Because of the world's increasing demand for petroleum products, it has been desirable to find alternative hydrocarbon feedstock for fuel. For example, it is known to convert coal to liquid fuels using a family of processes known as coal liquefaction. Such processes are disclosed in, for example, U.S. Pat. No. 4,487,683, the disclosure of which is fully incorporated herein by reference. It is also known to upgrade liquid hydrocarbon to fuel-quality products. Such processes are disclosed in, for example, U.S. Pat. No. 7,022,505, the disclosure of which is fully incorporated herein by reference.
Many current liquefaction and hydrocarbon upgrading processes are practically and/or economically unable to meet the scale required for commercial production. Although it is desirable that the processing be done on a continuous basis, the system periodically needs to be stopped, shut down, and vacuumed to remove carbon deposits within the system. Accordingly, improved systems for converting and upgrading hydrocarbon fuel products are needed.
This document describes methods and systems that are directed to the problems described above.
In an embodiment, a method of operating a hydrocarbon material processing system includes feeding a hydrocarbon feedstock from a hydrocarbon feedstock source into a reaction tube positioned within an opening of a waveguide, feeding a process gas from a process gas source into the reaction tube, receiving microwaves in the waveguide from a microwave generator, propagating energy from the waveguide in the reaction tube to cause the feedstock and process gas to react and form into a product stream comprising a fuel product. The method also includes periodically delivering a cleaning gas into the reaction tube, without stopping the propagation of the energy and without pausing the feeding of the hydrocarbon feedstock and the process gas into the reaction tube.
Optionally, the method may also include forming a plasma from the cleaning gas, and maintaining the plasma for a period of time within the tube sufficient to burn off carbon residue from an inner sidewall of the reaction tube.
The method may further include vacuuming or flushing the carbon residue from the reaction tube, and resuming the feeding of the hydrocarbon feedstock and the process gas into the reaction tube after the vacuuming or flushing.
In various embodiments, the cleaning gas may include oxygen, argon, steam, and mixtures thereof. In certain other embodiments, the hydrocarbon feedstock may include coal, bitumen, oil sands, tar sands, oil shale, petroleum resids, asphaltenes, pre-asphaltenes or other vitrinite and kerogen-containing materials and fractions or derivatives thereof, in each case mixed with catalyst. The process gas source may include, for example, helium, argon, krypton, neon, xenon, methane, propane, butane, ethane, acetylene, propylene, butylene, ethylene, carbon monoxide, carbon dioxide, water vapor, hydrogen, and nitrogen.
The method may further include extracting the cleaning gas from the product stream.
In certain embodiments, the method may include synchronizing the pausing of the feeding of the hydrocarbon feedstock and the process gas into the reaction tube with a duty cycle of the microwave generator. In alternate embodiments, the method may include determining whether the reaction tube is coated with an unacceptable amount of deposits, and delivering the cleaning gas if such amount of deposits is determined to be present.
In an alternate embodiment, a system for processing hydrocarbon materials includes: a hydrocarbon feedstock source, wherein the hydrocarbon feedstock source; a process gas source; a cleaning gas source; a waveguide configured to receive microwaves from a microwave generator and propagating energy in a reaction tube. When the hydrocarbon feedstock from the feedstock source and process gas from the process gas source are fed into the reaction tube, and energy are propagated in the reaction tube, the feedstock and process gas react and form into a product stream. Additionally, the cleaning gas source is configured to periodically, without stopping the propagation of the energy and without pausing the feeding of the hydrocarbon feedstock and the process gas into the reaction tube, deliver a cleaning gas into the reaction tube.
In an alternate embodiment, a system for processing hydrocarbon materials includes: a hydrocarbon feedstock source, wherein the hydrocarbon feedstock source; a process gas source; a cleaning gas source; a coaxial transmitter configured to receive microwaves from a microwave generator and propagating energy in a reaction chamber. The coaxial transmitter further includes an antenna. When the hydrocarbon feedstock from the feedstock source and process gas from the process gas source are fed into the reaction chamber, and energy are propagated in the reaction chamber, the feedstock and process gas react and form into a product stream. Additionally, the cleaning gas source is configured to periodically, without stopping the propagation of the energy and without pausing the feeding of the hydrocarbon feedstock and the process gas into the reaction chamber, deliver a cleaning gas into the reaction chamber.
As used in this document, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. As used in this document, the term “comprising” means “including, but not limited to.”
This document describes systems for processing hydrocarbon materials, such as through liquefaction or through upgrading into a fuel-grade material or intermediate material. The processing may include altering the arrangement of carbon and hydrogen atoms and/or removal of heteroatoms such as sulphur, nitrogen, and oxygen. The examples described below will use coal as an example of the material to be processed. However, the system may be used to process various naturally occurring hydrocarbon-based materials such as fossil hydrocarbons and biomass. Examples of fossil hydrocarbons may include coal, bitumen, oil sands, tar sands, oil shale, resins, petroleum resids, asphaltenes, pre-asphaltenes and other kerogen-containing materials and fractions or derivatives thereof. The system may also be used to process hydrocarbon gases such as natural gas, methane, propane, ethylene, and other hydrocarbon compounds, and their mixtures, which are normally in a gaseous state of matter at room temperature and atmospheric pressure. The system also may be used to process other hydrocarbon-based materials such as municipal waste, sludge, or other carbon-rich materials.
