This disclosure pertains generally to plasma reactors and more particularly to a vertically oriented plasma reactor.
Plasma activation of biochar material was disclosed in U.S. Pat. No. 9,754,733 entitled “Method for Plasma Activation of Biochar Material” issued to Fan (one of the co-inventors of the present application) on Sep. 5, 2017. This patent is incorporated by reference herein. While this patent is a significant advance in the industry, further improvements are now desirable.
In accordance with the present invention, a vertically oriented plasma reactor is provided. In another aspect, a plasma reactor includes a vertically elongated vacuum chamber, a wall internally projecting within a middle section of the housing, magnets, electrodes and a radio frequency source. A further aspect employs a workpiece-entry port and an opposite workpiece-exit port, with one located adjacent a top end and the other adjacent a bottom end of a vertically elongated reactor housing or vacuum chamber. Yet another aspect employs a moving or falling-bed plasma reactor for use in activating biochar material.
A further aspect uses a slide or auger which spirals around a central elongated axis along which a workpiece material, preferably biochar, travels during plasma activation. An additional aspect employs a falling bed plasma reactor including a central rod and an outer electrode, one of which is coupled to a radio frequency source and the other of which is grounded such that a primary middle vector of an internal magnetic field is generally perpendicular to an electric field within the reactor. Another aspect uses a series of overlapping and oppositely projecting baffles which create a generally serpentine flow path for a workpiece material, which is preferably biochar. A method of activating a biochar material moving in a primarily vertical direction while between offset baffles or along a spiral wall, is additionally disclosed.
The present reactor is advantageous over prior devices. For example, the present reactor can more efficiently process a higher quantity of biochar in a faster manner than can conventional horizontally oriented devices. Furthermore, some versions of the vertical arrangement of the present reactor employ gravity feeding to optimize continuous workpiece feeding within the radio frequency and plasma activation area. Some versions of the present vertically oriented plasma reactor do not require moving mechanical components, such as conventional conveyors or air blowers, within the vacuum chamber, thereby reducing complexity, cost and maintenance. Moreover, the present reactor takes up less floor space in a manufacturing factory. Additional advantages and features will be disclosed in the following description and claims as well as in the appended drawings.
Biomass, as can be obtained from decomposed cornstalks, wood or other biodegradable materials, is manufactured into biochar through a manufacturing process including pyrolysis. Pyrolysis is a thermochemical decomposition of the biomass at elevated temperatures in the absence of oxygen. The biochar usually has pores with sizes of 2-8 μm and wall thicknesses of approximated 1 μm. The biochar must therefore be activated to create activated biochar. Activation creates nanostructures with a high surface energy necessary for efficient ionic attraction and/or impurity trapping. Plasma is employed for the activation process and advantageously creates nano-porous morphology while also improving a distribution of different pore sizes which achieves a high specific capacitance. For example, plasma activated biochar includes significantly more mesopores compared with chemically activated biochar, which advantageously increases adsorption and/or ion transportation thereby leading to lower impedance and higher specific capacitance.
A first embodiment of a magnetic field enhanced plasma reactor 21 is illustrated in
A gas supply cylinder or tank 41 is coupled to an end of vacuum chamber 23 at either ports 43 or 45 through a mass flow controller, and a vacuum pump 47 is coupled to at least one of ports 49 and 51. A reactive gas or mixture of reactive gases flows from gas tank 41 into vacuum chamber 23 at a vacuum pressure lower than nominal ambient atmospheric pressure at sea level. Examples of such reactive gases include oxygen, hydrogen, nitrogen, argon or other inert gases, or mixtures thereof, optionally including carbon, methane, silane or metalorganic gases. Oxygen is preferably employed. It is noteworthy that low gas pressures are employed, preferably ten milliTorr to fifty milliTorr, by way of nonlimiting example.
