaceous materials and, more particularly, to the production of gas mixtures containing carbon monoxide and hydrogen ... from such solid carbonaceous materials as ... various coals (and) cellulosic materials";

be converted into a synthesis gas, or syngas, blend of "carbon monoxide and hydrogen" suitable, as seen and explained further in our report of:

French Government Coal + Biomass to CO2-free Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent Application 20140288195 - Processes for the Thermochemical Conversion of a Carbon-Based Feedstock to Synthesis Gas Containing Predominantly H2 and CO; 2014; Inventors: Pierre Castelli, et. al., France; Assignee: Commissariat A L'Energie Atomique Et Aux Energies Alternatives; Abstract: The invention relates to a novel process for the thermochemical conversion of a carbon-based feedstock to synthesis gas containing predominantly hydrogen (H2) and carbon monoxide (CO). ... Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas containing predominantly hydrogen (H2) and carbon monoxide (CO), comprising the following steps: (a) oxycombustion of the carbon-based feedstock to create a cogeneration of electricity and of heat; (b) high-temperature electrolysis (HTE) of water using at least the heat produced according to step (a); (c) reverse water gas shift (RWGS) reaction starting from the carbon dioxide (CO2) produced according to step (a) and the hydrogen (H2) produced according to step (b). ... Process for the thermochemical conversion of a carbon-based feedstock to synthesis gas ...  wherein the carbon monoxide (CO) and the hydrogen (H2) derived from the cleaning according to step (d) are injected as input products of a step (e) according to which a Fischer Tropsch (FT) synthesis is carried out to obtain a liquid fuel. ... The invention relates to a novel process for the thermochemical conversion of a carbon-based (carbonaceous) feedstock to synthesis gas containing predominantly hydrogen (H2) and carbon monoxide (CO), with a view to producing liquid (Fischer-Tropsch "FT" diesel, dimethyl ether "DME", methanol or gaseous (synthetic natural gas (SNG) fuels, or other synthetic chemicals ... . The main intended application of the invention is that for which the carbon-based feedstock is biomass (but) "carbon-based feedstock" designates any combustible material constituted of carbon-containing compounds (and, it) It may thus be biomass, in other words any inhomogeneous material of plant origin containing carbon, such as lignocellulosic biomass, forest or farming (straw) waste, which may be quasi-dry or soaked with water, such as household wastes. It may also be ... coal";

for use in a "Fischer Tropsch (FT) synthesis ... to obtain a liquid fuel", like "diesel", and/or even "synthetic natural gas". And, as further explained for one example in our report of:

Bayer Improves Fischer-Tropsch Hydrocarbon Synthesis | Research & Development | News; concerning: "United States Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis; 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. ... 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";

the Fischer-Tropsch hydrocarbon synthesis technology itself is being made increasingly sophisticated, with provisions being made to extract heat from the exothermic Fischer-Tropsch reaction, in order to control the mix, the composition, of the hydrocarbons being synthesized; to extend the catalyst life; and, to make the heat energy extracted from the exothermic chemical reactions available for use in other processes related to the overall system for converting unconventional resources, via an initial production of Carbon Monoxide and Hydrogen synthesis gas, into synthetic liquid petroleum-based fuels and substitute natural gas. 

Further, as we've seen now in a number of reports, as for one especially pertinent example:

Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Inventors: Joseph Hartvigsen, et. al., Utah; Assignee: Ceramatec, Inc., Salt Lake City; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell. Synthesis gas is also produced by the coelectrolysis of carbon dioxide and steam in a solid oxide fuel cell or solid oxide electrolytic cell. The synthesis gas produced may then be further processed and eventually converted into a liquid fuel suitable for transportation or other applications";

the technology is now available to make such valuable hydrocarbon synthesis gas blends of Carbon Monoxide and Hydrogen from nothing but water, H2O, i.e., "steam", and, as harvested from whatever convenient source, Carbon Dioxide.

In passing, note that the above Ceramatec CO2-to-syngas technology was, as seen for one example in:

More USDOE CO2 "Syntrolysis" | Research & Development | Newsconcerning: "Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas; Fifth International Fuel Cell Science, Engineering and Technology Conference; 2007; Idaho National Laboratory, USDOE; and Ceramatec, Inc., Utah; An experimental study has been completed to assess the performance of single-oxide electrolysis cells ... simultaneously electrolyzing steam and carbon dioxide for the direct production of syngas. Syngas, a mixture of hydrogen and carbon monoxide, can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes.";

developed by Ceramatec, in concert with the United States Department of Energy, specifically so that the Carbon Dioxide-derived "mixture of hydrogen and carbon monoxide" could, with apologies for the repetition, "be used for the production of synthetic liquid fuels via Fischer-Tropsch processes".

