The invention is in the field of the chemical conversion of materials using plasma.
Synthesis gas is a gaseous mixture that contains various amounts of carbon monoxide and hydrogen. Synthesis gas, or syngas, is typically generated by the gasification of a carbon containing fuel into a gaseous product. There may be several uses for syngas, including the production of energy through combustion of the syngas as well as using the syngas as an intermediate for the production of chemicals such as synthetic petroleum.
Current methods of production of syngas may include partial oxidation, steam reforming, “dry” reforming with CO2, and autothermal reforming. These and other processes reform the hydrocarbon to produce syngas. However, current methods of syngas production from low quality hydrocarbons (e.g. bio-mass) typically require relatively large amounts of energy input to maintain the process at a steady state. Low quality hydrocarbons are those that have a relatively low heat calorific value. Thus, the energy released by the partial oxidation typically is insufficient to support the process. Further, a significant portion of the energy that is produced is typically lost because of design limitations. Partial oxidation of high quality hydrocarbons, e.g. liquid fuels, is also a process that difficult to control and typically results in soot formation in high temperature flame zones.
There is a need for an improved way to efficiently reform hydrocarbon fuel into syngas.
In some embodiments, the invention concerns the use of a two stage process that uses non-equilibrium or non-thermal plasma to convert liquid, gaseous or solid hydrocarbon fuel into syngas. Without being bound by any theory of operation, it is believed that the plasma acts as a catalyst, which may reduce the energy input required to stimulate the process.
In some embodiments, the invention concerns a two stage process using non-equilibrium plasma as a catalyst to oxidize hydrocarbons. In a first stage, a first reactor is used having a reaction volume optimized to partially oxidize at least a portion of the incoming fuel. In some embodiments, the first reactor may be a plasmatron device. The partially oxidized fuel is then inputted into a second reactor having a larger reaction volume. The fuel is oxidized to create syngas. In some embodiments, the overall oxygen to carbon (0/C) ratio from both reactors is about 1. In still further embodiments, the ratio in the smaller first reactor may be less than 1 while the ratio in the second reactor may be more than 1. Products of the second partial oxidation stage may comprise synthesis gas—H2 and CO (with N2 admixture in the case of air use for partial oxidation), and remaining light hydrocarbons such as methane (CH4), acetylene (C2H2), ethylene (C2H4), and ethane (C2H6).
In some embodiments, the input stream may be comprised of various components, including gasoline, diesel, natural gas, biomass and jet propellant such as JP5 or JP8 fuel. In some embodiments, the input stream may also be comprised of an oxidizing gas such as air, oxygen or a mixture of gases having oxygen and steam, and/or carbon dioxide
In one exemplary and non-limiting example of the present subject matter, a process is disclosed for reforming liquid hydrocarbon fuel. In first stage reactor, liquid hydrocarbon fuel and an oxidizing gas is inputted and partially reformed using non-thermal plasma. The partially reformed fuel is inputted into a second reactor with additional oxidizing gas and is reformed into synthesis gas. In one example, the second reactor flow pattern may be characterized as a reverse vortex flow pattern. In another example, the first reactor may also have a flow pattern that is characterized as a reverse vortex flow pattern.
In another embodiment, the remaining light hydrocarbons such as methane (CH4), acetylene (C2H2), ethylene (C2H4), and ethane (C2H6) may be further reformed in a solid oxide fuel cell to produce additional synthesis gas.
These and other features of the subject matter are described below.
The foregoing summary, as well as the following detailed description of the subject matter is better understood when read in conjunction with the appended drawings. For the purposes of illustration, there are shown in the drawings exemplary embodiments; however, these embodiments are not limited to the specific methods and instrumentalities disclosed. In the drawings:
Certain specific details are set forth in the following description and figures to provide a thorough understanding of various embodiments of the subject matter. Certain well-known details often associated with computing and software technology are not set forth in the following disclosure to avoid unnecessarily obscuring the various embodiments of the subject matter. Further, those of ordinary skill in the relevant art will understand that they can practice other embodiments of the subject matter without one or more of the details described below. Finally, while various methods are described with reference to steps and sequences in the following disclosure, the description as such is for providing a clear implementation of embodiments of the subject matter, and the steps and sequences of steps should not be taken as required to practice this subject matter.
A reactor configured to reform liquid, gaseous or solid hydrocarbon fuel and a process is provided for the production of synthesis gas. The reactor is configured to stimulate the process of partial oxidation or autothermal reforming through a plasma. In one configuration, a non-equilibrium or non-thermal plasma is used.
