Patent Application
20250186964
This disclosure concerns production of catalyst particles. Additionally, this disclosure concerns synthesis of carbon-based high-aspect-ratio molecular structures, particularly by floating-catalyst chemical vapor deposition.
Films comprising networks of carbon-based high-aspect-ratio molecular structures (HARMSs), such as carbon nanotubes and carbon nanobuds, may be used in various applications in which films of high electrical conductivity and optical transmittance are required.
Various methods have been developed for synthesizing HARMSs. One of the most promising synthesis methods for industrial-scale production of HARMSs is so-called floating-catalyst chemical vapor deposition (FCCVD) due to its low cost, high throughput, as well as the high degree of control attainable by FCCVD over various structural parameters, e.g., lengths, diameters, and/or functional group densities, of synthesized HARMSs.
In FCCVD, catalyst composition and size are critical process parameters that have a major impact on the morphology and properties of synthesized HARMSs. Although FCCVD synthesis methods have already been utilized to form HARMS films with sheet resistances as low as approximately 100 Ω/sq at more than 95% optical transmittance, improved control of catalyst composition and size could lead to further improvements in the properties of FCCVD-grown HARMS networks.
In light of the above, it may be desirable to develop new solutions related to methods for producing catalyst particles.
This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.
According to a first aspect, an apparatus for producing catalyst particles is provided. The apparatus comprises a flow reactor and a laminar injector configured to introduce a catalyst particle precursor into the flow reactor. The laminar injector comprises a temperature-controlled flow straightener arranged upstream of the flow reactor.
According to a second aspect, a method for producing catalyst particles is provided. The method comprises introducing a catalyst particle precursor into a flow reactor via a temperature-controlled flow straightener arranged upstream of the flow reactor.
It is specifically to be understood that catalyst particles may generally be produced according to any method in accordance with the second aspect using an apparatus in accordance with the first aspect. Similarly, an apparatus in accordance with the first aspect may be provided with means for producing catalyst particles according to any method in accordance with the second aspect.
In an embodiment, the apparatus for producing catalyst particles and/or the method for producing catalyst particles is implemented as an apparatus for producing high-aspect-ratio molecular structures (HARMS) and/or a method for producing HARMS.
According to a third aspect, a HARMS network is provided. The HARMS network comprises carbon-based HARMSs obtainable by an apparatus and a method in accordance with the preceding embodiment.
It is specifically to be understood that an apparatus for producing HARMS in accordance with the first aspect and/or a method for producing HARMS in accordance with the second aspect may be used to produce a HARMS network in accordance with the third aspect.
The present disclosure will be better understood from the following detailed description read in light of the accompanying drawings, wherein:
Unless specifically stated to the contrary, any drawing of the aforementioned drawings may be not drawn to scale such that any element in said drawing may be drawn with inaccurate proportions with respect to other elements in said drawing in order to emphasize certain structural aspects of the embodiment of said drawing.
Moreover, corresponding elements in the embodiments of any two drawings of the aforementioned drawings may be disproportionate to each other in said two drawings in order to emphasize certain structural aspects of the embodiments of said two drawings.
Concerning apparatuses and methods discussed in this detailed description, the following shall be noted.
Throughout this specification, a “high-aspect-ratio molecular structure” or a “HARMS” may refer to a nanostructure, i.e. a structure with one or more characteristic dimensions in nanoscopic scale, e.g., greater than or equal to 0.1 nanometers (nm) and less than or equal to about 100 nm. Additionally or alternatively, a HARMS may refer to a structure having dimensions in two perpendicular directions with significantly different orders of magnitude. For example, a HARMS may have a length which is tens or hundreds of times higher than its thickness and/or width.
Further, a “carbon-based” HARMS may refer to a HARMS consisting primarily of carbon (C). Additionally, or alternatively, a carbon-based HARMS may refer to a HARMS comprising at least 50 atomic percent (at. %), or at least 60 at. %, or at least 70 at. %, or at least 80 at. %, or at least 90 at. %, or at least 95 at. % of carbon.
Generally, carbon-based HARMSs may be doped with non-carbon dopants, for example, to alter their electrical and/or thermal properties. Examples of carbon-based HARMSs include carbon nanotubes, carbon nanobuds, graphene nanoribbons, and combinations thereof.
In this disclosure, a “high-aspect-ratio molecular structure network” or “HARMS network” may refer to a plurality of mutually interconnected HARMSs. Generally, a HARMS network may form a solid and/or monolithic material at a macroscopic scale, wherein individual HARMSs are non-oriented, i.e., substantially randomly oriented or randomly oriented, or oriented. Typically, a HARMS network may be arranged in various macroscopic forms, for example, as films, which may or may not be optically transparent and/or possess high electrical conductivity.
