ADSORBENT COMPOSITION, CANISTER SYSTEM FOR EVAPORATIVE EMISSION CONTROL, ADSORBENT ARTICLE AND METHOD FOR ITS PREPARATION

Abstract

LOW EMISSION ADSORBENT. The present invention relates to adsorbent compositions and materials and systems comprising the same that provide low emission performance of DBL (Diesel Low Emission Limit). The materials described provide unexpected production advantages compared to currently available materials.

Description

1 / 80 ADSORBENT COMPOSITION, CANISTER SYSTEM FOR EVAPORATIVE EMISSION CONTROL, ADSORBENT ARTICLE AND METHOD FOR ITS PREPARATION CROSS-REFERENCE TO RELATED REQUESTS

[0001] This application claims the benefit of the Application for Provisional Patent Serial No. US 62 / 942,615, filed December 2, 2019, and entitled: “Low Bleed Emission Adsorbent”, which is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention. The present invention, in various aspects and embodiments, relates to adsorbent materials and evaporative emission control systems comprising them.

[0003] 2. Basic Information. The evaporation of gasoline fuel from motor vehicle fuel systems is a significant source of hydrocarbon air pollution. These fuel vapor emissions occur when the vehicle is running, refueling, or parked with the engine off. Such emissions can be controlled by canister systems that use activated carbon to adsorb the fuel vapor emitted by the fuel systems. Under certain engine operating modes, the adsorbed fuel vapor is periodically removed from the activated carbon by purging the canister systems with ambient air to desorb the fuel vapor from the activated carbon. The regenerated carbon is then ready to adsorb additional fuel vapor.

[0004] It is well known in the art that a more space-efficient activated carbon adsorbent for this application is characterized by an n-butane vapor adsorption isotherm that exhibits adsorption capacity sloping strongly towards high partial vapor pressures (US 6,540,815). Thus, the Petition 870260058209, dated 06 / 15 / 2026, page 5 / 180 The 2 / 80 adsorbent exhibits a high capacity at relatively high concentrations of the type of vapors present with gasoline fuel, and the adsorbent favors the release of these captured vapors when exposed to a low vapor concentration or partial pressure, such as during purging. These high-performance activated carbons exhibit a large amount of pore volume as small mesopores (e.g., SAE Technical Documents 902119 and 2001-03-0733, and Burchell 1999, pp. 252-253), which are preferably about 1.8 nm to about 5 nm in size, as measured by the BJH method of nitrogen adsorption isotherm analysis (e.g., US 5,204,310). (According to the IUPAC classification, these are pores approximately 1.8-2 nm in size within the micropore size range < 2 nm, plus pores approximately 2-5 nm in size within the mesopore size range of 2-50 nm.)Small mesopores are small enough to capture vapors as a condensed phase and yet readily empty upon exposure to a low partial pressure of vapor. Consequently, the volume in these pores correlates linearly with the vapor recoverable capacity of the adsorbent in a canister volume, known as gasoline working capacity (GWC), and also correlates linearly with the butane working capacity ASTM (BWC) of the adsorbent, as measured by the ASTM 5228 standard method, which are incorporated herein by reference.Generally, the ASTM BWC range of commercial activated carbon products for this application is from about 3 to about 17 g / dL, with 9+ g / dL of BWC carbons favored for working capacity towards the fuel vapor source of the canister system, and lower BWC carbons used in one or more subsequent volumes towards the atmospheric port or vent side (i.e., adsorbent volumes). Petition 870260058209, dated 06 / 15 / 2026, p. 6 / 180 3 / 80 vent side).

[0005] Increased environmental concerns have continued to drive stringent hydrocarbon emission standards. When a vehicle is parked in a hot environment during the heat of the day (i.e., daytime heating), the temperature in the fuel tank increases, resulting in an increase in vapor pressure in the fuel tank. Typically, to prevent fuel vapor from leaking from the vehicle into the atmosphere, the fuel tank is vented through a conduit to a canister containing suitable fuel adsorbent materials that can temporarily adsorb the fuel vapor. The canister defines a vapor or fluid flow path so that when the vehicle is at rest, the fuel vapor from the fluid passes from the fuel tank, through the fuel tank conduit, through one or more volumes of adsorbent, and out through a vent port, which opens to the atmosphere.A mixture of fuel vapor and air from the fuel tank enters the canister through a canister fuel vapor inlet and diffuses into the adsorbent volume where the fuel vapor is adsorbed into temporary storage and the purified air is released to the atmosphere through a canister vent port. Once the engine is started, ambient air is drawn into the canister system through the canister vent port. Purge air flows through the adsorbent volume inside the canister and desorbs the fuel vapor adsorbed in the adsorbent volume before entering the internal combustion engine through a fuel vapor purge conduit. The purge air does not absorb all the fuel vapor adsorbed in the adsorbent volume, resulting in a residual hydrocarbon (hold) that may be emitted to the atmosphere.

[0006] Furthermore, this retention is in local equilibrium with the phase Petition 870260058209, dated 06 / 15 / 2026, page 7 / 180 4 / 80 gaseous fuel also allows fuel vapors from the fuel tank to migrate through the canister system as emissions. Such emissions typically occur when a vehicle is parked and subjected to diurnal temperature changes over a period of several days, commonly referred to as daytime loss emissions (DBL). In the US, the California Low Emission Vehicle Regulations have made it desirable for DBL emissions from the canister system to be less than about 10 mg (PZEV) for several vehicles beginning with the 2003 model year and below about 50 mg, typically below 20 mg, (LEV-II) for a larger number of vehicles beginning with the 2004 model year.

[0007] Now, the California Low Emission Vehicle Standard (LEV-III) and United States Federal Tier 3 standards require that canister DBL emissions not exceed 20 mg, as per the Bleed Emissions Test Procedure (BETP), as written in California Evaporative Emissions Standards and Test Procedures for 2001 and Subsequent Model Motor Vehicles, March 22, 2012. Furthermore, the DBL emission standards continue to create challenges for evaporative emission control systems, especially when the purge air level is low.For example, the potential for DBL emissions may be more severe for a hybrid vehicle, including a vehicle whose powertrain is an internal combustion engine and an electric motor (HEV), and a vehicle where there is a start / stop system that automatically shuts off and restarts the internal combustion engine to reduce the amount of time the engine spends idling, thereby reducing fuel consumption and tailpipe emissions.

[0008] In such hybrid vehicles, the internal combustion engine is Petition 870260058209, dated 06 / 15 / 2026, page 8 / 180 5 / 80 off almost half the time during vehicle operation. Since the fuel vapor adsorbed onto the adsorbents is purged only when the internal combustion engine is running, the adsorbents in a hybrid vehicle's canister are purged with fresh air less than half the time compared to conventional vehicles, and often within the range of 55 BV to 100 BV, where BV is the ratio of the total purge flow volume to the adsorbent volumes in the canister system. Furthermore, hybrid vehicles can generate almost the same amount of evaporative fuel vapor as conventional vehicles. The lower purge frequency and lower purge volume of the hybrid vehicle may be insufficient to clear residual hydrocarbon retention from the adsorbents in the canister, resulting in high DBL emissions.Other powertrains, when designed for optimal unit performance, fuel efficiency, and tailpipe emissions, are equally challenged to provide a high level of purge to cool the canister and are challenged to provide ideal air-fuel mixtures and ratios to the engine. These powertrains include turbocharged or turbo-assisted engines, start / stop systems, high-speed transmissions, and gasoline direct injection (GDI) engines.

[0009] Globally, in contrast, evaporative emission standards have been less stringent than in the US, but the trend now is toward stricter regulations, as the US has adopted. There is greater recognition of the benefits of stricter controls for better vehicle fuel use and cleaner air, especially in regions where the use of light commercial vehicles is growing rapidly and air quality problems require urgent attention. As a notable example, the Ministry of Environmental Protection of the People's Republic of China released standards in 2016 that include limitations on fuel vapor emissions, Petition 870260058209, dated 06 / 15 / 2026, page 9 / 180 6 / 80 for implementation in 2020 (See Limits and Measurement Methods for Emissions from Light-Duty Vehicles, GB 18352.6-2016, also known as China 6). This standard specifies the limits and measurement methods for light vehicles, including hybrid electric vehicles, equipped with positive ignition engines for exhaust emissions at steady and low temperatures, actual driving emissions (RDE), crankcase emissions, evaporative emissions and refueling emissions, technical requirements and durability measurement methods for pollution control equipment and on-board diagnostics (OBD) systems. On-board refueling vapor recovery (ORVR) is required in addition to evaporative emission control.Evaporative emissions are defined as hydrocarbon vapors emitted from the fuel (gasoline) system of a motor vehicle and include: (1) breath losses in the fuel tank (daytime losses), which are hydrocarbon emissions caused by temperature changes in the fuel tank, and (2) hot immersion losses, which are hydrocarbon emissions from the fuel system of a stationary vehicle after a period of driving. Although the test protocol and emission limits for the entire vehicle test are provided in the regulations, there is leeway in the allocation by vehicle manufacturers for the design limits of components that contribute to total emissions (e.g., evaporative emission control canister system, fuel tank walls, hoses, pipes, etc.).Among the allocations, the limit for the evaporative emission control canister system is generally defined in the fuel system and vehicle design processes to be less than 100 mg for day 2 dBBL emissions as part of the design balance to meet the overall vehicle requirements of China Standard 6. Petition 870260058209, dated 06 / 15 / 2026, page 10 / 180 7 / 80

[0010] However, in view of the need for high-capacity work performance and to design systems for fuel emissions within regulatory limits, there is a disproportionate increase in exhaust emission performance as the performance of GWC and BWC properties are enhanced, as is well known in the art. See, for example, SAE Technical Document 2001-01-0733; and US 6,540,815 in the Table (comparative and inventive data for 11 BWC versus 15 BWC activated carbons).

[0011] To satisfy the seemingly opposing needs of high working capacity and low DBL emission performance, several approaches have been reported. One approach is to significantly increase the purge gas volume to improve desorption of residual hydrocarbon retention from the adsorbent volume. See US 4,894,072. This approach, however, has the disadvantage of complicating fuel / air mixture control to the engine during the purge step and tends to negatively affect tailpipe emissions. Although at the cost of design and installation, an auxiliary pump can be used somewhere within the evaporative emission control system to supplement, assist, or augment the purge flow or volume, as a means of supplementing engine vacuum and avoiding some problems with engine performance and tailpipe emission control when, for some reason, reliance on engine vacuum alone occurs.

[0012] Another approach is to design the canister to have a relatively low cross-sectional area on the vent side of the canister, either by redesigning the existing canister dimensions or by installing a supplementary vent-side canister of appropriate dimensions. This approach reduces residual hydrocarbon retention by increasing purge air intensity. A disadvantage Petition 870260058209, dated 06 / 15 / 2026, page 11 / 180 The drawback of this approach is that the relatively low cross-sectional area imposes excessive flow restriction on the canister. See US 5,957,114.

[0013] An additional approach to increase purge efficiency is to heat the purge air or a portion of the adsorbent volume containing adsorbed fuel vapor, or both. However, this approach increases the complexity of control system management and presents some safety issues. See US 6,098,601 and US 6,279,548.

[0014] Another approach is to direct the fuel vapor through a volume of fuel-side adsorbent, which is located close to the fuel source in the fluid stream, and then through at least one subsequent (i.e., vent-side) adsorbent volume, which is located downstream of the fuel-side adsorbent, before escaping to the atmosphere, wherein the fuel-side adsorbent volume (in this document, the initial adsorbent volume) exhibits a higher isothermal slope, defined as an incremental adsorption capacity, than the subsequent (i.e., vent-side) adsorbent volume. See US RE38,844.It is noteworthy that US RE38,844 considers the trade-off in DBL exhaust emissions performance with BWC as an inevitable consequence of the high slope properties of the adsorption isotherms present with high BWC adsorbents according to the dynamics of vapor concentration gradients and adsorption along the vapor flow path during adsorption, purge, and immersion cycles. This approach has the disadvantage of requiring multiple volumes of adsorbents in series with varying properties to generate low emissions, which increases system size, complexity, and design and manufacturing costs.

[0015] Another approach, especially useful when only one Petition 870260058209, dated 06 / 15 / 2026, page 12 / 180 9 / 80 low-level purge may be available, directing fuel vapor through at least one subsequent adsorbent (i.e., vent side) comprising an incremental adsorption capacity window, BWC, a particular g-total BWC capacity, and a substantially uniform structure that facilitates approximately uniform vapor and air flow distribution across its flow path cross-section. See US 9,732,649 and US 2016 / 0271555A1.

[0016] Thus, the dilemma of excessive DBL exhaust emissions for high-working-capacity carbons is recognized and typically addressed by adding an auxiliary chamber comprising an additional adsorbent, for example, an adsorbent volume having a relatively low BWC. See US 9,657,691. However, one of the disadvantages of such a system is the additional cost of including the supplementary adsorbent volume. For example, manufacturing complexities limit production rates and duration.

[0017] Consequently, it is desirable to have an evaporative emission control system that is as low cost, simple and compact as possible to provide the necessary low daytime breath loss (DBL) emissions even when a low level of purge air is used, or when the adsorbents in the canister are purged less frequently, as in the case of hybrid or start / stop vehicles, or both. SUMMARY

[0018] An adsorbent material is presently described which surprisingly and unexpectedly demonstrates desirable emissions performance when incorporated into vehicle emissions control canisters and, at the same time, offers certain manufacturing advantages compared to conventional honeycomb-type adsorbents. By Petition 870260058209, dated 06 / 15 / 2026, page 13 / 180 For example, the described adsorbent material is lighter and surprisingly can be extruded at a higher rate and produces less wear on the extrusion dies. Consequently, the adsorbent material, as described, is less expensive to manufacture and performs as well as or better than conventional adsorbent materials.

[0019] Thus, in one aspect, the description provides an adsorbent composition comprising: from about 10 to about 50% by weight of an activated adsorbent material; from about 3 to about 40% by weight of glass microspheres; and the difference of 100% by weight with at least one additive material.

[0020] In any aspect or embodiment described herein, the additive material comprises at least one of an organic binder, an inorganic binder, or a combination thereof. In any aspect or embodiment described herein, the organic binder is a cellulosic binder. In any aspect or embodiment described herein, the inorganic binder is at least one of clay, silica, or a combination thereof. In certain embodiments, the silica comprises a silica sol material.

[0021] In any aspect or embodiment described in this document, the description provides an adsorbent composition comprising: from about 10 to about 50% by weight of an activated adsorbent material, for example, a material comprising or consisting essentially of an activated adsorbent powder; from about 2 to about 10% by weight of a binder Petition 870260058209, dated 06 / 15 / 2026, page 14 / 180 11 / 80 organic; from about 2 to about 50% by weight of an inorganic binder (for example, at least one of clay, silica, or a combination thereof); and from about 3 to about 40% by weight of glass microspheres.

[0022] In any aspect or embodiment described herein, the description provides an adsorbent composition comprising from about 0 to about 5% by weight of a silica sol.

