JPWO2020015591A5 - - Google Patents

Description

The present disclosure relates generally to hydrocarbon emission control systems. More specifically, the present disclosure provides substrates coated with hydrocarbon adsorbent coating compositions, evaporative emission control system components, and evaporative emissions for controlling evaporative emissions of hydrocarbons from automotive engines and fuel systems. control system;

Evaporative loss of gasoline fuel from the fuel system of a vehicle powered by an internal combustion engine can be a major contributor to hydrocarbon air pollution. Evaporative emissions are defined as emissions originating from a vehicle's exhaust system. A major contributor to a vehicle's total evaporative emissions is hydrocarbon fuel vapors originating from the fuel and intake systems. Canister systems that use activated carbon to adsorb fuel vapors emitted from the fuel system are used to limit such evaporative emissions. All vehicles now have a fuel vapor canister containing activated carbon pellets to control evaporative emissions. Activated carbon is the standard sorbent material used in all automotive evaporative emission control technology, typically utilizing activated carbon as the sorbent material for the temporary adsorption of hydrocarbons.

The activated carbon is then periodically regenerated by purging air from the intake system and the hydrocarbons are desorbed and carried to the engine. Accordingly, activated carbon undergoes thousands of adsorption/desorption cycles over the life of a vehicle. During each adsorption cycle, a small amount of irreversible adsorption occurs that is not regenerated. Over the life of the vehicle, this small amount of irreversible adsorption slowly increases, reducing the total effective adsorption capacity of the activated carbon. This phenomenon is called heel or heel build.

Many fuel vapor canisters also house additional control devices to capture fuel vapors escaping from the carbon bed on the hot side of the daytime temperature cycle. Current control devices for such emissions accommodate only carbon-containing honeycomb adsorbents for pressure drop reasons. In such systems, the adsorbed fuel vapor is periodically removed from the activated carbon by purging the canister system with fresh ambient air and desorbing the fuel vapor from the activated carbon, thereby further adsorbing the fuel vapor. Regenerate carbon. Exemplary U.S. patents disclosing canister-based evaporative loss control systems include U.S. Pat. Nos. 4,877,001, 4,750,465, and 4,308,841. be done.

With the enactment of stringent regulations on hydrocarbon emission allowances, there is a need for increasingly tighter control of hydrocarbon emissions from vehicles, even when they are not in use. During such periods (i.e., while parked), the vehicle's fuel system may be exposed to a warm environment, resulting in increased vapor pressure within the fuel tank and consequent vaporization of fuel to the atmosphere. may be lost.

The aforementioned canister systems have certain limitations in terms of capacity and performance. For example, purge air does not desorb all fuel vapors adsorbed in the sorbent -containing spatial regions , resulting in residual hydrocarbons (“heels”) that can be vented to the atmosphere. As used herein, the term "heel" refers to residual hydrocarbons generally present on the adsorbent material when the canister is in a purged or "clean" state, which can lead to a reduction in adsorption capacity of the adsorbent. have a nature. Bleed discharge, on the other hand, refers to discharge that escapes from the adsorbent material. Bleeding can occur, for example, when the equilibrium between adsorption and desorption significantly favors desorption over adsorption. Such emissions, which can occur when a vehicle is exposed to diurnal temperature changes over several days, are commonly referred to as "diurnal breathing loss." Certain regulations make it desirable that these diurnal breathing loss (DBL) emissions from the canister system be maintained at very low levels. For example, as of March 22, 2012, California's Low Emissions Regulations (LEV-III) requires that the canister's two-day DBL emissions for 2001 and later model vehicles be Should not exceed 20 mg. Bleed emission traps are currently installed in such fuel canisters to achieve such low bleed emission values. These traps consist of an extruded carbon monolith and are intended to absorb 100-500 mg emissions from the fuel canister over a two day day cycle.

Previously disclosed carbonization under severe DBL conditions by directing the fuel vapor to a first sorbent -containing spatial region and then to at least one subsequent sorbent -containing spatial region before venting to the atmosphere. A method of limiting hydrogen emissions wherein the initial sorbent- containing spatial region has a higher adsorption capacity than subsequent sorbent- containing spatial regions . See US Pat. No. RE38,844.

It also has high purge efficiency and moderate butane working capacity with initial and at least one subsequent sorbent-containing spatial region , and effective butane working capacity (BWC) of less than 3 g/dL, from 2 grams. Also previously disclosed is an evaporative emission control canister system device having a g-total butane working capacity of 6 grams and a 2-day DBL emissions of no more than 20 mg at no more than about 210 liters of purge applied after a 40 g/hr butane charge. ing. See US Patent Application No. 2015/0275727.

Activated carbons used in current state-of-the-art evaporative emission control canisters are generally obtained from natural sources such as coal or agricultural by-products and typically have a surface area in the range of 1100-2200 m ² /g and a surface area of 0.8 m 2 /g. It has a total pore volume in the range of ˜1.5 cm ³ /g. In particular, when plotting pore volume as a function of pore radius, all of these activated carbons have a peak just before 20 Angstroms (Å) and relatively small pore volumes in the 30-80 Å range.

Tighter regulations on DBL emissions will continue to drive the development of improved evaporative emission control systems, particularly for use in vehicles with reduced purge volumes (ie, hybrid vehicles). Otherwise, such vehicles may produce higher DBL emissions due to less frequent purging, which equates to a lower total purge amount and a higher residual hydrocarbon heel. Therefore, it is desirable to have an evaporative emission control system that produces low DBL emissions despite low volume and/or low purge cycles. Moreover, even previously disclosed devices for capturing evaporative hydrocarbon emissions from fuel systems reduce the required space and weight while further reducing the amount of potential evaporative emissions under a variety of conditions. There remains a need for highly efficient evaporative emission control systems for Particularly desirable are evaporative emission control articles and systems with even lower heel build.

