Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
11752459 · 2023-09-12
Assignee
Inventors
Cpc classification
B01D39/2044
PERFORMING OPERATIONS; TRANSPORTING
C04B35/528
CHEMISTRY; METALLURGY
B01D39/2062
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01D39/20
PERFORMING OPERATIONS; TRANSPORTING
C04B35/528
CHEMISTRY; METALLURGY
Abstract
Methods of forming solid carbon products include disposing nanostructure carbon in a container, disposing the container in a press, compressing the nano structured carbon within the container, and fastening a lid to the container to form a filter. Further processing may include sintering the nanostructured carbon within the container and heating the nanostructured carbon within the container in an inert environment to form bonds between adjacent particles of nanostructured carbon. Other methods may include forming a plurality of compressed nanostructured carbon modules, placing the plurality of compressed nanostructured carbon modules within a container, and placing a lid on the container to form a filter structure. Related structures are also disclosed.
Claims
1. A composite structure comprising: a container comprising at least one enclosure wall defining a volume within the container; and a porous mass of compressed nanostructured carbon within the volume defined by the container.
2. The composite structure of claim 1, wherein the porous mass of compressed nanostructured carbon substantially fills the volume defined by the container.
3. The composite structure of claim 1, wherein particles of the nanostructured carbon are interbonded to one another.
4. The composite structure of claim 1 wherein at least a portion of the at least one enclosure wall comprises a substantially non-porous, malleable material.
5. The composite structure of claim 1 wherein at least a portion of the at least one enclosure wall is in contact with the mass of compressed nanostructured carbon and exerts a compressive stress thereon.
6. The composite structures of claim 5, wherein the at least one enclosure wall defines at least two openings in fluid communication with the mass of compressed nanostructured carbon.
7. The composite structure of claim 5, wherein at least a portion of the at least one enclosure wall comprises a porous material.
8. The composite structure of claim 1 wherein the at least one enclosure wall comprises at least one outer wall and a lid crimped to the at least one outer wall.
9. The composite structure of claim 1 wherein the compressed nanostructured carbon comprises carbon nanofibers.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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MODE(S) FOR CARRYING OUT THE INVENTION
(6) This disclosure describes methods of forming solid carbon products by applying pressure to CNTs and other forms of nanostructured carbon within a container, and methods for applying heat to the solid products formed by such processes. Solid carbon products may be useful in various filtering applications. Such solid carbon products may exhibit enhanced properties (e.g., strength, electrical or thermal conductivity, specific surface area, porosity, etc.) with respect to conventional materials. In some embodiments, solid carbon products contain a compressed nanostructured carbon within a container. When such masses are sintered, covalent bonds form between at least some of the carbon particles, forming solid shapes. This product has numerous useful filter applications. For example, some forms of nanostructured carbon that may benefit from such processes include graphene, fibrous carbon, buckminsterfullerenes, single-wall CNTs, multi-wall CNTs, or bimodal CNTs (i.e., CNTs having a bimodal distribution of diameters and/or a bimodal distribution of lengths). Nanostructured carbon may have any selected size and morphology, even helical.
(7) As used herein, the term “sintering” means and includes annealing or pyrolizing nanostructured carbon at temperatures and pressures sufficient to induce carbon—carbon covalent bonding between at least some of the adjacent particles between at least some of their contact points.
(8) As used herein, the term “catalyst residual” means and includes any non-carbon elements associated with the nanostructured carbon. Such non-carbon elements may include, for example, nanoparticles of metal catalyst in growth tips of CNTs, and metal atoms or groups of atoms randomly or otherwise distributed throughout and on the surfaces of the nanostructured carbon.
(9) As used herein, the term “green” means and includes any solid carbon product that has not been sintered.
(10) Nanostructured carbon may be formed through any method known to the art, including arc discharge, laser ablation, hydrocarbon pyrolysis, the Boudouard reaction, the Bosch reaction and related carbon oxide reduction reactions, or wet chemistry methods (e.g., the Diels-Alder reaction). The methods described herein are applicable to nanostructured carbon regardless of the method of manufacture or synthesis.