Herein, a “film” may refer to a structure having its lateral dimensions substantially larger than its thickness. Generally, a film may have any suitable shape, for example, a flat and/or smooth shape or a curved and/or uneven shape.
Throughout this specification, a “catalyst particle” may refer to a particulate piece of matter suitable for increasing the rate of a reaction via catalysis. Additionally or alternatively, a catalyst particle may refer to a particle suitable for heterogenous catalysis. Additionally or alternatively, a catalyst particle may refer to a piece of particulate catalyst material suitable for catalysis of production of carbon-based HARMSs, for example, by chemical vapor deposition, e.g., floating-catalyst chemical vapor deposition (FCCVD).
Generally, a catalyst particle, may comprise, consist substantially of, or consist of one or more transition metals, such as iron (Fe), cobalt (Co), and/or nickel (Ni). Typically, a catalyst particle may have any suitable diameter, for example, a diameter in a range from 0.1 nm to 300 nm, or from 1 nm to 200 nm, or from 5 nm to 100 nm, or from 10 nm to 50 nm.
In the embodiment of
Herein, a “flow reactor” may refer to a reactor into which one or more catalyst particle precursors and, optionally, one or more reactants, such as a carbon source, and/or one or more auxiliary substances, e.g., catalysts and/or growth promoters, such as sulfur (S); phosphorus (P); nitrogen (N); one or more sulfur-containing compounds, e.g., hydrogen sulfide (H2S), carbon bisulfide (CS2), and/or thiophene (C4H4S); one or more phosphorus-containing compounds, e.g., phosphane (PH3); one or more nitrogen-containing compounds, e.g., ammonia (NH3) and/or nitric oxide (NO); and/or redox agents, e.g., oxygen (O2), water (H2O), carbon dioxide (CO2), and/or hydrogen (H2), are introduced, for example, continuously introduced, and wherefrom one or more products are collected, for example, continuously collected. Additionally or alternatively, a flow reactor may refer to a reactor through which one or more reactants pass and wherein catalysis is in progress. Typically, a flow reactor may be formed of any suitable material(s), for example, stainless steel, fused silica, or fused quartz.
In the embodiment of
Throughout this disclosure, a “precursor” may refer to a chemical substance from which another chemical substance or other product may be formed. Generally, a precursor may be used in any suitable state of matter, e.g., in solid, gaseous, or liquid form. Naturally, a “catalyst particle precursor” may then refer to a precursor for forming catalyst particles. Additionally or alternatively, a catalyst particle precursor may refer to a precursor comprising, consisting substantially of, or consisting of one or more iron-containing organometallic or metalorganic compounds, such as ferrocene (Fe(C5H2)2), iron pentacarbonyl (Fe(CO)5), and/or iron(II)phthalocyanine (C32H16FeN8); and/or one or more nickel-containing organometallic or metalorganic compounds, such as nickelocene (Ni(C5H5)2); and/or one or more cobalt-containing organometallic or metalorganic compounds, such as cobaltocene (Co(C5H5)2).
In this specification, a “laminar injector” or “laminar gas distributor” may refer to a device configured to introduce one or more catalyst particle precursors and optionally, one or more reactants and/or one or more further auxiliary substances, e.g., catalysts, into a flow reactor. Additionally or alternatively, a laminar injector may refer to a device suitable for or configured to introduce one or more fluids, such as gases, and/or aerosols into a flow reactor such that a laminar flow profile is maintained at an upstream end of said flow reactor.
Herein, a “laminar flow profile” being maintained at a specific position of a flow reactor may refer to maintaining a Reynolds number (Re) less than or equal to 2300, or less than or equal to 2100, or less than or equal to 2000 at said position.
In the embodiment of
Throughout this disclosure, a “flow straightener” or “honeycomb” may refer to a device or structure suitable for or configured to reduce, minimize, or remove swirl from a flow of one or more fluids and/or one or more aerosols. Additionally or alternatively a “flow straightener” or “honeycomb” may refer to a device suitable for or configured to reduce, minimize, or remove non-symmetry of such flow.
Further, a flow straightener being arranged “upstream of” a flow reactor may refer to said flow reactor comprising an upstream end and said flow straightener being arranged towards a countercurrent direction from said upstream end. Additionally or alternatively, a flow straightener being arranged upstream of a flow reactor may refer to said flow straightener being configured to discharge a catalyst particle precursor towards an injection direction and said flow reactor comprising an upstream end towards said injection direction from said flow straightener. Additionally or alternatively, a flow straightener being arranged upstream of a flow reactor may refer to said flow straightener being arranged outside of said flow reactor.