Coated substrates adapted for hydrocarbon adsorption and evaporative emission control articles and systems including coated substrates are provided. The disclosed coated substrates, articles, and systems are useful for controlling evaporative hydrocarbon emissions and can provide low diurnal breathing loss (DBL) emissions even under low purge conditions. The coated substrate removes evaporative emissions produced by internal combustion engines and/or associated fuel source components before the emissions can be released to the atmosphere. The coated substrate comprises an activated carbon with a novel pore size distribution that, like state-of-the-art activated carbons, maintains a low heel build over many adsorption/desorption cycles while exhibiting higher adsorption capacity at low hydrocarbon concentrations. I will provide a. Surprisingly, we have found that only certain combinations of surface area, pore volume distribution, and butane isotherm shape can qualify coating carbons to meet stringent emission regulations. Accordingly, in a first aspect there is provided a coated substrate adapted for hydrocarbon adsorption, the coated substrate having at least one surface and a coating on the at least one surface. , the coating comprising particulate carbon and a binder, the particulate carbon having a BET surface area of at least about 1300 m ² /g, and (i) a butane affinity greater than 60% at 5% butane, ( ii) a butane affinity greater than 35% at 0.5% butane, (iii) a micropore volume greater than about 0.2 ml/g and a mesopore volume greater than about 0.5 ml/g.

In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g.

In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2500 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g.

In some embodiments, particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g. In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g.

In some embodiments, particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g. In certain specific embodiments, the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g.

In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted helix, ribbon, structured media in extruded form, structured media in wound form, folded form. structure media, pleated structure media, corrugated structure media, infused structure media, bonded structure media, and combinations thereof. In some embodiments, the substrate is a monolith. In some embodiments, the monolith is ceramic. In some embodiments, the substrate is plastic. In some embodiments, the plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester , and polyurethane. In some embodiments, the substrate is a nonwoven. In some embodiments, the substrate is an extrusion medium. In some embodiments, the extrusion media are honeycombs. In other embodiments, the substrate is foam. In some embodiments, the foam has greater than about 10 pores per inch. In some embodiments, the foam has greater than about 20 pores per inch. In some embodiments, the foam has about 15 to about 40 pores per inch. In some embodiments, the foam is polyurethane. In some embodiments, polyurethanes are polyethers or polyesters. In some embodiments, the foam is reticulated polyurethane.

In some embodiments, the coating thickness is less than about 500 microns.

In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon. In some embodiments the binder is an organic polymer. In some embodiments, the binder is an acrylic/styrene copolymer latex.

In another aspect, a bleed exhaust scrubber is provided, the scrubber comprising an adsorbent-containing spatial region comprising a coated substrate adapted for hydrocarbon adsorption, the coated substrate comprising at least one and a coating on at least one surface thereof, the coating comprising particulate carbon and a binder, the particulate carbon having a BET surface area of at least about 1300 m ² /g and (i) greater than 60% butane affinity at 5% butane, (ii) greater than 35% butane affinity at 0.5% butane, and (iii) greater than about 0.2 ml/g micropore volume. and a mesopore volume greater than about 0.5 ml/g.

In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g.

In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2100 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g. In some embodiments, particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g.

In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g.

In some embodiments, particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g. In certain specific embodiments, the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g.

In some embodiments, the sorbent- containing spatial region has a g-total butane working capacity (BWC) of less than about 2 grams. In some embodiments, the sorbent- containing spatial region has a g-total BWC from about 0.2 grams to about 1.6 grams.

In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted helix, ribbon, structured media in extruded form, structured media in wound form, folded form. structure media, pleated structure media, corrugated structure media, infused structure media, bonded structure media, and combinations thereof. In some embodiments, the substrate is a monolith. In some embodiments, the monolith is ceramic. In some embodiments, the substrate is plastic. In some embodiments, the plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester , and polyurethane.

In some embodiments, the coating thickness is less than about 500 microns.

In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon. In some embodiments the binder is an organic polymer. In some embodiments, the binder is an acrylic/styrene copolymer latex.

In a further aspect, an evaporative emission control canister system is provided, the evaporative emission control canister system comprising a first sorbent-containing spatial region contained within a first canister and a a fuel vapor inlet conduit for venting the fuel tank to the first canister; and a vent conduit for venting the first canister to atmosphere and allowing purge air into the first canister. , a second sorbent-containing spatial region comprising a bleed exhaust scrubber as disclosed herein, the second sorbent -containing spatial region being in fluid communication with the first sorbent -containing spatial region. A bleed exhaust scrubber is housed in the first canister or in the second canister, and the evaporative emission control canister system causes the fuel vapor to separate the first sorbent -containing spatial region and the second canister. configured to allow sequential contact with two sorbent- containing spatial regions .

In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g.

In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2500 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g.

In some embodiments, particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g. In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g.

In some embodiments, particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g. In certain specific embodiments, the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.7 ml/g.

In some embodiments, the bleed discharge scrubber is contained in the first canister.

In some embodiments, the bleed discharge scrubber is housed in a second canister.

In some embodiments, the second sorbent- containing spatial region has an effective butane working capacity (BWC) of less than about 3 g/dL and a g-total BWC of less than about 2 grams. In some embodiments, the second sorbent- containing spatial region has a g-total BWC from about 0.2 grams to about 1.999 grams. In some embodiments, the second sorbent -containing spatial region further comprises a third sorbent- containing spatial region , wherein the third sorbent- containing spatial region comprises at least about 0.05 grams of g-total BWC have

In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted helix, ribbon, structured media in extruded form, structured media in wound form, folded form. structure media, pleated structure media, corrugated structure media, infused structure media, bonded structure media, and combinations thereof. In some embodiments, the substrate is a monolith. In some embodiments, the monolith is ceramic. In some embodiments, the substrate is plastic. In some embodiments, the plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester , and polyurethane.