[0023] In a further aspect, the description provides methods for preparing an extruded adsorbent composition according to the steps comprising: (a) mixing (i) from about 10 to about 50% by weight of an activated adsorbent material, for example, an activated adsorbent composition comprising an activated adsorbent powder, (ii) from about 3 to about 40% by weight of glass microspheres, and (iii) the difference to 100% by weight with at least one additive material to form an adsorbent composition; and (b) extruding and optionally drying the adsorbent composition to produce an extruded adsorbent composition. In any aspect or embodiment, the additive material comprises at least one of an organic binder, an inorganic binder, or a combination thereof. In any aspect or embodiment described herein, the organic binder is a cellulosic binder.In any aspect or embodiment described herein, the inorganic binder is at least one of clay, silica, or a combination thereof. In certain embodiments, the silica comprises a silica sol material. In any of the aspects or embodiments described, a honeycomb-type mold is used in the extrusion step to produce an extruded adsorbent material with a structure of... Petition 870260058209, dated 06 / 15 / 2026, p. 15 / 180 12 / 80 honeycomb. In any of the aspects or embodiments described herein, the binder of the adsorbent composition or the extruded adsorbent composition produced as described herein comprises at least one of a clay binder, a calcined binder, mineral flux, water, or a combination thereof. In any of the aspects or embodiments described herein, the adsorbent composition or the extruded adsorbent composition produced as described herein comprises from about 5 to about 50% by weight of a clay binder, from about 5 to about 45% by weight of a calcined binder, from about 2 to about 20% by weight of a mineral flux, or a combination thereof.

[0024] In any of the aspects or embodiments described, the description provides an extruded adsorbent composition or article produced according to the steps comprising: (a) mixing (i) from about 10 to about 50% by weight of an activated adsorbent material, for example, an activated adsorbent material comprising an activated adsorbent powder; (ii) from about 2 to about 10% by weight of an organic binder; (iii) from about 5 to about 50% by weight of a clay binder; (iv) from about 5 to about 45% by weight of a calcined clay binder; (v) from about 2 to about 20% of a mineral flux; (vi) from about 0 to about 5% by weight of a silica solder; and (vii) from about 3 to about 40% by weight of glass microspheres to form an adsorbent composition; and (b) extruding the adsorbent composition to form an extruded adsorbent composition or article.In certain embodiments, a honeycomb-type die is used in the extrusion step to produce an extruded adsorbent composition with a honeycomb structure.

[0025] In any of the aspects or embodiments described in this document, the extrudable adsorbent composition Petition 870260058209, dated 06 / 15 / 2026, page 16 / 180 13 / 80 comprises from about 10 to about 50% by weight of an activated adsorbent material comprising an activated adsorbent powder; from about 2 to about 10% by weight of a polymeric organic binder; from about 5 to about 50% by weight of a clay binder; from about 5 to about 45% by weight of a calcined binder; from about 2 to about 20% of a mineral flux; from about 0 to about 5% by weight of a silica sol; and from about 3 to about 40% by weight of glass microspheres.

[0026] In any of the aspects or embodiments described herein, the extrudable adsorbent composition or extruded adsorbent article comprises a pore volume ratio of 0.05-1 micrometer to 0.05-100 micrometer, as described herein, which is greater than about 70%, or greater than about 75%, greater than about 80%, or greater than about 90%.

[0027] In any of the aspects or embodiments described herein, the extrudable adsorbent composition or extruded adsorbent article comprises a pore volume ratio of 0.05-0.5 micrometers to 0.05-100 micrometers, as described herein, which is greater than about 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%.

[0028] In another aspect, the invention provides an evaporative emission control canister system comprising at least one fuel-side adsorbent volume and at least one vent-side adsorbent volume, wherein at least one of at least one of the fuel-side adsorbent volumes or at least one vent-side comprises the extruded adsorbent composition as described herein.

[0029] In any of the aspects or modalities described in this document, the canister system comprises one or more Petition 870260058209, dated 06 / 15 / 2026, page 17 / 180 14 / 80 volumes of vent-side adsorbent with a uniform cell structure, that is, approximately all cells in the adsorbent volume are the same size.

[0030] In any of the aspects or embodiments described herein, the extruded adsorbent composition, as described herein, demonstrates two-day daylight loss-of-breath (DBL) emissions of 100 mg or less, for example from about 5 mg to about 100 mg in a specified amount of purge air volume applied after a butane loading step of 40 g / h, as determined by the 2012 California Bleed Emissions Test Procedure (BETP).

[0031] In a further aspect, the description provides methods for reducing fuel vapor emissions in an evaporative emission control system, the method comprising contacting the fuel vapor with an evaporative emission control system, as described herein, comprising an extruded adsorbent composition, as described herein.

[0032] The foregoing general areas of utility are given only as examples and are not intended to be limiting in the scope of the present invention and appended claims. The additional objects and advantages associated with the compositions, methods, and processes of the present invention will be appreciated by those skilled in the art by taking into account the immediate claims, description, and examples. For example, the various aspects and embodiments of the invention can be used in numerous combinations, all of which are expressly contemplated by the present description. These additional advantages, objects, and embodiments are expressly included in the scope of the present invention. Publications and other materials used in Petition 870260058209, dated 06 / 15 / 2026, p. 18 / 180 15 / 80 of this document, to clarify the fundamentals of the invention and, in particular cases, to provide additional details respecting practical application, are incorporated by reference. BRIEF DESCRIPTION OF THE FIGURES

[0033] The accompanying drawings, which are incorporated herein and form part of the specification, illustrate various embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The figures are for illustrative purposes only of an embodiment of the invention and should not be interpreted as limiting the invention. Other objects, features and advantages of the invention will become apparent from the following detailed description made in conjunction with the accompanying figures showing illustrative embodiments of the invention, in which:

[0034] Figure 1 is a cross-sectional view of an exemplary evaporative emission control canister system illustrating possible locations where an adsorbent volume (such as a PPAV), as described in this document, can be used.

[0035] Figure 2 is a cross-sectional view of an exemplary evaporative emission control canister system illustrating additional possible locations where an adsorbent volume (such as a PPAV) as described in this document can be used.

[0036] Figure 3 is a cross-sectional view of an exemplary evaporative emission control canister system illustrating possible locations where an adsorbent volume (such as a PPAV), as described in this document, can be used.

[0037] Figure 4 is a cross-sectional view of an exemplary evaporative emission control canister system illustrating possible locations where an adsorbent volume (such as a PPAV) as described in this document can be used.

[0038] Figure 5 is a cross-sectional view of a canister system. Petition 870260058209, dated 06 / 15 / 2026, page 19 / 180 16 / 80 of exemplary evaporative emission control illustrating the system with which the DBL emission performance of the comparative and inventive examples was measured when there were only two volumes of adsorbent in the main canister and there were two PPAV honeycomb structures present within the auxiliary vent side canisters of the series.

[0039] Figure 6 is a cross-sectional view of an exemplary evaporative emission control canister system illustrating the system with which the DBL emission performance of the comparative and inventive examples was measured when there were two PPAV honeycomb structures present within the auxiliary vent side canisters of the series.

[0040] Figure 7 shows a comparison of worst-day emission (mg) for exemplary and comparative formulations for two different sample sizes.

[0041] Figure 8 shows the effect on mold wear for the comparative examples compared with exemplary formulations, as described in this document.

[0042] Figure 9 shows the effect on mold wear for the comparative examples compared with exemplary formulations, as described in this document. DETAILED DESCRIPTION

[0043] The present invention will be described in more detail hereafter, but not all embodiments of the invention are shown. Although the invention is described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. Furthermore, many modifications may be made to adapt a specific structure or material to the teachings of Petition 870260058209, dated 06 / 15 / 2026, page 20 / 180 17 / 80 invention without departing from its essential scope.

[0044] The figures accompanying the application are for illustrative purposes only. They are not intended to limit embodiments of the present invention. Furthermore, the figures are not drawn to scale. Common elements among the figures may retain the same numerical designation.

[0045] If a range of values ​​is provided, it is understood that each value intervening between the upper and lower limits of that range and any other stated or intervening value within that indicated range is encompassed within the invention. The upper and lower limits of those smaller ranges may independently be included in the smaller ranges also encompassed within the invention, subject to any limit specifically excluded in the indicated range. Wherever the indicated range includes one or both limits, ranges excluding both included limits are also included in the invention.

[0046] The following terms are used to describe the present invention. In cases where a term is not specifically defined in this document, that term is given a meaning recognized in the art by those skilled in the art, applying that term in the context of its use in the description of the present invention.

[0047] The articles "a" and "an," as used in this document and the attached claims, are used in this document to refer to one or more than one (i.e., at least one) of the grammatical object of the article, unless the context clearly indicates otherwise. As an example, "an element" means one element or more than one element.

[0048] The phrase and / or, as used in this document, in the descriptive report and in the claims, should be understood as meaning one or both elements in such a set, that is, Petition 870260058209, dated 06 / 15 / 2026, p. 21 / 180 18 / 80 elements that are present jointly in some cases and disjunctively in others. Several elements listed with and / or should be interpreted in the same way, that is, one or more of the elements in such a set. Other elements may optionally be present in addition to the elements specifically identified by the and / or clause, whether or not they are related to those specifically identified elements. Thus, as a non-limiting example, a reference to A and / or B, when used in conjunction with open language, such as including, may refer, in one embodiment, to only A (optionally including elements other than B); in another embodiment, to only B (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0049] As used in this document, in the descriptive report and in the claims, "or" should be understood as having the same meaning as "and / or" as defined above. For example, when separating items in a list, "or" or "and / or" should be interpreted as being inclusive, that is, including at least one, but also including more than one, of a number or list of elements and, optionally, additional items not listed. Only terms clearly indicated to the contrary, such as "only one of" or "exactly one of," or, when used in the claims, "consisting of," refer to the inclusion of exactly one element of a number or list of elements. In general, the term "or" as used in this document should only be interpreted as indicating exclusive alternatives (i.e., one or the other, but not both) when preceded by terms of exclusivity, such as "or," "one of," "only one of," or "exactly one of."

[0050] In the claims, as well as in the descriptive report above, all transitional expressions such as including, Petition 870260058209, dated 06 / 15 / 2026, page 22 / 180 19 / 80 including, carrying, having, containing, involving, holding, composed of and the like should be understood as open, that is, as meaning including, but not limiting. Only the transition phrases consisting of and consisting essentially of should be closed or semi-closed transition phrases, respectively, as presented in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.

[0051] As used in this document, in the descriptive report and in the claims, the phrase "at least one," in reference to a list of one or more elements, should be understood as meaning at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of all elements and not excluding any combination of elements in the list of elements. This definition also allows other elements, in addition to the elements specifically identified within the list of elements to which the phrase "at least one" refers, to optionally be present, whether or not they are related to those specifically identified elements.Thus, as a non-limiting example, at least one of A and B (or, equivalently, at least one of A or B or, equivalently, at least one of A and / or B) may refer, in one embodiment, to at least one, optionally including more than one, A, without the presence of B (and, optionally, including elements other than B); in another embodiment, to at least one, optionally including more than one, B, and without the presence of A (and, optionally, including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and... Petition 870260058209, dated 06 / 15 / 2026, p. 23 / 180 20 / 80 (optionally including other elements); etc. It should also be understood that, unless clearly indicated otherwise, in any method claimed in this document that includes more than one step or act, the order of the steps or acts of the method is not necessarily limited to the order in which the steps or acts of the method are recited.

[0052] As used in this document, the terms fluid, gas or gaseous and vapor or vaporous are used in a general sense and, unless the context indicates otherwise, are intended to be interchangeable.

[0053] US Patent Application Serial No. 15 / 656,643 entitled: Particulate Adsorbent Material and Methods of Making the Same, filed July 21, 2017; U.S. Patent Publication 2016 / 0271555A; U.S. Patent No. 9,732,649; and U.S. Patent 6,472,343 are incorporated herein by reference in their entirety for all purposes.

[0054] An adsorbent material is now described which surprisingly and unexpectedly demonstrates desirable emissions performance when incorporated into conventional vehicle emissions control canisters and, at the same time, offers certain manufacturing advantages compared to conventional honeycomb-type adsorbents. For example, the described adsorbent material is lighter, can be extruded at a higher rate, and produces less wear on the extrusion dies. Consequently, the adsorbent material as described is less expensive to manufacture.

[0055] Thus, in one aspect, the description provides an adsorbent composition comprising: from about 10 to about 50% by weight of an activated adsorbent material; from about 3 to about 40% by weight of microspheres Petition 870260058209, dated 06 / 15 / 2026, page 24 / 180 21 / 80 glass; and a 100% weight difference with at least one additive material.

[0056] In any aspect or embodiment described herein, the additive material comprises at least one of an organic binder, an inorganic binder, a mineral flux, or a combination thereof. In any aspect or embodiment described herein, the organic binder is a cellulosic binder.

[0057] In any aspect or embodiment described herein, the description provides an adsorbent composition comprising: from about 10 to about 50% by weight of an activated adsorbent material, for example, a material comprising or consisting essentially of an activated adsorbent powder; from about 2 to about 10% by weight of an organic binder; from about 2 to about 50% by weight of an inorganic binder (for example, at least one of clay, silica, or a combination thereof); and from about 3 to about 40% by weight of glass microspheres.

[0058] In any aspect or embodiment described herein, the description provides an adsorbent composition comprising from about 0 to about 5% by weight of a silica sol.

[0059] In any of the aspects or embodiments described, the organic binder of the adsorbent composition or the extruded adsorbent composition produced as described herein comprises at least one of a clay binder, a calcined binder, mineral flux, water, or a combination thereof. Petition 870260058209, dated 06 / 15 / 2026, page 25 / 180 22 / 80 of these. In any aspect or embodiment described herein, the inorganic binder is at least one of clay, silica, or a combination thereof. In certain embodiments, the silica comprises a silica sol material. In any of the aspects or embodiments described herein, the adsorbent composition or the extruded adsorbent composition produced as described herein comprises from about 5 to about 50% by weight of a clay binder, from about 5 to about 45% by weight of a calcined binder, from about 2 to about 20% by weight of a mineral flux, or a combination thereof.

[0060] The adsorbent compositions and extruded adsorbent compositions, as described herein, adsorb volatile organic compounds and other chemical agents. As will be appreciated by those skilled in the art, a variety of adsorbent materials, for example, activated carbon, can be used in this invention. The most suitable adsorbent material will depend on the intended application, particularly the nature of the volatile species to be adsorbed. Thus, the physical properties of the adsorbent compositions and extruded adsorbent compositions, as described herein, such as surface area and pore structure, may vary depending on the application.

[0061] In any of the aspects or embodiments described in this document, the activated adsorbent material includes activated carbon, carbon dioxide, zeolites, clays, porous polymers, porous alumina, porous silica, molecular sieves, kaolin, titania, ceria, or combinations thereof. In certain embodiments, the activated adsorbent material is activated carbon. The activated carbon has been processed to make it highly porous (i.e., having a large number of pores per unit volume), which confers a high surface area. Activated carbons can be generated from a Petition 870260058209, dated 06 / 15 / 2026, page 26 / 180 23 / 80 variety of materials, however, most commercially available activated carbons are made from peat, coal, lignite, wood, and coconut shells. Based on the source, the carbon can have different pore sizes, ash content, surface order, and / or impurity profiles. Coconut shell-based carbon predominantly exhibits a microporous pore size, while chemically activated wood-based carbon contains significant pore volume within the mesoporous size range. In a preferred embodiment, the activated adsorbent material comprises an activated carbon powder.

[0062] In any of the aspects or embodiments described herein, the activated adsorbent material precursor is wood. The activated adsorbent material precursor may be activated by heating the adsorbent material precursor and treating it with added oxidizing agents, such as exogenously added activating agents (i.e., oxidants) such as carbon dioxide, oxygen, acids, or superheated steam. An exemplary activated adsorbent material includes NUCHAR® (Ingevity South Carolina, LLC, SC), which is derived from wood and activated with phosphoric acid.