A slide or auger 71 has a helical upper flight or wall 73 spiraling about a central post 75. Wall 73 has a continuous surface which is offset angled in a generally oblique angle from both vertical and horizontal directions 77 and 79, respectively. The offset pitch angle is between 0° and 90° and the slope angle is between 0° and 90°. Slide/auger 71 and post 75 are inwardly spaced from the cylindrically shaped vacuum chamber 23, and are retained thereto by brackets 78. If slide/auger 71 rotates relative to the stationary vacuum chamber in one construction, then the slide or auger are rotated therein via an electromagnetic or fluid powered actuator 81 and connected transmission, such as a chain and sprocket, belt and pulley, gears, or the like. But if slide 71 is stationary, then it is fixedly secured within vacuum chamber 23 and relies upon gravity to move the workpiece material in a primarily vertical and downward direction (with a helical vector), although the slide may optionally be mechanically vibrated although some of the preferred benefits may not be achieved.
In this exemplary embodiment, a feeding hopper 101 is mounted to a top end of vacuum chamber 23 above a central plasma reactor section 103. Biochar 33 is stored in hopper 101 and the desired volume is automatically dropped onto an upper end of slide 71 from a flow restricting feeding inlet 105 advantageously using gravity. A discharge section 107 is located adjacent a bottom end of plasma reactor section 103.
Activated biochar 33 falls from a lower end of slide 71 into discharge section 107, with the assistance of gravity, where it is collected and temporarily stored. A discharge valve 109 and outlet 111 allow biochar 33 to exit reactor 21. A pressure gauge 113 may be employed to monitor and control the flow of the process gas within vacuum chamber 23. Brackets, legs or other mounting structures secure plasma reactor 21 to a factory floor.
As best observed in
Static and permanent magnets 141 are coupled or mounted adjacent to, or more preferably, outside of the internal vacuum cavity but inside an optional protective and cylindrical exterior casing 143 defining reactor 21. Each permanent magnet 141 is preferably of a large ring or annular shape with a central opening 145 therethrough. An exemplary permanent magnet material is NdFeB, grade MGO 42, with a central axial direction essentially coaxially aligned with vertical direction 77. A magnetic induction field vector B flows from one magnet 141 to the other, a majority middle segment of which is generally parallel with vertical direction 77, albeit in a slightly curved or arcuate path therebetween. In this embodiment, the majority middle segment of magnetic field vector B primarily flows in a direction generally perpendicular to a primary majority direction of RF electrical field vector E, and certainly in an offset angular direction therefrom.
The present magnetic field beneficially confines high energy electrons e (see
A pre-heater is optionally employed to heat the biochar above room temperature but less than 500° C. The pre-heater may be adjacent the vacuum chamber or remote therefrom.
Reference should now be made to
Reference should now be made to
A left set of baffles 371 and a right set of baffles 372 are stationarily mounted to an inside surface 374 of vacuum chamber 323. Each baffle 371 and 372 includes an upper wall surface 373 which is somewhat obliquely offset angled from the vertical and horizontal directions; preferably 30°-80° from horizontal. In
The configuration of
The
Reference should now be made to another embodiment illustrated in
With all of these stationary baffles of
Regardless, it is alternately envisioned that a greater or lesser quantity of baffles or spiraling flights may be employed depending on the quantity of biochar to be processed, the RF and magnetic strength, and whether supplemental heating is employed or not. Moreover, alternate workpiece materials may be processed within any of the presently disclosed embodiments. These alternate workpiece materials include catalyst impregnation of solids in heterogeneous chemical gas space reactions. These alternate workpiece materials may include liquid-gas reactions in an aerosol field primarily in a non-baffled configuration. It is also envisioned that multiple plasma reactor sections 103 and/or 303 can be stacked upon each other for any of the embodiments.
While various embodiments have been disclosed, other variations are possible. For example, the permanent magnets may be replaced by helical coils [on] of wires, thereby creating inductive coil magnets. The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. It is alternately envisioned that the dependent claims are all multiply dependent on each other in some aspects of the present application. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope and spirit of the present invention.
This application is a 371 U.S. National Phase entry of International Application No. PCT/US2019/041355, filed on Jul. 11, 2019, which claims the benefit of U.S. Provisional Patent Application No. 62/696,562, filed on Jul. 11, 2018, which are incorporated by reference herein.