In some embodiments, the coating thickness is less than about 500 microns.

In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon. In some embodiments the binder is an organic polymer. In some embodiments, the binder is an acrylic/styrene copolymer latex.

In some embodiments, the third sorbent- containing spatial region comprises reticulated polyurethane foam.

In some embodiments, the evaporative emission control canister system has a first sorbent- containing spatial area of about 1.9 to about 3.0 liters and is tested under the California Bleed Emission Test Protocol (BETP) as follows: of: i. 2.5 L of the first adsorbent- containing spatial region and a purge volume of 80 bed volumes, or ii. It exhibits a 2-day diurnal breathing loss (DBL) of less than about 20 mg when tested under test conditions of a first adsorbent -containing spatial region of 1.9 L and a purge volume of 135 bed volumes.

In some embodiments, the second sorbent -containing spatial region has a g-total BWC of less than about 2 grams, while the evaporative emission control canister has a g-total BWC of less than about 20 mg for 2 days under California BETP. Maintain DBL.

In a still further aspect, there is provided an evaporative emission control system as disclosed herein, the system including a fuel tank for fuel storage and an internal combustion engine adapted to consume the fuel. , the evaporative emission control system is defined by a fuel vapor flow path from the fuel vapor inlet conduit to the first canister to the second sorbent volume and to the vent conduit, and from the vent conduit to the second sorbent volume. It is defined by a reciprocal air flow path to the containment space region , to the first canister, and to the fuel vapor purge pipe.

In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g.

In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2100 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g.

In some embodiments, particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g. In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g.

In some embodiments, particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g. In certain specific embodiments, the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.7 ml/g.

In some embodiments, the bleed discharge scrubber is contained in the first canister. In some embodiments, the bleed discharge scrubber is housed in a second canister.

In some embodiments, the second sorbent- containing spatial region has an effective butane working capacity (BWC) of less than about 3 g/dL and a g-total BWC of less than about 2 grams. In some embodiments, the second sorbent- containing spatial region has a g-total BWC from about 0.2 grams to about 1.999 grams. In some embodiments, the second sorbent -containing spatial region further comprises a third sorbent- containing spatial region , wherein the third sorbent-containing spatial region comprises at least about 0.05 grams of g-total BWC have

In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted helix, ribbon, structured media in extruded form, structured media in wound form, folded form. structure media, pleated structure media, corrugated structure media, infused structure media, bonded structure media, and combinations thereof. In some embodiments, the substrate is a monolith. In some embodiments, the monolith is ceramic. In some embodiments, the substrate is plastic. In some embodiments, the plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester , and polyurethane.

In some embodiments, the coating thickness is less than about 500 microns.

In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon. In some embodiments the binder is an organic polymer. In some embodiments, the binder is an acrylic/styrene copolymer latex.

In some embodiments, the third sorbent- containing spatial region comprises reticulated polyurethane foam.

In some embodiments, the first sorbent- containing spatial area is about 1.9 to about 3.0 liters and the 2-day diurnal breathing loss (DBL) is and the following test conditions: i. 2.5 L of the first adsorbent- containing spatial region and a purge volume of 80 bed volumes, or ii. Less than about 20 mg when tested under test conditions of 1.9 L of the first adsorbent -containing spatial region and a purge volume of 135 bed volumes.

In a still further aspect, an evaporative emission control canister system is provided, the evaporative emission control canister system including at least one canister sorbent-containing spatial region comprising a canister sorbent material, and at least one bleed exhaust. and at least one bleed discharge scrubber including a scrubber sorbent- containing spatial region , the scrubber sorbent- containing spatial region comprising a scrubber sorbent material and having a g-total BWC of less than about 2 grams. , the bleed exhaust scrubber is in fluid communication with the evaporative emission control canister, the evaporative emission control canister allowing fuel vapor to continuously contact the canister sorbent- containing spatial region and the scrubber sorbent- containing spatial region; and was tested under the California Bleed Emission Test Protocol (BETP) under the following test conditions: i. 2.5 L of the first adsorbent- containing spatial region and a purge volume of 80 bed volumes, or ii. It has a 2-day diurnal breathing loss (DBL) of less than about 20 mg when tested under test conditions of a first adsorbent -containing spatial region of 1.9 L and a purge volume of 135 bed volumes.

In some embodiments, the evaporative emission control canister system includes: a fuel vapor purge line for connecting the evaporative emission control canister system to the engine; a fuel vapor inlet conduit for venting the fuel tank to the evaporative emission control canister; and a vent conduit for venting the evaporative emission control canister to the atmosphere and admitting purge air into the evaporative emission control canister.

In some embodiments, the canister sorbent material is the group consisting of activated carbon, carbon charcoal, zeolites, clays, porous polymers, porous alumina, porous silica, molecular sieves, kaolin, titania, ceria, and combinations thereof. is selected from In some embodiments, the activated carbon is wood, wood dust, wood flour, cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruit seeds, fruit kernels, nuts. husks, nut seeds, sawdust, palms, vegetables, synthetic polymers, natural polymers, lignocellulosic materials, and combinations thereof.

In some embodiments, the scrubber sorbent material comprises particulate carbon, the particulate carbon having a BET surface area of at least about 1300 m ² /g, and (i) 60% in 5% butane (ii) greater than 35% butane affinity at 0.5% butane; (iii) greater than about 0.2 ml/g micropore volume and greater than about 0.5 ml/g mesopore volume; have

In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg.

In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g.

In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2500 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g.

In some embodiments, particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g. In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g.

In some embodiments, particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g.

In some embodiments, the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g.