[0063] In any of the aspects or embodiments described in this document, the adsorbent composition is extruded. In any of the aspects or embodiments described in this document, the adsorbent composition includes from about 10 to about 50% by weight of an activated adsorbent material, or from about 10 to about 45% by weight, from about 10 to about 40% by weight, from about 10 to about 35% by weight, from about 10 to about 30% by weight, from about 10 to about 25% by weight, or from about 10 to about 20% by weight, or from about 15 to about 30% by weight, or from about 15 to about 25% by weight, or from about 15 to about 30% by weight, from about 15 to about 35% by weight, from about 15 Petition 870260058209, dated 06 / 15 / 2026, p. 27 / 180 24 / 80 to about 40% by weight, from about 15 to about 45% by weight, or from about 15 to about 50% by weight, each based on the total weight of the adsorbent composition.

[0064] In any of the aspects or embodiments described herein, the activated adsorbent material comprises activated carbon, carbon dioxide, zeolites, clays, porous polymers, foams, porous alumina, porous silica, molecular sieves, kaolin, titania, ceria, or combinations thereof. In any of the aspects or embodiments described herein, the adsorbent material is activated carbon. The activated adsorbent material may be derived from an activated adsorbent material precursor. By way of non-limiting example, activated adsorbent material precursors may be wood, wood powder, wood flour, cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coal tar, fruit pits, fruit stones, nut shells, sawdust kernels, palm, vegetables such as rice husks or straw, synthetic polymer, natural polymer, lignocellulosic material, or combinations thereof.Furthermore, activated adsorbent material can be produced using a variety of processes, including, but not limited to, chemical activation, thermal activation, or combinations thereof.

[0065] Generally, the larger the surface area of ​​the activated adsorbent material, the greater its adsorption capacity. For example, the available surface area of ​​activated carbon depends on its pore volume. Since the surface area per unit volume decreases as the individual pore size increases, a large surface area is usually maximized by maximizing the number of very small pore dimensions and / or minimizing the number of very large pore dimensions.

[0066] The Brunauer-Emmet-Teller surface area method Petition 870260058209, dated 06 / 15 / 2026, page 28 / 180 25 / 80 (BET) can characterize the specific surface area of ​​a material. Preferably, the activated adsorbent material has a nitrogen BET surface area of ​​about 600 to about 2000, about 800 to about 1800, or about 1000 to about 1600 m² per gram. Suitable activated carbon can also be characterized by having a particle size such that more than 40% by weight of the activated carbon passes through a 325 mesh screen and, more desirably, by having a particle size such that more than 65% by weight of the activated carbon passes through a 325 mesh screen.

[0067] In any aspect or embodiment described herein, the activated adsorbent powder, for example, activated carbon powder, has a butane activity (pBACT) of at least about 50 g / 100 g. In certain embodiments, the pBACT of the activated adsorbent precursor is at least about 50 g / 100 g, 55 g / 100 g, 60 g / 100 g, 65 g / 100 g, 70 g / 100 g, 75 g / 100 g, 80 g / 100 g, 85 g / 100 g, 90 g / 100 g, 95 g / 100 g or more, including all intermediate values.In certain embodiments, the pBACT of the activated adsorbent powder, for example, activated carbon powder, is approximately 50 g / 100 g to approximately 95 g / 100 g, approximately 50 g / 100 g to approximately 90 g / 100 g, approximately 50 g / 100 g to approximately 85 g / 100 g, approximately 50 g / 100 g to approximately 80 g / 100 g, approximately 50 g / 100 g to approximately 75 g / 100 g, approximately 50 g / 100 g to approximately 70 g / 100 g, approximately 50 g / 100 g to approximately 65 g / 100 g, approximately 50 g / 100 g to approximately 60 g / 100 g, and including all overlapping ranges, intermediate ranges and subsumed values.

[0068] In any of the aspects or embodiments described in this document, the adsorbent composition or extruded adsorbent composition comprises from about 2 to about 10% by weight of an organic binder. In any of the aspects or embodiments described in this document, the organic binder. Petition 870260058209, dated 06 / 15 / 2026, p. 29 / 180 26 / 80 comprises a polymeric binder. In any of the aspects or embodiments described herein, the polymeric binder is cellulosic, for example, cellulose, a cellulose derivative, or a combination thereof. In any of the aspects or embodiments described herein, the polymeric binder comprises at least one of carboxymethylcellulose (CMC), methylcellulose, ethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose (HPC), hydroxyethyl methylcellulose (HEMC), hydroxypropyl methylcellulose (HPMC), methylhydroxyethylcellulose, and hydroxyethylcellulose, or a combination thereof. In any of the aspects or embodiments described herein, the polymeric binder is a cellulose ether. In any of the aspects or embodiments described herein, the cellulose ether is methylhydroxyethylcellulose.In any of the aspects or embodiments described in this document, the cellulose ether is sublimated during the calcination of the adsorbent.

[0069] In any of the aspects or embodiments described herein, the binder may comprise any suitable binder generally known in the art or that may become known. In any of the embodiments described herein, the adsorbent composition or extruded adsorbent composition may comprise a polymeric binder selected from nylon, polyacrylic, fluoropolymer (PVDF). Those skilled in the art will recognize that certain types of binders are particularly useful for microporous or nanoporous monolithic carbonaceous articles, which are expressly contemplated herein. For example, in certain embodiments, the binder is at least one of methylcellulose, methylcellulose ether, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose, sodium alginate, hydroxyethylmethylcellulose, carboxymethylcellulose (CMC) and its derivatives and Petition 870260058209, dated 06 / 15 / 2026, page 30 / 180 27 / 80 its metallic salts (e.g., sodium carboxymethylcellulose), Teflon, novolac phenolic resin, sodium salt derived from humic acid, guar gum, cellulose, starch, lignin, polyvinyl alcohol, polyacrylic acid, styrene-butadiene resins (SBR), phenolic resin, polystyrene acrylic acid resins, reaction products of polyacrylic acid with selected polyols from the glycerin group, polyvinyl alcohol, lignin and hydroxyethylcellulose, as well as their derivatives and mixtures, crystalline salts of aromatic sulfonates, polyfurfuryl alcohol, etc. An alternative to aqueous binders is the use of certain non-solubilized and non-aqueous binders, such as clays, phenolic resins, polyacrylates, polyvinyl acetates, polyvinylidene chloride (PVDC), ultra-high molecular weight polyethylene (UHMWPE), etc.In certain embodiments, the non-aqueous binder of the present invention is at least one binder selected from the group consisting of a fluoropolymer (e.g., polyvinylidene difluoride), polytetrafluoroethylene, fluorinated ethylene propylene, or perfluoroalkoxy alkanes), a polyamide (e.g., Nylon-6,6' or Nylon-6), a polyamide, fibrillated cellulose, a high-performance plastic (e.g., polyphenylene sulfide), a copolymer with a fluoropolymer, a copolymer with a polyamide, a copolymer with a polyimide, a copolymer with a high-performance plastic, or a combination thereof.

[0070] In certain embodiments, the binder comprises thermosetting polymeric binders, hot melt polymeric binders, or a combination thereof. Thermosetting polymeric binders are compositions based on thermosetting resins that are liquid or solid at room temperature and, in particular, those of the urea-formaldehyde, melamine-urea-formaldehyde, or phenolformaldehyde type, with melamine-urea-formaldehyde resins being preferred, as well as emulsions of thermosetting (co)polymers in latex foam. Crosslinking agents may be incorporated into Petition 870260058209, dated 06 / 15 / 2026, p. 31 / 180 28 / 80 mixture. Ammonium chloride can be mentioned as an example of a crosslinking agent. Hot-melt polymeric binders are generally solid at room temperature and are based on hot-melt resins. Pitch, tar, or any other known polymeric binder can also be used as polymeric binders.

[0071] In any of the aspects or embodiments described, the adsorbent composition or extruded adsorbent composition may further comprise a polymeric binder selected from phenolic resins, lignins, lignosulfonates, polyacrylates, polyvinyl acetates, polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), ultra-high molecular weight polyethylene (UHMWPE), etc., fluoropolymer, for example, polyvinylidene difluoride (PVDF), polyvinylidene dichloride (PVDC), a polyamide (for example, Nylon 6,6' or Nylon-6), a high-performance plastic (for example, polyphenylene sulfide), polyketones, polysulfones, and liquid crystal polymers, copolymers with a fluoropolymer (for example, poly(vinylidene difluoride)), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene, or perfluoroalkoxy alkanes), copolymers with a polyamide (for example, Nylon-6,6' or Nylon-6), a copolymer with a polyimide, a copolymer with a high-performance plastic (for example, polyphenylene sulfide) or a combination thereof.

[0072] In any of the aspects or embodiments described, the adsorbent composition or extruded adsorbent composition, as described herein, is produced from the crosslinking of a polymeric binder of a ground precursor activated carbon material, wherein the ground activated carbon material is in the form of a powder. For example, in certain embodiments, the extrudable composition, as described herein, is produced by taking a powdered activated carbon material and applying the technology Petition 870260058209, dated 06 / 15 / 2026, page 32 / 180 29 / 80 crosslinking polymer linker of US 6,472,343.

[0073] In any of the aspects or embodiments described in this document, the polymeric binder is included in an amount of about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, or about 10% by weight, including all values ​​and ranges therefrom, each based on the total weight of the adsorbent or extrudable composition.

[0074] In any of the aspects or embodiments described, the amount of polymeric binder is less than about 10% by weight, for example, from about 0.05% by weight to about 10% by weight, from about 0.1% by weight to about 10% by weight, from about 0.5% by weight to about 10% by weight, from about 1.0% by weight to about 10% by weight, from about 1.5% by weight to about 10% by weight, from about 2.0% by weight to about 10% by weight, from about 2.5% by weight to about 10% by weight, from about 3.0% by weight to about 10% by weight, from about 3.5% by weight to about 10% by weight, or from about 4.0% by weight to about 10% by weight, including all values ​​in between, each based on the total weight of the extrudable adsorbent composition.In any of the aspects or embodiments described, the polymeric binder is methylhydroxyethyl cellulose and is present in an amount of less than about 10% by weight, for example, from about 0.05% by weight to about 10% by weight, from about 0.1% by weight to about 10% by weight, from about 0.5% by weight to about 10% by weight, from about 1.0% by weight to about 10% by weight, from about 1.5% by weight to about 10% by weight, from about 2.0% by weight to about 10% by weight, from about 2.5% by weight to about 10% by weight, from about 3.0% by weight to about 10% by weight, from about 3.5% by weight. Petition 870260058209, dated 06 / 15 / 2026, page 33 / 180 30 / 80 weight to about 10% by weight, or from about 4.0% by weight to about 10% by weight, including all intermediate values, each based on the total weight of the adsorbent composition or extrudable adsorbent composition. It was observed that, at the claimed amount of polymeric binder, the resulting extruded materials provided surprisingly and unexpectedly advantageous BWC, as well as relatively low DBL.

[0075] Conventional compositions include a substantial portion of moldable inorganic binder material that is plastic in nature and thus, when mixed with liquid, can be molded or extruded into a shape and will retain that shape through drying and firing. An example of a moldable inorganic binder material used in conventional compositions is spherical clay, such as the commercially available OLD MINE #4 spherical clay (available from the Kentucky-Tennessee Clay Company of Mayfield, KY, USA). However, undesirably, the high loading of materials such as spherical clay required in conventional compositions can cause increased wear on extrusion dies, which can increase production costs.

[0076] Advantageously, the adsorbent materials and compositions of the present invention minimize or eliminate the use of spherical clay and therefore reduce wear on the extrusion die used in the extrusion process.

[0077] In any of the aspects or embodiments described in this document, the adsorbent materials or compositions include an inorganic binder. In any of the aspects or embodiments described in this document, the inorganic binder comprises or is a clay binder. In some of the aspects or embodiments described in this document, the clay binder may include at least one of zeolite clay, bentonite clay, Petition 870260058209, dated 06 / 15 / 2026, p. 34 / 180 31 / 80 montmorillonite clay, illite clay, French green clay, pascalite clay, Redmond clay, Terramin clay, viva clay, Fuller Earth clay, ormalite clay, vitalite clay, reitoria clay, cordierite, spherical clay, kaolin, or a combination thereof. Preferably, the clay filler is a hydrated kaolin. Hydrated kaolin is characterized by its fine particle size, lamellar or plate-like particle shape, and chemical inertness. In some embodiments, the clay filler excludes spherical clay. An example of hydrated kaolin is Rogers Kaolin (commercially available from Imerys Kaolin, Inc.).

[0078] In any of the aspects or embodiments described in this document, the adsorbent composition includes from about 5 to about 50% by weight of a clay binder. In any of the aspects or embodiments described in this document, the clay binder is relatively poor in crystalline silica (e.g., less than about 5%). In any of the aspects or embodiments described in this document, the amount of clay is minimized in order to reduce wear and extend the service life of production equipment, e.g., extrusion molds.

[0079] In any of the aspects or embodiments described in this document, the adsorbent composition or extruded adsorbent composition includes from about 5 to about 45% by weight of a calcined binder material, including, for example, clay and / or silica sol. In any of the aspects or embodiments described in this document, the calcined clay binder is a combination of fine and medium-sized particles. In any of the aspects or embodiments described in this document, the kaolin clay binder includes fine and medium-sized calcined kaolin particles. For example, GLOMAX® kaolin (Imerys Kaolin, Inc., GA) is a medium-sized calcined kaolin. The materials Petition 870260058209, dated 06 / 15 / 2026, p. 35 / 180 32 / 80 Calcined binders may include calcined kyanite, mullite, cordierite, clay, silica, alumina, and other calcined or non-plastic refractory ceramic materials and combinations thereof. In any of the aspects or embodiments described herein, the calcined binder material includes calcined kaolin clay, for example, GLOMAX LL (Imerys Kaolin, Inc., GA).

[0080] In any of the aspects or embodiments described herein, the calcined binder material is present in the adsorbent composition or extrudable adsorbent composition in an amount of about 5 to about 45% by weight, about 5 to about 40% by weight, about 5 to about 35% by weight, about 5 to about 30% by weight, about 5 to about 25% by weight, about 2 to about 20% by weight, about 2 to about 15% by weight, about 2 to about 10% by weight, about 2 to about 8% by weight, or about 5 to about 10% by weight, each based on the total weight of the composition.

[0081] In any of the aspects or embodiments described herein, the adsorbent composition or extruded adsorbent composition includes from about 2 to about 20% by weight of a mineral flux. In certain embodiments, the mineral flux comprises a feldspar mineral. In certain embodiments, the mineral flux is nepheline syenite, a naturally occurring silica-deficient sodium-potassium aluminosilicate, for example, MINEX® (Covia Canada, Ltd., Ontario, CA). MINEX contains less than one-tenth of one percent free crystalline silica.

[0082] In any of the aspects or embodiments described herein, the adsorbent composition or extrudable adsorbent composition includes from about 0 to about 5% by weight of an inorganic binder, such as, for example, silica sol. In any of the aspects or embodiments described, the silica sol is Petition 870260058209, dated 06 / 15 / 2026, page 36 / 180 33 / 80 sodium silicate that increases the strength of both the dry, but unfired, extruded article and the fired extruded article, and acts as a flow material. In any of the aspects or embodiments described, the silica sol is present in an amount of about 0 to about 5% by weight, about 0 to about 4% by weight, about 0 to about 3% by weight, about 0 to about 2.5% by weight, about 0 to about 2% by weight, about 0 to about 1.5% by weight, or about 0 to about 1.2% by weight, each based on the total weight of the adsorbent composition or the extrudable composition. A suitable commercially available silica sol is amorphous SiO2 (e.g., Bindzil 2040 NH4 available near Akzo Nobel). In certain embodiments, the extrudable adsorbent composition excludes sodium silicate.

