Textured adsorbent sheets, assemblies containing them, and molds for producing them

Abstract

The textured sorbent sheet provides improved performance in vapor adsorption applications over conventional sheets, systems, canisters, and other emission control devices. The textured sorbent sheet can be formed as part of a compact, lightweight system, canister, or integrated into a fuel tank. In some embodiments, the textured sorbent sheet comprises activated carbon.

Description

[Background technology]

[0001] REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 877,125, filed July 22, 2019, the contents of which are incorporated herein by reference in their entirety.

[0002] Activated carbon sheets have very low permeability and are therefore used in a flow-across arrangement rather than a flow-through arrangement. These sheets can be stacked or spirally wound, naturally creating voids between the sheets for gas or liquid flow. By using smooth flat sheets, these stacks and spirals are physically stable in tightly wound configurations with porosities as low as 10%. To reduce pressure loss, higher porosities can be used, but in such cases the sheet stacks or sheet spirals can slip out of place, resulting in uneven sheet spacing, higher pressure loss, and uneven flow distribution.

[0003] Corrugating refers to squeezing or bending a material into pleats. Corrugated sheets, combinations of corrugated and flat sheets, or sheets with dimple patterns pressed into them were also not stable due to relaxation of the corrugations or pressed patterns back into flat sheets. In all these cases, the sheet is the same thickness as the original flat sheet, but the corrugated or dimpled patterns are pressed onto the flat sheet. These techniques were borrowed from the paper industry. The result was again physically unstable stacked or spiral sheet configurations with voids over 10%. An inherent problem was that corrugated or dimpled activated carbon sheets could relax back into their original flat sheets, either with reduced or eliminated corrugations in the case of corrugations, or to the same thickness as the original flat sheet in the case of dimples.

[0004] Two planar spacers and / or porous / permeable separators can also be used as part of a wound or layered adsorber to overcome these problems, but they add volume to the adsorber without any adsorption benefit.

[0005] These and other concepts are described in U.S. Patent Application No. 15 / 885,317, entitled "SORBENT DEVICES," filed January 31, 2018, and incorporated herein by reference in its entirety. The present disclosure further improves upon these concepts by providing, inter alia, thicker, textured carbon sheets, molds for producing them, and assemblies including rolled or stacked configurations. The present application discloses various embodiments, but is not limited to the described embodiments, as will be apparent to one of ordinary skill in the art upon reading this disclosure. The prior art documents relevant to the invention of this application are as follows (including documents cited during the international phase after the international filing date and documents cited when the application entered the national phase in other countries). 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"Mercury Speciation in Fluorescence Lamps by Thermal Release Analysis" 2003, Waste Management 23(10):879-886 Summary of the Invention

[0006] This Abstract is provided to comply with 37 CFR § 1.73, requiring a summary of the invention concisely indicating the nature and substance of the invention. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims.

[0007] In one embodiment, a textured adsorbent sheet is defined comprising an adsorbent and a binder, the textured adsorbent sheet defining an upper surface and a lower surface, at least one of the upper surface and the lower surface being a textured adsorbent sheet comprising a texture defined by a series of hills and valleys.

[0008] In another embodiment, the textured adsorbent has a thickness measured at the valley selected from less than about 1 mm, from about 0.1 mm to about 1.0 mm, from about 0.2 mm to about 0.90 mm, from about 0.5 to about 0.95 mm, from about 0.5 to about 0.90 mm, or any individual thickness or range subsumed within these example ranges.

[0009] In another embodiment, the textured adsorbent sheet may have a thickness measured at a hill or peak selected from about 1.0 to about 1.5 mm, about 1.4 mm, about 1.3 mm, about 1.2 mm, or any individual thickness or range encompassed by any two of these values.

[0010] In another embodiment, the distance from the tip of the hill to the bottom of the valley is selected from about 1.0 mm to about 0.1 mm, about 0.5 mm to about 0.1 mm, about 0.4 mm, about 0.3 mm, about 0.2 mm, or any individual distance or range encompassed by any two of these values.

[0011] In another embodiment, each of the upper and lower surfaces includes a texture defined by a series of hills and valleys.

[0012] In another embodiment, the texture of the upper surface is the same as the texture of the lower surface.

[0013] In another embodiment, the texture of the upper surface is different from the texture of the lower surface.

[0014] In one embodiment, a textured sorbent sheet product comprises at least two textured sorbent sheets according to the first embodiment, each textured sorbent sheet stacked and arranged such that adjacent upper and lower surfaces of another sheet are substantially parallel and arranged for fluid flow between at least the adjacent upper and lower surfaces.

[0015] In another embodiment, at least one of the textured adsorbent sheets is configured to be flat, wound into a spiral cylinder, wound into an oval, wound into an elongated rectangular rod, folded, laminated into an "S" shape, formed as concentric cylinders, formed as concentric ellipses, formed as concentric rectangular rods, or a combination of these configurations.

[0016] In another embodiment, the hill and valley portions are present on adjacent sheets and are nested.

[0017] In another embodiment, the peaks and valleys are on adjacent sheets and are not nested.

[0018] In one embodiment, a rolled textured adsorbent sheet product comprises a textured adsorbent sheet according to the first embodiment, the textured adsorbent sheet being spirally rolled to form adjacent sheet layers and to allow fluid flow around and between the adjacent sheet layers.

[0019] In another embodiment, the rolled textured adsorbent sheet product has a generally cylindrical shape with a length greater than its diameter.

[0020] In another embodiment, a vapor adsorption canister comprises the textured adsorbent sheet product of the previous embodiment and a housing at least partially enclosing the textured adsorbent sheet product.

[0021] In another embodiment, the vapor adsorption canister of the previous embodiment, wherein the housing is flexible.

[0022] In one embodiment, a rolled textured adsorbent sheet product and a housing that at least partially encapsulates the rolled textured adsorbent.

[0023] In one embodiment, a tank with integrated vapor adsorption comprises a tank structure, at least one textured adsorbent sheet according to the first embodiment, and at least one fastening device for fastening the textured adsorbent sheet to a surface of the tank that is not periodically immersed in a volatile liquid contained within the tank.

[0024] In another embodiment, the fastening device is an adhesive layer formed between one surface of the textured adsorbent sheet and the wall of the tank.

[0025] In another embodiment, a vehicle-mounted refueling vapor recovery device comprising the textured sorbent sheet of the previous embodiment.

[0026] In another embodiment, a device comprises the rolled textured adsorbent sheet product of the previous embodiment.

[0027] In one embodiment, an on-board refueling vapor recovery device comprising the vapor adsorption canister of the previous embodiment. [Brief description of the drawings]

