The present disclosure relates to filters including fiber compositions, such as catalytic fiber compositions, for use in industrial processes such as waste gas treatment, hydrogenation, and dehydrogenation. More particularly, the disclosure is related to catalytic filters for hydrogenation and/or emissions control of waste gas streams.
Many manufacturing, industrial and other processes generate waste gases which must be processed to some degree prior to discharge into the environment. For example, electrical power generation is sometimes performed by combusting carbon-based fuels to generate heat, which can be converted into electricity via steam turbines. Similarly, concrete and glass production plants combust fuels to generate heat as part of the production processes. Further, internal combustion engines, which may be used in numerous systems, generate electrical and/or motive power by combusting fuels, such as gasoline or diesel fuel. All of these processes are capable of generating waste gases which must be processed to a degree prior to discharge to the environment.
These waste gases may include carbon monoxide, carbon dioxide, nitrogen oxides, nitrous oxide, ammonia slip, sulfur oxides, hydrogen chloride, hydrogen fluoride, arsenic, boron, lead, mercury, and other harmful gases (e.g., unburned hydrocarbons (“HC”) and volatile organic compounds (“VOC”)) and/or particles. Some or all of these undesirable components of waste gases may be removed by various conventional techniques, many of which involve filters and/or catalyst supports which may physically remove and/or chemically alter the undesirable components prior to discharge to the environment.
Many of the conventional components for conducting these abatement processes suffer from deficiencies. For example, in certain circumstances, ceramic honeycomb filters/catalyst supports are used to remove and/or chemically modify undesirable components found in exhaust gases. These supports may be undesirably heavy, may have low heat tolerance, and/or may be expensive to install and/or operate.
An example of an industrial process which generates waste gases which must be processed prior to discharge into the environment is fluid catalytic cracking (“FCC”). FCC processes are used to convert high molecular weight hydrocarbons to more valuable shorter-chain hydrocarbon groups, such as gasoline or olefins. FCC processes consume large amounts of energy in producing steam, heating the feedstock, and regenerating the catalysts. FCC processes would benefit from lower cost catalytic support materials which may reduce the amount of energy required to catalyze the feedstocks and regenerate the catalyst support materials, as well as materials which would increase the efficiency of processing the waste gases generated by FCC processes.
Other industrial processes may also benefit from improved catalytic support materials, such as: synthesis of ethylene oxide using silver catalyst on alumina; desulfurization of petroleum using molybdenum-cobalt catalyst on alumina; benzene hydrogenation to cyclohexane using nickel/platinum catalysts; production of synthesis gas (“syn gas”) using nickel catalysts; reforming of naphtha using platinum and rhenium catalysts on alumina; making epoxyethane using silver catalysts on alumina; or making sulfuric acid using vanadium catalysts.
An issue that is common across all waste gas treatment devices (reactors) is pressure drop (dP). The dP has to be mitigated when designing the reactor for several reasons. In particular, in a power generation system, high dP will require additional pumps to provide the power needed to move fluid through the reactor/reactor beds or the high dP will yield decreased power output. Further, high dP can result in crushing and compression of catalyst material, which can damage the reactor and decrease efficiency. Additionally, high dP can have negative effects on safety of pressure vessels and upstream systems. In conventional reactors, in order to increase the surface area of the catalyst bed, additional material (e.g., catalyzed spheres or shaped materials) are added, but this undesirably increases dP.
What is needed is light-weight, high temperature resistant, lower cost and/or energy efficient components for waste gas treatment systems and other manufacturing/ industrial processes that do not lead to increased dP. Such product forms may be capable of replacing existing ceramic substrates such as spheres, powders, or monoliths with such compositions/product forms.
Embodiments of the subject matter are disclosed with reference to the accompanying drawings which are for illustrative purposes only. The subject matter is not limited in its application to the details of construction, or the arrangement of the components illustrated in the drawings. Like reference numerals are used to indicate like components, unless otherwise indicated.
The following descriptions are provided to explain and illustrate embodiments of the present disclosure. The described examples and embodiments should not be construed to limit the present disclosure.