[0083] In any of the described aspects or embodiments, the adsorbent composition or extrudable adsorbent composition includes glass microspheres. In certain embodiments, the glass microspheres are non-hollow or hollow glass microspheres (e.g., glass bubbles) which provide an additional advantage in increasing the speed and ease of extrusion and provide a more economical process.

[0084] In any aspects or embodiments described herein, the glass microspheres of the adsorbent compositions or extrudable adsorbent compositions have an average diameter of less than about 500 micrometers, less than about 450 micrometers, less than about 400 micrometers, less than about 350 micrometers, less than about 300 micrometers, less than about 250 micrometers, less than about 200 micrometers, less than about 150 micrometers, less than about 100 micrometers, less than about 50 micrometers, less than about 40 micrometers, less than about 30 micrometers, less than about 25 micrometers, Petition 870260058209, dated 06 / 15 / 2026, page 37 / 180 34 / 80 less than about 20 micrometers, less than about 15 micrometers, less than about 10 micrometers, less than about 5 micrometers; or from about 10 micrometers to about 100 micrometers, from about 10 micrometers to about 50 micrometers, from about 10 micrometers to about 40 micrometers, from about 10 micrometers to about 30 micrometers, from about 10 micrometers to about 25 micrometers, or from 10 micrometers to about 20 micrometers.

[0085] In any aspect or embodiment, glass microspheres are glass bubbles. Glass bubbles, also commonly known as glass microbubbles, hollow glass microspheres, or hollow glass spheres, can be useful for reducing weight and improving the processability, dimensional stability, and flow properties of compositions. Generally, it is desirable for glass bubbles to be strong to avoid being crushed or broken during extrusion. Useful hollow glass particles include those marketed by 3M Co. (St. Paul, Minn.) under the trade name 3M GLASS BUBBLES (e.g., grades - S32, K37, S38, S38HS, S38XHS, K46, D32 / 4500, H50 / 10000, S60, S60HS, and iM30K); Glass bubbles marketed by Potters Industries, Valley Forge, Pa., (an affiliate of PQ Corporation) under the trade names Q-CEL HOLLOW SPHERES and SPHERICAL HOLLOW GLASS SPHERES and hollow glass particles marketed by Silbrico Corp., Hodgkins, Ill.under the trade name SIL-CELL. Exemplary glass bubbles include soda-lime-borosilicate glass bubbles (hollow spheres) with an average particle diameter (18 µm), density of 0.6 g / cc; crush resistance (90% survival) of 27 kpsi.

[0086] Glass microspheres can be useful for reducing weight and improving the processing, dimensional stability, and flow properties of compositions. In certain embodiments, glass microspheres are used as a filler and / or diluent, so as to Petition 870260058209, dated 06 / 15 / 2026, page 38 / 180 35 / 80 minimize or eliminate the need for abrasive binders, for example, spherical clay. In certain embodiments, glass microspheres reduce BWC.

[0087] In any of the aspects or embodiments described in this document, the adsorbent composition or extrudable adsorbent composition comprises from about 10 to about 50% by weight of activated adsorbent material (e.g., activated carbon), from about 2 to about 10% by weight of polymeric binder (e.g., methylcellulose, cellulose ether (METHOCEL)), from about 5 to about 10% by weight of clay binder (e.g., Rogers kaolin), from about 5 to about 45% by weight of a calcined clay binder (e.g., GLOMÁX LL), from about 2 to about 20% by weight of mineral flux (e.g., MINEX, The Cary Company), from about 0 to about 5% by weight of silica sol, and from about 5 to about 40% by weight of glass microspheres (e.g., glass microspheres). (e.g., iM30K glass bubbles, 3M).

[0088] In a further aspect, the description provides methods for preparing an extruded adsorbent composition according to the steps comprising: (a) mixing (i) from about 10 to about 50% by weight of an activated adsorbent material, for example, an activated adsorbent composition comprising an activated adsorbent powder, (ii) from about 3 to about 40% by weight of glass microspheres, and (iii) the difference to 100% by weight with at least one additive material to form an adsorbent composition; and (b) extruding the adsorbent composition to produce an extruded adsorbent composition. In any aspect or embodiment, the additive material comprises at least one of an organic binder, an inorganic binder, or a combination thereof. In any aspect or embodiment described herein, the organic binder is a cellulosic binder. In any aspect or embodiment described Petition 870260058209, dated 06 / 15 / 2026, page 39 / 180 36 / 80 in the present document, the inorganic binder is at least one of clay, silica, or a combination thereof. In certain embodiments, the silica comprises a silica sol material. In any of the aspects or embodiments described, a honeycomb matrix is ​​used in the extrusion step to produce an extruded adsorbent material with a honeycomb structure.

[0089] As would be understood by one skilled in the art, the dry ingredients of the extruded adsorbent composition will be moistened to form a paste before extrusion and drying. As such, in any aspect or embodiment described herein, water is added to components (i)-(ii) to form a wet mass or paste before the extrusion step (b).

[0090] In any of the aspects or embodiments described herein, the binder of the adsorbent composition or the extruded adsorbent composition produced as described herein comprises at least one of a clay binder, a calcined binder, mineral flux, water, or a combination thereof. In any of the aspects or embodiments described herein, the adsorbent composition or the extruded adsorbent composition produced as described herein comprises from about 5 to about 50% by weight of a clay binder, from about 5 to about 45% by weight of a calcined binder, from about 2 to about 20% by weight of a mineral flux, or a combination thereof.

[0091] In any of the aspects or embodiments described, the description provides an extruded adsorbent composition produced according to the steps comprising: (a) mixing (i) from about 10 to about 50% by weight of an activated adsorbent material, for example, an activated adsorbent material comprising an activated adsorbent powder; (ii) from about 2 to about 10% by weight of a binder Petition 870260058209, dated 06 / 15 / 2026, page 40 / 180 37 / 80 organic; (iii) from about 5 to about 50% by weight of a clay binder; (iv) from about 5 to about 45% by weight of a calcined clay binder; (v) from about 2 to about 20% of a mineral flux; (vi) from about 0 to about 5% by weight of a silica sol; and (vii) from about 3 to about 40% by weight of glass microspheres to form an adsorbent composition; and (b) extrude the adsorbent composition to form an extruded adsorbent composition. In certain embodiments, a honeycomb-type die is used in the extrusion step to produce an extruded adsorbent composition with a honeycomb structure.

[0092] In any of the aspects or embodiments described herein, the extruded composition comprises from about 10 to about 50% by weight of an activated adsorbent material comprising an activated adsorbent powder; from about 2 to about 10% by weight of a polymeric organic binder; from about 5% to about 50% by weight of a clay binder; from about 5% to about 45% by weight of a calcined binder; from about 2% to about 20% of a mineral flux; from about 0% to about 5% by weight of a silica sol; and from about 3% to about 40% by weight of glass microspheres.

[0093] In any of the described aspects or embodiments, the described adsorbent composition or extrudable adsorbent composition can be extruded at a rate that is faster than conventional formulations. Attempts at faster extrusion with conventional formulations result in a temperature increase due to friction, and the extruded part becomes unviably rigid. In any of the described aspects or embodiments, the adsorbent compositions, as described in this document, can be extruded at least about 40% faster than the conventional formulation, which is (about 3.5 in. / s).

[0094] In any of the aspects or modalities described in Petition 870260058209, dated 06 / 15 / 2026, p. 41 / 180 38 / 80 of this document, the composition of extrudable adsorbent or extruded adsorbent article comprises a pore volume ratio of 0.05-1 micrometer to 0.05-100 micrometer, as described in this document, which is greater than about 70%, or greater than about 75%, greater than about 80%, or greater than about 90%.

[0095] In any of the aspects or embodiments described herein, the extrudable adsorbent composition or extruded adsorbent article comprises a pore volume ratio of 0.05-0.5 micrometers to 0.05-100 micrometers, as described herein, which is greater than about 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%.

[0096] Different types of extruded adsorbent articles can be prepared from the adsorbent compositions or extrudable adsorbent compositions as described in this document. These include (but are not limited to) granules, pellets (e.g., cylindrical pellets), spheres, sheets, ribbons, trilobes, and monoliths, including articles with parallel internal passages extending through them (i.e., a parallel passage adsorbent volume or PPAV), such as, for example, a honeycomb structure, for example, a uniform or non-uniform honeycomb. In principle, any desired shape of the extruded article can be formed with a suitable forming device.Thus, forms such as monoliths, blocks, and other modular forms are also envisioned, including uniformly shaped particulate media, non-uniformly shaped particulate media, extruded structured media, coiled structured media, folded structured media, pleated structured media, wavy structured media, hollow structured media, glued structured media, nonwovens, woven fabrics, sheet, paper, foam, hollow cylinder, star, twisted spiral, asterisk, configured tapes, and combinations thereof. Petition 870260058209, dated 06 / 15 / 2026, page 42 / 180 39 / 80 formulations as described in this document are particularly useful for the extrusion of PPAVs, for example, honeycomb-type adsorbent articles.

[0097] In another aspect, the invention provides an evaporative emission control canister system comprising at least one fuel-side adsorbent volume and at least one vent-side adsorbent volume, wherein at least one of at least one fuel-side or at least one vent-side adsorbent volume comprises the adsorbent composition or the extruded adsorbent article, as described herein.

[0098] In any of the aspects or embodiments described in this document, the evaporative emissions control canister system comprises one or more vent-side adsorbent volumes with a uniform cell structure, i.e., approximately all cells in the adsorbent volume are the same size.

[0099] In any of the aspects or embodiments described herein, the evaporative emission control canister system comprising a vent-side extruded adsorbent article, as described herein, demonstrates two-day daytime loss of respiration (DBL) emissions of 100 mg or less. In certain embodiments, the evaporative emission control canister system comprising a vent-side extruded adsorbent article, as described herein, demonstrates two-day daytime loss of respiration (DBL) emissions of 100, 90, 80, 70, 60, 50, 40, 30 or 20 mg or less.

[00100] In any of the aspects or embodiments described herein, the extruded adsorbent composition, as described herein, demonstrates loss emissions of Petition 870260058209, dated 06 / 15 / 2026, page 43 / 180 40 / 80 two-day daylight breathing (DBL) of 100 mg or less, for example from about 5 mg to about 100 mg in a specified amount of purge air volume applied after a butane loading step of 40 g / h, as determined by the California Exhaust Emissions Test Procedure of 2012 (BETP). In any of the embodiments described herein, the evaporative emission control system may further comprise a heating unit.

[00101] In a further aspect, the description provides methods for reducing fuel vapor emissions in an evaporative emission control system, the method comprising contacting the fuel vapor with an evaporative emission control system as described herein, comprising an extruded adsorbent article as described herein.

[00102] In certain additional embodiments, the adsorbent composition or extrudable adsorbent composition, as described herein, is formed in a structure comprising a matrix with approximately uniform cell or geometric structure, for example, a honeycomb configuration, which allows or facilitates the approximately uniform distribution of air or vapor flow through the subsequent adsorbent volume. In other embodiments, the adsorbent material is formed in a structure that includes a combination of any of the foregoing.

[00103] The extruded adsorbent composition or article may include any one or more of the above features, which may be combined in any number of ways as described herein and are expressly contemplated herein.

[00104] In any of the aspects or embodiments described in this document, the extruded adsorbent article, for example, adsorbent honeycomb structure, is dried in a way that prevents Petition 870260058209, dated 06 / 15 / 2026, p. 44 / 180 41 / 80 cracks in the structure. To alleviate cracks, the extruded honeycomb structure is dried so that water is removed substantially at the same rate throughout the entire extruded honeycomb structure. Preferred drying methods include vacuum drying, freeze-drying, microwave drying, radio frequency (RF) drying, and moisture control drying. More conventional drying methods can be used to dry the extruded honeycomb structure of the present invention, but are less commercially practical. Such conventional methods include dielectric drying and hot air drying with the monolith wrapped in plastic.

[00105] Vacuum drying of the extruded honeycomb structure involves placing the extruded monolith in a vacuum chamber initially at ambient temperature and atmospheric pressure inside the vacuum chamber, reducing the pressure inside the vacuum chamber to a rate and level sufficient to rapidly freeze the water in the extruded honeycomb structure, and maintaining a reduced pressure inside the vacuum chamber for a sufficient time for the frozen water in the extruded honeycomb structure to sublimate until the extruded honeycomb structure is dry. This drying cycle may be temporarily interrupted to remove the extruded honeycomb structure to another chamber after the extruded honeycomb structure has been frozen. Freezing the water in the extruded honeycomb structure immobilizes the water and stabilizes the size and shape of the extruded honeycomb structure.Ideally, the initial vacuum should be a deep vacuum to quickly and uniformly freeze the extruded honeycomb structure. The vacuum freezes the extruded honeycomb structure more uniformly than if it were frozen in a cold chamber under atmospheric pressure. After freezing, the extruded honeycomb structure can then be moved to a second chamber that does not require such a deep vacuum. Petition 870260058209, dated 06 / 15 / 2026, page 45 / 180 42 / 80 as to the first chamber. Sublimation can be completed in this second chamber. Desirably, during vacuum drying, the pressure inside the vacuum chamber is reduced, within about 1 minute, from atmospheric pressure to a pressure less than about 1 torr, and desirably within the range of 30 micrometers to 1 torr. Alternatively, this second chamber can be at atmospheric pressure and subfreezing temperature and the frozen extruded honeycomb structure can be dried with recirculating dehumidified air.

[00106] Freeze-drying of the extruded honeycomb structure is carried out in the same manner as vacuum drying, except that the structure undergoes flash freezing before being placed in a vacuum chamber for sublimation drying. The wet extruded honeycomb structure is frozen by placing the wet extruded honeycomb structure in a super-cold chamber cooled by liquid nitrogen or other means known to those skilled in the art.Alternatively, the extruded honeycomb structure can be flooded or submerged in super-cold liquid, such as liquid nitrogen, to freeze the extruded honeycomb structure.

[00107] During the freeze-drying or vacuum drying stage where the extruded honeycomb structure is subjected to a vacuum, the temperature of the extruded honeycomb structure can be varied by applying energy via radiation, conduction, convection, or RF or microwave energy independently during drying to improve water removal. Vacuum levels similar to those used for vacuum drying are used. The temperature of the extruded honeycomb structure should be maintained at or below a maximum of 32°F to prevent uneven water loss and cracking.

[00108] The drying of the moisture control of the wet extruded honeycomb structure includes the placement of the structure Petition 870260058209, dated 06 / 15 / 2026, p. 46 / 180 43 / 80 of wet extruded honeycomb is extruded into a chamber initially exhibiting a relative humidity within the chamber of at least 92 percent and gradually reducing the relative humidity within the chamber until the extruded honeycomb structure is dry. Desirably, the initial relative humidity level in the chamber should be 98% or higher. The humidity in the chamber can be reduced in stages to effect substantially uniform moisture loss throughout the extruded honeycomb structure during each drying stage. Humidity-conditioning air is circulated through the drying chamber and the passages of the extruded honeycomb structure to ensure a uniform rate of moisture removal throughout the extruded honeycomb structure. The temperature inside the chamber can be varied to enhance the drying action.