[0028] [Figure 1] FIG. 1 is a profile diagram of the top surface of a rhomboid mold. [Diagram 2] FIG. 2 is a side view of a rhomboid mold. [Diagram 3] FIG. 3 is a bottom view of the diamond-shaped mold. [Figure 4] FIG. 4 is a profile view of the top surface of a round rib style #1 mold. [Diagram 5]FIG. 5 is a side view of a round rib style #1 mold. [Figure 6] FIG. 6 is a bottom view of the Round Rib Style #1 mold. [Figure 7] FIG. 7 is a profile view of the top surface of a round rib style #2 mold. [Figure 8] FIG. 8 is a side view of a round rib style #2 mold. [Figure 9] FIG. 9 is a bottom view of a round rib style #2 mold. [Figure 10] FIG. 10 is a profile view of the top surface of a round rib style #3 mold. [Figure 11] FIG. 11 is a side view of a round rib style #3 mold. [Figure 12] FIG. 12 is a bottom view of a round rib style #3 mold. [Figure 13] FIG. 13 is a profile view of the top surface of a round rib style #4 mold. [Figure 14] FIG. 14 is a side view of a round rib style #4 mold. [Figure 15] FIG. 15 is a profile view of the top surface of a triangle rib style #1 mold. [Figure 16] FIG. 16 is a side view of a triangle rib style #1 mold. [Figure 17] FIG. 17 is a bottom view of a triangle rib style #1 mold. [Figure 18] FIG. 18 is a profile view of the top surface of a triangle rib style #2 mold. [Figure 19] FIG. 19 is a side view of a triangle rib style #2 mold. [Figure 20] FIG. 20 is a profile view of the top surface of a carbon sheet with single sided textured round rib style #1 and a textured backing for added strength. [Figure 21]FIG. 21 is a side view of a carbon sheet with one sided texture made in a Round Rib Style #1 mold and a textured backing for added strength. [Figure 22] FIG. 22 is a profile view of the top surface of a carbon sheet with single-sided texture made with a round rib style #3 mold. [Figure 23] FIG. 23 is a side view of a carbon sheet with one-sided texture made with a round rib style #3 mold. [Figure 24] FIG. 24 is a profile view of the top surface of a carbon sheet with single-sided texture made with a round rib style #4 mold. [Diagram 25] FIG. 25 is a side view of a carbon sheet with one side texture made with a round rib style #4 mold. [Figure 26] FIG. 26 is a profile view of the top surface of a carbon sheet with double-sided texture made with a Round Rib Style #1 mold. [Figure 27] FIG. 27 is a side view of a carbon sheet with double sided texture made with a Round Rib Style #1 mold. [Figure 28] FIG. 28 is a profile view of the top surface of a carbon sheet with double-sided texture made with a round rib style #4 mold. [Figure 29] FIG. 29 is a side view of a carbon sheet with double sided texture made with a round rib style #4 mold. [Diagram 30] FIG. 30 is a profile view of the top surface of a carbon sheet with double-sided texture created with a Round Rib Style #4 mold, with the molds offset from one another. [Diagram 31] FIG. 31 is a side view of a carbon sheet with double sided texture made with a Round Rib Style #4 mold, with the molds offset from each other. [Diagram 32]FIG. 32 is a profile view of the top surface of a carbon sheet with a combination pattern made with a diamond mold on the top surface and a triangle rib style #1 mold on the bottom. [Diagram 33] FIG. 33 is a side view of a carbon sheet with a combination pattern made with a diamond mold on the top surface and a triangle rib style #1 mold on the bottom. [Diagram 34] FIG. 34 is a profile view of the top surface of a carbon sheet with a combination pattern made with a diamond mold on the top surface and a round rib style #2 mold on the bottom. [Diagram 35] FIG. 35 is a side view of a carbon sheet with a combination pattern made with a diamond mold on the top surface and a round rib style #2 mold on the bottom. [Diagram 36] FIG. 36 is a profile view of the top surface of a carbon sheet with a combination pattern made with a diamond mold on the top surface and a round rib style #4 mold on the bottom. [Figure 37] FIG. 37 is a side view of a carbon sheet with a combination pattern made with a diamond mold on the top surface and a round rib style #4 mold on the bottom. [Figure 38] FIG. 38 is a profile view of the top surface of a carbon sheet with a combination pattern made with a Round Rib Style #3 mold on the top surface and a Triangle Rib Style #2 mold on the bottom. [Figure 39] FIG. 39 is a side view of a carbon sheet with a combination pattern made with a Round Rib Style #3 mold on the top surface and a Round Rib Style #2 mold on the bottom surface. [Diagram 40] FIG. 40 is a profile view of the top surface of a carbon sheet with single sided texture made with a Triangle Rib Style #1 mold. [Diagram 41]FIG. 41 is a side view of a carbon sheet with single sided texture made with a Triangle Rib Style #1 mold. [Diagram 42] FIG. 42 is a profile view of the top surface of a carbon sheet with double sided texture made with a Triangle Rib Style #1 mold. [Diagram 43] FIG. 43 is a side view of a carbon sheet with double sided texture made with a Triangle Rib Style #1 mold. [Diagram 44] FIG. 44 is a profile view of the top surface of a carbon sheet with double sided texture made with a Triangle Rib Style #1 mold and with vertical molds made from thin carbon sheets. [Diagram 45] FIG. 45 is a profile view of a carbon sheet with double sided texture made with a Triangle Rib Style #1 mold and with vertical molds made from thin carbon sheets. [Diagram 46] FIG. 46 is a profile view of the top surface of a carbon sheet with double sided texture made with a Triangle Rib Style #1 mold and a vertical mold made from a thick carbon sheet. [Figure 47] FIG. 47 is a profile view of a carbon sheet with double sided texture made with a Triangle Rib Style #1 mold and with vertical molds made from a thick carbon sheet. [Figure 48] FIG. 48 is a profile view of the top surface of a carbon sheet with double-sided texture created with a diamond mold. [Figure 49] FIG. 49 is a side view of a carbon sheet with double-sided texture made with a diamond mold. [Figure 50] FIG. 50 is a graph of ΔP / g Carbon at 65 LPM for certain embodiments disclosed herein. [Figure 51]Figure 51A is an image of a configuration of an embodiment disclosed herein. Figure 51B is an image of a configuration of an embodiment disclosed herein. Figure 51C is an image of a configuration of an embodiment disclosed herein. [Figure 52] FIG. 52 is a graph of ΔP / g carbon at 70 LPM for certain embodiments disclosed herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] Before describing the compositions and methods of the present invention, it is to be understood that the present invention is not limited to the specific processes, compositions, or methodologies described, as these may vary. It is also to be understood that the terms used in the description are only for the purpose of describing the particular versions or embodiments, and are not intended to limit the scope of the present invention, which is limited only by the appended claims. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, the preferred methods, devices, and materials are described herein. All publications mentioned herein are incorporated by reference in their entirety. Nothing herein should be construed as an admission that the present invention is not entitled to antedate such disclosure by prior invention.

[0030] Also, it should be noted that as used herein and in the appended claims, the singular forms "a," "an," and "the" include the plural unless the context clearly dictates otherwise. Thus, for example, reference to a "combustion chamber" is a reference to "one or more combustion chambers," and equivalents thereof known to those skilled in the art, and so forth.

[0031] As used herein, the term "about" refers to a number that is plus or minus 10% of the number with which it is used, so about 50% means a range of 45% to 55%.

[0032] As used herein, the term "sorbent" is meant to encompass all known materials from any source that are capable of adsorbing and / or absorbing liquids and / or gases. For example, adsorbents include, but are not limited to, activated carbon, natural and synthetic zeolites, silica, silica gel, alumina, zirconia, and diatomaceous earth.

[0033] As used herein, descriptions and claims of multiple sorbent sheets mean that there are multiple separate sheets with sides and / or surfaces in close proximity to one another. Alternatively, descriptions and claims of multiple sorbent sheets mean that there is only a single sheet, but that it is rolled or folded on itself to result in a stacked, rolled, or otherwise constructed mass of sheets with the sides and / or surfaces of the sheets in close proximity to one another. The term also contemplates multiple sheets being stacked together and rolled or folded to form alternating layers in a single mass.

[0034] Embodiments of the present invention relate to apparatus including one or more textured sheets of sorbent material, as well as molds and methods for making the textured sorbent sheets, and apparatus comprising these sheets. In various embodiments, the textured sorbent sheets are comprised of a sorbent and a binder and can have a thickness sufficient to allow portions of the sheets to be compressed to create hills and valleys of a desired cross-sectional size and shape. The apparatus of various embodiments can include one or more of a housing and a textured sorbent sheet.

[0035] A very thick sheet of activated carbon, e.g., greater than 1.25 mm, was pressed between the flat and textured surfaces of a mold. The overall average thickness of the sheet was reduced and texture was added to only one side of the sheet. The thickness of the sheet varied with the hills and valleys of the texture pattern. This single sheet was stable over time and temperature since there was no way to relax the sheet to its original thickness. This method was possible due to the malleability of the thicker activated carbon sheet material.

[0036] In contrast, corrugated or dimpled patterns relax with time and temperature to a shape closer to the original flat sheet shape. One solution has been to add spacers between the sheets to obtain stable voids and helical structures. However, spacers increase cost and buildup without any adsorption performance. The best solution has been to glue small strips of activated carbon sheets to the flat sheets to provide a spacer that also adsorbs. This worked well in adsorption and pressure drop testing, but was labor intensive, introduced adhesives into the system, and was impractical for prototyping. These systems differ from corrugated sheets in that the sheets are not squeezed, bent, or folded, rather the sheet material is constructed by adding layers in selected locations and patterns. Much of this disclosure is concerned with emulating the construction of the material using embossing or compression techniques, whereby the desired texture of hills and valleys is formed in a relatively thick activated carbon sheet. This is distinct from dimpled patterns, where dimples are applied to a relatively thin sheet, resulting in a concave portion on one side of the sheet and a corresponding convex portion on the opposite side of the sheet. Over time, these dimples relax leaving a substantially flat sheet. The methods and textures described herein do not exhibit the same behavior.

[0037] The single sheet method, with one side flat and the other side having a textured pattern, creates a physically robust spiral, is practical to manufacture, and is stable over time and temperature since the original thick sheet had no means of relaxation. When finished, spirally wound or with flat sheets stacked together, the texture fits onto the flat surface, creating equally spaced and sized grooves for the fluid to flow through. Uniformity in the size and placement of these grooves means the lowest possible pressure drop for a given porosity, and the best flow distribution which improves adsorption performance.

[0038] The sheet may be textured on one or both sides. In some embodiments, the pattern and resulting channels are parallel or co-linear with the flow of fluid through the sheet to achieve low pressure loss. The texture itself may also form channels and flows that are not linear, e.g., slanted, serpentine, irregular, or more complex.