(11) CNTs occur as single-wall and multi-wall CNTs of various diameters ranging from a few nanometers to 100 nanometers in diameter or more. CNTs have a wide variety of lengths and morphologies, and may occur as substantially parallel “forests,” randomly tangled masses, or “pillows” of structured agglomerations. For example, CNTs may be formed as described in U.S. Patent Publication 2015/0064092, “Methods and Reactors for Producing Solid Carbon Nanotubes, Solid Carbon Clusters, and Forests,” published Mar. 5, 2015, the entire disclosure of which is incorporated herein by this reference. CNTs may also form or be compounded to form many different mixtures of CNTs with various combinations and distribution of the above characteristics (number of walls, diameters, lengths, morphology, orientation, etc.). Various mixtures, when compounded and used to form the solid carbon products described herein, may result in products with specifically engineered properties. For example, the median void size of interstitial spaces between CNTs comprising solid carbon products typically is approximately proportional to the characteristic diameters of the CNTs used in forming the solid carbon products. The median void size influences the overall porosity and density of the solid carbon products.
(12) Various CNT features and configurations are illustrated in
(13) The CNT 100 has an inside diameter related to the number of carbon atoms 102 in a circumferential cross section. The CNT 100 depicted in
(14) CNTs having more than one wall are called multi-wall CNTs.
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(17) CNTs are typically formed in such a way that a nanoparticle of catalyst material is embedded in the growth tip of the CNT. This catalyst material may be left in place or removed by mild washing (e.g., by an acid wash). Without being bound to a particular theory, it is believed that if the catalyst material is left in place, catalyst atoms become mobilized during the sintering process, and may migrate to the surface or within the pores of the CNTs. This process may disperse the catalyst atoms randomly, uniformly, or otherwise throughout the solid carbon product mass and may have a significant influence on the properties of the solid carbon product. For example, catalyst material may affect electrical conductivity or the ability to catalyze other chemical reactions.
(18) The catalyst particles may be selected to catalyze other reactions in addition to the formation of solid carbon. Catalyst particles may be any material, such as a transition metal or any compound or alloy thereof. Typical catalysts include metals selected from groups 2 through 15 of the periodic table, such as from groups 5 through 10 (e.g., nickel, molybdenum, chromium, cobalt, tungsten, manganese, ruthenium, platinum, iridium, etc.), actinides, lanthanides, alloys thereof, and combinations thereof. Note that the periodic table may have various group numbering systems. As used herein, group 2 is the group including Be, group 3 is the group including Sc, group 4 is the group including Ti, group 5 is the group including V, group 6 is the group including Cr, group 7 is the group including Mn, group 8 is the group including Fe, group 9 is the group including Co, group 10 is the group including Ni, group 11 is the group including Cu, group 12 is the group including Zn, group 13 is the group including B, group 14 is the group including C, and group 15 is the group including N. For example, catalyst particles may include nickel, vanadium oxide, palladium, platinum, gold, ruthenium, rhodium, iridium, etc.
(19) Because the catalyst particles are attached to or otherwise associated with CNTs, each catalyst particle may be physically separated from other catalyst particles. Thus, the catalyst particles may collectively have a much higher surface area than a bulk material having the same mass of catalyst. Catalyst particles attached to CNTs may therefore be particularly beneficial for decreasing the amount of catalyst material needed to catalyze a reaction and for reducing the cost of catalysts. Compressed solid carbon products used as catalysts may, in many applications, benefit from the catalytic activity of both the CNT and the metal catalyst particles embedded in the growth tip of the CNTs.
(20) The CNTs used in the processes herein may be single-wall CNTs, multi-wall CNTs, or combinations thereof, including bi-modally sized combinations of CNTs, mixtures of single-wall and multi-wall CNTs, mixtures of various sizes of single-wall CNTs, mixtures of various sizes of multi-wall CNTs, etc. For example, CNTs may have a bi-modal distribution, as described in U.S. Patent Publication 2015/0064097, “Carbon Nanotubes Having a Bimodal Size Distribution,” published Mar. 5, 2015, the entire disclosure of which is incorporated herein by this reference. The CNTs may be in forms such as a sheet-molded compound, a pressure-molded compound, or as a pourable liquid.
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(23) The nanostructured carbon 230 may optionally be sintered. Sintering appears to cause covalent bonds to form between particles of nanostructured carbon at contact points. That is, any given particle may “cross-link” with an adjacent particle at the physical point of contact of the two particles. A sintered particle may be covalently bound to numerous other particles (single-wall CNTs, multi-wall CNTs, CNTs with attached nanobuds, carbon nanofibers, graphene sheets, etc.). This may increase the strength of the resulting structure because the particles do not appear to slide or slip at the bonding points. Unsintered particles (e.g., in buckyrock) appear to slide with respect to each other. Because the covalent bonding caused by sintering may occur at numerous sites in the nanostructured carbon, the sintered body may have significantly increased strength, toughness, impact resistance, and conductivity over conventional agglomerations of nanostructured carbon. A sintered mass of nanostructured carbon may have the bond strength necessary to resist the mechanical force of a gas or fluid passing through the mass of nanostructured carbon.