In some embodiments, a bleed discharge scrubber includes a substrate. In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted helix, ribbon, structured media in extruded form, structured media in wound form, folded form. structure media, pleated structure media, corrugated structure media, infused structure media, bonded structure media, and combinations thereof. In some embodiments, the substrate is co-molded, formed, or extruded with a mixture comprising the scrubber sorbent material. In some embodiments, the substrate comprises a coating, and the coating comprises a scrubber adsorbent material and a binder. In some embodiments, the substrate is a monolith. In some embodiments, the monolith is ceramic. In some embodiments, the substrate is plastic. In some embodiments, the plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester , and polyurethane.

In some embodiments, the coating thickness is less than about 500 microns.

In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon. In some embodiments the binder is an organic polymer. In some embodiments, the binder is an acrylic/styrene copolymer latex.

In some embodiments, the second sorbent- containing spatial region has an effective BWC of less than about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region has an effective BWC from about 0.5 grams/dl to about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region is from about 0.5, about 0.6, about 0.7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0 grams It has an effective BWC up to /dL. In some embodiments, the second sorbent- containing spatial region has a g-total BWC from about 0.1 grams to less than about 2 grams. In some embodiments, the second sorbent- containing spatial region is about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.5. 7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about Have a g-total BWC of up to 1.7, about 1.8, or about 1.9 grams.

In some embodiments, the evaporative emission control canister has a canister sorbent- containing spatial area of 3.5 L or less, 3.0 L or less, 2.5 L or less, or 2.0 L or less.

In some embodiments, the evaporative emission control canister system is a single canister sorbent- containing spatial region , the canister sorbent- containing spatial region comprising at least one chamber, and filled within the at least one chamber. a single canister sorbent- containing spatial region and a single bleed discharge scrubber, wherein at least one bleed discharge scrubber includes a scrubber sorbent- containing spatial region , the scrubber A single bleed discharge scrubber and about 1.5 L to about 2.0 L of canister sorbent containing space, wherein the sorbent containing space region comprises a scrubber sorbent material and has a g-total BWC of less than about 2 grams. and wherein the evaporative emission control canister has a 2-day diurnal breathing loss (DBL) of less than about 20 mg under the California Bleed Emission Test Protocol (BETP) at a purge volume of 135 bed volumes.

In some embodiments, the evaporative emission control canister system has a 2-day DBL of less than about 10 mg under BETP.

In some embodiments, the evaporative emission control canister system is a single canister sorbent- containing spatial region , the canister sorbent- containing spatial region comprising at least one chamber, and within the at least one chamber: comprises a single canister sorbent -containing spatial region in which filled canister sorbent material resides, a single bleed discharge scrubber, and a canister sorbent- containing spatial region of about 2.5 L to about 3.0 L; The evaporative emission control canister system has a 2-day diurnal respiratory loss (DBL) of less than about 20 mg under the California Bleed Emission Test Protocol (BETP) at a purge volume of 80 bed volumes. In some embodiments, the evaporative emission control canister has a 2-day DBL of less than about 10 mg under BETP at a purge volume of 80 bed volumes.

In some embodiments, the canister sorbent- containing spatial region comprises two chambers, with a canister sorbent material charged within each chamber. In some embodiments, the second sorbent- containing spatial region has an effective BWC of less than about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region has an effective BWC from about 0.5 grams/dl to about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region is from about 0.5, about 0.6, about 0.7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0 grams It has an effective BWC up to /dL. In some embodiments, the second sorbent- containing spatial region has a g-total BWC from about 0.1 grams to less than about 2 grams. In some embodiments, the second sorbent- containing spatial region is about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.5. 7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about Have a g-total BWC of up to 1.7, about 1.8, or about 1.9 grams.

This disclosure includes, but is not limited to, the following embodiments.

Embodiment 1. A substrate having at least one surface and a coating on the at least one surface, the coating comprising particulate carbon and a binder, the particulate carbon having a BET surface area of at least about 1300 m ² /g and (i) greater than 60% butane affinity at 5% butane, (ii) greater than 35% butane affinity at 0.5% butane, (iii) greater than about 0.2 ml/g micro A coated substrate adapted for hydrocarbon adsorption having at least one of a pore volume and a mesopore volume greater than about 0.5 ml/g.

Embodiment 2. A coated substrate according to embodiment 1, wherein the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 3. The coated substrate of any of embodiments 1-2, wherein the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 4. Particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g at an n-butane pressure of about 3 mmHg. , about 75 ml/g, or up to about 80 ml/g, the coated substrate of any of embodiments 1-3.

Embodiment 5. The coated substrate of any of embodiments 1-4, wherein the particulate carbon has a BET surface area of from about 1300 m ² /g to about 2100 m ² /g.

Embodiment 6. The coated substrate of any of embodiments 1-5, wherein the particulate carbon has a BET surface area of from about 1400 m ² /g to about 1600 m ² /g.

Embodiment 7. A coated substrate according to any of embodiments 1-6, wherein the particulate carbon has a micropore volume of from about 0.20 ml/g to about 0.35 ml/g.

Embodiment 8. particulate carbon from about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0 The coated substrate of any of embodiments 1-7, having a micropore volume of up to .33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 9. The coated substrate of any of embodiments 1-8, wherein the particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g.

Embodiment 10. particulate carbon from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about 0.75 ml/g, or The coated substrate of any of embodiments 1-9, having a mesopore volume of up to about 0.8 ml/g.

Embodiment 11. Any of embodiments 1-10, wherein the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g. A coated substrate as described.

Embodiment 12. The substrate may be foams, monolithic materials, nonwovens, fabrics, sheets, paper, twisted spirals, ribbons, structured media in extruded form, structured media in rolled form, structured media in folded form, or in pleated form. 12. The coated substrate of any of embodiments 1-11, selected from the group consisting of structured media, corrugated structured media, injected structured structured media, bonded structured structured media, and combinations thereof.

Embodiment 13. A coated substrate according to any of embodiments 1-12, wherein the substrate is a monolith.