[0039] Mold or wrap

[0040] Central to this disclosure is the production of textured adsorbent sheets by a method of pressing selected portions of a relatively thick carbon sheet. As mentioned above, this can be accomplished by passing the carbon sheet through one or more rollers with a negative mold. Steel or other rollers with a grooved pattern are one option. It has been found that various molds can be formed in the form of wraps that can be attached around the rollers with rubber or other suitable material to achieve the desired textures and patterns. The wrap needs to be of a material that is stiff enough to imprint and compress the adsorbent sheet, but also flexible enough to wrap around the roller. The wrap includes a series of hills and valleys that correspond to, but are opposite to, the desired pattern of the textured adsorbent sheet. These various molds are shown in the various figures, as well as the resulting textured sheets. Steel or metal rolls can also be patterned. Molds can also be used as flat molds, or continuous feed belts past a main roller, specifically rubber molds. The figures are representative only and are not intended to be limiting. Various textures and patterns can be used depending on the desired properties. Figures 1-19 show various mold shapes. The shapes, textures, thicknesses, dimensions, and other features shown are exemplary. The actual molds are not limited to these designs. By selecting the shape, dimensions, and location of the hills and valleys, various properties of the resulting textured adsorbent sheet can be controlled.

[0041] Figures 1-3 show some standard views of a mold according to some embodiments. The mold 100 itself may be rubber and defines a front surface 200 and a back surface 300. The front surface 200 is defined by a series of hills 210 and valleys 220 that form a texture, here a repeating diamond texture. These hills and valleys create corresponding hills and valleys in the resulting textured adsorbent sheet. See, for example, Figures 20-49. The back surface 300 may be smooth, patterned, or textured. As used herein, "patterned" is different from "textured." The back surface 300 may include a pattern resulting from transferring a pattern during a texturing process. Surprisingly, it has been found that imprinting a pattern on the back surface of the sheet improves handling properties such as strength, grip (frictional retention), etc. These patterns can be imparted by patterns on a roll, e.g., a print roll, a transfer roll, a guide roll, etc., or by printing techniques. These patterns are not as extensive as the patterns of hills and valleys found on the "textured" surface of the sheet. Thus, as used herein, "texture" refers to the hills and valleys that are used in the mold to form complementary hills and valleys on the textured sheet. In the textured sheet, the texture (i.e., the hills and valleys) provide paths for fluid flow.

[0042] In some embodiments, the mold or wrap can be configured to imprint the adsorbent sheet in multiple passes. For example, the mold or wrap can be used in one orientation and then rotated, e.g., vertically, for a second pass to create a new texture. Figures 44-47 show textured sheets made from such a process.

[0043] Adsorbent Sheet

[0044] The sorbent sheets of the present invention can include any of the sorbent materials described above, including, but not limited to, activated carbon, carbon nanotubes, graphene, natural and synthetic zeolites, silica, silica gel, alumina, zirconia, clay, carbon black, and diatomaceous earth. In some embodiments, the sorbent sheets may be comprised of activated carbon. The sorbents may be used alone or in combination.

[0045] Activated carbon may be of various grades and types selected based on performance requirements, cost, and other considerations. Activated carbon may be granular from re-agglomeration of powders, granular by grinding or sizing nut shells, wood, coal, or pellets made by extrusion, or powdered activated carbon. Activated carbon may be formed by a process of carbonization and activation. Raw materials, such as wood, nut shells, coal, pitch, etc., are oxidized and devolatilized, and activated with steam and / or gasified carbon dioxide to form the pore structure of the activated carbon that is useful for adsorption. The initial oxidation and devolatilization and activation process may include chemical treatment with dehydrating chemicals, such as phosphoric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, and combinations thereof.

[0046] Various activation processes are known in the art. The most useful process for obtaining activated carbon for the sorbent sheets of the claimed invention involves obtaining wood and / or wood by-products, acid treating the wood and / or wood by-products by exposure to phosphoric acid, and carbonizing the wood and / or wood by-products using steam and / or carbon dioxide gasification. This process results in activated carbon particles with the highest butane working capacity (BWC), a measure of activated carbon performance. In this disclosure, the BWC measurement is referred to in two ways. One test method is the ASTM D5228 method, "Standard Test Method for Determination of Butane Working Capacity of Activated Carbon." In this disclosure, this method is referred to as ASTM BWC. The second method is referred to as EPA BWC and is referenced in the U.S. Code of Federal Regulations, CFR 86.132-96, section (h). These methods have been modified as necessary to accommodate the various textured sheet configurations described below. Specifically, in the ASTM BWC method, the sheet is tightly rolled to occupy a volume of the same diameter as the test method calls for, but with a smaller diameter. For the EPA BWC method, five cycles of adsorption and purging were performed for laboratory evaluation, and the last three were averaged to obtain a value.

[0047] Activated carbon can be formed from materials including bagasse, bamboo, coconut shells, peat, wood, such as sawdust and scrap forms of hardwood and softwood sources, lignite, coal and coal tar (bituminous and subbituminous), petroleum pitch, asphalt and bitumen, corn stalks and husks, wheat straw, spent grain, rice husks and shells, nut shells, and combinations thereof.

[0048] The sorbent sheet may further include one or more binders. The embodiments are not limited to specific binders including polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF2 or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO), UV curable acrylates, UV curable methacrylates, thermosetting divinyl ethers, polybutylene terephthalates, acetals or polyoxymethylene resins, fluoroelastomers such as perfluoroelastomers (FFKM) and tetrafluoroethylene / propylene rubbers (FEPM), aramid polymers such as para-aramid polymers and meta-aramid polymers, polytrimethylene terephthalate, ethylene acrylic elastomers, polyimides, polyamide-imides, polyurethanes, low and high density polyethylene, polypropylene, biaxially oriented polypropylene (BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers, and combinations thereof. The binder may be thermoplastic or thermosetting depending on the conditions and may include a mixture of thermoplastic and thermosetting compounds.

[0049] The amount of binder may be about 5% to about 40% by weight of the total composition, and in some embodiments, the amount of binder may be about 5% to about 20% by weight, about 5% to about 15% by weight, or about 5% to about 10% by weight of the total composition, or any individual amount or range encompassing these exemplary amounts. In some embodiments, the amount of binder is about 11% by weight. In some embodiments, the sorbent sheet may include a solvent, which may generally be present in a small residual amount, for example, less than about 10% by weight, less than about 5% by weight, or less than about 2% by weight and greater than about 0.1% by weight or about 0.2% by weight. Specifically, in some embodiments, the sorbent sheet may have no solvent (0%). When the amounts of materials above are selected, in some embodiments, the remaining balance of the material is the sorbent described above.

[0050] In some embodiments, the textured adsorbent sheet may have a thickness measured at the valley of less than about 1 mm, about 0.1 mm to about 1.0 mm, about 0.2 mm to about 0.90 mm, about 0.5 to about 0.95 mm, about 0.5 to about 0.90 mm, or any individual thickness or range encompassed by these example ranges.

[0051] In some embodiments, the textured adsorbent material sheet may have a thickness measured at the hills or peaks of about 1.0 to about 1.5 mm, about 1.5 mm, about 1.4 mm, about 1.3 mm, about 1.2 mm, about 1.1 mm, about 1.0 mm, or any individual thickness or range encompassed by any two of these values.

[0052] In some embodiments, the distance from the tip of the hill to the bottom of the valley is about 0.5 mm to about 1.0 mm, hi some embodiments, the distance is about 0.6 mm, about 0.5 mm, about 0.4 mm, about 0.3 mm, about 0.2 mm, 0.1 mm, or any individual distance or range encompassed by any two of these values.

[0053] The adsorbent sheets of various embodiments can have a density of about 0.05 g / mL to about 2.0 g / mL as measured by a Particle Density Test, and in other embodiments, the adsorbent sheets can have a density of about 0.08 g / mL to about 1.5 g / mL, about 0.1 g / mL to about 1.3 g / mL, or any density or range encompassed within these example ranges, as measured by a Particle Density Test. The ASTM BWC of each adsorbent sheet may be greater than about 10 g / 100 mL, and in some embodiments, the ASTM BWC may be from about 7.0 g / 100 mL to about 30 g / 100 mL, from about 8.0 g / 100 mL to about 25 g / 100 mL, from about 10 g / 100 mL to about 20 g / 100 mL, from about 10 g / 100 mL to about 15 g / 100 mL, from about 11 g / 100 mL to about 15 g / 100 mL, from about 12 g / 100 mL to about 15 g / 100 mL, or any individual BWC or range encompassed within these example ranges. In another embodiment, the ASTM BWC may be about 9 g / 100 mL to about 15 g / 100 mL, about 12 g / 100 mL to about 20 g / 100 mL, about 13 g / 100 mL to about 20 g / 100 mL, about 14 g / 100 mL to about 20 g / 100 mL, or about 15 g / 100 mL to about 20 g / 100 mL. It is also contemplated that any of the endpoints of the above ranges may be combined to form new, separate ranges. In some embodiments, each adsorbent sheet has a density of about 0.08 g / mL to about 1.5 g / mL.