Partial oxidation process has two primary stages: an exothermic stage of combustion and a slow endothermic stage of interaction of CO2 and H2O with gaseous hydrocarbons. The reaction rate of the first stage may vary depending upon the state of the reacting hydrocarbon. Thus, the residence time of the reactants in the reactor may be varied to maintain a consistent degree of conversion. On the second stage to increase H2 production the steam could be introduced. Partial oxidation and steam reforming reactions could be balanced to provide overall energy neutrality while also taking into account heat losses.
The present invention may be understood more readily by reference to the following detailed description taken in connection with the accompanying figures and examples, which form a part of this disclosure. It is to be understood that this invention is not limited to the specific devices, methods, applications, conditions or parameters described and/or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of the claimed invention.
Also, as used in the specification including the appended claims, the singular forms “a,” “an,” and “the” include the plural, and reference to a particular numerical value includes at least that particular value, unless the context clearly dictates otherwise. The term “plurality”, as used herein, means more than one. When a range of values is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. All ranges are inclusive and combinable.
It is to be appreciated that certain features of the invention which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, references to values stated in ranges include each and every value within that range.
The term “gliding arc” is used in the present subject matter as is understood by those skilled in the art. It should be understood that a plasma discharge in the present subject matter may be generated in various ways, for example, glow discharge. In a reactor implementing a glow discharge, a cathode current may be controlled mostly by the secondary electron emission, as occurs in glow discharge, instead of thermionic emission, as occurs in electrical arcs.
In the present disclosed subject matter, a gliding arc discharge plasma may be used in two reactors to cause the partial oxidation of a hydrocarbon. For example, the first stage, or first reactor, may be used to evaporate some or all of the liquid fuel using a plasma and plasma supported flame while the chemical process of oxidation (or ignition) of the evaporated liquid may be initiated in the second reactor. A gliding arc discharge reactor is configured to cause a high-voltage electrical discharge to glide over the surface of one or more electrodes. The properties of the plasma discharge may be adjusted depending upon the configuration of the reactor. The reactor of the present example may be further configured to utilize a reverse-vortex flow pattern. Reverse vortex flow means that the vortex flow has axial motion initially from a swirl generator to a “closed” end of reaction chamber.
Referring now to the drawings, wherein like reference numerals designate corresponding structure throughout the views, and referring in particular to
In the present embodiment, nozzles 14a and 14b may be tangential nozzles that introduce input fluid 2 into reaction chamber 12 tangentially. This present embodiment is for illustrative purposes only, as the rotation may be caused by other means, such as baffles inside of reaction chamber 12. Further, in some embodiments, input fluid 2 may be introduced into reaction chamber 12 at or near sonic velocity having mostly the tangential component of the velocity vector. Input fluid 2, in the present example, may be an input fluid comprising solid hydrocarbons.
It should also be understood that, although the reactor 10 of
In one embodiment, input fluid 2 may be an input stream of air or other gas and hydrocarbons. It should be understood that input fluid 2 may also have substances or compounds other than air and hydrocarbons. The present subject matter is not limited to input fluid 2 being a pure fluid input, but rather, discusses the partial oxidation of the hydrocarbon component of input fluid 2.
Referring back to
In the present embodiment, reactor 10 has input fluid 2 and two output streams, output stream 22 and output stream 24. Output stream 22 is preferably stream comprising synthesis gas, i.e. hydrogen and carbon monoxide, as well as other gases such as nitrogen if air is input into the reactor. Depending upon the reactions within reactor 10, output stream 24 may be composed of solid reaction products such as ash. It should be understood that output streams 22 and 24 may not be pure but may contain other compounds because of impurities in input fluid 2 or incomplete oxidation and/or separation of the solid reaction products from the gaseous reaction products in the chamber. For example, in output stream 22, ash may be present that may require the installation of one or more filters further downstream.
Input fluid 2 is introduced to reaction chamber 12 via nozzles 14a, 14b, the outputs of which are preferably oriented tangential relative to wall 13 of reaction chamber 12, as shown by
By introducing input fluid 2 in this manner, as discussed above, a rotational force is imparted upon the fluids in reaction chamber 12, thus causing a rotation of the fluids in reaction chamber 12 in a clockwise direction in this embodiment. Thus, the velocity at which input fluid 2 enters reaction chamber 12 effects the rotational speed of the contents in reaction chamber 12. It should be noted that the input direction may be in a direction reverse to that shown in
Referring back to
Referring back to
The diameter of opening 32 may also be configured to establish, or prevent, a recirculation zone from forming. Reactor 10 may be configured to provide a way in which relatively hot fluids flowing from plasma region 40 may exchange a portion of their heat with fluids flowing to plasma region 40. For example, exemplary fluids 38a-c, which are flowing generally towards plasma region 40 receive heat from exemplary fluid 42a, which is flowing from plasma region 40. Exemplary fluid 42a, after exchanging heat with exemplary fluids 38a-c, may than flow back to plasma region 40, as shown by exemplary fluid 42b. Thus, a portion of the reaction heat generated in plasma region 40 and a portion of fluids in reaction chamber 12 recirculate within reactor 10. In one embodiment, if a recirculation zone is desired, the diameter of opening 32 in flange 30 may be approximately 10% up to 75% of the diameter of reaction chamber 12.