[00109] In any of the described aspects or embodiments, after a drying step, the extruded and dried honeycomb structure is fired or calcined at a temperature of about 500 to about 1150 °C, or about 1000 to about 1150 °C, in a nitrogen atmosphere or other non-oxidizing or slightly reducing atmosphere. The extruded honeycomb structure must be fired at a temperature sufficient to react the ceramic-forming materials together to create a matrix to hold the activated carbon and maintain the honeycomb shape of the extrusion. The bonds created by firing must be sufficient to create a matrix with a strength capable of withstanding the handling and use of the extruded honeycomb structure in intended applications, such as in an ozone filter for a xerographic device, a fuel adsorbent in an automotive air intake system, or a catalyst support.When used as a catalyst support, the extruded honeycomb structure of the present invention can be coated with conventional catalyst coatings using conventional coating methods. The area. Petition 870260058209, dated 06 / 15 / 2026, page 47 / 180 The relatively high surface area of ​​the material forming the extruded honeycomb structure of the present invention makes it desirable as a catalyst support.

[00110] In any of the aspects or embodiments described, the extruded adsorbent article, as described herein, has a BWC that is from 1 g / dL to about 10 g / dL. The components of the adsorbent compositions disclosed herein can work with a variety of mixing, shaping, and heat treatment equipment. Different mixing devices, such as low-shear mullers, medium-shear paddle mixers, and high-shear pin mixers, have been shown to produce a material that is suitable for subsequent shaping. Shaping devices such as drill extruders, piston extruders, granulators, roll pelletizers, spheronizers, and tablet presses are suitable depending on the applications. Drying and curing of the wet carbon bodies can be carried out at temperatures below 270 °C.with a variety of different devices, such as a convection tray furnace, a vibratory fluid bed dryer, and a rotary kiln. In contrast, higher temperatures of around 500-1200 °C can be used for heat treatment of carbons bonded to clay and phenolic resin, usually using a rotary kiln.

[00111] In certain embodiments, the adsorbent compositions and articles described in this document have a pore volume ratio of 0.05-1 micrometer to 0.05-100 micrometer that is greater than about 70%, greater than about 75%, or greater than about 80%, including all intermediate values. In certain embodiments, the pore volume ratio of 0.05-1 micrometer to 0.05-100 micrometer is about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, Petition 870260058209, dated 06 / 15 / 2026, p. 48 / 180 45 / 80 approximately 78%, approximately 79%, or approximately 80%, including all intermediate values. In certain embodiments, the pore volume ratio from 0.05-1 micrometer to 0.05-100 micrometer is 70-80%, or 75-80%, and including all overlapping intervals, intervals, and values ​​subsumed between them.

[00112] In certain embodiments, the adsorbent materials and compositions described in this document have a pore volume ratio of 0.05-0.5 micrometers to 0.05-100 micrometers that is less than about 90%, less than about 80%, less than about 75%, less than about 70%, less than about 65%, less than about 60%, less than about 55%, less than about 50%, or less than about 45%, less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, including all intermediate values. In certain embodiments, the pore volume ratio from 0.05-0.5 micrometers to 0.05-100 micrometers is approximately 20%, approximately 21%, approximately 22%, approximately 23%, approximately 24%, approximately 25%, approximately 26%, approximately 27%, approximately 28%, approximately 29%, approximately 30%, approximately 31%, approximately 32%, approximately 33%, approximately 34%, approximately 35%, approximately 36%, approximately 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, approximately 52%, approximately 53%, approximately 54%, approximately 55%, approximately 56%, approximately 57%, approximately 58%, approximately 59%, or approximately 60% or more. In certain embodiments, the pore volume ratio of 0.05-0.5 micrometers to 0.05-100 micrometers is approximately 20-90%, approximately 20-85%, approximately 20-80%, approximately 20-75%, approximately 20-70%, approximately 20-65%, approximately 20-60%, approximately 20-55%, approximately 20-50%, approximately 20-45%, approximately 20-40%, approximately 20-35%, approximately 20-30%, or approximately 20-25%, including the overlap values ​​between the values. Petition 870260058209, dated 06 / 15 / 2026, page 49 / 180 46 / 80 of variation and overlap between them.

[00113] In certain embodiments, the extruded material also exhibits at least one of: (i) a pore volume ratio of 0.05-1 micrometers to 0.05-100 micrometers as described herein, for example, greater than about 70%, (ii) a pore volume ratio of 0.05-0.5 micrometers to 0.05-100 micrometers as described herein, for example, greater than about 20%, or (iii) a combination thereof. In certain embodiments, the shaping step is performed by extrusion.

[00114] In certain additional embodiments, the method includes the step (e) of drying, curing or calcining the extruded adsorbent composition or article. In certain embodiments, the drying, curing or calcining step is carried out for about 30 minutes to about 20 hours. In certain embodiments, the drying curing or calcining step is carried out for about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19 or about 20 hours, including all intermediate values. In certain methods, the drying, curing, or calcination stage is carried out at a temperature ranging from approximately 100 °C to approximately 650 °C.In certain embodiments, the drying, curing or calcination step is carried out at a temperature of approximately 100 °C, approximately 110 °C, approximately 120 °C, approximately 130 °C, approximately 140 °C, approximately 150 °C, approximately 160 °C, approximately 170 °C, approximately 180 °C, approximately 190 °C, approximately 200 °C, approximately 250 °C, approximately 300 °C, approximately 350 °C, approximately 400 °C, approximately 450 °C, approximately 500 °C, approximately 550 °C, approximately 600 °C, approximately 650 °C, approximately 700 °C, or approximately 750 °C, or approximately 800 °C, or approximately 850 °C, or approximately 900 °C. °C, or about 950 °C, or about 1000 °C, or about 1050 °C, or about 1100 °C. Petition 870260058209, dated 06 / 15 / 2026, p. 50 / 180 47 / 80

[00115] In certain aspects, the extruded adsorbent composition or article, as described herein, is enclosed in a canister. When the extruded adsorbent composition or article is enclosed in a canister system, the canister demonstrates two-day DBL exhaust emissions performance (second-day day loss of breathing (DBL) emissions) of about 100 mg or less, about 90 mg or less, about 80 mg or less, about 70 mg or less, about 60 mg or less, about 50 mg or less, about 40 mg or less, about 30 mg or less, about 20 mg or less, or about 10 mg or less at a specified purge volume applied after a butane loading step of 40 g / h, as determined by the 2012 BETP.In any aspect or embodiment, the extruded adsorbent composition or article is included in a canister system, the canister demonstrates two-day DBL exhaust emissions performance (second-day daytime loss of breathing (DBL) emissions) of about 100 mg or less, about 90 mg or less, about 80 mg or less, about 70 mg or less, about 60 mg or less, about 50 mg or less, about 40 mg or less, about 30 mg or less, about 20 mg or less, about 10 mg or less.In any aspect or embodiment described herein, the system is purged with more than 315 L of purge applied after a butane loading step of 40 g / h as determined by the 2012 BETP, not more than about 315 liters (i.e., about 150 BV based on the nominal volume of the base canister) of purge applied after a butane loading step of 40 g / h as determined by the 2012 BETP, or with not more than 210 liters (i.e., 100 BV) of purge applied after a butane loading step of 40 g / h as determined by the 2012 BETP.

[00116] In certain modes, the amount of purge is greater than Petition 870260058209, dated 06 / 15 / 2026, page 51 / 180 48 / 80 approximately 150 bed volumes (BV), from approximately 25 BV to approximately 150 BV, from approximately 35 to approximately 150 BV, from approximately 40 BV to approximately 150 BV, from approximately 50 BV to approximately 150 BV, including all intermediate overlapping ranges and values. In additional embodiments, the purge volume is from approximately 25 BV to approximately 140 BV, from approximately 25 BV to approximately 130 BV, from approximately 25 BV to approximately 120 BV, from approximately 25 BV to approximately 110 BV, from approximately 25 BV to approximately 100 BV, from approximately 25 BV to approximately 90 BV, from approximately 25 BV to approximately 80 BV, from approximately 25 BV to approximately 70 BV, from approximately 25 BV to approximately 60 BV, from approximately 25 BV to approximately 50 BV, and including all overlapping ranges and intermediate values. In certain embodiments, the purge volumes above are based on a 2.1 liter canister system.

[00117] In certain embodiments, the extruded adsorbent composition or article is enclosed in a 2.1 liter canister, as described herein, exhibiting a two-day daytime loss of respiration (DBL) emission of not more than 100 mg in sufficient purge volume applied after the butane loading step of 40 g / h.In certain embodiments, the extruded adsorbent composition or article is included in a 2.1-liter canister, as described herein, and exhibits two-day daytime respiratory loss (DBL) emissions not exceeding 100 mg in 150 purge bed volumes (BV) applied after the 40 g / h butane loading step, as determined by the California Exhaust Emissions Test Procedure (BETP) of 2012, or a DBL of not more than 90 mg in 150 purge bed volumes applied after the 40 g / h butane loading step, as determined by the BETP of 2012, or a DBL not exceeding 80 mg in 150 purge bed volumes applied after the 40 g / h butane loading step, as determined by the BETP. Petition 870260058209, dated 06 / 15 / 2026, page 52 / 180 49 / 80 of 2012, or a DBL of not more than 70 mg in 150 purge bed volumes applied after the 40 g / h butane loading step, as determined by the BETP of 2012, or a DBL of not more than 60 mg in 150 purge bed volumes applied after the 40 g / h butane loading step, as determined by the BETP of 2012, or a DBL of not more than 50 mg in 150 purge bed volumes applied after the 40 g / h butane loading step, as determined by the BETP of 2012, or a DBL of not more than 40 mg in 150 purge bed volumes applied after the 40 g / h butane loading step, as determined by the BETP of 2012, or a DBL of not more than 30 mg in 150 purge bed volumes applied after the 40 g / h butane loading step, as determined by the 2012 BETP, or a DBL of no more than 20 mg in 150 purge bed volumes applied after the 40 g / h butane loading step, as determined by the 2012 BETP.including all intermediate values.

[00118] In certain aspects, the evaporative emission control canister system comprises at least one fuel-side adsorbent volume and at least one subsequent (i.e., vent-side) adsorbent volume, wherein at least one of the at least one fuel-side adsorbent volume or at least one subsequent adsorbent volume includes an extruded adsorbent composition or article, as described herein.

[00119] In certain embodiments, the evaporative emission control canister system exhibits two-day daytime respiratory loss (DBL) emissions not exceeding about 100 mg, not exceeding about 95 mg, not exceeding about 90 mg, not exceeding about 85 mg, not exceeding about 80 mg, not exceeding about 75 mg, not exceeding about 70 mg, not Petition 870260058209, dated 06 / 15 / 2026, page 53 / 18050 / 80 exceeding approximately 65 mg, not exceeding approximately 60 mg, not exceeding approximately 55 mg, not exceeding approximately 50 mg, not exceeding approximately 45 mg, not exceeding approximately 40 mg, not exceeding approximately 35 mg, not exceeding approximately 30 mg, not exceeding approximately 25 mg, not exceeding approximately 20 mg, not exceeding approximately 15 mg, or not exceeding approximately 10 mg in a specified purge volume after a 40 g / h butane loading step, as determined by the 2012 California Exhaust Emissions Test. In certain embodiments, the purge volume does not exceed approximately 315 liters, does not exceed approximately 310 liters, does not exceed approximately 300 liters, does not exceed approximately 290 liters, does not exceed approximately 280 liters, does not exceed approximately 270 liters, not more than about 260 liters, not more than about 250 liters, not more than about 240 liters, not more than about 230 liters,not exceeding approximately 220 liters, not exceeding approximately 210 liters, not exceeding approximately 200 liters, not exceeding approximately 190 liters, not exceeding approximately 180 liters, not exceeding approximately 170 liters, not exceeding approximately 160 liters, not exceeding approximately 150 liters, not exceeding approximately 140 liters, not exceeding approximately 130 liters, not exceeding approximately 120 liters, not exceeding approximately 110 liters, not exceeding approximately 100 liters, not exceeding approximately 90 liters, or not exceeding approximately 80 liters of purge applied after a 40 g / h butane loading step as determined by the 2012 California Exhaust Emissions Test. In certain embodiments, the amount of purge volume that provides the above two-day DBL emissions as determined by the BETP of 2012, it is from about 50 liters to about 315 liters, from about 75 liters to about 315 liters, from about 100 liters to about 315 liters,from about 125 liters to about 315 liters, from about 150 liters to about 315 liters, from about 175 liters to about 315 liters, from about, Petition 870260058209, dated 06 / 15 / 2026, page 54 / 180 51 / 80 200 liters to approximately 315 liters, from approximately 210 liters to approximately 315 liters, from approximately 220 liters to approximately 315 liters, from approximately 230 liters to approximately 315 liters, from approximately 240 liters to approximately 315 liters, or from approximately 250 liters to approximately 315 liters, including all overlapping, subsumed, and intermediate values ​​and ranges.

[00120] In certain embodiments, the evaporative emission control canister system exhibits two-day daytime respiratory loss (DBL) emissions not exceeding about 100 mg, not exceeding about 95 mg, not exceeding about 90 mg, not exceeding about 85 mg, not exceeding about 80 mg, not exceeding about 75 mg, not exceeding about 70 mg, not exceeding about 65 mg, not exceeding about 60 mg, not exceeding about 55 mg, not exceeding about 50 mg, not exceeding about 45 mg, not exceeding about 40 mg, not exceeding about 35 mg, not exceeding about 30 mg, not exceeding about 25 mg, not exceeding about 20 mg, not exceeding about 15 mg or not more than about 10 mg not more than about 150 BV, not more than approximately 145 BV, no more than approximately 140 BV, no more than approximately 135 BV, no more than approximately 130 BV, no more than approximately 125 BV, no more than approximately 120 BV,not more than about 115 BV, not more than about 110 BV, not more than about 105 BV, not more than about 100 BV, not more than about 95 BV, not more than about 90 BV, not more than about 85 BV, not more than about 80 BV, not more than about 75 BV, not more than about 70 BV, not more than about 65 BV, not more than about 60 BV, not more than about 55 BV, not more than about 50 BV, not more than about 45 BV, or not more than about 40 BV of purge applied after a 40 g / h butane loading step as determined by the 2012 California Exhaust Emissions Test.

[00121] The term fuel-side adsorbent volume is, Petition 870260058209, dated 06 / 15 / 2026, p. 55 / 180 52 / 80 is used in reference to a volume of adsorbent material that is proximal to the fuel vapor source and therefore earlier in the fuel vapor flow path relative to a subsequent adsorbent volume, which is necessarily positioned closer to the vent orifice (here, a vent-side adsorbent volume). As those skilled in the art would appreciate, during a purge cycle, a subsequent or vent-side adsorbent volume is contacted earlier in the purge airflow path. For convenience, the fuel-side adsorbent may be referred to as the initial adsorbent volume because it is positioned upstream in the fuel vapor flow path relative to the vent-side or subsequent adsorbent volume, but the initial adsorbent volume is not necessarily required to be the first adsorbent volume in the canister.

[00122] Figure 1 illustrates an embodiment of the evaporative emission control canister system 100 with adsorbent volumes in series within a single canister 101. The canister system 100 includes screens or foams 102, a partition wall 103, a fuel vapor inlet 104 from a fuel tank, a vent port 105 to an atmosphere, a purge outlet 106 to an engine, the fuel side or initial adsorbent volume 201, and the vent side or subsequent adsorbent volume 202. The screens or foams 102 provide containment and support for the adsorbent volumes, as well as serving as a distributor to equalize the vapor flow distribution in the adsorbent volumes. The two chambers containing adsorbent volumes 201 and 202 are separated by partition wall 103 and connected for sequential vapor flow purposes below a support screen 102 by means of passage 107, called the canister plenum.When an engine is switched off, fuel vapor from a fuel tank enters. Petition 870260058209, dated 06 / 15 / 2026, page 56 / 180 53 / 80 in the canister system 100 through the fuel vapor inlet 104. The fuel vapor diffuses or flows into the initial adsorbent volume or fuel side 201, and then the subsequent adsorbent volume or vent side 202, which together define an air and vapor flow path, before being released to the atmosphere through the vent port 105 of the canister system. Once the engine is started, ambient air is drawn into the canister system 100 through the vent port 105. Purge air flows through volumes 202 in the canister 101 and finally through the fuel-side or initial adsorbent volume 201. This purge flow desorbs the fuel vapor adsorbed in the adsorbent volumes 201 to 202 before entering an internal combustion engine through the purge outlet 106.In any of the embodiments of the evaporative emission control canister system described in this document, the canister system may include more than one vent-side or subsequent adsorbent volume. For example, vent-side adsorbent volume 201 may have an additional volume or a plurality of vent-side adsorbent volumes 202 before the support screen 102 above the plenum 107, as shown in Figure 2. Additional vent-side adsorbent volumes 203 and 204 may be found on the other side of the partition wall.