[0054] The sorbent sheets of the present invention have higher performance, as measured by ASTM BWC, than conventional sorbents provided in powder or other particulate form.

[0055] The sorbent sheets of the embodiments can be made by any suitable process. In some embodiments, the sorbent sheets can be made by grinding granular or pelleted sorbent into a powder and mixing the powder with a binder to form a mixture. High shear mixing of the mixture is preferred, and the mixture is rolled to form the sorbent sheet. Heating can also be used to aid in mixing and rolling the materials. The grinding step can produce sorbent particles having an average particle size of about 0.001 mm to about 0.2 mm, about 0.005 mm to about 0.1 mm, about 0.01 mm to about 0.075 mm, or any individual particle diameter or range included within these example ranges, and in some embodiments, the ground sorbent particles can have an average particle size of about 0.001 mm to about 0.01 mm. The step of mixing the powder with the binder can include mixing about 5% to about 40% by weight or about 5% to about 10% by weight of the total composition, or any individual amount or range included within these example ranges. The optional heating can be carried out at any temperature sufficient to remove residual solvent, for example, from about 50°C to about 200°C.

[0056] The sorbent sheets of the present invention may include various distributions of particles of different sizes to enhance the packing efficiency of the powder within the sorbent sheet. Selecting different sized particles also improves the rheological properties of the powder and surrounding binder, improving mixing and uniform particle distribution prior to forming the sorbent sheet. In some embodiments, the particles of the sorbent sheet can have a single particle size distribution, while in other embodiments, the particles can have two different particle size distributions. In another embodiment, the particles can have at least three different particle size distributions.

[0057] The average particle sizes of at least two different particle populations, each having a particular size distribution, can be selected such that they have a ratio between about 1:1 and about 1:15. In another embodiment, the average particle sizes of the two different particle populations can have a ratio of about 1:1 to about 1:10. The average particle sizes may also have a ratio of about 1:1 to about 1:5, or any combination of the above ratios.

[0058] The spiral and stacked sheet assemblies have significantly higher ASTM BWC sorbent capacity for a given volume than prior art fuel vapor recovery sorbents. This feature can be exploited in a variety of ways. In some embodiments, the sorbent sheets can provide enhanced pollution control in jurisdictions where such high levels of control are required. In other embodiments, the overall size, cost, and weight of an on-board refueling vapor recovery (ORVR) system can be reduced for a particular level of performance. In another embodiment, an ORVR adsorber can be designed with improved performance over conventional adsorption canisters, thereby allowing designers to omit costly and complex returnless fuel pumping systems that would otherwise be required to reduce evaporative emissions. Higher performance adsorbers may also obviate the need for active condensing vapor systems, thereby avoiding the size, weight, and cost of compressor pumps and condensate storage tanks. However, it should be understood that ORVR adsorbers using the sorbent sheets of the present invention can also be combined with these systems for very high performance, as well as minimal size, weight, and cost penalties, compared to conventional systems.

[0059] The sorbent sheets can be configured together in a variety of ways depending on the physical space they must fit into, the device performance required, and the functions to be included in close proximity to the sheets. In some embodiments, the sheets may include folds and / or holes or openings to increase the surface area of ​​the sorbent sheets exposed to the passing fluid, thus increasing performance for a given total sheet surface area. The various folds, holes, and openings can also be sized and positioned to make way for internal and external functions, such as fluid channels, tubes, sensors, valves. The folds of the sorbent sheets can take a variety of forms, such as a spirally wrapped configuration in either a cylindrical or elliptical form. The folds can also be in the form of an "S" shape, or a convex or concave "C" shape, depending on the dimensions of the device required and / or any other required internal or external features. The sorbent sheets can also be stacked in flat or curved configurations, and the stacked sheets can be square, rectangular, circular, elliptical, or other irregular shapes as needed to fit a given space. This, in combination with the housing features described below, allows devices formed from sorbent sheets to fit into smaller, more irregularly shaped spaces than prior art canister devices, maximizing interior space in the vehicle.

[0060] In addition to the above configurations, the sorbent sheets can also have surface features. In some embodiments, the sorbent sheets can have protrusions, and in other embodiments, the sorbent sheets can have protrusions. These surface features can be combined within the same sheet. Protrusions and / or recesses on the sheets can be used to form various configurations between the sheets when the sheets are stacked, wrapped, etc. For example, the sheets can be arranged such that the protrusions and / or recesses nest with each other, thereby bringing adjacent sheets closer together. The sheets can also be arranged such that the protrusions and / or recesses do not nest with each other, thereby forming gaps between adjacent sheets. The registration can be used to form various channels for vapor adsorption between the sheets.

[0061] A sheet of activated carbon thicker than 0.9 mm is pressed between a flat surface and a textured surface. This compression can be done during the manufacture of the sheet in a roll mill with one smooth roll and one roll with machined grooves or indentations. The mill and both rolls must be able to withstand high hydraulic pressure to form the sheet in one step (e.g., chrome steel rolls). In some embodiments, the roll with grooves can be a roll with grooves integrally formed in the roll, or it can have a mold (or wrap) applied to the roll, such as a rubber mold with grooves formed in it. In either case, the grooves form a negative of the desired pattern in the textured adsorbent sheet. That is, the hills of the mold shape the valleys in the textured sheet and the valleys of the mold shape the hills in the textured sheet.

[0062] The texture is selected to achieve the desired properties including, but not limited to, voids.

[0063] Alternatively, a high pressure roll mill with two smooth rolls can be used to produce activated carbon sheets thicker than necessary, for example 1 mm. This thicker sheet then passes through a second mill with one smooth roll and another roll with grooves or indentations machined into the roll. The second mill can also have two textured rolls. This second mill does not require as much pressure because the sheet density and durability was achieved in the first mill. As a result, the second mill can use a wrap (made of rubber or polymer, for example) with a textured surface pattern around one of the rolls. This simplifies the equipment required and reduces the cost of changing the texture pattern.

[0064] Alternatively, a wrap (e.g., made of rubber or polymer) with a textured surface pattern can be imprinted into a thick sheet that is placed on a flat surface. This can be done manually on a flat table or in a calendaring unit.

[0065] In all three methods, the average thickness of the entire sheet can be reduced by compression, and in the process a texture pattern is added to one side of the sheet. The thickness of the sheet varies with the hills and valleys of the texture pattern. Starting with a thicker sheet than necessary ensures that even the minimum thickness (in the valleys of the pattern) contains enough sheet to provide physical strength.

[0066] It should also be noted that in sheets where a "smooth" side is employed during manufacture, some minimal texture transferred from the rollers actually provides additional strength. Thus, in some embodiments, one side of a textured sheet is provided with texture in the sense of creating hills and valleys that create pressure drop, and the other side is patterned such that the pattern adds strength to the sheet without necessarily contributing significantly to pressure drop.

[0067] Adsorbent Sheet Products

[0068] The textured sorbent sheets described above are combined into textured sorbent sheet products. The combination of textured sorbent sheets takes advantage of one or more of the features described above, such as increased surface area / volume ratio, reduced voids, improved sorption performance, etc. Generally, the individual textured sorbent sheets are positioned adjacent to one another to form the textured sorbent sheet product, which comprises sheets that are stacked, rolled, wrapped, folded, and / or laminated together, such that the surfaces of the sorbent sheets are in close proximity or adjacent to one another. Regardless of the arrangement, the goal is to maximize the surface area of ​​the sheets exposed to the vapor, fluid, and / or gas flow, and therefore maximize the performance of the textured sorbent sheet.

[0069] Laminated Textured Adsorbent Sheet Products: The laminated textured adsorbent sheet products of the present invention comprise two or more adsorbent sheets, each defining an upper and lower surface and having a known total surface area, each adsorbent sheet comprising a textured adsorbent and a binder, and adjacent adsorbent sheets stacked and arranged such that adjacent upper and lower surfaces are substantially congruent with one another and arranged such that fluid can flow between at least the adjacent upper and lower surfaces. Alternatively, two textured sheets, independently textured on one or both sides, can be separated by a smooth sheet. Any combination of textured and smooth sheets can be used to achieve the desired effect.