Embodiment 14. 14. The coated substrate of any of embodiments 1-13, wherein the monolith is ceramic.

Embodiment 15. A coated substrate according to any of embodiments 1-14, wherein the substrate is plastic.

Embodiment 16. The plastic is selected from the group consisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester, and polyurethane. Selected coated substrates according to any of embodiments 1-15.

Embodiment 17. A coated substrate according to any of embodiments 1-16, wherein the thickness of the coating is less than about 500 microns.

Embodiment 18. 18. The coated substrate of any of embodiments 1-17, wherein the binder is present in an amount of about 10% to about 50% by weight relative to the particulate carbon.

Embodiment 19. A coated substrate according to any of embodiments 1-18, wherein the binder is an organic polymer.

Embodiment 20. The coated substrate of any of embodiments 1-19, wherein the binder is an acrylic/styrene copolymer latex.

Embodiment 21. A bleed exhaust scrubber comprising an adsorbent-containing spatial region comprising a coated substrate adapted for hydrocarbon adsorption, the coated substrate having at least one surface; a coating on at least one surface, the coating comprising particulate carbon and a binder, the particulate carbon having a BET surface area of at least about 1300 m ² /g, and (i) 5% butane (ii) greater than 35% butane affinity at 0.5% butane, (iii) greater than about 0.2 ml/g micropore volume and greater than about 0.5 ml/g mesopore volume.

Embodiment 22. 22. The bleed exhaust scrubber of any of embodiments 1-21, wherein the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 23. 23. The bleed discharge scrubber of any of embodiments 1-22, wherein the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 24. Particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g at an n-butane pressure of about 3 mmHg. , about 75 ml/g, or up to about 80 ml/g, the bleed discharge scrubber of any of embodiments 1-23.

Embodiment 25. 25. The bleed exhaust scrubber of any of embodiments 1-24, wherein the particulate carbon has a BET surface area of from about 1300 m ² /g to about 2100 m ² /g.

Embodiment 26. 26. The bleed exhaust scrubber of any of embodiments 1-25, wherein the particulate carbon has a BET surface area of from about 1400 m ² /g to about 1600 m ² /g.

Embodiment 27. 27. The bleed discharge scrubber of any of embodiments 1-26, wherein the particulate carbon has a micropore volume of from about 0.20 ml/g to about 0.35 ml/g.

Embodiment 28. particulate carbon from about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0 28. The bleed discharge scrubber of any of embodiments 1-27, having a micropore volume of up to .33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 29. 29. The bleed discharge scrubber of any of embodiments 1-28, wherein the particulate carbon has a mesopore volume of from about 0.5 ml/g to about 0.8 ml/g.

Embodiment 30. particulate carbon from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about 0.75 ml/g, or 30. The bleed discharge scrubber of any of embodiments 1-29, having a mesopore volume of up to about 0.8 ml/g.

Embodiment 31. Any of embodiments 1-30, wherein the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g. Bleed discharge scrubber as described.

Embodiment 32. 32. The bleed discharge scrubber of any of embodiments 1-31, wherein the sorbent -containing spatial region has a g-total butane working capacity (BWC) of less than about 2 grams.

Embodiment 33. 33. The bleed discharge scrubber of any of embodiments 1-32, wherein the sorbent -containing spatial region has a g-total BWC of from about 0.2 grams to about 1.6 grams.

Embodiment 34. The substrate may be foams, monolithic materials, nonwovens, fabrics, sheets, paper, twisted spirals, ribbons, structured media in extruded form, structured media in rolled form, structured media in folded form, or in pleated form. 34. The bleed discharge scrubber of any of embodiments 1-33, selected from the group consisting of structured media, structured media in corrugated form, structured media in injected form, structured media in combined form, and combinations thereof.

Embodiment 35. 35. The bleed discharge scrubber of any of embodiments 1-34, wherein the substrate is a monolith.

Embodiment 36. 36. The bleed discharge scrubber of any of embodiments 1-35, wherein the monolith is ceramic.

Embodiment 37. 37. A bleed discharge scrubber according to any preceding embodiment, wherein the substrate is plastic.

Embodiment 38. The plastic is selected from the group consisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester, and polyurethane. 38. A bleed discharge scrubber according to any of embodiments 1-37 selected.

Embodiment 39. 39. The bleed exhaust scrubber of any of embodiments 1-38, wherein the coating has a thickness of less than about 500 microns.

Embodiment 40. 40. The bleed exhaust scrubber of any of embodiments 1-39, wherein the binder is present in an amount of about 10% to about 50% by weight relative to the particulate carbon.

Embodiment 41. 41. The bleed discharge scrubber of any of embodiments 1-40, wherein the binder is an organic polymer.

Embodiment 42. 42. The bleed discharge scrubber of any of embodiments 1-41, wherein the binder is an acrylic/styrene copolymer latex.

Embodiment 43. a first sorbent- containing spatial region contained within the first canister; a fuel vapor purge line for connecting the first canister to the engine; and a fuel vapor for venting the fuel tank to the first canister. A second sorbent- containing spatial region comprising an inlet conduit, a vent conduit for venting the first canister to the atmosphere and for admitting purge air into the first canister, and a bleed exhaust scrubber of any previous embodiment. and wherein a second sorbent -containing spatial region is in fluid communication with the first sorbent -containing spatial region , and a bleed exhaust scrubber is positioned within the first canister. Contained or contained within a second canister, the evaporative emission control system permits fuel vapor to continuously contact the first sorbent -containing spatial region and the second sorbent- containing spatial region an evaporative emission control canister system configured to:

Embodiment 44. 44. The evaporative emission control canister system of any of embodiments 1-43, wherein the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 45. 45. The evaporative emission control canister system of any of embodiments 1-44, wherein the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 46. Particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g at an n-butane pressure of about 3 mmHg. 46. The evaporative emission control canister system of any of embodiments 1-45, having an n-butane adsorption capacity of up to about 75 ml/g, or about 80 ml/g.