This invention was made with government support under 1700785, 1700787 and 1724941, awarded by the National Science Foundation. The government has certain rights in the invention.
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/US2019/041355 | 7/11/2019 | WO |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2020/014448 | 1/16/2020 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
4892633 | Welty | Jan 1990 | A |
5026466 | Wesemeyer et al. | Jun 1991 | A |
5032202 | Tsai et al. | Jul 1991 | A |
5246532 | Ishida | Sep 1993 | A |
5346579 | Cook et al. | Sep 1994 | A |
5380420 | Tsuji | Jan 1995 | A |
5415754 | Manley | May 1995 | A |
5505780 | Dalvie et al. | Apr 1996 | A |
5731046 | Mistry et al. | Mar 1998 | A |
5972185 | Hendricks et al. | Oct 1999 | A |
5976308 | Fairbairn et al. | Nov 1999 | A |
5988103 | Fetherston et al. | Nov 1999 | A |
6740212 | Fan et al. | May 2004 | B2 |
7879203 | Weaver et al. | Feb 2011 | B2 |
8316797 | Asmussen et al. | Nov 2012 | B2 |
8387561 | Weaver et al. | Mar 2013 | B2 |
8668962 | Asmussen et al. | Mar 2014 | B2 |
8911868 | Scheibe et al. | Dec 2014 | B2 |
9139909 | Asmussen et al. | Sep 2015 | B2 |
9496376 | Yamazaki et al. | Nov 2016 | B2 |
9754733 | Fan et al. | Sep 2017 | B2 |
20030150562 | Quon | Aug 2003 | A1 |
20070034501 | Bender | Feb 2007 | A1 |
20110073471 | Weaver et al. | Mar 2011 | A1 |
20110140367 | Shi | Jun 2011 | A1 |
20110277823 | Fan et al. | Nov 2011 | A1 |
20130209767 | Kolev et al. | Aug 2013 | A1 |
20130244293 | Balan et al. | Sep 2013 | A1 |
20130306495 | Smith, Jr. | Nov 2013 | A1 |
20130307414 | Choi | Nov 2013 | A1 |
20130316156 | Kennedy et al. | Nov 2013 | A1 |
20140238861 | Foret | Aug 2014 | A1 |
20140260955 | Aharonov | Sep 2014 | A1 |
20140313574 | Bills et al. | Oct 2014 | A1 |
20150041454 | Foret | Feb 2015 | A1 |
20150068113 | Conner et al. | Mar 2015 | A1 |
20150203777 | Ramm et al. | Jul 2015 | A1 |
20150274567 | Boughton | Oct 2015 | A1 |
20150307360 | Bills et al. | Oct 2015 | A1 |
20150369426 | Smith, Jr. | Dec 2015 | A1 |
20160076141 | Hirota | Mar 2016 | A1 |
20160090535 | Abdullah et al. | Mar 2016 | A1 |
20160215111 | Bilek et al. | Jul 2016 | A1 |
20160245224 | Ruona et al. | Aug 2016 | A1 |
20160322174 | Fan et al. | Nov 2016 | A1 |
20160351404 | Aramaki et al. | Dec 2016 | A1 |
20170166753 | Slagter et al. | Jun 2017 | A1 |
20170189877 | Abdullah et al. | Jul 2017 | A1 |
20190366298 | Fan et al. | Dec 2019 | A1 |
20210291138 | Fan | Sep 2021 | A1 |
20240082811 | Fan | Mar 2024 | A1 |
Number | Date | Country |
---|---|---|
WO-2004013661 | Feb 2004 | WO |
WO-2011097183 | Aug 2011 | WO |
WO-2017209632 | Dec 2017 | WO |
WO-2018175689 | Sep 2018 | WO |
WO-2020014448 | Jan 2020 | WO |
Entry |
---|
Hopwood, J., et al., “Langmuir probe measurements of a radio frequency induction plasma,” Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, 1993. |
Dehkhoda, AM, et al., “A novel method to tailor the porous structure of KOH-activated biochar and its application in capacitive deionization and energy storage,” Biomass and Bioenergy, 2016. |