[0070] The improved performance of the laminated textured sorbent sheet products of the present invention can also be measured by comparing the performance of a product containing a particular amount of activated carbon to the performance of the same amount and grade of activated carbon when provided in pelleted, granular, or powdered form in a canister. In some embodiments, the laminated sorbent sheet products have an ASTM BWC that is about 3% higher, about 5% higher, about 7% higher, about 9% higher, about 10% higher, about 12% higher, about 14% higher, and about 16% higher than the same amount and grade of activated carbon in pelleted or powdered form in a canister. Ranges based on these amounts are also contemplated, e.g., about 5-14% higher, about 5-10% higher, about 10-16% higher performance, etc.

[0071] These improvements are measured only between the volume of pelletized or powdered activated carbon and the laminated textured sorbent sheet product, without accounting for other improvements of the laminated textured sorbent sheet product. One important difference above is the elimination of the rigid canister body that would otherwise be required in prior art systems involving pelletized or powdered activated carbon, because loose activated carbon cannot stand on its own, driving further weight reduction and therefore further performance for a given weight.

[0072] The laminated adsorbent sheet product has an ASTM BWC that is at least 10% higher than the ASTM BWC of the pelletized / powdered form of the same volumetric amount of textured adsorbent in the adsorbent sheet. The laminated adsorbent sheet product has an ASTM BWC of greater than about 10 g / 100 mL. The laminated adsorbent sheet product has an ASTM BWC of about 7.0 g / 100 mL to about 30 g / 100 mL, or greater than about 12 g / 100 mL, or greater than about 13 g / 100 mL, or greater than about 14 g / 100 mL, or greater than about 15 g / 100 mL, or greater than 20 g / 100 mL. For example, ranges of about 10-20 g / mL, about 10-12 g / mL, about 10-14 g / mL, about 12-14 g / mL, about 12-15 g / mL, and about 15-20 g / mL are also contemplated.

[0073] In some embodiments, the laminated sheets are held at a distance that controls one or more of the void volume, flow rate, pressure loss, and other properties. Spacing can also be achieved using various folds in the sheets, as well as by corresponding protrusions and / or recesses in the sheets that are arranged to form gaps between the sheets. If the sheets are intentionally arranged so that the protrusions and / or recesses of the sheets do not nest between the sheets, this will result in another spacing between the sheets where fluid can flow. If the sheets are intentionally arranged so that at least some of the protrusions and / or recesses nest between the sheets, this will cause the sheets to stack more closely together, reducing the spacing between the sheets and correspondingly reducing or even ceasing fluid flow. A combination of these features can be used to form a laminated adsorbent sheet product with oriented areas or channels for fluid flow and barriers or edge seals to prevent fluid leakage. These features for fluid flow also include holes, slits, or openings through one or more of the sheets of the laminated adsorbent sheet product.

[0074] Each sorbent sheet defines opposing side edges that are substantially parallel to the fluid flow. The corresponding side edges of adjacent sorbent sheets may be separate from one another, joined together, or some combination thereof. In this manner, the edges of the laminated textured sorbent sheet product may be sealed, partially sealed, or unsealed. Sealing or non-sealing can be selected to achieve a desired result, such as altering the fluid flow rate and / or pattern or other characteristics.

[0075] In some embodiments, the laminated textured sorbent product provides a void volume of about 10% or more, in some embodiments, the void volume is about 10%-40%, and others 15%-30%.

[0076] In some cases, the textured sorbent sheet product includes at least two populations of textured sorbent particles, each of the at least two populations having a different average particle size. See above discussion of bimodal particle size distribution as described with respect to individual textured sorbent sheets. For products formed from multiple textured sorbent sheets, the same distribution ratio between the populations of sorbent particles is contemplated. In some cases, the density of textured sorbent particles achieved by the at least two populations is greater than the density achieved by either population alone. The inclusion of a bimodal particle size distribution can improve the mechanical properties of the textured sorbent sheet product by making the polymer sheet more resistant to shear forces.

[0077] In some cases, the textured adsorbent sheet product comprises at least two textured adsorbent sheets, each having defined upper and lower surfaces having a combined total surface area, each textured adsorbent sheet comprising a textured adsorbent and a binder, each textured adsorbent sheet arranged in a stack such that adjacent upper and lower surfaces of separate sheets are substantially parallel and are arranged to allow fluid flow at least between the adjacent upper and lower surfaces.

[0078] Textured sorbent sheet products having ASTM BWC values ​​that are about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, and about 50% higher than the ASTM BWC of an equal volume of sorbent in pellet, granular, or powder form. These can be combined to form ranges, e.g., about 5-25% higher. The invention also contemplates these amounts as end points of a range, e.g., at least about 40% higher.

[0079] The textured sorbent sheet of the textured sorbent sheet product may be flat, wound into a spiral cylinder, wound into an oval, wound into an elongated rectangular rod, folded, laminated into an "S" shape, formed as concentric cylinders, formed as concentric ellipses, formed as concentric rectangular rods, or configured as a combination of these configurations.

[0080] In some embodiments, the textured sorbent sheet product comprises a single textured sorbent sheet that is rolled or wrapped to achieve desired properties including, but not limited to, density, voids, pressure drop, etc.

[0081] Rolled / Rolled Textured Adsorbent Sheet Products: Textured adsorbent sheet products may also be rolled or rolled as an alternative to or in combination with the laminated embodiments. Rolled or rolled textured adsorbent sheet products include adsorbent sheets defining upper and lower surfaces, which together have a known total surface area, the adsorbent sheets including a textured adsorbent and a binder, and the adsorbent sheets are rolled in a spiral shape to shape adjacent sheet layers that allow for fluid flow around and between adjacent sheet layers.

[0082] Similar to stacked sheet arrangements, rolled sorbent sheet products provide improved performance over textured sorbent sheets alone and an equivalent volume of activated carbon provided in pellet or powder form.

[0083] The improved performance of the rolled textured sorbent sheet products of the present invention can also be measured by comparing the performance of a product containing a particular amount of activated carbon to the performance of the same amount and grade of activated carbon when provided in pelleted or powdered form in a canister. In some embodiments, the rolled sorbent sheet products have an ASTM BWC that is about 3% higher, about 5% higher, about 7% higher, about 9% higher, about 10% higher, about 12% higher, about 14% higher, and about 16% higher than the same amount and grade of activated carbon in pelleted or powdered form in a canister. Ranges based on these amounts are also contemplated, such as about 5-14% higher performance, about 5-10% higher performance, about 10-16% higher performance, etc.

[0084] The rolled sorbent sheet product has an ASTM BWC that is at least 10% higher than the ASTM BWC of the pelletized / powdered form of the same weight of textured sorbent in the sorbent sheet. The laminated sorbent sheet product has an ASTM BWC of greater than about 10 g / 100 mL. The laminated sorbent sheet product has an ASTM BWC of about 7.0 g / 100 mL to about 30 g / 100 mL, or greater than about 12 g / 100 mL, or greater than about 13 g / 100 mL, or greater than about 14 g / 100 mL, or greater than about 15 g / 100 mL, or greater than 20 g / 100 mL. For example, ranges of about 10-20 g / mL, about 10-12 g / mL, about 10-14 g / mL, about 12-14 g / mL, about 12-15 g / mL, and about 15-20 g / mL are also contemplated.

[0085] The rolled adsorbent sheet products described herein have a generally cylindrical shape with a length substantially greater than its diameter, although any size can be used, including conical or frusto-conical variations, as well as ellipsoidal or other shapes.

[0086] The density of the rolled adsorbent sheet product can be calculated based on the following formula: [Table 1]

[0087] The weight of the rolled adsorption sheet product is approximately 80 to 1500 kg / m 3 , about 500~2000kg / m 3 , about 750~1500kg / m 3 , about 900~1200kg / m 3 , about 900~1050kg / m 3 , about 400~500kg / m 3 , about 500~600kg / m 3 , about 500~550kg / m 3 , about 600~650kg / m 3 , about 650~700kg / m 3 , and about 700-750 kg / m 3 The wire can be wound to an average winding density of 0.1 to 1.0 μm.

[0088] The rolled adsorbent sheet product has an ASTM BWC of greater than about 10 g / 100 mL. In some embodiments, the rolled adsorbent sheet product has a BWC of about 7.0 g / 100 mL to about 30 g / 100 mL. The rolled adsorbent sheet product may also have the same ASTM BWC as the unrolled adsorbent sheet products described above.

[0089] Similar to the discussion above regarding laminated textured sorbent sheets, the rolled or wrapped textured sorbent sheets can include multiple particle size distributions or populations of pelletized or powdered activated carbon. The same ratios were considered above. As explained above, this allows for greater amounts of activated carbon to be incorporated into the sheet formed into the rolled sorbent sheet product, thus improving performance.