Embodiment 47. 47. The evaporative emission control canister system of any of embodiments 1-46, wherein the particulate carbon has a BET surface area of from about 1300 m ² /g to about 2100 m ² /g.

Embodiment 48. 48. The evaporative emission control system of any of embodiments 1-47, wherein the particulate carbon has a BET surface area of from about 1400 m ² /g to about 1600 m ² /g.

Embodiment 49. 49. The evaporative emission control canister system of any of embodiments 1-48, wherein the particulate carbon has a micropore volume of from about 0.20 ml/g to about 0.35 ml/g.

Embodiment 50. particulate carbon from about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0 49. The evaporative emission control canister system of any of embodiments 1-49, having a micropore volume of up to .33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 51. 51. The evaporative emission control canister system of any of embodiments 1-50, wherein the particulate carbon has a mesopore volume of from about 0.5 ml/g to about 0.8 ml/g.

Embodiment 52. particulate carbon from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about 0.75 ml/g, or 52. The evaporative emission control canister system of any of embodiments 1-51, having a mesopore volume of up to about 0.8 ml/g.

Embodiment 53. 53. Any of embodiments 1-52, wherein the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.7 ml/g. The evaporative emission control canister system described.

Embodiment 54. 54. The evaporative emission control canister system of any of embodiments 1-53, wherein the bleed emission scrubber is disposed within the first sorbent -containing spatial region of the evaporative emission control canister.

Embodiment 55. 55. The evaporative emission control canister system of any preceding embodiment, wherein the bleed emission scrubber is located in a separate canister in fluid communication with the evaporative emission control canister.

Embodiment 56. 56. Evaporative emission according to any of embodiments 1-55, wherein the second sorbent- containing spatial region has an available butane working capacity (BWC) of less than about 3 g/dL and a g-total BWC of less than about 2 grams. Control canister system.

Embodiment 57. 57. The evaporative emission control canister system of any of embodiments 1-56, wherein the second sorbent- containing spatial region has a g-total BWC of from about 0.2 grams to about 1.999 grams.

Embodiment 58. 58. The method of embodiments 1-57, wherein the second sorbent- containing spatial region further comprises a third sorbent- containing spatial region , the third sorbent -containing spatial region having a BWC of at least about 0.05 grams. An evaporative emission control system according to any one of the preceding claims.

Embodiment 59. The substrate may be foams, monolithic materials, nonwovens, fabrics, sheets, paper, twisted spirals, ribbons, structured media in extruded form, structured media in rolled form, structured media in folded form, or in pleated form. 59. The evaporative emission control canister system of any of embodiments 1-58, wherein the evaporative emission control canister system is selected from the group consisting of structured media, corrugated structured media, injected structured structured media, combined structured media, and combinations thereof.

Embodiment 60. 60. The evaporative emission control canister system of any of embodiments 1-59, wherein the substrate is a monolith.

Embodiment 61. 61. The evaporative emission control canister system of any of embodiments 1-60, wherein the monolith is ceramic.

Embodiment 62. 62. The evaporative emission control canister system of any of embodiments 1-61, wherein the substrate is plastic.

Embodiment 63. The plastic is selected from the group consisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester, and polyurethane. 63. The evaporative emission control canister system of any of embodiments 1-62 selected.

Embodiment 64. 64. The evaporative emission control canister system of any of embodiments 1-63, wherein the coating has a thickness of less than about 500 microns.

Embodiment 65. 65. The evaporative emission control canister system of any of embodiments 1-64, wherein the binder is present in an amount of about 10% to about 50% by weight relative to the particulate carbon.

Embodiment 66. 66. The evaporative emission control canister system of any of embodiments 1-65, wherein the binder is an organic polymer.

Embodiment 67. 67. The evaporative emission control canister system of any of embodiments 1-66, wherein the binder is an acrylic/styrene copolymer latex.

Embodiment 68. 68. The evaporative emission control canister system of any of embodiments 1-67, wherein the third sorbent -containing spatial region comprises reticulated polyurethane foam.

Embodiment 69.
The first adsorbent- containing spatial area is from about 1.9 to about 3.0 liters and the 2-day diurnal breathing loss (DBL) is measured under the California Bleed Emission Test Protocol (BETP) under the following test conditions: i.e. i. 2.5 L of the first adsorbent- containing spatial region and a purge volume of 80 bed volumes, or ii. 69. The evaporative emission control canister system of any of embodiments 1-68, wherein the evaporative emission control canister system of any of embodiments 1-68 is less than about 20 mg when tested under test conditions of a first sorbent -containing spatial region of 1.9 L and a purge volume of 135 bed volumes. .

Embodiment 70. An evaporative emission control system includes a fuel tank for fuel storage and an internal combustion engine adapted to consume the fuel, the evaporative emission control system extending from a fuel vapor inlet conduit to a first canister to a second canister. and bounded by a fuel vapor flow path to the vent conduit, and from the vent conduit to the second sorbent -containing spatial region to the first canister and to the fuel vapor purge pipe. 70. The evaporative emission control canister system of any of embodiments 1-69 defined by an air flow path.

Embodiment 71. 71. The evaporative emission control canister system of any of embodiments 1-70, wherein the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 72. 72. The evaporative emission control canister system of any of embodiments 1-71, wherein the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 73. Particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g at an n-butane pressure of about 3 mmHg. 75. The evaporative emission control canister system of any of embodiments 1-72, having an n-butane adsorption capacity of up to about 75 ml/g, or about 80 ml/g.

Embodiment 74. 74. The evaporative emission control canister system of any of embodiments 1-73, wherein the particulate carbon has a BET surface area of from about 1300 m ² /g to about 2100 m ² /g.