And, herein we see that Ceramatec has gone on to, like Bayer Corporation in our above-cited report concerning "United States Patent 8,557,880 - Multi-stage Adiabatic Method for Performing the Fischer-Tropsch Synthesis", improve the Fischer-Tropsch hydrocarbon synthesis process itself, to make better use of the "syngas" produced, via the process of their above-cited "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water", from H2O and Carbon Dioxide.

Comment follows excerpts from the initial link in this dispatch to:

"United States Patent 9,011,788 - Advanced Fischer Tropsch System

Advanced fischer tropsch system - Ceramatec, Inc

Patent US9011788 - Advanced fischer tropsch system - Google Patents

Date: April 21, 2015

Inventors: Joseph Hartvigsen, et. al., Utah and Idaho

Assignee: Ceramatec, Inc., Salt Lake City

(Note, that, as can be learned separately via:

http://www.netl.doe.gov/research/coal/project-information/proj?k=FE0023863;

Ceramatec has been contracted again by the USDOE and the USDOE's National Energy Technology Laboratories to further develop their technologies so that Coal, via combined gasification with biomass, and subsequent Fischer-Tropsch synthesis, can be converted into, specifically, liquid hydrocarbon jet fuel with, overall, lower CO2 emissions than jet fuel made conventionally from OPEC petroleum. One pertinent excerpt:

"Ceramatec intends to demonstrate the production of jet fuel from a coal and glycerol or other biomass. The project will integrate several unique technologies to produce a product that may be directly blended with jet fuel from petroleum based sources. The cost is anticipated to be competitive with jet fuel from petroleum, and generate approximately 30 percent less Greenhouse Gas (GHG) emissions compared to conventional petroleum-based jet fuel. Process modeling will be performed to determine the mix of coal and ... biomass to achieve the target emission reduction and cost. Successful completion of this project will provide the data required for design of a commercial facility capable of providing jet fuel meeting specification and establishing the ability to produce jet fuel from coal with reduced GHG emissions".)

Abstract: A Fischer Tropsch ("FT") unit that includes an FT tube that is packed with a catalyst. The catalyst is designed to catalyze an FT reaction to produce a hydrocarbon. An insert that is positioned within the FT tube. The insert comprises at least one cross-piece that contacts an inner surface of the FT tube and at least one cross-fin extending from the cross-piece. There may be a corresponding second cross-fin adjacent each cross-fin. Both the cross-fins and the second cross-fins may be disposed radially outwardly such that the edge of the cross-fins are closer to the inner surface of the FT tube than is the base of the cross-fins.

Claims: A Fischer Tropsch ("FT") unit comprising: an FT tube; an insert that is positioned within the FT tube, the insert comprising: at least one cross-piece that contacts an inner surface of the FT tube; and wherein each cross-piece comprises a plurality of cross-fins along the cross-piece and extending from the cross-piece, wherein each cross-fin positioned closer to the FT tube is longer than each cross-fin positioned closer to a center of the insert (and) wherein the three cross-pieces generally form a "snowflake" configuration. 

The FT unit ... wherein the end of each cross-piece comprises a pad, wherein each pad contacts the inner surface of the FT tube (and) wherein there is a corresponding second cross-fin that is positioned adjacent each cross-fin (and) wherein each cross-fin and each corresponding second cross-fin are disposed towards the inner surface of the FT tube. 

The FT unit ... wherein each cross-piece comprises two cross-fins and two corresponding second cross-fins (and) further comprising a thermocouple in communication with the insert (and) wherein the insert is made of aluminum. 

(Additional claims go on to specify optimal sizes and dimensions.)

The FT unit ... further comprising a heat removal media in communication with an outer surface of the FT tube (and) wherein the heat removal media comprises a cooling fluid (either) water or oil (and) further comprising means for controlling the temperature of the FT unit (and) wherein the FT unit is configured to operate at a temperature ... between about 210 C  and about 235 C (and otherwise as specified). 

An insert that is designed to be positioned within an Fischer Tropsch ("FT") reactor tube, the insert comprising: three cross-pieces arranged to have dihedral symmetry; a plurality of cross-fins along each cross-piece and extending from the cross-piece, wherein each cross-fin positioned closer to the FT tube is longer than each cross-fin positioned closer to a center to the insert, wherein each cross-fin extends radially outwardly from the cross-piece such that the edge of the cross-fin is closer to the inner surface of the FT reactor tube than the base of the cross-fin.

Background and Field: The present disclosure relates to devices and methods for more efficiently performing Fischer Tropsch ("FT") processing of a syngas stream. More specifically, the present disclosure relates to a device and method for FT processing with improved catalyst and temperature control for more efficient results. 