[0090] As used herein, a rolled or rolled sorbent sheet product refers to any form of layering of one or more textured sorbent sheets by rolling (of any cross-sectional shape, e.g., circular, oval, square, triangular, rectangular, etc.), spiral winding, concentrically layered tubes, or combinations thereof. For example, a single textured sorbent sheet may be spirally wound along its length to form a cylindrical rolled textured sorbent sheet product. As another example, multiple textured sorbent sheets can be stacked and then rolled together to form a similar cylindrical shape. As another alternative, several sheets formed into a cylinder, each with a slightly different diameter than the next, can be arranged such that they consist of concentric rings of similarly sized cylindrical cross-sections. As described elsewhere herein, various combinations of these and other arrangements can be used to fill a space within a housing or canister of any shape.

[0091] A spiral winding method was explored. Four spiral configurations were co-wound on approximately 100g of carbon mass and tested in a 250mL canister. Each configuration had a 0.5mm thick double-sided round rib textured sheet similar to that shown in Figure 26, co-wound with a second 0.5mm or 1.0mm sheet, either smooth or perforated. Configuration 1 employed 0.5mm textured sheet / 1.0mm smooth sheet, configuration 2 employed 0.5mm textured sheet / 1.0mm perforated sheet, configuration 3 employed 0.5mm textured sheet / 0.5mm smooth sheet, and configuration 4 used 0.5mm textured sheet / 0.5mm perforated sheet. As shown in the graph below, configuration 1 provided the greatest margin in terms of ΔP, 30% less than the other configurations. Configuration 1 exhibited a ΔP of 3.4 inches of water, with a maximum target of 6.0 inches of water. Additional carbon was added to Configuration 1 at approximately 7.7%, resulting in a disproportionate increase of 75% up to the 6.0 inch water limit. The EPA BWC increased by 5.1% from 50.1 g / L to 52.6 g / L butane. See Figure 50 for a graph showing ΔP / g carbon at 65 LPM for these embodiments.

[0092] The use of thick (1.0 mm) smooth sheets in configuration 1 appeared to be advantageous. The stiffer structure of the smooth, thick sheets may offer better resistance to compression when placed in a canister, and ΔP provides a good indication for screening promising helical designs, but the increase in pressure drop may not be proportional to the increase in carbon mass, limiting the increase in BWC.

[0093] Void evaluation

[0094] Using 1.0 mm thick sheets, three single sheets were spirally wound with a carbon mass of 26 g. For screening, the volume was 0.07 L. Configuration A: textured inwards, Configuration B: textured outwards, Configuration C: textured on both sides. A tension of 100 g was applied during the winding process. Configurations A and C had the lowest ΔP / g. Using the EPA BWC test method, Configuration A had 12% more BWC compared to Configuration C. The voids in Configuration B appear to be stretched / flattened by the outwards winding. See images 51A, 51B, and 51C of these configurations.

[0095] Analysis of the photographs shows that Configuration A has more consistent openings and maintains the shape of the texture, the openings in Configuration B appear to collapse closer to the central core, and the texture in Configuration C is more open but less consistently distributed. See Figure 52 for a graph of ΔP / g Carbon at 70 LPM for several embodiments disclosed herein.

[0096] The above image was analyzed to determine the amount of voids present (based on pixel color).

[0097] result:

[0098] [Table 2]

[0099] [Table 3]

[0100] [Table 4]

[0101] [Table 5]

[0102] [Table 6]

[0103] [Table 7]

[0104] [Table 8] Configurations A and C were further tested in 250 mL canisters, yielding EPA BWC values ​​of 55 g / L and 51 g / L, respectively, demonstrating the advantage of the A configuration.

[0105] [Table 9] Configurations A and C were further tested in 250 mL canisters, yielding EPA BWC values ​​of 55 g / L and 51 g / L, respectively, demonstrating the advantage of the A configuration.

[0106] Conclusion:

[0107] The pressure drop of the spiral depends on the voids. More voids reduces the pressure drop. Less void space increases the pressure drop. Therefore, the voids can be controlled by manipulating the size of the hills and valleys of the textured adsorbent sheet and the spiral winding characteristics.

[0108] housing

[0109] The present invention also contemplates the use of a housing that partially or completely encapsulates the textured sorbent sheet. The housing may be configured in a variety of shapes, such as tetrahedrons, cubes and cube-like shapes, cylinders, spheres, single-sheet hyperboloid shapes, cones, ellipses, rectangles, hyperbolic paraboloid shapes, elongated rod shapes, paraboloids, and combinations of these shapes. The combinations may be selected to have different sections, each with a different shape or different shaped sections. The housing may also comprise sections separated and connected by another component, such as at least one hose or tube designed to transport fuel vapors as needed, or a thin section of the housing that includes the textured sorbent sheet. The housing may also be configured shapeless, such as a flexible bag or pouch that includes the textured sorbent sheet.

[0110] One of the primary advantages of the present invention is that the textured sorbent sheets are both flexible and self-supporting, and can be laminated, rolled, coiled, folded, or stacked in various configurations within a housing to fit a variety of mechanical requirements within the confines of a vehicle. In such an embodiment, the housing would be designed to match or fit into the space available to store the device. For example, the housing can be sized and shaped to fit into wheel wells, drive shafts, batteries for hybrid powertrains, spare tires, tire changing tools, tire patching tools, vehicle trunks or other storage spaces, vehicle bumpers and body panels, exhaust systems, other emission control devices such as urea or other injection tanks, fuel lines, vehicle frames, suspension components, spaces in or around engine compartments, spaces under passenger seats, spaces within passenger seats, and other spaces that are too small or difficult to reach to be effectively utilized as passenger or cargo space.

[0111] To further reduce weight and size and utilize a free-standing textured sorbent sheet, the housing can be in the form of a thin-walled bag or pouch. This is possible because the textured sorbent sheet has a mechanical structure and is free-standing, eliminating the need for a rigid outer container as in conventional canisters. The film material forming the bag can have a thickness of about 10 μm to about 250 μm. In another embodiment, the film of the bag can have a thickness of about 20 μm to about 175 μm, and the film of the bag can have a thickness of about 50 μm to about 125 μm.

[0112] The bag or pouch may be formed from any material used in fuel systems, particularly a material designed to withstand the chemical effects of contained fuel vapors. Bag materials include polytetrafluoroethylene (PTFE or TEFLON), polyvinylidene fluoride (PVF2 or PVDF), ethylene-propylene-diene (EPDM) rubber, polyethylene oxide (PEO), UV curable acrylates, UV curable methacrylates, thermosetting divinyl ethers, polybutylene terephthalate, acetal or polyoxymethylene resins, fluoroelastomers such as perfluoroelastomers (FFKM) and tetrafluoroethylene / propylene rubbers (FEPM), aramid polymers such as para-aramid and meta-aramid polymers, polytrimethylene terephthalate, ethylene acrylic elastomers, polyimides, polyamide-imides, polyurethanes, low and high density polyethylene, polypropylene, biaxially oriented polypropylene (BoPP), polyethylene terephthalate (PET), biaxially oriented polyethylene terephthalate (BoPET), polychloroprene, and copolymers, and combinations thereof. The bags are usually thermoplastic for flexibility, but may also be combined with amounts of thermosetting resins or be in the form of cured rubber or elastomers.

[0113] The housing, bag, or pouch can also be designed to function as a vapor barrier to the adsorbed fuel vapors contained therein. This barrier property may be inherent in the polymer itself or may be achieved by using at least one barrier additive and / or at least one barrier layer. Examples of barrier additives that can be formed as layers or as particulate fillers include polymers such as epoxies, polyamides, polyamideimides, fluoropolymers, fluororubbers, and combinations thereof. Barrier layers can also be made of metals such as aluminum, steel, titanium, and alloys thereof. Metallic barrier layers can be formed by conventional mechanical means, such as coextrusion or adhesion with other layers of the housing, or they can be chemically deposited, such as by chemical vapor deposition or electroplating. Metallic barrier layers can be formed from foils having a thickness of less than about 25 μm, less than about 20 μm, less than about 15 μm, less than about 10 μm, or less than about 5 μm.

[0114] The housing and its material may also be selected to be compatible with "ship-in-bottle" fuel systems. In such systems, many or all of the fuel system components, including the fuel pump, ORVR, fuel filter, valves, and other components, are mounted within the vehicle's fuel tank. Such systems are advantageous because they reduce assembly time and the amount of space required for the fuel system. In such systems, the housing must be of a material that can be immersed in the selected fuel, usually gasoline, for extended periods of time within the vehicle's fuel tank, while at the same time being able to withstand the effects of fuel vapors adsorbed therein.