[00123] Furthermore, in further embodiments, the canister system may include more than one type of vent-side adsorbent volume, which may be independently selected and / or which is comprised in one or more containers. For example, as shown in Figure 3, an auxiliary chamber 300 containing a vent-side adsorbent volume 301 may be in series in terms of air and vapor flow with the main canister 101 containing multiple adsorbent volumes, connected for vapor flow purposes by means of Petition 870260058209, dated 06 / 15 / 2026, page 57 / 180 54 / 80 of a connecting hose or snorkel 108. As shown in Figure 4, auxiliary chamber 300 may contain two vent-side adsorbent volumes in series 301 and 302. Adsorbent volumes 301 and 302 may also be contained within series chambers or auxiliary canisters, instead of the single chamber 300 of Figure 4.

[00124] In any of the embodiments described in this document, the evaporative emission control system may also comprise a heating unit or a means for adding heat by means of electrical resistance or heat conduction.

[00125] In any of the aspects or embodiments described in this document, the canister system comprises one or more vent-side adsorbent volumes with a uniform cellular structure at or near the end of the fuel vapor flow path.

[00126] In certain embodiments, at least one initial or fuel-side adsorbent volume and at least one subsequent or vent-side adsorbent volume (or volumes) are in vaporous or gaseous communication and define an air and vapor flow pathway through them. The air and vapor flow pathway allows or facilitates the directional flow of air or vapor or diffusion between the respective adsorbent volumes in the canister system. For example, the air and vapor flow pathway facilitates the flow or diffusion of fuel vapor from at least one initial or fuel-side adsorbent volume to at least one subsequent or vent-side adsorbent volume (or volumes).

[00127] In any of the embodiments described herein, at least one initial or fuel-side adsorbent volume and at least one subsequent or vent-side adsorbent volume may be located within a single Petition 870260058209, dated 06 / 15 / 2026, page 58 / 180 55 / 80 canister, separate canisters, or a combination of both. For example, in certain embodiments, the system comprises a canister comprising an initial adsorbent volume on the fuel side and one or more subsequent adsorbent volumes on the vent side, wherein the subsequent adsorbent volumes on the vent side are connected to the initial adsorbent volume on the fuel side so that they are in vaporous or gaseous communication forming a vapor flow pathway and allowing air and / or vapor to flow or diffuse through them. In certain aspects, the canister allows sequential contact of the adsorbent volumes by air or fuel vapor.

[00128] In further embodiments, the system comprises a canister comprising an initial adsorbent volume and one or more subsequent adsorbent volumes connected to one or more separate canisters comprising at least one additional subsequent adsorbent volume, wherein the subsequent adsorbent volumes are connected to the initial adsorbent volume such that they are in vaporous or gaseous communication forming a vapor flow pathway and allowing air and / or fuel to flow or diffuse through them.

[00129] In certain embodiments, the system comprises a canister comprising a fuel side or an initial adsorbent volume, and one or more vent-side or subsequent adsorbent volumes connected to one or more separate canisters comprising at least one additional subsequent adsorbent volume, wherein one or more vent-side adsorbent volumes and at least one additional subsequent adsorbent volume are connected to the initial adsorbent volume such that they are in vaporous or gaseous communication forming a vapor flow pathway, and allowing air and / or fuel vapor to pass through. Petition 870260058209, dated 06 / 15 / 2026, page 59 / 180 56 / 80 flows or diffuses through it, wherein at least one of the adsorbent volumes in the system is an extruded adsorbent material, as described in this document, having a BWC of about 1 g / dL to about 10 g / dL.

[00130] In certain embodiments, the system comprises a canister comprising an initial or fuel-side adsorbent volume, and one or more vent-side or subsequent adsorbent volumes connected to one or more separate canisters comprising at least one additional subsequent adsorbent volume, wherein one or more vent-side adsorbent volumes and at least one additional subsequent adsorbent volume connected to the initial fuel-side adsorbent volume such that they are in vaporous or gaseous communication forming a vapor flow pathway, and allowing air and / or fuel vapor to flow or diffuse through it, wherein at least one of the adsorbent volumes in the system is an extruded adsorbent material, as described herein.

[00131] In any of the aspects or embodiments described in this document, the fuel side or initial adsorbent volume is the first and / or second adsorbent volume, as such, the vent side or subsequent adsorbent volumes are those downstream in the fluid flow path towards the vent port, whether in the same or in a separate canister or both.

[00132] In any aspects or embodiments described herein, the canister system comprises at least one volume of extruded adsorbent, as described herein, as a vent-side adsorbent volume having at least one of: (i) an effective incremental adsorption capacity at 25 °C of 1 gram of n-butane / L less than 35 Petition 870260058209, dated 06 / 15 / 2026, page 60 / 180 57 / 80 grams of n-butane / L between vapor concentrations of 5% by volume and 50% by volume of n-butane, (ii) a BWC less than 3 g / dL, (iii) a total BWC less than 20 grams, or (iv) a combination of these. In certain embodiments, the canister comprises at least one vent-side adsorbent material, as described in this document, with an incremental adsorption capacity at 25 °C of about 35, about 34, about 33, about 32, about 31, about 30, about 29, about 28, about 37, about 36, about 35, about 34, about 23, about 22, about 21, about 20, about 19, about 18, about 17, about 16, about 15, about 14, about 13, about 12, about 11, about 10, about 9, about 8, about 7, about 6, about 5, about 4, about 3, about 2, or about 1 g / L between vapor concentrations of 5% by volume and 50% by volume of n-butane.

[00133] In any of the aspects or embodiments described in this document, the canister system comprises at least one fuel-side adsorbent volume with an effective incremental adsorption capacity at 25 °C greater than about 35 grams of n-butane per liter (g / L) to about 90 g / L between a vapor concentration of 5% by volume and 50% by volume of n-butane, or about 36, about 37, about 38, about 39, about 40, about 41, about 42, about 43, about 44, about 45, about 46, about 47, about 48, about 49, about 50, about 51, about 52, about 53, about 54, about 55, about 60, about 65, about 70, approximately 75, approximately 80, approximately 85, approximately 90 or more grams of n-butane per liter (g / L) between a vapor concentration of 5% by volume and 50% by volume of n-butane.In any of the aspects or embodiments described in this document, the canister system comprises at least one fuel-side adsorbent volume with an effective incremental adsorption capacity at 25 °C greater. Petition 870260058209, dated 06 / 15 / 2026, p. 61 / 180 58 / 80 to approximately 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or more grams of n-butane per liter (g / L) to approximately 90 g / L between a vapor concentration of 5% by volume and 50% by volume of n-butane.

[00134] In any aspects or embodiments described in this document, the canister system comprises at least one vent-side adsorbent material, as described in this document, with an effective incremental adsorption capacity at 25 °C of less than about 35 grams of n-butane per liter (g / L) between a vapor concentration of 5% by vol. and 50% by vol. of n-butane, or about 34, about 33, about 32, about 31, about 30, about 19, about 18, about 17, about 16, about 15, about 14, about 13, about 12, about 11, about 10, about 9, about 8, about 7, about 6, about 5, about 4, about 3, about 2, or about 1 gram of n-butane per liter (g / L) between the vapor concentration of 5% by vol. and 50% by vol. of n-butane.

[00135] In a particular embodiment, the evaporative emission control system includes: a fuel tank for storing fuel; an engine with an air induction system and adapted to consume the fuel; an evaporative emission control canister system comprising one or more canister(s); a fuel vapor inlet duct from the fuel tank to the canister system; a fuel vapor purge duct from the canister system to the engine's air induction system; and a vent duct for venting the canister system when the engine is off and for purge air intake into the canister system when the engine is on.The evaporative emission control canister system is defined by a fuel vapor flow path from the fuel vapor inlet conduit to the initial adsorbent volume towards at least one subsequent adsorbent volume and the vent conduit, and by... Petition 870260058209, dated 06 / 15 / 2026, page 62 / 180 59 / 80 an airflow path from the vent duct to at least one subsequent adsorbent volume toward the initial adsorbent volume and the fuel vapor purge duct. In certain embodiments, the initial adsorbent volume and at least one subsequent adsorbent volume are located within a single canister, or the initial adsorbent volume and at least one subsequent adsorbent volume are located in separate canisters that are connected to allow sequential fuel vapor contact. In certain embodiments, the evaporative emission control canister system exhibits a two-day daytime loss-of-breath (DBL) emission of no more than 20 mg in sufficient purge air volume applied after the 40 g / h butane loading step.

[00136] The disclosed evaporative emission control system can provide low daytime emission loss (DBL) emissions even under low purge conditions. The evaporative emission performance of the disclosed evaporative emission control system can be within the regulatory limits defined by the California Emissions Test Procedure (BETP), which is 20 mg less, even under low purge conditions.

[00137] The term low purge, as used in this document, refers to a purge level of 210 liters or below applied after the 40 g / h butane loading step (i.e., 100 bed volumes for a 2.1 liter adsorbent component system).

[00138] The evaporative emission control system can provide low daytime loss (DBL) emissions even when purged at or below 210 liters applied after the 40 g / h butane loading step. In some embodiments, the evaporative emission control system can be purged at or below 157.5 liters applied after the 40 g / h butane loading step. Petition 870260058209, dated 06 / 15 / 2026, page 63 / 180 60 / 80 g / h.

[00139] In further aspects, the adsorbent composition or extruded adsorbent composition, as described herein, is incorporated into a fluid separation system. In any aspect or embodiment, the fluid separation system includes any liquid or gas phase separation or purification application that uses an adsorbent in form, such as granule, pellet, monolith or honeycomb. For example, by way of non-limiting example, the adsorbent composition or extruded adsorbent composition, as described herein, is incorporated into a system for purifying air or other gases, such as hydrocarbons (e.g., methane, natural gas, propane, butane, ethylene, solvents) and non-hydrocarbons (e.g., hydrogen, nitrogen, oxygen, carbon dioxide, noble gases) and water, non-process and non-aqueous process liquids. Examples

[00140] Unless otherwise indicated, the quantity of each component is given as a percentage by weight (% by weight), based on the total weight of the composition. Table 1. Exemplary formulations of adsorbent compositions. Component Unit E1 E2 E3 E4 E5 E6 Adsorbent % by weight 16.0 18.0 20.0 12.0 29.0 44.0 Glass Microspheres % by weight 25.3 24.7 24 6.7 21.4 15.5 Additives % by weight 58.6 57.4 56 81.3 49.5 40.5 Total % by weight 100 100 100 100 100 100 Pore volume ratio 0.05-1% 89 88 85 87 90 85 Petition 870260058209, dated 06 / 15 / 2026, page 64 / 180 61 / 80 Pore ​​volume ratio 0.05-0.5 μm to 0.05-100 μm % 64 63 37 86 40 54 BACT* g / 100g 8.05 8.14 9.38 5.99 12.81 19.61 BWC* g / dL 2.22 2.36 2.43 2.24 2.95 3.88 AD* g / mL 0.304 0.320 0.294 0.401 0.251 0.230 BPR* % 90.6 90.6 88.2 93.3 91.8 86.2 *Measured in 29x100-200 pieces Table 1 -continued- Component Unit E7 E8 E9 E10 C1 C2 Adsorbent % by weight 36.8 12.0 20.0 12.0 N / AN / A Glass Microspheres % by weight 3.5 40 36 26.6 0 0 Additives % by weight 59.7 48.1 44 61.4 N / AN / A Total % by weight 100 100 100 100 100 100 Pore volume ratio 0.05-1 μm to 0.05-100 μm % 87 85 76 83 90 93 Pore volume ratio 0.05-0.5 μm to 0.05-100 μm % 86 29 19 50 89 92 BACT* g / 100g 14.10 5.63 9.16 5.74 4.53 13.16 BWC* g / dL 4.19 1.50 2.10 1.84 2.15 4.21 AD* g / mL 0.300 0.269 0.248 0.337 0.499 0.379 BPR* % 99.2 99.1 92.5 95.3 95.5 84.5

[00141] Formulations E1 - E10 in Table 1 were prepared by mixing the dry ingredients in a plow mixer followed by the addition of liquid ingredients and sufficient water to produce a Petition 870260058209, dated 06 / 15 / 2026, p. 65 / 180 62 / 80 extrudable paste. Once all ingredients are present, further mixing in a plow mixer is used to ensure dispersion of all ingredients. The resulting wet mix was then intensively mixed in a sigma blade mixer or in a single-screw extruder or kneader with extrusion through a multi-hole die plate to form a paste. The paste was then extruded through a single-screw extruder fitted with a honeycomb die. The extruded portions were rough cut for drying and calcination in a high-temperature inert atmosphere, followed by cutting to exact length for testing. C1 and C2 are the commercially available honeycomb formulations Nuchar® HCA-LBE and Nuchar HCA® (Ingevity®, North Charleston, SC, USA), respectively. Neither of these formulations contains glass microspheres.

[00142] Determination of Apparent Density, BWC and Butane Activity in Powder

[00143] The ASTM D 2854 standard method (hereinafter the Standard Method) can be used to determine the apparent volume density of particulate adsorbents, such as granular and pelletized adsorbents of the size and shape typically used for evaporative emission control for fuel systems.

[00144] The ASTM D5228 standard method can be used to determine the butane working capacity (BWC) of adsorbent volumes containing granular and / or particulate pelletized adsorbents. Retentivity is calculated as the difference, in g / dL units, between the volumetric butane activity (i.e., the apparent density g / cc multiplied by the butane activity g / 100g) and the BWC in g / dL.

[00145] For powdered activated carbon ingredients for extrusion, a powdered butane activity (pBACT) can be measured by Petition 870260058209, dated 06 / 15 / 2026, page 66 / 180 63 / 80 any method known to those skilled in the art recognized as equivalent for verifying this value, that is, the balanced weighted gram capacity of the oven-dried powder sample when exposed to 1.00 atm partial pressure of n-butane, for the sample thermostated at 25°C. A suitable alternative to pBACT, for example, is based on the ASTM 5228 method, as described in US 2019 / 0226426A1, which is incorporated herein by reference.

[00146] A modified version of the ASTM D5228 method can be used to determine the nominal volume butane working capacity (BWC) of particularized volumes of honeycomb, monolith, and / or sheet adsorbent. The modified method can also be used for particulate adsorbents, where the particulate adsorbents include fillers, voids, structural components, or additives. Furthermore, the modified method can be used where the particularized adsorbents are not compatible with the standard ASTM D5228 method, for example, a representative adsorbent sample may not be readily available as per the filling of the 16.7 mL test sample tube.