A flow of process gas from a process gas source 107 may be injected or otherwise delivered to the hydrocarbon feedstock before, after, or as it enters the reaction chamber 101. The process gas will react with the feedstock in the reaction chamber to yield the final product. The process gas may include, for example, hydrogen, methane or other compounds of hydrogen and carbon. Multiple process gas sources 107 may be available so that a combination of process gases is directed into the reaction chamber. An example process gas combination includes an inert gas such as argon, helium, krypton, neon or xenon. The process gas also may include carbon monoxide (CO), carbon dioxide (CO2), water vapor (H2O), methane (CH4), hydrocarbon gases (CnH2n+2, CnHn, CnHn, where n=2 through 6), and hydrogen (H2) gases.
The system includes a microwave generator 111, along with a waveguide 113 that directs radiation from the generator 111 into the chamber 101. The reaction chamber may include a reaction tube 103 made of quartz, borosilicate glass, alumina, sapphire, or another suitable dielectric material that enhances reaction of materials within the tube when microwave radiation is directed into the chamber 101. In some embodiments, the reaction tube 103 is made of similar conductive material as chamber 101 and may form the inner wall of the chamber 101. When provided at a suitable intensity and time duration, the microwave radiation forms a standing wave and resonates within the chamber 101, and causes a plasma to form within the reaction tube 103. The reaction may include processes such as chemical vapor deposition, gasification, thermal pyrolysis, radical reaction chemistry, ion reactions, microwave-enhanced reactions, and/or ion sputtering. The result of the reaction may be a product stream comprising a plurality of products characterized by different chemical and/or physical properties than the original reactant, as a result of rearrangement of atoms within the molecules, change in number of atoms per molecule, or number of molecules present, that may be delivered to one or more product storage vessels 109.
In certain embodiments, the reaction tube 103 may not be present, and the waveguide 113 may be connected to the chamber 101 via an entry port (not shown here). In certain other embodiments, the entry port may include a window to prevent the plasma and other chamber gases from entering the waveguide. The window may be made of quartz, borosilicate glass, alumina, sapphire, or another suitable dielectric material.
The reaction may occur at relatively low bulk process temperatures and pressures. For example, conversion and upgrading may occur with average reaction chamber pressures between 0.1 and 10 atmospheres, temperatures between −182° C. and 200° C. (the average reaction chamber temperature) and between 200° C. and 1600° C. (localized plasma temperature), and residence times between 0.001 and 600 seconds. Other parameters are possible.
Any of the features described above may be incorporated into an alternate embodiment uses a waveguide with the reaction tube. Examples of a waveguide may include a waveguide surfatron, a surfatron, or a surfaguide. With such a system, the microwaves are launched by a wave launcher having a circular gap. As shown in
For example,
Optionally, the reaction tube may be the coaxial waveguide component 412 along with a larger chamber 403. If so, the coaxial waveguide component may be considered a reaction tube in which a portion of the plasma begins to form.
The tube or chamber 403 is connected to a first end of the coaxial waveguide component 412, and a second end of the coaxial waveguide component 412 is connected to the lateral waveguide component 411. Here, “connected to” again may include a physical connection, or a structure in which one element is received into an opening of the other element. The energy may cause the formation of a plasma or other generation of electrical or magnetic discharges within the reaction tube 403, along with activation or ionization of process gas, thus converting or upgrading the feedstock for delivery into a product storage facility 409. As shown, the tube/chamber 403 has a wider portion and a tapered portion, so that the tapered portion is connected to the coaxial waveguide component 412. The waveguide surfatron may include good tuning capabilities of a surfatron and the high power capabilities of a sufaguide, and may be included in a large scale reaction chamber.
Example energy frequencies that may be applied from the microwave generator(s) may include those in the range of 10 Hz-10 GHz, or any frequencies that may promote ionization of process gas. Example processing times may be less than a second (on order of 100 ms), but can have a 0.001-600 second range, as well as other ranges. The frequency and intensity of the energy, the specific composition of the process gases introduced and the processing time may be sufficient to process the feedstock into a final product, such as synthetic crude oil with hydrocarbon fraction having at least one of the following properties: low molecular weight, low boiling point, and low percentage of aromatics. When energy is applied in the reaction chamber, process gas passing through the reaction chamber is ionized and activated as result of the microwave or electric discharge. Process gas may also be heated. The particles of coal or other hydrocarbon material are contacted by with discharges and heated as they pass through the reactor while in contact with the microwave or electric discharge. The coal or other hydrocarbon may additionally be heated through dielectric heating, as its structure may change after a certain temperature and its conductive and dielectric properties may change. In particular, when the hydrocarbon material is rapidly heated, the following may occur: (1) volatile compounds and/or moisture present in the particles are rapidly vaporized and may cause rapid (explosive) disintegration of the particles; (2) these vaporized compounds, which may vary in molecular weight, may react with radicals and ions in the activated, excited and/or ionized process gas; (3) large hydrocarbon molecule(s) (macromolecules) start breaking apart, and the broken-off compounds varying in molecular weight are vaporized and capped by hydrogen and methyl radicals (by-products of process gas ionization; and (4) some macromolecules may not be broken up or only partially broken up, resulting in partially reacted or unreacted hydrocarbon particles. In some embodiments, bulk temperatures (gas stream temperatures) on the exit from reactor generally do not exceed 200-300° C., although other and higher temperatures are possible.