[0115] The housing may also be a thin metal housing. Thin metal housings can be formed from flexible or rigid metals, such as steel, aluminum, titanium, and alloys thereof. Metal housings can be formed from foils having a thickness of about 5-100 μm, or about 10-250 μm. In some embodiments, the foils may be about 1 mm thick. Whether the housing is flexible or rigid depends on the choice of material, thickness, and any treatments applied to the metal, such as heat treatments or hot or cold working.

[0116] In some embodiments, the housing for the textured sorbent sheet may be omitted entirely, and the textured sorbent sheet is contained within the fuel tank itself. In such a configuration, the textured sorbent sheet can be attached to a portion of the interior of the fuel tank that is not in regular contact with liquid fuel and is free to adsorb fuel vapors. This portion is typically the top or side of the fuel tank, or a combination thereof. The fuel tank can also include a textured sorbent sheet and a recess on the top or side designed to allow the textured sorbent sheet to adsorb fuel vapors. Such an embodiment in which the textured sorbent sheet is attached to the interior of the fuel tank not only provides the greatest space and weight savings by eliminating a canister structure, but also simplifies manufacturing and installation, since the sheet is already installed within the fuel tank during assembly of the vehicle.

[0117] The housing can also be eliminated by forming a rolled or folded sorbent sheet and then selectively curing the outer sheet, which forms a durable hardened shell that acts as a support for the inner rolled or folded sorbent sheet. Such selective curing can be accomplished thermally or with a chemical bath, or by actinic radiation, e.g., ultraviolet light, or by electron beam curing.

[0118] In embodiments where the textured sorbent sheet omits the housing and is contained within the vehicle fuel tank itself, the textured sorbent sheet can be attached to the fuel tank in a variety of ways. The textured sorbent sheet can be secured using mechanical fasteners, such as screws, rivets, clamps, or the textured sorbent sheet can be secured using an adhesive backing disposed between the fuel tank wall and the textured sorbent sheet. The adhesive backing may be a single layer adhesive or a double-sided adhesive tape or sheet. Adhesives used for the adhesive backing can include pressure sensitive adhesives, UV curable adhesives, heat curable adhesives, hot melt adhesives, and reactive multi-part adhesives. Adhesive compositions include acrylics and (meth)acrylics, acrylates and (meth)acrylates, epoxies in one-part and two-part formulations, and urethanes.

[0119] The textured sorbent sheet can be applied in a variety of ways during manufacturing. In some embodiments, the fuel tank can be formed and the textured sorbent sheet is applied in a separate step after the adhesive is applied. In another embodiment, the textured sorbent sheet is placed on the inside of a mold, with or without an adhesive backing as appropriate, and the fuel tank is injection molded or blow molded around the textured sorbent sheet. In another embodiment, the textured sorbent sheet may be co-extruded with panels of material that make up the sides of the fuel tank, and the edges of these panels are glued or welded together to seal the finished tank with the textured sorbent sheet on the interior.

[0120] When the textured sorbent sheet is contained within a vehicle fuel tank without a housing, the fuel tank may include additional valves and ports to accommodate adsorption and desorption of fuel vapors within the fuel tank. For example, during engine operation, air may be introduced into the fuel tank to desorb fuel vapors contained on the textured sorbent sheet and present in the tank. These desorbed fuel vapors are then sent to the engine for combustion in an optimal cycle as required by the engine control unit (ECU).

[0121] When the textured sorbent sheets are provided without a housing and are contained within a tank, such as a fuel tank of a vehicle, they can be positioned such that they are not periodically immersed in the volatile liquid normally contained within the tank. This prevents the textured sorbent sheet from becoming saturated faster than normal and also exposes sufficient surface area to vapors within the fuel tank to allow for vapor adsorption. This feature contemplates that the textured sorbent sheets can be placed in portions of the tank that are not filled, such as the ullage or headspace of the tank, or adjacent baffles that prevent liquid from sloshing on the textured sorbent sheet. The textured sorbent sheets can also be placed in dedicated portions of the tank, such as small chambers or crevices that liquid cannot enter.

[0122] The apparatus of various embodiments can include a housing and a textured sorbent sheet as described above. The housing can be of any shape and can be configured to purify a gas or liquid. For example, in some embodiments, the housing can be of any shape, such as cuboid, cubic, or cylindrical. The textured sorbent sheet can be sized to fit within the housing and substantially fill the space within the housing through which the gas or liquid passes. In some embodiments, two or more textured sorbent sheets can be stacked to substantially fill the housing, and in other embodiments, the textured sorbent sheets can be rolled to form a spirally wound sheet or pressed to form a stacked sheet. In some embodiments, the stacked or pressed sheets can be such that the sides of adjacent sheets are substantially adjacent. In other embodiments, the stacked or pressed sheets can be arranged such that adjacent sheets are spaced apart. For example, in some embodiments, the sheets can be corrugated with the textured sorbent sheets forming a series or parallel ridges and grooves, and in some embodiments, the corrugated textured sorbent sheets can be separated by flat textured sorbent sheets. The corrugated textured adsorbent sheets may be disposed within the housing in a stacked or rolled / spiral wound configuration.

[0123] In various embodiments, the porosity may be about 30% to about 32% less than the void volume of current devices, and in some embodiments, the porosity may be as low as 10%. For example, the devices may have a porosity of about 45% to about 10%, about 35% to about 10%, about 25% to about 10%, or any individual porosity or range encompassed by these exemplary ranges. The devices of various embodiments may exhibit less flow restriction, e.g., pressure loss, than devices that use granular or pelleted textured adsorbents. Thus, more textured adsorbents may be incorporated into such devices without reducing the flow rate of the device.

[0124] The devices of such embodiments may have an EPA BWC of greater than about 5.0 g / 100 mL, and in some embodiments, the devices may have an EPA BWC of about 4.0 g / 100 mL to about 20 g / 100 mL, 5.0 g / 100 mL to about 18 g / 100 mL, about 7.0 g / 100 mL to about 16 g / 100 mL, or about 8.0 g / 100 mL to about 15 g / 100 mL, or any individual BWC or range within these example ranges. The devices may exhibit a pressure drop up to equal to a conventional dense packed bed of activated carbon or other active compound powder, pellets, or granules. This feature is advantageous because the textured sorbent sheet products, whether stacked, rolled, coiled, or otherwise configured, still have the ability to process and transport vapors and gases similar to conventional devices, despite the improved performance of the sorbent.

[0125] The laminated or rolled textured sorbent may be combined with a housing to serve as a vapor loss canister or other device. As noted above, the geometry and properties achieved by the laminated or rolled product allow for unique configurations and enhanced performance.

[0126] According to some embodiments, the vapor loss canister comprises a housing having at least one sidewall defining an interior space, an adsorbent sheet product, and an adsorbent sheet media sized and configured to fit within the housing and to substantially fill the entire interior space within the housing, the interior space being substantially free of other interior materials other than the adsorbent sheet media. That is, conventional vapor loss canisters require springs, filters, support substrates, etc. to hold and maintain the loose carbon powder or pellets. The adsorbent sheet is substantially freestanding and does not require these additional support structures. This allows more material to be included or a smaller canister to be used without sacrificing performance.

[0127] In some embodiments, the adsorbent sheet product comprises a laminated adsorbent sheet medium comprising as described above. In such cases, the housing or canister can be of any shape as described above, but in some embodiments is relatively flat and flexible to accommodate the laminated adsorbent sheet medium having a height substantially less than its length or width. In these cases, the housing can be a flexible bag or pouch as described above.

[0128] In some cases, the canister is adapted for placement on or within the fuel tank.

[0129] In some embodiments, the adsorbent sheet product comprises a rolled adsorbent sheet product as described above.In some cases, at least a portion of the housing sidewall defines a filter without occupying substantially any of the interior canister space.

[0130] In some embodiments, a fuel tank may include an integral vapor sorption tank, comprising a tank structure, at least one stacked or rolled sorbent sheet product, and at least one fastening device for fastening the textured sorbent product to a surface of the tank that is not periodically immersed in the volatile liquid contained within the tank. The fastening device may be an adhesive layer formed between one surface of the textured sorbent product and a wall of the tank.

[0131] Such adhesives may be at least one of pressure sensitive adhesives, UV curable adhesives, heat curable adhesives, hot melt adhesives, reactive multi-part adhesives, acrylic and (meth)acrylic adhesives, acrylate and (meth)acrylate adhesives, epoxy adhesives in one and two part formulations, urethane adhesives, and copolymers and combinations thereof.

[0132] The tank may further include one or more of at least one fuel pump, a fuel delivery line, a fuel return line, an atmospheric vent line, a port, a valve, a sensor, an air inlet, an open cell foam, a baffle, a bladder, and combinations thereof.