Turning to
The inlet 102 allows fluid, such as waste gas in need of treatment, to enter an interior of the hollow body 112. As shown in
The closed end 104 is positioned opposite the inlet 102 such that fluid flows out of the filter cartridge 100 through side portions of the hollow body 112 between the inlet 102 and the closed end 104 (i.e., through the filter layer 106). In some embodiments, the closed end 104 is a solid sheet, such as a metal end cap. In other embodiments, the closed end 104 may be permeable or semi-permeable and may include a filter material, such as that forming the filter layer 106, optionally including one or more permeable layers, such as the inner and outer permeable layers 108, 110 described herein. In yet other embodiments, the closed end 104 may be sealed by a second filter cartridge, as described in detail below with reference to
Turning to
The filter layer 106 is porous and allows fluid to flow therethrough. The filter layer 106 may be catalyzed in order to aid in treatment of one or more pollutants contained within the fluid (waste gas). The filter layer 106 may include inorganic fibers and a catalyst, such as those described in U.S. Pat. Application Publication No. 20190309455 A1, which is incorporated herein in its entirety. In some embodiments, the fibers have a median diameter of about 1-13 microns, about 4-10 microns, about 4 microns, about 5-9 microns, about 6-8 microns, or about 7 microns. In some embodiments, the catalyst is a platinum group metal. In some embodiments, the catalyst is platinum, rubidium, antimony, copper, silver, palladium, ruthenium, bismuth, zinc, nickel, cobalt, chromium, cerium, titanium, iron, vanadium, gold, manganese, or combinations thereof. In some embodiments, the catalyst is present in an amount of about 0.1-40 wt%, about 1-20 wt%, or about 3-10 wt%, based on a total weight of the fibers and the catalyst.
In some embodiments, the filter layer 106 has a thickness d2 of about 25 mm, about 10-40 mm, about 15-35 mm, about 20-30 mm, about 55-65 mm, about 50-70 mm, about 40-80 mm, or about 30-100 mm. In one or more embodiments, the filter layer 106 may have a density of about 0.1 g/cc, about 0.05-0.5 g/cc, about 0.075-0.3 g/cc, about 0.09-0.25 g/cc, or about 0.1-0.2 g/cc.
In some embodiments, the filter layer 106 has a variable density. For example, in some embodiments, the density of the filter layer is higher near the inlet 102 and/or near the closed end 104 as compared with a middle portion of the filter layer. By increasing the density at one or both of the ends of the filter layer 106, the filter cartridge 100 may have a tighter seal to minimize or eliminate fluid passing through untreated. In some embodiments, the density of the filter layer 106 may be variable along the length thereof in order to even out fluid flow through the filter layer 106.
Although the filter cartridge 100 is depicted herein as having a cylindrical shape, it is not so limited and may be, e.g., a triangular prism, a square prism, a rectangular prism, an irregular shape, etc. Each filter cartridge 100 may be configured to suit the particular needs of the industrial process in which it is being employed.
Turning to
In some embodiments, the second filter cartridge 100b includes a flange 114b that is configured to attach to the first filter cartridge 100a. In some embodiments, the first filter cartridge 100a may include a structure proximate the end 104a configured to attach to the flange 114b. For example, the first filter cartridge 100a may include perforations at end 104a that align with perforations of the flange 114b.
In some embodiments, the end 104a may include a filter layer positioned between the first filter cartridge 100a and the inlet 102b of the second filter cartridge 100b. In such embodiments, the filter layer of the end 104a may include components such as the filter layer 106, the inner permeable layer 108, and the outer permeable layer 110 described herein. In some embodiments, the end 104a may be more permeable than the filter layer 106a of the first filter cartridge 100a.