(24) As a non-limiting example, the side walls 260 and the end wall 245 of the container 210 may include a material such as metal, plastic, ceramic, paper, cloth, a composite, or any combination thereof. For example, the side walls 260 and the end wall 245 of the container 210 may include a metal such as aluminum or steel. Alternatively, the side walls 260 and the end wall 245 may include a ceramic or a composite material. In certain applications, side walls 260 and end wall 245 may include a plastic material, such as polycarbonate, or a paper or paper-like material, such as cardboard.
(25) As a non-limiting example, side walls 260 of the container 210 may be configured to be compressed when a piston 300 presses the nanostructured carbon 230 (e.g., the side walls 260 may have an outside dimension smaller than an outside dimension of the piston). Alternatively, side walls 260 of the container 210 may be configured to not be compressed when a piston presses the nanostructured carbon 230 (e.g., the side walls 260 may have an outside dimension larger than an outside dimension of the piston). In the embodiment shown in
(26) The container 210 may be formed in any suitable shape, depending on the configuration and the application of filter structure 200. As a non-limiting example, a cross-section of the container 210 from a top-view may be a circle, an ellipse, a rectangle, a triangle, or another polygon. Furthermore, the container 210 may have any appropriate dimensions for a given application, including height and thickness of side walls 260 and dimensions of the top-view cross-section of the container 210. As a non-limiting example, side walls 260 may have a height of between about 1 cm to 50 cm, and side walls 260 may have a thickness of about 10 μm to 1 mm.
(27) The end wall 245 of the container 210 may also define an opening 270. During use of a filter structure 200, the opening 270 may be connected to a gas and/or fluid source, allowing gases and/or fluids to pass into the container 210. As a non-limiting example, the opening 270 may have any appropriate cross-sectional shape, such as a circle, ellipse, rectangle, or triangle. Furthermore, the opening 270 may have any appropriate cross-sectional dimensions. The opening 270 may be configured to be coupled to an exterior system from which gases or other fluids flow to the filter structure 200. The opening 270 may be connected to the gas and/or fluid source by a hose, a threaded pipe fitting, a weldable pipe fitting, or a nipple fitting.
(28) The diffuser plate 240 may be a substantially porous material that allows gases compressed during compression of the nanostructured carbon 230 to pass through the nanostructured carbon 230 and exit through the opening 270, allowing compression of the nanostructured carbon 230 without a pressure build-up from the gases. The diffuser plate 240 may also be used to diffuse the gases and liquids that enter through opening 270 during a subsequent filtering process, such that the gases or fluids flow in an evenly distributed pattern over the cross-sectional area of the nanostructured carbon 230′ (shown in
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(30) The container 210 may be placed within an appropriate compression apparatus and may be sized and configured to receive the piston 300. The container 210 may include side walls 260 which are compressible by a compressive force exerted by the piston 300.
(31) The diffuser plate 240 may prevent the nanostructured carbon 230 from exiting the container 210 upon compression by the piston 300. In subsequent use, fluids and/or gases may pass through the diffuser plate 240 to the compressed nanostructured carbon 230′, the compressed nanostructured carbon 230′ acting as a filter.
(32) The piston 300 may compress the nanostructured carbon 230 in an inert atmosphere. The inert atmosphere under which compression takes place may include an atmosphere of N.sub.2. The piston 300 may compress the nanostructured carbon 230 at a temperature of between about 1,500° C. and 2,000° C. The piston 300 may remain in compression for a time period from about 1 to about 600 seconds, such as approximately 30 seconds. The piston 300 may compress the nanostructured carbon 230 into a substantially unitary form using a pressure of between about 10 MPa to about 1,000 MPa.
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(34) The compressed nanostructured carbon 230′ within the filter structure 200 may substantially fill the compressed container 210′. The compressed nanostructured carbon 230′ within the container 210′ may be in substantial contact with the diffuser plate 240 and the side walls 260′. The diffuser plate 240 and the side walls 260′ may exert a compressive stress on the compressed nanostructured carbon 230′ after compression. The end wall 245 may define at least one inlet opening 270. The inlet opening 270 may be in fluid communication with the nanostructured carbon 230′ (i.e., a fluid passing through the inlet opening 270 may pass into the nanostructured carbon 230′. Though referred to herein as an inlet opening 270 and an outlet opening 280, the inlet opening 270 may be used as an outlet and the outlet opening 280 may be used as an inlet.