[0133] In some embodiments, the tank is a fuel tank in a "ship-in-a-bottle" configuration.

[0134] Some embodiments depict an on-board refueling vapor recovery (ORVR) device comprising a textured sorbent sheet product as described herein. The on-board refueling vapor recovery device can comprise a vapor sorption canister as described herein. The on-board refueling vapor recovery device can comprise a tank with integral vapor sorption.

[0135] Another component

[0136] The present invention may include sensors, such as fuel composition sensors. A fuel composition sensor may be used to detect the mixture of gasoline and ethanol contained within the housing and textured sorbent, and this information may be communicated to the ECU so that the vapors later released to the engine can be more accurately used during engine combustion. Other sensors include temperature sensors, vapor pressure sensors, oxygen sensors, etc. Sensors may operate based on principles such as electrochemical interaction, electronic such as thermocouples, electromechanical, refractive index, infrared spectroscopy, etc., depending on the type of information required by the ECU. Sensors may be included in the housing, alone or in combination, or in the area containing the textured sorbent sheet if no housing is specified. Sensors may be included in holes or notches cut from the sheet, or in the spaces between the sheets, with the sheets wrapped or folded around the sensors.

[0137] The present invention can include inlets, outlets, hoses, and associated valves to control the flow of fuel vapors to and from the textured sorbent of the present invention. The openings can be static or have valves that are opened and closed as needed by the ECU to control the flow of vapors to and from the sorbent sheets of the present invention. For example, during refueling, the outlet valves remain closed to ensure that exhausted fuel vapors do not escape to the atmosphere. However, when the engine is running and the ECU requests it, at least one outlet valve opens to release the adsorbed vapors to the engine for combustion. Vents and valves to the atmosphere can also be provided in case there are too many fuel vapors for the textured sorbent sheets of the present invention to safely adsorb. Inlets and valves for air or other gases, such as inert exhaust gases, can further be provided to desorb the fuel vapors as they are sent to the engine for combustion.

[0138] The present invention also contemplates the inclusion and integration of other components that make up the ORVR system and apparatus, including active compressors and condensers, fuel tank heaters, fuel tank heat exchange coils for cooling the enclosed fuel, fuel fill necks, fuel fillers, capless fuel fillers, fuel vapor vents, fuel lines for fuel delivery, fuel return lines, vent and vehicle rollover valves, fuel pumps, and air intake or purge valves.

[0139] The invention further contemplates devices and structures that can be combined with the textured sorbent sheets to improve or control the adsorption and desorption of fluids and gases. For example, a fan or pump can be included to force fluid or vapor onto the textured sorbent sheet during assembly, allowing the textured sorbent sheet to be packed or rolled more tightly, or allowing for a larger device than would otherwise be able to spread the same amount of fluid over the sheet. Alternatively, the device can include a resistive element heater, or a Peltier effect heater or cooler, designed to heat and / or cool the fluid and thus move it over the textured sorbent sheet of the claimed invention. For example, a heated and expanding fluid can be expelled upwards at the bottom of a rolled or coiled article oriented vertically to take advantage of the effects of gravity, drawing in more fluid.

[0140] Other uses

[0141] In addition to automotive applications, the inventors believe that the sorbent sheets of the claimed invention can be used in any situation where a tank or other enclosed space is designed to contain volatile liquids, particularly volatile hydrocarbons, such as fuels, solvents, and other volatile compounds. Examples include, but are not limited to, aircraft fuel tanks, ship and other marine fuel tanks, truck fuel tanks, chemical tanks in rail cars, barges, ships, trucks, vehicles, and other bulk carriers, and stationary chemical tanks. The textured sorbent sheets of the claimed invention can also be attached or adhered to walls of confined spaces where the presence of volatile compounds is detrimental, for example, in chemical facilities where operators and maintenance personnel must periodically enter the space. Such textured sorbent sheets, when used in such complex spaces, can not only increase safety for operators and maintenance personnel, but also reduce the need for cumbersome protective equipment.

[0142] In some embodiments, the device may not filter microscopic particles, making it useful outside the field of fuel vapor recovery. Devices containing granular or pelleted textured sorbents filter particles that are about 1% larger than the particle diameter, removing these particles from the gas or liquid being treated using the device. Devices containing stacked or rolled / spiral wound textured sorbent sheets allow such particles to pass unfiltered, so the devices of various embodiments can be useful for filtering liquids. In particular, such textured sorbent sheets can be useful for filtering bodily fluids, such as blood, where red and white blood cells and platelets, etc., must pass through the filter without being physically filtered from the blood. Other contaminants can be adsorbed onto the textured sorbent sheets and removed from the blood filtrate.

Claims

1. 1. A textured adsorbent sheet comprising: A textured sorbent sheet is defined comprising a sorbent and a binder, the textured sorbent sheet defining an upper surface and a lower surface, at least one of the upper surface and the lower surface comprising a texture defined by a series of hills and valleys; a different one of the upper surface and the lower surface having a pattern; A textured adsorbent sheet, wherein the depth of the pattern is less than the depth of the texture.

2. 10. The textured adsorbent sheet of claim 1, wherein the textured adsorbent sheet has a thickness measured in the valleys selected from less than 1 mm, 0.1 mm to 1.0 mm, 0.2 mm to 0.90 mm, 0.5 to 0.95 mm, 0.5 to 0.90 mm, or any individual thickness or range subsumed within these example ranges.

3. 10. The textured adsorbent sheet of claim 1, wherein the textured adsorbent sheet may have a thickness measured at a hill or peak selected from 1.0 to 1.5 mm, 1.2 mm, 1.3 mm, 1.4 mm, or any individual thickness or range encompassed by any two of these values.

4. 10. The textured adsorbent sheet of claim 1, wherein the distance from the peak of a hill to the bottom of a valley is selected from 0.1 mm to 1.0 mm, 0.1 mm to about 0.5 mm, 0.2 mm, 0.3 mm, 0.4 mm, or any individual distance or range encompassed by any two of these values.

5. 10. The textured adsorbent sheet of claim 1, wherein the texture of said upper surface is the same as the texture of said lower surface.

6. The textured adsorbent sheet of claim 1 , wherein the texture of said upper surface is different than the texture of said lower surface.

7. 1. A textured adsorbent sheet product comprising:

2. A method for manufacturing a cellular membrane comprising: A textured sorbent sheet product, wherein each textured sorbent sheet is stacked and arranged such that adjacent upper and lower surfaces of said separate sheets are substantially parallel and arranged for at least fluid flow between said adjacent upper and lower surfaces.

8. 8. The textured adsorbent sheet product of claim 7, wherein at least one of the textured adsorbent sheets is configured to be flat, wound into a spiral cylinder, wound into an oval, wound into an elongated rectangular rod, folded, laminated into an "S" shape, formed as concentric cylinders, formed as concentric ellipses, formed as concentric rectangular rods, or a combination of these configurations.

9. The textured adsorbent sheet product of claim 7, wherein the hills and valleys on adjacent sheets are nested.

10. 8. The textured adsorbent sheet product of claim 7, wherein said hills and valleys are present on adjacent sheets and are not nested.

11. 1. A rolled textured adsorbent sheet product comprising: A method of manufacturing a textured adsorbent sheet comprising: A rolled textured adsorbent sheet product, wherein the textured adsorbent sheet is spirally rolled to form adjacent sheet layers and allows fluid to flow around and between the adjacent sheet layers.

12. 12. The rolled textured adsorbent sheet product of claim 11, wherein the rolled textured adsorbent sheet product has a generally cylindrical shape having a length greater than its diameter.

13. 1. A vapor adsorption canister comprising: The textured adsorbent sheet product of claim 7; a housing at least partially enclosing said textured adsorbent sheet product.

14. 14. The vapor adsorption canister of claim 13, wherein the housing is flexible.

15. 1. A vapor adsorption canister comprising:

12. The rolled textured adsorbent sheet product of claim 11; a housing at least partially enclosing said rolled textured adsorbent sheet product.

16. 1. A tank having integral vapor adsorption, comprising: A tank structure; At least one textured adsorbent sheet according to claim 1; and at least one fastening device for fastening the textured adsorbent sheet to a surface of the tank that is not periodically immersed in a volatile liquid contained within the tank.

17. 17. The tank with integral vapor adsorption of claim 16, wherein the fastening device is an adhesive layer formed between one surface of the textured adsorbent sheet and a wall of the tank.

18. 10. An on-board refueling vapor recovery device comprising the textured sorbent sheet of claim 1.

19. 12. An on-board refueling vapor recovery device comprising the rolled textured sorbent sheet product of claim 11.

20. 16. An on-board refueling vapor recovery system comprising the vapor adsorption canister of claim 15.

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