Embodiment 75. 75. The evaporative emission control canister system of any of embodiments 1-74, wherein the particulate carbon has a BET surface area of from about 1400 ^m2 /g to about 1600 ^m2 /g.

Embodiment 76. 76. The evaporative emission control canister system of any of embodiments 1-75, wherein the particulate carbon has a micropore volume of from about 0.20 ml/g to about 0.35 ml/g.

Embodiment 77. particulate carbon from about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0 77. The evaporative emission control canister system of any of embodiments 1-76, having a micropore volume of up to .33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 78. 78. The evaporative emission control canister system of any of embodiments 1-77, wherein the particulate carbon has a mesopore volume of from about 0.5 ml/g to about 0.8 ml/g.

Embodiment 79. particulate carbon from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about 0.75 ml/g, or 79. The evaporative emission control canister system of any of embodiments 1-78, having a mesopore volume of up to about 0.8 ml/g.

Embodiment 80. 80. Any of embodiments 1-79, wherein the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.7 ml/g. The evaporative emission control canister system described.

Embodiment 81. 81. The evaporative emission control canister system of any of embodiments 1-80, wherein a bleed emission scrubber is contained in the first canister.

Embodiment 82. 82. The evaporative emission control canister system of any of embodiments 1-81, wherein the bleed emission scrubber is contained in the second canister.

Embodiment 83. 83. Evaporative emission according to any of embodiments 1-82, wherein the second sorbent- containing spatial region has an effective butane working capacity (BWC) of less than about 3 g/dL and a g-total BWC of less than about 2 grams. Control canister system.

Embodiment 84. 84. The evaporative emission control canister system of any of embodiments 1-83, wherein the second sorbent- containing spatial region has a g-total BWC of from about 0.2 grams to about 1.999 grams.

Embodiment 85. Embodiment 1, wherein the second sorbent -containing spatial region further comprises a third sorbent- containing spatial region , wherein the third sorbent -containing spatial region has a g-total BWC of at least about 0.05 grams. 84. The evaporative emission control canister system according to any of the claims 1-84.

Embodiment 86. The substrate may be foams, monolithic materials, nonwovens, fabrics, sheets, paper, twisted spirals, ribbons, structured media in extruded form, structured media in rolled form, structured media in folded form, or in pleated form. 86. The evaporative emission control canister system of any of embodiments 1-85, wherein the evaporative emission control canister system is selected from the group consisting of structured media, corrugated structured media, injected structured structured media, bonded structured structured media, and combinations thereof.

Embodiment 87. 87. The evaporative emission control canister system of any of embodiments 1-86, wherein the substrate is a monolith.

Embodiment 88. 88. The evaporative emission control canister system of any of embodiments 1-87, wherein the monolith is ceramic.

Embodiment 89. 89. The evaporative emission control canister system of any of embodiments 1-88, wherein the substrate is plastic.

Embodiment 90. The plastic is selected from the group consisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester, and polyurethane. 90. The evaporative emission control canister system of any of embodiments 1-89 selected.

Embodiment 91. 91. The evaporative emission control canister system of any of embodiments 1-90, wherein the coating thickness is less than about 500 microns.

Embodiment 92. 92. The evaporative emission control canister system of any of embodiments 1-91, wherein the binder is present in an amount of about 10% to about 50% by weight relative to the particulate carbon.

Embodiment 93. 93. The evaporative emission control canister system of any of embodiments 1-92, wherein the binder is an organic polymer.

Embodiment 94. 94. The evaporative emission control canister system of any of embodiments 1-93, wherein the binder is an acrylic/styrene copolymer latex.

Embodiment 95. 95. The evaporative emission control canister system of any of embodiments 1-94, wherein the third sorbent- containing spatial region comprises reticulated polyurethane foam.

Embodiment 96. The first adsorbent- containing spatial area is from about 1.9 to about 3.0 liters and the 2-day diurnal breathing loss (DBL) is measured under the California Bleed Emission Test Protocol (BETP) under the following test conditions: i.e. i. 2.5 L of the first adsorbent- containing spatial region and a purge volume of 80 bed volumes, or ii. 96. The evaporative emission control canister system of any of embodiments 1-95, wherein the evaporative emission control canister system of any of embodiments 1-95 is less than about 20 mg when tested under test conditions of a first sorbent -containing spatial region of 1.9 L and a purge volume of 135 bed volumes. .

Embodiment 97. Any of embodiments 1-96, wherein the 2-day DBL is less than about 20 mg under California BETP and the volume of the second absorbent has a g-total BWC of less than about 2 grams. Evaporative emission control canister system as described in .

Embodiment 98. 1. Evaporative emission control canister system comprising: an evaporative emission control canister comprising at least one canister sorbent- containing spatial region comprising canister sorbent material; and an evaporative emission control canister comprising at least one bleed exhaust scrubber, wherein at least one One bleed discharge scrubber includes a scrubber sorbent- containing spatial region , the scrubber sorbent- containing spatial region includes a scrubber sorbent material and has a g-total BWC of less than about 2 grams, and the bleed discharge scrubber has an evaporative discharge. In fluid communication with the control canister, the evaporative emission control canister is configured to allow fuel vapor to continuously contact the canister sorbent- containing spatial region and the scrubber sorbent- containing spatial region; The emission control canister system was tested under the California Bleed Emission Test Protocol (BETP) under the following test conditions: total canister sorbent in a 2.5 L evaporative emission control canister and a purge volume of 80 bed volumes. An evaporative emission control canister system having a 2-day diurnal breathing loss (DBL) of less than about 20 mg when tested under conditions.