In some embodiments, the filter structure 1000 comprises two filter cartridges 100a and 100b. In some embodiments, the filter structure 1000 comprises at least two filter cartridges 100a, 100b... 100n. Each of the filter cartridges 100a, 100b... 100n may be as described herein with respect to the filter cartridge 100. In some embodiments, the filter structure 1000 includes filter cartridges 100a and 100b that differ in length, inner diameter, outer diameter, filter layer thickness, filter layer composition (fiber type, catalyst type or amount, fiber diameter, fiber length, etc.), filter layer thickness, filter layer density, and/or inlet configuration. In some embodiments, each of the filter cartridges 100a, 100b... 100n is identical except that the last filter cartridge includes a sealed end cap (or an end cap comprising a filter layer) while the other filter cartridges have a permeable end opposite their respective inlet that allows fluid to flow into the inlet of the adjacent downstream filter cartridge.
In some embodiments, the filter structure 1000 may be modular and comprise two or more filter cartridges, wherein the filter cartridges 100a, 100b... 100n may be connected to one another onsite. This design allows for easier installation in applications where space is limited (e.g., in a reactor). The modular design also allows for easy retrofitting of the filter structures 1000 into existing reactors.
In some embodiments, the filter structure 1000 comprises two filter cartridges 100a and 100b connected in series, wherein a flow distribution between the first and second filter cartridges 100a and 100b differs by 1% or less. As used herein, the flow distribution is measured as the volume percentage of fluid that passes through the filter layer 106a versus the filter layer 106b.
In one or more embodiments, filter cartridge 100 (or filter structure 1000) may form a portion of a catalyst bed of a reactor, such as a hydrogenation reactor, wherein fluid (gas and/or liquid) processed through the reactor undergoes catalytic hydrogenation. For example, the fluid may undergo selective hydrogenation of diolefins to avoid gum and green oil formation, conversions of light mercaptans and sulfides into heavier sulfur molecules, and/or conversions of acetylenes and dienes to primarily olefins. A plurality of filter cartridges 100 may be used as the catalyst bed of a reactor, with the number of filter cartridges 100 being determined based on the dimensions of the reactor and the filter cartridges 100.
A conventional tail-end hydrogenation reactor including catalyst beds comprising catalyzed spheres may have the specifications as shown in Table 1 below.
Conversely, a tail-end hydrogenation reactor comprising catalyst beds comprising filter cartridges 100 described herein may have the specifications as shown in Table 2 below.
As shown above, using the filter cartridges 100 according to the present disclosure allows for vastly increased throughputs, faster flow potential, and better use of existing bed space. The reactor using filter cartridges 100 also consumes less energy and allows for better heat transfer due to the increased surface area. The filter cartridges 100 can be retrofitted into existing reactors and the compact design thereof allows for installation through existing access points. The replacement of a standard fixed bed of pellets, spheres, etc. with the filter cartridge array will increase the surface area of the system resulting in improved yield, while reducing the volume and weight of the catalyst.
Further, the array of the filter cartridges 100 or filter structures 1000 described herein can reduce the overall dP of a reactor bed by increasing the frontal area of the system. Using conventional catalyst beds, additional shaped material would be added to increase the catalyst surface area. If the externals of the reactor are not changed, this addition of catalyst mass would dramatically raise the dP of the system. Conversely, as noted above, the filter cartridges 100 or filter structures 1000 increased frontal surface area, which reduces dP. That is, the increased dP caused by additional surface area of the filter cartridges 100 or filter structures 1000 is offset by the increased frontal surface area thereof such that the overall dP of the catalyst bed can be maintained or lowered.
According to embodiments of the present disclosure, the ratio of surface area to dP in a reactor bed comprising the filter cartridges 100 or filter structures 1000 can be increased by a ratio of 3 or more as compared to conventional reactor beds.