As discussed above, reverse vortex flow as used herein means that the vortex flow has axial motion initially caused by nozzles 14a and 14b along wall 13 of the chamber and then the flow turns back and moves along the axis to the “open” end of the chamber towards opening 32. An example in nature of this flow pattern may be similar to the flow inside a dust separation cyclone. Input fluid 2 travels in a circular motion, traveling in a downward and inward direction towards plasma region 40, as shown by exemplary fluids 38a-c.
A reverse vortex flow in reaction chamber 12 causes the contents of reactor 10 in reaction chamber 12 to rotate around plasma region 40, while output stream 22 travels in a direction upwards from the bottom of reactor 10 to opening 32. Along with other benefits that may not be explicitly disclosed herein, the rotation may provide necessary time for the heating of the contents flowing to and in the relatively hot plasma region 40 as the contents move downwardly around plasma region 40. Another benefit of the rotation may be that the reverse vortex flow may increase the residence time of reactants and products inside reaction chamber 12. A still further benefit of the rotation may be that the heat generated as a result of a reaction in plasma region 40 may be insulated from the walls of the reactor, thus reducing the insulating requirements of reactor 10 as well as reducing heat loss, and thus, possibly increasing efficiency.
A vortex flow, such as the reverse-vortex flow described in
Plasmatrons are electrical heating devices that take advantage of the finite conductivity of gases at very elevated temperatures. At these temperatures, the gas is partially ionized. Plasmatrons provide highly controllable electrical heating of this ionized gas. The high temperatures can be used to reform a wide range of hydrocarbon fuels, and particularly heavy hydrocarbons into hydrogen, carbon monoxide and a small amount of methane without the use of a catalyst. One exemplary use of a plasmatron would be to boost the temperature and kinetic actions in a reformer, resulting in hydrogen-rich gas production throughout a wide dynamic range.
The boosting of the conversion process would occur as a result of the creation of a small, very high temperature region (2000-5000 K) where radicals are produced and as a result of increasing the average temperature in an extended region. The additional heating provided by the plasmatron would serve to ensure a sufficiently high number of chemically reactive species, ionization states, and temperatures for the partial oxidation or other reforming reaction to occur with negligible soot production and a high conversion of hydrocarbon fuel into hydrogen rich gas. The effective conversion of JP8 or diesel fuel is aided by both the high peak temperature in the plasma and the high turbulence created by the reverse vortex flow.
In some configurations, plasmatrons may be able provide a number of advantages over conventional reformers. For example, a plasmatron using plasma may be catalyst-free. A plasmatron using plasma may not require any catalysts or water for its operation. That leads to higher reliability, zero maintenance (no parts to replace) and simple low-cost design. A plasmatron using plasma may be insensitive to sulfur or carbon poisoning. A plasmatron using plasma may be fuel-independent. In other words, the same hardware can reform both liquid (such as JP8, diesel, gasoline and biofuel) and various gaseous fuels. Depending upon its size and electrical configuration, a plasmatron using plasma may allow for a faster start-up. For example, some plasmatrons requires less than five seconds to achieve 90% of its output capacity. The first 15% of H2 yield is produced in less than two seconds. It offers quick transient response when needed. A plasmatron using plasma may be capable of “freeze-start” and are typically designed for unlimited “start-stop” cycles.
In
While the embodiments have been described in connection with the preferred embodiments of the various figures, it is to be understood that other similar embodiments may be used or modifications and additions may be made to the described embodiment for performing the same function without deviating therefrom. Therefore, the disclosed embodiments should not be limited to any single embodiment but rather should be construed in breadth and scope in accordance with the appended claims.
This application claims the benefit of U.S. Patent Application Ser. No. 61/317,530, filed Mar. 25, 2010, which is incorporated by reference herein in its entirety.
This invention was made with government support under contract W56HZV-07-C-0577 awarded by the United States Army. The government has certain rights in this invention.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US11/25386 | 2/18/2011 | WO | 00 | 10/3/2013 |
Number | Date | Country | |
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61317530 | Mar 2010 | US |