[00147] To determine the nominal BWC of the hives, the modified version of the ASTM D5228 method was used as follows. The adsorbent sample is oven-dried for a minimum of eight hours at 110±5°C and then placed in desiccators to cool. The dry mass of the adsorbent sample is recorded. The mass of the empty test set is determined before the adsorbent sample is mounted on a test set. Then, the test set is installed in the flow apparatus and charged with n-butane gas for a minimum of 25 minutes (±0.2 min) at a butane flow rate of 500 mL / min at 25°C and 1 atm pressure. The test set is then removed from the BWC test apparatus. The mass of the test set is measured and recorded with Petition 870260058209, dated 06 / 15 / 2026, page 67 / 180 64 / 80, the approximation is 0.001 grams. This butane loading step is repeated for successive 5-minute flow intervals until constant mass is achieved. For example, the total butane loading time for a 35 mm diameter x 150 mm honeycomb length was 87-92 minutes. The test assembly can be a support for a monolith or honeycomb piece, for cases where the nominal volume can be removed and tested intact. Alternatively, the nominal volume may need to be a section of the canister system, or a suitable reconstruction of the nominal volume with the contents appropriately oriented to the gas flows, as observed in the canister system.

[00148] The test assembly is reinstalled in the test apparatus and purged with 2.00 liters / min of air at 25°C and 1 atm pressure for a selected purge time (±0.2 min) defined according to the formula: Purge Time (min) = (719 x Nominal Volume (mL)) / (2000 (mL / min)).

[00149] The direction of the air purge flow in the BWC test is in the same direction as the purge flow to be applied to the canister system. After the purge step, the test set is removed from the BWC test apparatus. The mass of the test set is measured and recorded to the nearest 0.001 grams for 15 minutes after the test is completed.

[00150] The nominal butane working capacity (BWC) of the adsorbent sample was determined using the following equation:

[00151] Nominal BWC volume (g / dL) = Amount of Purified Butane (g) / Nominal Adsorbent Volume (dL), where Amount of Purified Butane = Mass of test set after loading / Mass of test set after purging.

[00152] The term g-total BWC, as used in this document, refers to the quantity g of butane purged. Petition 870260058209, dated 06 / 15 / 2026, page 68 / 180 65 / 80

[00153] The Nominal Adsorbent Volume (mL) is calculated as, V = (π Do2L / 4) / 1000 , where Do = average adsorbent diameter (mm) and L = average adsorbent length (mm).

[00154] The Nominal Apparent Density (g / mL) is calculated as Nominal Volume (mL) / Adsorbent Mass (g).

[00155] Butane Activity (g / 100g) is calculated as BACT (g / 100g) = amount of butane loaded (g) / (100 x mass of adsorbent (g)).

[00156] The Butane Purge Ratio (%) = BPR (%) is calculated as the amount of butane purged (g) / the amount of butane loaded (g) x 100. Determination of Daytime Loss of Breath (DBL) Emissions According to a BETP Test Table 2. Examples 1-4. Description Ex. 1 Ex. 2 Ex. 3 Ex. 4 Main Canister Type #1 #1 #2 #2 Nominal Fuel Side Volume (L) 2.10 2.10 1.80 1.80 Adsorbent Type BAX 1100 LD BAX 1100 LD BAX 1500 BAX 1500 Nominal Vent Side Volume (L) N / A / A 0.30 0.30 Adsorbent Type N / A / A BAX LBE BAX LBE Additional Vent Side Adsorbent #1 C2 29x100200 C2 29x100-200 C2 35x150200 C2 35x150200 Nominal BWC (g / dL) Total BWC (g) 4.2 2.8 4.2 2.8 4.2 6.1 4.2 6.1 Petition 870260058209, dated 06 / 15 / 2026, page 69 / 180 66 / 80 Description Ex. 1 Ex. 2 Ex. 3 Ex. 4 Additional Vent Side Adsorbent #2 E1 29x100-200 E1 29x100-200 E1 35x150-200 E1 35x150-200 Nominal BWC (g / dL) Total BWC (g) 2.2 1.5 2.2 1.5 2.3 1.5 2.3 1.5 Fuel Tank Size (Total Gallon) 15 15 20 20 Total Nominal Canister System Volume (L) 2.13 2.13 2.39 2.39 Purge Applied After Butane Loading Step of 40 g / h (L) 210 210 157.5 157.5 Purge Applied After Butane Loading Stage BV of 40 g / h 98.6 98.6 66.0 66.0 DBL Emissions on the worst day, mg 7 7 12 10 Table 3. Comparative Examples 1-4. Description CEx. 1 CEx. 2 CEx. 3 CEx. 4 Main Canister Type #1 #1 #2 #2 Nominal Fuel Side Volume (L) 2.10 2.10 1.80 1.80 Adsorbent Type BAX 1100 LD BAX 1100 LD BAX 1500 BAX 1500 Nominal Vent Side Volume (L) N / A / N 0.30 0.30 Petition 870260058209, dated 06 / 15 / 2026, pp. 70 / 180 67 / 80 Description CEx. 1 CEx. 2 CEx. 3 CEx. 4 Adsorbent Type N / AN / A BAX LBE BAX LBE Additional Vent Side Adsorbent #1 C2 29x100-200 C2 29x100-200 C2 35x150-200 C2 35x150-200 Nominal BWC (g / dL) Total BWC (g) 4.2 2.8 4.2 2.8 4.2 6.1 4.2 6.1 Additional Vent Side Adsorbent #2 C1 29x100-200 C1 29x100-200 C1 35x150-200 C1 35x150-200 Nominal BWC (g / dL) Total BWC (g) 2.3 1.5 2.3 1.5 2.0 2.9 2.1 3.0 Fuel Tank Size (Total Gallons) 15 15 20 20 Total Nominal Volume of Canister System (L) 2.13 2.13 2.39 2.39 Purge Applied After Butane Loading Step of 40 g / h (L) 210 210 157.5 157.5 Purge Applied After Loading Step of 98.6 98.6 66.0 66.0 Petition 870260058209, dated 06 / 15 / 2026, page 71 / 180 68 / 80 Description CEx. 1 CEx. 2 CEx. 3 CEx. 4 Butane BV of 40 g / h DBL emissions on the worst day, mg 5 5 13 12

[00157] The evaporative emission control systems in the examples were tested using a protocol that includes the following. For tests with the type #1 canister system, the defined 2.1 L canister used to generate the DBL emission data was of the type illustrated in Figure 5. The two pellet bed volumes 501 and 202 were located in a main canister 101, containing 1.40 L and 0.70 L of Nuchar® BAX 1100 LD pellets (Ingevity®, N. Charleston, SC, USA), respectively. There were two auxiliary canisters in the series, as illustrated in Figure 5. The first auxiliary canister 300 contained a PPAV honeycomb as adsorbent volume 502 and the second auxiliary canister in the series 503 contained a PPAV honeycomb as adsorbent volume 504, with o-ring seals (not shown) and with non-adsorbent open-cell foam discs 102 at each end of the two PPAV honeycombs.

[00158] For testing with the type #2 canister system, the defined 2.1 L canister used to generate the DBL emission data was of the type illustrated in Figure 6. The three pellet bed volumes 501, 203, and 204 were located in a main canister 101, containing 1.40 L, 0.40 L, and 0.30 L of pellets, respectively. Again, there were two auxiliary cartridges in series. The first auxiliary canister 300 contained a PPAV honeycomb as adsorbent volume 502, and the second auxiliary canister in series 503 contained a PPAV honeycomb as adsorbent volume 504, with o-ring seals (not shown) and with non-adsorbent open-cell foam discs 102 at each end of the two PPAV honeycombs. In the type system Petition 870260058209, dated 06 / 15 / 2026, page 72 / 180 In section 69 / 80 #2, there was 1.40 L of Nuchar® BAX 1500 (Ingevity®, North Charleston, South Carolina, USA) as adsorbent volume 501, approximately 19.5 cm high above support screen 102 located above plenum 107, plus a 0.40 L adsorbent volume 203 of BAX 1500 approximately 11.1 cm high above support screen 102 located above plenum 107, and a further 0.30 L adsorbent volume 204 of Nuchar® BAX LBE (Ingevity®, N. Charleston, SC, USA) approximately 8.4 cm high above support screen 102 between adsorbent volumes 203 and 204. Adsorbent volume 501 had an average width of 9.0 cm from partition wall 103 to the right side wall of the canister, and adsorbent volumes 203 and 204 have average widths of approximately 4.5 cm from partition wall 103 to its left side wall. Adsorbent volumes 501, 203, and 204 had similar depths (as shown on page 6 in Figure 6) of 8.0 cm.Each adsorbent pellet bed was filled with the dry basis mass determined by the apparent density that would meet the respective target volume (mass filling = AD x target volume).

[00159] Each example canister was uniformly preconditioned (aged) by repetitive gasoline vapor adsorption cycling using certified Tier 3 fuel (8.7-9.0 RVP, 10% by vol. ethanol) and 300 nominal dry air purge bed volumes at 22.7 LPM based on the main canister (e.g., 630 liters for a 2.1 L main canister). (US RE38,844 work was performed with certified TF-1 fuel.) The gasoline vapor loading rate was 40 g / h and the hydrocarbon composition was 50% by volume, generated by heating two liters of gasoline to about 38 °C and bubbling air at 200 mL / min. The two-liter fuel quota was automatically replaced with fresh gasoline every 1 hour and 55 minutes until a level of 5000 ppm was reached, at which point butane was detected by a FID (flame ionization detector) or detector. Petition 870260058209, dated 06 / 15 / 2026, page 73 / 180 70 / 80 infrared. A minimum of 25 aging cycles were used in a virgin canister. Gasoline working capacity (GWC) was measured as the average weight gain of charged vapors and loss of purged vapors for the last 2-3 cycles and is reported as grams per liter of adsorbent volumes in the canister system. In proceeding to measure exhaust emission performance, the GWC aging cycles were followed by a single butane adsorption / air purge step. This step involved charging butane at 40 g / hour at a concentration of 50% by vol. in air in an atmosphere at 5000 ppm saturation, soaking for one hour, and then purging with dry air for 21 minutes with a total purge volume achieved by selecting the appropriate constant air purge rate for that period. The canister system was then soaked with the doors sealed for approximately 14-18 hours at around 25°C (where 12-36 hours is the required soaking time).The total purge volume after the single butane adsorption loading above was 210 L, equivalent, for example, to approximately 92-94 BV for a complete canister system that includes all adsorbent volumes present, for example, the 2.1 L adsorbent volume fills of the defined canister, plus one activated carbon honeycomb type adsorbent 502 from the vent side placed in the subsequent auxiliary canister 300, or two activated carbon honeycomb type adsorbents 502 and 504 placed in subsequent series auxiliary canisters 300 and 503. In these configurations, the volume to be added to the adsorbent pellet volumes in the defined main canister was the dimensional volume measured by the gauge of the activated carbon honeycomb present within the auxiliary canister 300, plus, if present, the dimensional volume measured by the gauge of the second activated carbon honeycomb within the series auxiliary canister. 503. Petition 870260058209, dated 06 / 15 / 2026, page 74 / 180 71 / 80

[00160] DBL emissions were subsequently generated by attaching the tank door of the example to a fuel tank filled with CARB LEV III fuel (6.9-7.2 RVP, 10% ethanol). (US work RE38,844 was conducted with CARB Phase II fuel.) Canister system examples with most pellets present as CARB BAX 1500 in the main canister were connected to a 20-gallon (total volume) tank filled with 6.2 gallons of liquid fuel (13.8 gallons fill). Canister system examples with BAX 1100 LD in the main canister were connected to a 15-gallon (total volume) tank filled with 4.0 gallons of liquid fuel (11 gallons fill).

[00161] Prior to fix-in, the full fuel tank had been stabilized at 18.3 °C for 18–20 hours during venting (where 1236 hours is the immersion time requirement during venting). The tank and canister system were then temperature cycled according to the CARB two-day temperature profile, each day from 18.3 °C to 40.6 °C over 11 hours, then back to 18.3 °C over 13 hours. Emission samples were collected from the exemplary vent at 6 hours and 12 hours during the warm-up stage in Kynar bags (to allow the fuel in the tank to reach peak temperature). The Kynar bags were filled with nitrogen to a known total volume based on pressure and then evacuated into an FID to determine hydrocarbon concentration. The FID was calibrated with a precisely known butane standard of approximately 5000 ppm concentration.Based on the volume of the Kynar bag, the concentration of emissions, and assuming an ideal gas, the mass of emissions (such as butane) was calculated. For each day, the mass of emissions at 6 hours and 12 hours was added. Following the CARB protocol, the day with the highest total emissions was reported as emissions from 2 days. Petition 870260058209, dated 06 / 15 / 2026, p. 75 / 180 72 / 80 in all cases, the highest emissions were on Day 2. This procedure is generally described in SAE Technical Document 2001-01-0733, entitled Impact and Control of Canister Bleed Emissions, by RS Williams and CR Clontz, and in the LEV III BETP procedure of CARB (section D. 12 in Evaporative Emission Standards and Test Procedures for 2001 and Subsequent Model Engine Vehicles, March 22, 2012).

[00162] Exemplary and comparative examples 1 - 2 used the 2.1L main canister filled with BAX 1100 LD (nominal BWC > 11 g / dL and nominal IAC > 35 g / L) and the 15-gallon total volume fuel tank. Exemplary and comparative examples 3 - 4 used the 2.1L main canister filled with 1.8L BAX 1500 (nominal BWC > 14.8 g / dL and nominal IAC > 35 g / L) and 0.3L BAX LBE (nominal BWC 5 - 7.5 g / dL and nominal IAC < 35 g / L) and the 20-gallon total volume fuel tank.

[00163] After the main canister, each example first had a commercial hive with nominal BWC > 3 g / dL and nominal IAC < 35 g / L (Nuchar® HCA, Ingevity®, N. Charleston, SC, USA) followed by a hive of lower capacity (nominal BWC < 3 g / dL and nominal IAC < 35 g / L). In the case of comparative examples, the hive of lower capacity was Nuchar® HCA-LBE (Ingevity®, N.Charleston, SC, USA); while for the exemplary examples, the lower capacity hive was as described in this document. The terms 29x100-200 and 35x150-200 represent the nominal hive dimensions as diameter (mm) x length (mm) - extruded cell density (cells per square inch).

[00164] The results in Tables 2 and 3 showed exemplary and comparative examples 1 and 2 that produced similar worst-day emissions; as did exemplary and comparative examples 3 and 4. This is also shown in Figure 7. The similarity in the results Petition 870260058209, dated 06 / 15 / 2026, page 76 / 180 The 73 / 80 difference in emissions between exemplary and comparative examples is surprising and unexpected, given the substantial simultaneous increase in extruder die life shown in Figures 8 and 9.