The Fischer Tropsch ("FT") process, which is sometimes called FT synthesis, is a chemical reaction used routinely in oil and gas processing. This process involves the conversion of carbon monoxide and hydrogen gas into a hydrocarbon chain and water.

Generally, a catalyst is used in this reaction. This FT process usually occurs at high temperatures and high pressures, such as, for example, at pressures of 150-300 psig and temperatures ranging from 200-300 C. (The input stream that is input into the FT reaction vessel is often called synthesis gas or "syngas").

The FT process will generally produce a mixture of liquid and gaseous hydrocarbons ... . In general, the liquid hydrocarbons (such as octane, hexane, and others hydrocarbons with carbon numbers greater than 5) tend to be more valuable than the gaseous products (such as methane, ethane, etc.) because these liquid products may be used in producing kerosene, diesel fuel and other desirable products. 

The FT process is highly exothermic ... . If the produced heat is not removed as part of the reaction conditions, the metallic catalyst can be damaged and the products generated will tend to be gases rather than the more valuable liquids and gases.

Summary and Description: An extruded aluminum (or other high heat conductive metal) fin is placed within a tubular Fischer Tropsch (FT) reactor. It is important that the catalyst bed in an FT reactor be maintained at an even temperature to maximize the production of the liquid (i.e., higher value) output from the FT reactor. The conduction of heat away from the center of the reactor catalyst bed will assist in maintaining an even temperature and allow control of the temperature within the desired range. 

To maintain the even bed temperature, a high heat conductive metal finned extrusion is included within the tubular fixed bed FT reactor. The extrusion would conduct heat from the reactor catalyst bed to the reactor walls and insure an improved temperature profile within the catalyst bed. The improved heat removal ability derived by including the fin within the catalyst bed also enables using much larger diameter reactors, thus reducing cost and increasing capacity. One embodiment of the finned extrusion involves a "snowflake" patterned extrusion within the tubular FT reactors embedded in a cooling block.

Fischer Tropsch (FT) processing is a method for the production of various hydrocarbons from the input of synthesis gas. It is a surface catalyzed carbon polymerization process that largely produces straight chain hydrocarbons ... . ... Maintaining the catalyst bed at an even temperature is important since higher bed temperatures tend to favor the formation of more of the gaseous (i.e. lower value) products while lower temperatures tend to favor production of waxes that are not easily transported by pipeline or directly usable as fuel. In other words, one of the purposes of this invention is to create a large tubular, fixed bed FT reactor and controlling the temperature of the catalyst bed within the reactor to prevent catalyst damage and improve yields in the liquid and wax range of FT products".

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So, whether made from Coal or, as in Ceramatec's own process of  "US Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water", Carbon Dioxide, "synthesis gas" can be efficiently converted into "liquid products" which then "may be used in producing kerosene (and) diesel fuel".

Further, the "wax range of" Ceramatec's "FT products", made from the syngas derived from Coal or CO2, can, as seen for one example in: 

USDOE Pays Mobil Oil to Refine CoalTL Wax | Research & Development | News; concerning: "United States Patent 4,684,756 - Process for Upgrading Wax from Fischer-Tropsch Synthesis; 1987; Assignee: 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";

be directly refined into "premium quality gasoline".

Clearly: We can convert our abundant United States Coal, our waste Biomass, and our freely-available natural resource of Carbon Dioxide into "synthesis gas"; and, that "syngas" can then be efficiently converted, via the process of our subject herein, "United States Patent 9,011,788 - Advanced Fischer Tropsch System", and follow-on processes like that of Mobil Oil's and the USDOE's "United States Patent 4,684,756 - Process for Upgrading Wax from Fischer-Tropsch Synthesis", into completely domestic, US jobs-creating, non-OPEC "diesel fuel" and "premium quality gasoline".

We know we have plenty of Coal in the USA, and some folks say we have too much Carbon Dioxide.

As herein, we have the technology.

All we're lacking, apparently, to set ourselves free from OPEC, and to create good-paying jobs for every United States citizen who might want one, is, first, the simple guts to publicly admit those facts, and, second, the straightforward sense of industry to get off our dead cans and make it happen.

As it is, it looks as if we'll all continue on in what tragically seems to have become the new American Way, where young single moms have to work double shifts at the local convenience store just to afford the gas to get back and forth to work in the first place; where fathers with good-paying jobs - in the Coal mining industry for example - have to constantly worry about and plan for layoffs and closures; and, where older parents have to worry about sending their young patriotic sons and daughters in uniform off to fight in yet another Persian Gulf oil war or, far worse, to mourn for those who have been sent to and lost in those wars.

We have the Coal and we have the Carbon Dioxide. We have the technology.

Do we, after all of this, have to find someone overseas to sell us the honesty, the courage and the will?