(35) The end wall 245 may include a porous material or a non-porous malleable material, as discussed herein.
(36) As discussed previously, the compressed nanostructured carbon 230′ may include single-walled CNTs (SWCNTs), multi-walled CNTs (MWCNTs), carbon nanofibers, graphene, etc. As a non-limiting example, the compressed nanostructured carbon 230′ may include only SWCNTs. Alternatively, the compressed nanostructured carbon 230′ may include only MWCNTs or only carbon nanfibers. Alternatively, the compressed nanostructured carbon 230′ may include a mixture of SWCNTs, MWCNTs, and carbon nanofibers. The compressed nanostructured carbon 230′ may be sintered or unsintered depending on the filter application.
(37) The compressed nanostructured carbon 230′ may have a bulk density suitable for a selected filter application. As a non-limiting example, the compressed nanostructured carbon 230′ may have a bulk density of from about 0.8 g/cm.sup.3 to about 2.2 g/cm.sup.3.
(38) The compressed nanostructured carbon 230′ within the compressed container 210′ may have attached chemical moieties. The chemical moieties may include, for example, whole functional groups or parts of functional groups as substructures. The chemical moieties may include alkyl groups, carbonyl groups, aromatics, non-aromatic rings, peptides, amino groups, hydroxyl groups, sulfate groups, phosphate groups, etc.
(39) The compressed nanostructured carbon 230′ may be an interbonded mass of nanostructured carbon, having multiple bonds that interconnect particles directly to other particles. The compressed nanostructured carbon 230′ may alternatively be bonded via a resin or a polymer adhesive. For example, such materials may be applied using chemical vapor deposition (CVD) or similar means in a micro-fine manner so as to provide interlocking bonding without encasing the compressed nanostructured carbon 230′ in droplets of resin. CVD techniques may be used to apply micro-thin layers of metals bonding particles together without interfering with the compressibility of the compressed nanostructured carbon 230′. Metals such as tin, copper and the like may be applied by CVD or similar techniques.
(40) Further embodiments are contemplated wherein a filter structure does not include a separate end wall, having only an enclosure wall comprising a porous diffuser plate. In such embodiments, the filter structure may be configured to interface directly with an exterior system such that gas or other fluids would pass from the exterior system directly to the enclosure wall comprising a porous diffuser plate. The filter structure may be connected to the gas and/or fluid source by a hose, a threaded pipe fitting, a weldable pipe fitting, or a nipple fitting.
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(42) A piston 500 may be configured to compress the container 400 having walls 410 with the nanostructured carbon 430 therein, as described above, to yield a compressed container 400′ having compressed walls 410′ with compressed nanostructured carbon 430′ therein (
(43) One or more of the compressed containers 400′ may be placed in a filter device 600, as shown in
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(47) After forming the compressed nanostructured carbon 830′ (i.e., by compressing the nanostructured carbon 830) and placing the porous diffuser plate 850 over the compressed nanostructured carbon 830′, the side walls 860 may be folded or crimped downward and inward in the directions shown by arrows 825, forming folded side walls 860′ (represented as dashed lines), sealing closed the filter structure 800. After or during the formation of the folded side walls 860′, an outlet opening 880 may be added to the enclosure formed by folded side walls 860′. Gases and fluids may then pass from inlet opening 870 through the porous lower enclosure wall 840, through the mass of compressed nanostructured carbon 830′ and the porous upper enclosure wall 850 and out of outlet opening 880. The outlet opening 880 may be configured to be coupled to an exterior system to which gases or other fluids flow from the filter structure 800. The outlet opening 880 may be connected to the exterior system by a hose, a threaded pipe fitting, a weldable pipe fitting, or a nipple fitting. In some embodiments, the sidewalls may be cut or sheared away above the porous diffuser plate 850 and a lid having an outlet opening may be fastened to the remaining walls 860, similar to methods previously discussed herein. In some embodiments, pellets of compressed nanostructured carbon may be placed in the container 810′. In certain embodiments, the compressed nanostructured carbon may be coated with a porous coating to form a filter medium, before the filter medium is placed in a container 810′.
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