In this specification, a device or structure of an apparatus or part thereof being “temperature-controlled” may refer to temperature of said device or structure being maintained within a pre-defined temperature range during operation of said apparatus. Typically, temperatures within such pre-defined temperature range may be distinct from an ambient temperature at the location of said an apparatus and/or part thereof. Generally, a temperature-controlled device or structure of an apparatus or part thereof may or may not be thermally coupled to one or more heating elements for heating said temperature-controlled device or structure.
The apparatus 1000 of the embodiment of
In the embodiment of
The catalyst particle precursor 1201 of the embodiment of
In the embodiment of
Throughout this disclosure, the term “tubular” is to be interpreted broadly. As such, the term tubular may refer to any elongate and hollow shape, which may have any suitable cross-sectional shape. An element having a tubular shape may or may not have a circular, substantially circular, elliptical, or polygonal cross-sectional shape. Additionally or alternatively, a tubular element may or may not be at least partly tapered, cylindrical, and/or curvilinear.
The flow reactor 1100 of the embodiment of
In the embodiment of
The flow straightener body 1211 of the embodiment of
In the embodiment of
In the embodiment of
In other embodiments, a laminar injector may or may not comprise at least one heating element, e.g., a lateral heating element, such as a band heater, and/or an internal heating element, for heating a flow straightener, wherein one or more of said at least one heating element may be electric heating elements. In some embodiments, a laminar injector may comprise a radiative heater, e.g., a laser source, and/or an induction heater in addition or as an alternative to electric heating elements.
In the embodiment of
In other embodiments, wherein at least one heating element comprises a lateral heating element and/or an internal heating element, said lateral heating element may or may not surround a flow straightener and/or said internal heating element may be arranged at least partly within a flow straightener body. For example, in some embodiments, a lateral heating element may extend only partially around a flow straightener and at least one heating element may optionally comprise two or more such lateral heating elements.
The laminar injector 1200 of the embodiment of
In other embodiments, wherein a laminar injector of an apparatus for producing catalyst particles comprises a temperature sensor for measuring a temperature of a flow straightener, said apparatus may or may not comprise an injector temperature control unit operatively coupled with said temperature sensor and at least one heating element for maintaining said temperature in any suitable temperature range, for example, in a range from 100° C. to 700° C., or from 200° C. to 600° C., or from 250° C. to 400° C.
In this specification, a “control unit” may refer to a device, e.g., an electronic device, having at least one specified function related to determining and/or influencing an operational condition, status, or parameter related to another device, unit, or element. A control unit may or may not form a part of a multifunctional control system.
Further, a control unit being “operatively coupled” with a device, unit, or element may refer to the control unit having at least one specified function related to determining and/or influencing an operational condition, status, or parameter related to said device, unit, or element.
A control unit being “configured to” perform a process may refer to capability of and suitability of said control unit for such process. This may be achieved in various ways. For example, a control unit may comprise at least one processor and at least one memory coupled to the at least one processor, the memory storing program code instructions which, when executed on said at least one processor, cause the processor to perform the process (es) at issue. Additionally or alternatively, any functionally described features of a control unit may be performed, at least in part, by one or more hardware logic components. For example, and without limitation, illustrative types of suitable hardware logic components include Field-programmable Gate Arrays (FPGAs), Application-specific Integrated Circuits (ASICs), Application-specific Standard Products (ASSPs), System-on-a-chip systems (SOCs), Complex Programmable Logic Devices (CPLDs), and the like. A control unit may generally be operated in accordance with any appropriate principles and by means of any appropriate circuitry and/or signals known in the art.
In the embodiment of
In other embodiments, wherein a laminar injector of an apparatus for producing catalyst particles comprises at least one gas inlet, said apparatus may or may not comprise an injector flow control unit configured to control volumetric flow rate through said at least one gas inlet such that any suitable residence time of a catalyst particle precursor in a flow straightener is maintained. For example, in some such embodiments, residence time of said catalyst particle precursor in said flow straightener may be greater than or equal to 150 ms, or to 400 ms, or to 800 ms, and/or less than or equal to 8500 ms, or to 4000 ms, or to 2500 ms.
The apparatus 1000 of the embodiment of
The carbon source 1202 of the embodiment of
In the embodiment of
In order to mix the catalyst particle precursor 1201 and the carbon source 1202 prior to injection into the flow reactor 1100, the laminar injector 1200 comprises a mixing chamber 1250 upstream of the flow straightener 1210 as well as a pre-mixing chamber 1260 upstream of the mixing chamber 1250. Generally, a laminar injector comprising both a mixing chamber upstream of a flow straightener and a pre-mixing chamber upstream of said mixing chamber may enhance mixing of a catalyst particle precursor and a carbon source, which may, in turn, promote increase homogeneity of carbon-based HARMSs produced by an apparatus comprising such laminar injector.