[00165] Figure 8 shows the lifespan of the die used to extrude PPAV adsorbents as a function of the amount of binder in exemplary and comparative formulations. Although the lifespan increases slightly as the binder content of the comparative formulations decreases, the lifespan is surprisingly significantly longer for the exemplary formulations due to the use of glass microspheres. The same can also be seen as a function of carbon content in Figure 9. The lifespan of the extruder die increases slightly with carbon content due to the reduction in binder content. But the lifespan of the die increases substantially in the case of exemplary formulations due to the use of glass microspheres. For both Figures 8 and 9, the exemplary formulations used were E1. Areas of Determination

[00166] Surface areas were measured by nitrogen physisorption using the Brunauer-Emmet-Teller (BET) method, according to ISO 9277:2010, on a Micromeritics ASAP 2420 (Norcross, GA). The sample preparation procedure was degassing at 250°C for at least two hours, typically at a stable vacuum < 2 μmHg with the sample isolated. The nitrogen adsorption isotherm was recorded at 77 K for a 0.1 g sample, applying the following pressures: 0.04, 0.05, 0.085, 0.125, 0.15, 0.18, 0.2, 0.355, 0.5, 0.63, 0.77, 0.9, 0.95, 0.995, 0.95, 0.9, 0.8, 0.7, 0.6, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.12, 0.1, 0.07, 0.05, 0.03, 0.01. The actual readings were recorded within an absolute or relative pressure tolerance of 5 mmHg or 5%, respectively, whichever is more stringent. The time between successive pressure readings during equilibration was 10 seconds. Petition 870260058209, dated 06 / 15 / 2026, page 77 / 180 74 / 80 seconds. The non-ideality factor was 0.0000620. The density conversion factor was 0.0015468. The diameter of the hard sphere of thermal transpiration was 3.860 Å. The molecular cross-sectional area was 0.162 nm². Data in the range of 0.05 to 0.20 relative pressure of the nitrogen adsorption isotherm were used to apply the BET model. Determination of Pore Volume

[00167] Pore volume in the range of 0.05 micrometers to 100 micrometers was measured by the ISO 15901-1:2016 mercury intrusion porosimetry method. The equipment used for the examples was the Micromeritics Autopore V (Norcross, GA). The samples used were approximately 0.4 g in size and pre-treated for at least 1 hour in an oven at 105 °C. The mercury surface tension and contact angle used for the Washburn equation were 485 dynes / cm and 130°, respectively. Determination of Incremental Adsorption Capacity Micromeritic method. As is known in the art, adsorption capacities can be equivalently measured by a number of means, including volumetric, gravimetric, and dynamic (flow) methods.

[00168] The micromeritic method is a volumetric method based on a gas-phase mass equilibrium for the adsorbent system containing a sample of known volume and temperature when exposed to changes in the adsorption gas-phase pressure. For examples in this document, a micromeritic model ASAP 2020A expansion unit was used (Micromeritics Instrument Corporation, Norcross, GA, USA). In this method, as an initial state, the adsorbate gas is contained in a container of known temperature, pressure, and volume, and the adsorbate gas is contained in a second container containing adsorbent of known volume and temperature, and Petition 870260058209, dated 06 / 15 / 2026, pp. 78 / 180 75 / 80 a known different pressure. The two containers are then brought into contact with the fluid by opening a connecting valve. After equilibrium to a final state (i.e., sufficient time for thermal equilibrium and balanced adsorption absorption by the adsorbent sample, as evidenced by a stabilized pressure of the connected system), the equilibrium mass difference in gas-phase adsorption between the initial and final states is the change in adsorbed mass adsorbed by the adsorbent sample. Note that in all examples reported in this document, the adsorbate is n-butane.

[00169] The first step in determining IAC is sample preparation. The representative adsorbent sample is oven-dried for more than 3 hours at 110 °C. The adsorbent sample should include representative amounts of any inert binders, fillers, and structural components present in the nominal volume of the adsorbent component when the determination of the Apparent Density value equivalently includes the mass of the inert binders, fillers, and structural components in its mass numerator. Conversely, the adsorbent sample should exclude these inert binders, fillers, and structural components when the Apparent Density value equivalently excludes the mass of the inert binders, fillers, and structural components in its numerator. The universal concept is to accurately define the adsorption properties for butane on a volume basis within the nominal volume.

[00170] A quartz sample tube is weighed with a rubber stopper and the weight is recorded (WO). Approximately 0.1 g of adsorbent sample is loaded into the tared sample tube and the rubber stopper is replaced. The rubber stopper is removed and the loaded sample tube is placed under a degassing port where the temperature is increased to 250 °C at a rate of 10 °C / min. A Petition 870260058209, dated 06 / 15 / 2026, page 79 / 180 The 76 / 80 sample is degassed at 250 °C for approximately 2 hours. The sample is allowed to cool, and the tube is filled with nitrogen. The rubber stopper is replaced, and the degassed tube is weighed (W). The weight of the dry sample is calculated as W-WO. The second step in the procedure is sample analysis. The water bath is set to 25 ± 0.1 °C. The sample pressure from the instrument is evacuated to less than 10 μmHg (usually less than 1 μmHg). The instrument plug and the sample rubber stopper are removed, and the degassed tube is placed in the sample analysis port. The test has begun. The instrument collects isothermal equilibrium butane data points around the following absolute pressures (mmHg): 10, 20, 30, 40, 45, 150, 300, 350, 400, 450, 600, 800, 600, 500, 450, 400, 350, 300, 150, 50, 45, 40, 35, 30, 25.The isothermal mass-adsorbed data point for 0.5 vol% at 1 atm (3.8 mmHg) reported in this document was calculated from a power-law regression (mass-adsorbed = a Pressure b) derived from a fit of the isothermal data points of 10, 20, 30, and 40 mmHg.

[00171] The IAC was defined as the incremental adsorption capacity between 5 and 50% n-butane at 25 °C. A 5% volume (by volume) n-butane concentration in one atmosphere is given by an equilibrium pressure inside the sample tube of 38 mmHg. A 50% n-butane concentration in one atmosphere is given by an equilibrium pressure inside the sample tube of 380 mmHg. Since equilibrium at precisely 38 mmHg and 380 mmHg may not be readily attainable, the mass of n-butane adsorbed per mass of adsorbent sample at 5 vol % n-butane concentration and at 50 vol % n-butane concentration is interpolated from a graph using the data points collected over the target pressures of 38 and 380 mmHg. In the examples provided in this document, this was typically done using linear regression of the pressures between approximately Petition 870260058209, dated 06 / 15 / 2026, pages 80 / 180 77 / 80 300 and approximately 450 mmHg and pressures between approximately 30 and 45 mmHg in the desorption branch of the isotherm. Using the ideal gas law for n-butane and the apparent density of the adsorbent, the IAC can then be calculated as the capacity in g / g at 50% by volume of n-butane minus the capacity at 5% by volume of n-butane multiplied by the apparent density in g / L.

[00172] The McBain method is a gravimetric method. The adsorbent sample was oven-dried for more than 3 hours at 110°C before being loaded onto a spring-loaded sample dish inside the sample tube. The sample tube was then installed in the apparatus as described. The adsorbent sample must include representative amounts of any inert binders, fillers, and structural components present in the nominal volume of the adsorbent component when the determination of the Apparent Density value equivalently includes the mass of the inert binders, fillers, and structural components in its mass numerator. Conversely, the adsorbent sample must exclude these inert binders, fillers, and structural components when the Apparent Density value equivalently excludes the mass of the inert binders, fillers, and structural components in its numerator.The universal concept is to precisely define the adsorption properties for butane on a volume basis within the nominal volume.

[00173] A vacuum of less than 1 torr is applied to the sample tube and the adsorbent sample is heated to 105°C for 1 hour. The mass of the adsorbent sample is then determined by the amount of spring extension using a catheter. After that, the sample tube is immersed in a water bath with a controlled temperature of 25°C. Air was pumped out of the sample tube until the pressure inside the sample tube was 10⁻⁴ torr. n-Butane was introduced into the sample tube until equilibrium was reached at a selected pressure. Petition 870260058209, dated 06 / 15 / 2026, page 81 / 180 78 / 80 Tests were conducted on two datasets at four selected equilibrium pressures, one taken at approximately 38 torr and the other at approximately 380 torr. The n-butane concentration was based on the equilibrium pressure within the sample tube. After each test at the selected equilibrium pressure, the mass of the adsorbent sample was measured based on the amount of spring extension using a catheter. The increased mass of the adsorbent sample was the amount of n-butane adsorbed by the adsorbent sample. The mass of n-butane adsorbed (in grams) per mass of the adsorbent sample (in grams) was determined for each test at different n-butane equilibrium pressures and plotted on a graph as a function of n-butane concentration (in % by volume). A n-butane concentration of 5% by volume (in volume) at one atmosphere is given by an equilibrium pressure within the sample tube of 38 torr.A concentration of n-butane of 50% in one atmosphere is provided by an equilibrium pressure inside the sample tube of 380 torr. Because precise equilibrium at 38 torr and 380 torr may not be easily achieved, the mass of n-butane adsorbed per mass of adsorbent sample at 5% n-butane concentration and at 50% n-butane concentration was interpolated from the graph using data points collected at the target pressures of 38 and 380 torr. The IAC was then calculated as described in this document. Determination of Effective Volumetric Properties

[00174] The above methods are applicable for defining the properties of nominal BWC, butane activity, IAC, and adsorbent density. In contrast, the effective volume of adsorbents takes into account air gaps, voids, and other volumes sandwiched between the nominal volumes of adsorbents along the vapor flow path that lacks adsorbent. For example, those volumes without adsorbent include, among others, the volumes between the volume of Petition 870260058209, dated 06 / 15 / 2026, page 82 / 180 79 / 80 adsorbent 301 and 302 in Figure 4, the volume between adsorbent volume 204 and 301 in Figure 4 which includes port 108 and the connecting conduit between canisters 101 and 300, and the volume between adsorbent volumes 202 and 203 in Figure 4 which includes plenum volume 107. Thus, the effective volumetric properties of the adsorbent refer to the average volume properties of the adsorbent volumes that take into account air gaps, voids, and other volumes between the nominal adsorbent volumes lacking adsorbent along the vapor flow path. These properties are determined as described in US Patent No. 9,732,649 and incorporated herein by reference.

[00175] The effective volume (Veff) for a given vapor flow path length is the sum of the nominal volumes of adsorbent (Vnom, i) present along that vapor flow path length plus volumes without adsorbent along that vapor flow path (Vgap, j). Veff = Σ Vnom, i + ΣVgap, j

[00176] Volumetric adsorptive properties of an effective volume (B eff), such as incremental adsorption capacity (g / L), apparent density (g / mL) and BWC (g / dL), is the sum of each property of the individual nominal volumes to be considered as part of the effective volume (Bnom, i) multiplied by each individual nominal volume (Vnom, i), then divided by the total effective volume (Veff): B eff = Σ (B nom, i X Vnom, i ) / Veff

[00177] Thus, the term effective incremental adsorption capacity is the sum of each nominal incremental adsorption capacity multiplied by each individual nominal volume and then divided by the total effective volume.

[00178] The term effective butane working capacity (BWC) is the sum of each BWC value multiplied by each individual nominal volume and then divided by the total effective volume. Petition 870260058209, dated 06 / 15 / 2026, page 83 / 180 80 / 80

[00179] The term effective apparent density is the sum of each apparent density multiplied by each individual nominal volume and then divided by the total effective volume.

[00180] The g-total BWC term of the effective volume is the sum of the g-total BWC values ​​in grams of the nominal volumes within the effective volume.

[00181] Those skilled in the art will recognize, or be able to determine, using no more than routine experiments, many equivalents to the specific embodiments described in this document. Such equivalents are intended to be covered by the following claims. It is understood that the detailed examples and embodiments described in this document are given as examples for illustrative purposes only and are not considered to be limiting to the invention. Various modifications or alterations in light thereof are suggested to individuals skilled in the art and are included in the spirit and view of this application and are considered within the scope of the appended claims. For example, the relative amounts of the ingredients may be varied to optimize the desired effects, additional ingredients may be added, and / or similar ingredients may be substituted for one or more of the ingredients described.Additional advantageous features and functionalities associated with the systems, methods, and processes of the present invention will be evident from the appended claims. Furthermore, any of the aspects or embodiments described herein may be combined collectively or alternatively, and all such combinations are expressly contemplated and do not represent intermediate generalizations. Petition 870260058209, dated 06 / 15 / 2026, page 84 / 180

Claims

1 / 3 CLAIMS 1. Adsorbent composition, characterized in that it comprises: 10 to 50% by weight of an activated adsorbent material; 3 to 40% by weight of glass microspheres or glass bubbles; 5 to 50% by weight of clay binder; and the difference to 100% by weight with at least one additive material; the adsorbent composition being in the form of a monolith.

2. Adsorbent composition, according to claim 1, characterized in that the activated adsorbent material comprises activated carbon powder, carbon dioxide, zeolites, clays, porous polymers, porous alumina, porous silica, molecular sieves, kaolin, titania, ceria or a combination thereof.

3. Adsorbent composition, according to claim 2, characterized in that the activated adsorbent material is derived from at least one of wood, wood powder, wood flour, cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coal tar, fruit pits, fruit stones, nut shells, nut kernels, sawdust, palm, vegetables, synthetic polymer, natural polymer, lignocellulosic material and combinations thereof.

4. Adsorbent composition, according to claim 2, characterized in that the activated carbon is defined by a BET nitrogen surface area of ​​600 to 2200 square meters per gram.

5. Adsorbent composition, according to claim 1, characterized in that the additive material comprises (i) Petition 870260058209, dated 06 / 15 / 2026, page 85 / 180 2 / 3 less one of an organic binder, a calcined clay binder, a mineral flux or a combination thereof, (ii) excluding spherical clay or (iii) a combination of (i) and (ii).

6. Adsorbent composition, according to claim 5, characterized in that the mineral flux is a feldspathic mineral.

7. Adsorbent composition, according to claim 5, characterized in that the mineral flux is nepheline syenite.

8. Adsorbent composition, according to claim 5, characterized in that the organic binder comprises cellulose, a cellulose derivative or a combination thereof.

9. Adsorbent composition, according to claim 8, characterized in that the organic binder comprises at least one of carboxymethyl cellulose, methylcellulose, ethyl cellulose, ethylmethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropylmethyl cellulose, methyl hydroxyethyl cellulose, hydroxyethyl cellulose, crystalline salts of aromatic sulfonates, polyfurfuryl alcohols, polyesters, polyepoxides, polyurethane polymers, polyvinyl alcohol or a combination thereof.

10. Adsorbent composition, according to claim 1, characterized in that the clay binder comprises zeolite clay, bentonite clay, montmorillonite clay, illite clay, French green clay, pascalite clay, Redmond clay, Terramin clay, viva clay, Fuller Earth clay, ormalite clay, vitalite clay, reitoria clay, cordierite, spherical clay, kaolin or a combination thereof.

11. Adsorbent composition, according to claim 10, characterized in that the clay binder is a hydrated kaolin.

12. Adsorbent composition, according to claim 11, characterized in that the clay binder comprises a calcined binder material including calcined kyanite, mullite, Petition 870260058209, dated 06 / 15 / 2026, page 86 / 180 3 / 3 cordierite, clay, silica, alumina and other calcined or non-plastic refractory ceramic materials, or a combination thereof.

13. Adsorbent composition, according to any one of claims 1 to 12, characterized in that the glass microspheres or glass bubbles have an average diameter of less than 500 micrometers.

14. Adsorbent article, characterized in that it comprises an extruded form of the adsorbent composition, as defined in any one of claims 1 to 13, wherein the extruded form is a honeycomb.

15. Canister system for evaporative emission control, characterized in that it comprises the adsorbent article, as defined in claim 14.

16. Method for preparing an extruded adsorbent article, characterized in that it comprises the steps of: a. mixing an adsorbent composition comprising: i. 10 to 50% by weight of an activated adsorbent material comprising an activated adsorbent powder; ii. 2 to 10% by weight of a polymeric binder; iii. 5 to 50% by weight of a clay binder; iv. 5 to 45% by weight of a calcined clay binder; v. 2 to 20% of a mineral flux; vi. 0 to 5% by weight of a silica sol; vii. 3 to 40% by weight of glass microspheres or glass bubbles; and viii. water; and b. extruding and drying the adsorbent composition to form an extruded adsorbent article; whereby, in step (b), the adsorbent composition is extruded in the form of a honeycomb. Petition 870260058209, dated 06 / 15 / 2026, p. 87 / 180

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