Referring to
Also disclosed herein is an emissions control unit, which may be used for a wide variety of flue gas treatments, such as CO oxidation, NOx reduction, and CO2 capture. The emissions control unit may include one or more filter modules 202, as shown in
Each filter 204 in the module 202 includes at least one inlet 206 and at least one closed end 208 opposite the inlet, such that gas flows into the inlet 206 and out through a porous catalytic layer 210. The catalytic layer 210 comprises at least one pleat. That is, the catalytic layer 210 is a folded sheet, which thereby forms the closed end 208 at the fold of the pleat and the inlet 206 opposite the closed end 208. The catalytic layer 210 may be formed of the same materials as the filter layer 106 described above. A thickness of the catalytic layer 210 may be about 9 mm, about 5-40 mm, about 7-30 mm, about 9-20 mm, or about 8-15 mm. A density of the catalytic layer 210 may be about 0.1 g/cc, about 0.05-0.5 g/cc, about 0.075-0.3 g/cc, about 0.09-0.25 g/cc, or about 0.1-0.2 g/cc.
In some embodiments, the filter 204 includes one or more permeable support layers 212. The permeable support layers 212 are porous and may be formed of, e.g., metal screens, which may comprise a metal mesh or fabric. In some embodiments, the filter 204 does not include any permeable support layers 212.
In some embodiments, the filter 204 include one or more support layers 214 positioned between the pleated layers of the catalytic layer 210. The support layers 214 may be shaped to match the dimensions of the pleats to provide rigidity to the filter 204 and maintain a shape of the catalytic layer 210. The support layers 214 may be perforated to allow transverse flow of waste gases within the filter 204.
Referring to
In some embodiments, the module 202 has a depth (measure in a direction from the inlets 206 to the closed ends 208) of about 4-24 inches, about 6-18 inches, about 6-12 inches, about 4 inches, about 6 inches, about 10 inches, about 12 inches, about 14 inches, or about 16 inches. In some embodiments, the module 202 has a width of about 6-40 inches, about 12-40 inches, about 24-36 inches, about 6 inches, about 10 inches, about 18 inches, about 20 inches, about 22 inches, about 24 inches, about 30 inches, about 36 inches, or about 40 inches. In some embodiments, the module 202 has a height of about 6-40 inches, about 12-40 inches, about 24-36 inches, about 6 inches, about 10 inches, about 18 inches, about 20 inches, about 22 inches, about 24 inches, about 30 inches, about 36 inches, or about 40 inches.
A conventional emissions control unit comprising a monolithic catalyst support may have the specifications as shown in Table 3 below.
Conversely, an emissions control unit comprising the module 202 described herein may have the specifications as shown in Table 4 below.
Using the module 202 described herein can maintain a similar or lower incumbent pressure drop (e.g., about 2 mbar or less) while providing the potential for lower CO and VOC oxidation and NOx reduction temperatures. Further, active catalysts can be directly applied to the fiber in the catalytic layer 210 without a wash coat (the same is true of filter layer 106). The greatly increased surface area of the support (i.e., fibers in catalytic layer 210) provides more available catalyst thereby improving reaction efficiency.
Computer Fluid Dynamics (CFD) analysis was used to analyze flow distribution and residence time across first and second filter cartridges aligned in series, as in filter structure 1000 shown in
A first test was run with straight inlets for each of the filter cartridges and fibers having a diameter of 7 microns (7-micron fibers). The resulting distribution was calculated as 48.0% in the first filter cartridge and 52% in the second filter cartridge.
A second test was run with straight inlets for each of the filter cartridges and fibers having a diameter of 4 microns (4-micron fibers). The resulting distribution was calculated as 48.9% in the first filter cartridge and 51.1% in the second filter cartridge.
A third test was run with straight inlets for each of the filter cartridges, the 4-micron fibers and a modified metal support structure around the fiber layer comprising less “dead zone” (i.e., a more porous support with a smaller solid, impermeable portion around the peripheries thereof). The resulting distribution was calculated as 49% in the first filter cartridge and 51% in the second filter cartridge.
A fourth test was run with the same parameters as the third test but with the addition of a converging inlet for the first filter cartridge. The resulting distribution was calculated as 49.4% in the first filter cartridge and 50.6% in the second filter cartridge. This result is shown in
In the above tests, it was found that as the difference in distribution increases, significant non-uniformities are observed in the first filter cartridge while flow in the second filter cartridge is significantly more homogenous. As such, the seemingly slight improvements yielded by modifying the inlet configuration and fiber geometry in the second and third tests greatly improved the flow distribution within the first filter cartridge.