In other embodiments, wherein a laminar injector is configured to introduce a catalyst particle precursor and a carbon source into a flow reactor, said laminar injector may or may not comprise a mixing chamber upstream of a flow straightener and a pre-mixing chamber upstream of said mixing chamber for mixing said catalyst particle precursor and said carbon source. For example, in some such embodiments, a laminar injector may comprise a mixing chamber upstream of a flow straightener in the absence of a pre-mixing chamber.
In the embodiment of
In other embodiments, wherein an apparatus for producing catalyst particles comprises a precursor conduit for feeding a catalyst particle precursor into a laminar injector, said precursor conduit may or may not comprise a precursor conduit temperature sensor for measuring a temperature of said precursor conduit and a precursor conduit heating element for heating the precursor conduit, and said apparatus may or may not further comprise a conduit temperature control unit operatively coupled with said precursor conduit temperature sensor and said precursor conduit heating element for maintaining said temperature in any suitable temperature range, for example, in a range from 30° C. to 200° C., or from 50° C. to 190° C., or from 100° C. to 180° C. For example, in some embodiments, precursor conduit heating elements with constant heating power per unit length of conduit may be used such that specific conduit temperature control units may be omitted.
The apparatus 1000 of the embodiment of
In other embodiments, wherein apparatus for producing catalyst particles comprises a carbon source conduit for feeding a carbon source into a laminar injector, said carbon source conduit may or may not comprise a carbon source conduit temperature sensor for measuring a temperature of the carbon source conduit and a carbon source conduit heating element for heating said carbon source conduit, and a conduit temperature control unit may or may not be operatively coupled with said carbon source conduit temperature sensor and said carbon source conduit heating element for maintaining said temperature in any suitable temperature range, for example, in a range from 30° C. to 200° C., or from 50° C. to 190° C., or from 100° C. to 180° C.
Although not explicitly shown in
In the embodiment of
In other embodiments, wherein a flow reactor of an apparatus for producing catalyst particles has an upstream portion and said apparatus comprises a tube furnace for holding said flow reactor such that said upstream portion extends out of said tube furnace, said apparatus may or may not comprise a ventilated collar configured to surround at least part of said upstream portion for adjusting a temperature of said upstream portion during operation of said apparatus.
The ventilated collar 1800 of the embodiment of
The tube furnace 1700 of the embodiment of
In the embodiment of
It is to be understood that the embodiments of the first aspect described above may be used in combination with each other. Several of the embodiments may be combined together to form a further embodiment.
Above, mainly structural features of apparatuses for producing catalyst particles and parts thereof are discussed. In the following, more emphasis will lie on features related to methods for producing catalyst particles. What is said above about the ways of implementation, definitions, details, and advantages related to the apparatuses apply, mutatis mutandis, to the methods discussed below. The same applies vice versa.
The method 3000 of the embodiment of
In this specification, a “process” may refer to a series of one or more steps, leading to an end result. As such, a process may be a single-step or a multi-step process. Additionally, a process may be divisible to a plurality of sub-processes, wherein individual sub-processes of such plurality of sub-processes may or may not share common steps. Herein, a “step” may refer to a measure taken in order to achieve a pre-defined result.
In the embodiment of
As indicated in
In the embodiment of
The method 3000 of the embodiment of
As indicated in
The process of introducing a carbon source into the flow reactor 3300 of the embodiment of
As indicated in
In other embodiments, wherein a method for producing catalyst particles comprises introducing a carbon source into the flow reactor and the process of introducing a carbon source into the flow reactor comprises mixing the catalyst particle precursor and the carbon source upstream of the flow straightener, the process of mixing the catalyst particle precursor and the carbon source may or may not comprise steps of pre-mixing and mixing the catalyst particle precursor and the carbon source in a pre-mixing chamber and in a mixing chamber arranged downstream from the pre-mixing chamber, respectively.
As indicated in
As indicated in
As indicated in
It is to be understood that the embodiments of the second aspect described above may be used in combination with each other. Several of the embodiments may be combined together to form a further embodiment.
The HARMS network 4000 of the embodiment of
The film 4100 of the embodiment of
In the embodiment of
It is obvious to a person skilled in the art that with the advancement of technology, the basic idea of the invention may be implemented in various ways. The invention and its embodiments are thus not limited to the examples described above, instead they may vary within the scope of the claims.
It will be understood that any benefits and advantages described above may relate to one embodiment or may relate to several embodiments. The embodiments are not limited to those that solve any or all of the stated problems or those that have any or all of the stated benefits and advantages.
The term “comprising” is used in this specification to mean including the feature(s) or act(s) followed thereafter, without excluding the presence of one or more additional features or acts. It will further be understood that reference to ‘an’ item refers to one or more of those items.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20225259 | Mar 2022 | FI | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FI2023/050166 | 3/24/2023 | WO |