Talukder, A-A, “Plasma treatment of zinc oxide thin film and temperature sensing using the zinc oxide thin film,” <https://openprairie.sdstate.edu/cgi/viewcontent.cgi>?article=2048&context=etd, 2016. |
Foggiato, J., “Handbook of Thin-Film Deposition Processes and Techniques, Second Edition—Chapter 3: Chemical Vapor Deposition of Silicon Dioxide Films,” Noyes Publications, 2002, 54 pages. |
Gabriel, O., et al., “Plasma monitoring and PECVD process control in thin film silicon-based solar cell manufacturing,” EPJ Photovoltaics 5, Feb. 5, 2014, 9 pages. |
Henkel, C. et al., “Deposition of dielectrics and metal gate stacks (CVC, ALD), Lecture 8,” KTH, Spring 2013, 57 pages. |
Menendez, A., et al., “Depositions of Thin Films: PECVD Process,” Silicon Based Thin Film Solar-Cells, 2013, pp. 29-57. |
Talukder, A., et al., “Improving electrical properties of sol-gel derived zinc oxide thin films by plasma treatment,” Journal of Applied Physics 120, 155303, 2016, 24 pages. |
Wang, K., et al., “Low-temperature plasma exfoliated n-doped graphene for symmetrical electrode supercapacitors,” Nano Energy Journal vol. 31, Journal Issue C, Journal ID: ISSN 2211-2855, Jan. 1, 2017, 27 pages. |
Summary of prior capacitively coupled and inductively coupled plasma sources—publicly used prior to of Jan. 2017. |
South Dakota State University, “Reducing cost of producing supercapacitors,” www.sciencedaily.com, Aug. 18, 2016, 2 pages. |
“SDSU Researchers Use Biochar to Develop Cost-Effective Supercapacitors,” www.azom.com, Aug. 22, 2016, 3 pages. |
South Dakota State University, “Transforming biochar into activated carbon,” www.sciencedaily.com, Jan. 30, 2015, 2 pages. |
Simpson, J., “Plasma Etching of Biochar Reduces Supercapacitor Costs,” Engineering 360, Sep. 7, 2016, 1 page. |
Zeng, A., et al., “Plasma Treated Active Carbon for Capacitive Deionization of Saline Water,” Journal of Nanomaterials, vol. 2017, Jul. 19, 2017, 17 pages. |
Neodymium Ring Magnets—RZ0Y0X0, www.kjmagnetics.com, published Dec. 7, 2016, 6 pages. |
Karpov, Dmitri A., “Arc Source Designs,” Efremov Scientific Research Institute of Electrophysical Apparatus, Jan. 1995, pp. 396-423. |
Schuelke, Thomas, Fraunhofer USA, Center for Coatings and Diamond Technologies, DIAMOR® Superhard, Low Friction and Wear Resistant Coating, Aug. 2015. |
Fraunhofer Center for Coatings and Diamond Technologies, “Improving Powertrain Efficiency With Low-Friction Wear Resistant DIAMOR® Coatings,” May 26, 2017. |
Rejowski, Edney Deschauer, et al., SAE International 2012-01-1329, Application of DLC Coating in Cylinder Liners for Friction Reduction, Apr. 16, 2012. |
Vetter, J., et al., “Surface Treatment Selections for Automotive Applications,” Science Direct, Surface and Coatings Technology, vol. 200, Issues 5-6, Nov. 21, 2005, pp. 1962-1968. |
Haubold, Lars, et al., “The influence of the surface texture of hydrogen-free tetrahedral amorphous carbon films on their wear performance,” Diamond and Related Materials, vol. 19, Issues 2-3, Feb.-Mar. 2010, pp. 225-228. |
Number | Date | Country | |
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20210291138 A1 | Sep 2021 | US |
Number | Date | Country | |
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62696562 | Jul 2018 | US |