There is a very delicate balance between increasing the active surface area in a reactor (resulting in increased yield) without sacrificing any benefit through an increase in dP. Increasing the frontal area of the catalyst bed will reduce the face/ linear/ approach velocity of the fluid to the catalyst bed. In doing so the dP will be lower relative to a bed with a smaller frontal area. Using the filter structure 1000 described herein in a catalyst bed allows for the introduction of additional frontal area. The addition of multiple sections of the filter structure 1000 reduces the dP while still providing a uniform fluid flow distribution between the multiple cartridges 100a, 100b... as the residency time of the fluid traveling in the filter layers 106a, 106b... can be configured to be nearly identical, as shown above.
By minimizing the difference in fluid distribution between the cartridges, the filter structure 1000 can be more efficiently utilized. That is, uneven flow distribution can yield dead zones where catalyst is underutilized. As such, the filter structure 1000 described herein can be effectively use the catalyst while increasing the frontal area and limiting dP.
Pressure drop (dP) was determined for three samples arranged in different configurations. One comparative sample was a 4″ diameter disc containing 19 g of fiber and having a thickness of 1″ (“fiber disc”). A second comparative sample was a commercial material comprising 130 g of shaped pellets (“commercial material”). The third configuration (“product form”) was a tube shaped form, as shown in
In
A reactor has been disclosed herein. The reactor includes a housing; one or more catalyst beds disposed within the housing. Each catalyst bed comprises a plurality of hollow filters each comprising an open end, a closed end opposite the open end, and a porous catalytic layer between the open end and the closed end; wherein the porous catalytic layer comprises inorganic fibers and a catalyst. The reactor may include any one or more of the following features:
A method of forming a catalyst bed and treating a waste gas has been disclosed herein. The method includes affixing a first hollow filter to a mounting plate, wherein the first hollow filter comprises: a first open end; a second open end opposite the first open end; a first porous catalytic layer disposed between the first open end and the second open end, the first porous catalytic layer comprising first inorganic fibers and a first catalyst; and a flange extending radially outward from the first open end; wherein affixing the first hollow filter comprises securing the flange to the mounting plate. The method further includes affixing a second hollow filter to the first hollow filter to form a filter unit, wherein the second hollow filter comprises: a third open end; a closed end opposite the third open end, the closed end being nonporous; a second porous catalytic layer disposed between the third open end and the closed end, the second porous catalytic layer comprising second inorganic fibers that are the same as or different from the first inorganic fibers and a second catalyst that is the same as or different from the first catalyst; and a second flange extending radially outward from the third open end; wherein affixing the second hollow filter comprises securing the second flange to the second open end of the first hollow filter. The method may include any one or more of the following features:
An emissions control module has been disclosed herein. The module includes a housing; and a filter disposed within the housing; wherein the filter comprises a porous filter layer pleated to form at least one open end and at least one closed end opposite the open end; and wherein the porous filter layer comprises inorganic fibers and a catalyst. The module may include any one or more of the following features:
Although the present disclosure has been described with reference to embodiments and optional features, modification and variation of the embodiments herein disclosed can be foreseen by those of ordinary skill in the art, and such modifications and variations are considered to be within the scope of the present disclosure. It is also to be understood that the above description is intended to be illustrative and not restrictive. For instance, it is noted that the diameter, length, thickness, and density values described above are illustrative only and can be readily adjusted by one of ordinary skill in the art to fit a wide range of potential reactors and processes. Many alternative embodiments will be apparent to those of ordinary skill in the art upon reviewing the above description. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the future shown and described or any portion thereof, and it is recognized that various modifications are possible within the scope of the disclosure.
The present application claims benefit of U.S. Provisional Pat. Application No. 63/209,702 filed Jun. 11, 2021, titled “Catalytic Filters for Hydrogenation and Emissions Control,” which is incorporated herein by reference in its entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/US2022/072869 | 6/10/2022 | WO |
Number | Date | Country | |
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63209702 | Jun 2021 | US |