During operation, to maximize production, it may be desirable to provide the flow of feedstock and process gas on a continuous basis. However, because of the nature of the reaction (which includes chemical vapor deposition), carbon and other process materials may become deposited on the inner walls of the reaction tube structure. This may form a film that may absorb microwave radiation, reducing its intensity inside the reaction tube and altering the microwave field distribution, and disrupting the standing wave necessary to sustain plasma and the reactions within. Accordingly, the system may need to be periodically taken offline for maintenance so that deposited materials may be vacuumed, flushed within an inert gas or process gas, scrubbed or otherwise cleaned from the sidewalls of the tube.
To avoid or reduce the need for such process interruptions, in one method of operating any of the systems described above, the hydrocarbon source and some or all of the process gas sources may be turned off or closed off (such as by the closing of one or more valves), and instead a flow of a cleaning gas such as oxygen or oxygen-containing gas mixture may be run through the system. When the microwave energy interacts with the oxygen or oxygen-containing gas in the tube, a plasma forms that will burn the film from the tube. Other gases such as argon or other inert gases, may be mixed with the oxygen to enhance plasma generation. The plasma may be maintained in the reaction tube for a period of time that is sufficient to burn off at least a part of carbon residue film from the reaction tube sidewalls. When the burn-off process is complete, the oxygen source may be closed and the process gas and hydrocarbon feedstock sources may be re-opened. The burn-off process may involve the following reactions:
2CO+O22CO2
C+O2CO2
Optionally, referring to
In certain embodiments, the cleaning gas containing oxygen may be extracted from the main product stream, and recycled into the system during the cleaning cycle. This may occur via an extraction unit such as a vacuum (as described above at 222), filter or other device.
In an embodiment, the carbon deposits in the system may react with oxygen in the presence of plasma to form a cleaning product stream which may include CO, CO2 and H2. In certain embodiments, all or a part of the cleaning may be directed towards and mixed with the product gas stream, and may be processed downstream with other products. In an embodiment, the ratio of CO to CO2 may depend on the concentration of oxygen in the input cleaning gas.
Alternatively and/or additionally, the cleaning gas may include steam or steam-containing gas mixture to remove the carbon deposits through steam reforming. Carbon in the presence of plasma may react with water in the steam to form a cleaning product stream, which may include CO2 and H2. In certain embodiments, the cleaning gas containing steam may be extracted from the main product stream by an extraction unit such as a vacuum, filter or other device, and recycled into the system during the cleaning cycle. The reforming process may involve the following reactions:
CO+H2OCO2+H2
C+2H2OCO2+2H2
In an alternate embodiment, the system may include a controller that controls various functions of the system. For example, the controller may regulate the delivery of the cleaning gas, instead of feedstock, into the chamber on a time cycle that corresponds to a duty cycle of the microwave generator. Thus, based on the generator's cycle, the controller may cause the system to alternate between running cleaning gas through the system and running feedstock through the system. The automation of this cycle may be implemented by a controller that includes a processor and computer-readable memory having programming instructions that, when executed, instruct the processor to generate and transmit appropriate signals to open and close system valves, or otherwise start and stop various sources, to implement the processes described above. Other options include a system on a chip, a programmed device such as a field programmable gate array, or other device that is configured to receive one or more parameters and generate one or more commands to various components of the system.
In an alternate embodiment, the delivery of the cleaning gas, instead of feedstock, into the chamber may be timed to correspond to making a determination whether the reaction tube is coated with an unacceptable amount of carbon deposits. The unacceptable amount of carbon deposits may be determined based on a predetermined decrease in the quantity or quality of the fuel products.
The above-disclosed features and functions, as well as alternatives, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations or improvements may be made by those skilled in the art, each of which is also intended to be encompassed by the disclosed embodiments.
This patent document claims priority to U.S. Provisional Patent Application No. 61/867,916, filed Aug. 20, 2013. The disclosure of the priority application is fully incorporated by reference. This patent document is also related to U.S. patent application Ser. Nos. 14/464,260 and 14/464,284, filed on the same date as this application.
Number | Date | Country | |
---|---|---|---|
61867916 | Aug 2013 | US |