Embodiment 99. a fuel vapor purge line for connecting the evaporative emission control canister to the engine; a fuel vapor inlet conduit for venting the fuel tank to the evaporative emission control canister; and a fuel vapor inlet conduit for venting the evaporative emission control canister to the atmosphere and vaporizing the purge air. 99. The evaporative emission control canister system of embodiment 98, further comprising a vent conduit for entering the emission control canister.

Embodiment 100. Embodiments wherein the canister sorbent material is selected from the group consisting of activated carbon, carbon charcoal, zeolites, clays, porous polymers, porous alumina, porous silica, molecular sieves, kaolin, titania, ceria, and combinations thereof. 100. The evaporative emission control canister system of any of Claims 1-99.

Embodiment 101. Activated carbon is found in wood, wood dust, wood flour, cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruit seeds, fruit kernels, nut shells, nut seeds, 101. The evaporative emission control canister of any of embodiments 1-100, derived from a material comprising a member selected from the group consisting of sawdust, palm, vegetables, synthetic polymers, natural polymers, lignocellulosic materials, and combinations thereof. system.

Embodiment 102. The scrubber sorbent material comprises particulate carbon, the particulate carbon having a BET surface area of at least about 1300 m ² /g, and (i) a butane affinity of greater than 60% at 5% butane, (ii a) butane affinity greater than 35% at 0.5% butane; (iii) micropore volume greater than about 0.2 ml/g and mesopore volume greater than about 0.5 ml/g, Embodiments 1- 102. The evaporative emission control canister system of any of Claims 101.

Embodiment 103. 103. The evaporative emission control canister system of any of embodiments 1-102, wherein the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 104. 104. The evaporative emission control canister system of any of embodiments 1-103, wherein the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg.

Embodiment 105. Particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g to about 70 ml/g at an n-butane pressure of about 3 mmHg. 105. The evaporative emission control canister system of any of embodiments 1-104, having an n-butane adsorption capacity of up to about 75 ml/g, or about 80 ml/g.

Embodiment 106. 106. The evaporative emission control canister system of any of embodiments 1-105, wherein the particulate carbon has a BET surface area of from about 1300 m ² /g to about 2500 m ² /g.

Embodiment 107. 107. The evaporative emission control canister system of any of embodiments 1-106, wherein the particulate carbon has a BET surface area of from about 1400 m ² /g to about 1600 m ² /g.

Embodiment 108. 108. The evaporative emission control canister system of any of embodiments 1-107, wherein the particulate carbon has a micropore volume of from about 0.20 ml/g to about 0.35 ml/g.

Embodiment 109. particulate carbon from about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0.25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0.32 ml/g, about 0 109. The evaporative emission control canister system of any of embodiments 1-108, having a micropore volume of up to .33 ml/g, about 0.34 ml/g, or about 0.35 ml/g.

Embodiment 110. 110. The evaporative emission control canister system of any of embodiments 1-109, wherein the particulate carbon has a mesopore volume of from about 0.5 ml/g to about 0.8 ml/g.

Embodiment 111. particulate carbon from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about 0.75 ml/g, or 111. The evaporative emission control canister system of any of embodiments 1-110, having a mesopore volume of up to about 0.8 ml/g.

Embodiment 112. 112. Any of embodiments 1-111, wherein the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g. The evaporative emission control canister system described.

Embodiment 113. 113. The evaporative emission control canister system of any of embodiments 1-112, wherein the bleed emission scrubber comprises a substrate.

Embodiment 114. The substrate may be foams, monolithic materials, nonwovens, fabrics, sheets, paper, twisted spirals, ribbons, structured media in extruded form, structured media in rolled form, structured media in folded form, or in pleated form. 114. The evaporative emission control canister system of any of embodiments 1-113, wherein the evaporative emission control canister system is selected from the group consisting of structured media, corrugated structured media, injected structured structured media, bonded structured structured media, and combinations thereof.

Embodiment 115. 115. The evaporative emission control canister system of any of embodiments 1-114, wherein the substrate is molded, formed, or extruded with a mixture comprising the scrubber sorbent material.

Embodiment 116. 116. The evaporative emission control canister system of any of embodiments 1-115, wherein the substrate comprises a coating, and the coating comprises a scrubber sorbent material and a binder.

Embodiment 117. 117. The evaporative emission control canister system of any of embodiments 1-116, wherein the substrate is a monolith.

Embodiment 118. 118. The evaporative emission control canister system of any of embodiments 1-117, wherein the monolith is ceramic.

Embodiment 119. 119. The evaporative emission control canister system of any of embodiments 1-118, wherein the substrate is plastic.

Embodiment 120. The plastic is selected from the group consisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester, and polyurethane. 120. The evaporative emission control canister system of any of embodiments 1-119 selected.

Embodiment 121. 121. The evaporative emission control canister system of any of embodiments 1-120, wherein the coating has a thickness of less than about 500 microns.

Embodiment 122. 122. The evaporative emission control canister system of any of embodiments 1-121, wherein the binder is present in an amount of about 10% to about 50% by weight relative to the particulate carbon.

Embodiment 123. 123. The evaporative emission control canister system of any of embodiments 1-122, wherein the binder is an organic polymer.

Embodiment 124. 124. The evaporative emission control canister system of any of embodiments 1-123, wherein the binder is an acrylic/styrene copolymer latex.

Embodiment 125. 125. The evaporative emission control canister system of any of embodiments 1-124, wherein the second sorbent- containing spatial region has an effective BWC of less than about 2 grams/dl.

Embodiment 126. 126. The evaporative emission control canister system of any of embodiments 1-125, wherein the second sorbent- containing spatial region has an effective BWC of from about 0.5 grams/dl to about 2 grams/dl.

Embodiment 127. 127. The evaporative emission control canister system of any of embodiments 1-126, wherein the second sorbent- containing spatial region has a g-total BWC of from about 0.1 grams to less than about 2 grams.

Embodiment 128. 128. Evaporative emission control according to any of embodiments 1-127, wherein the evaporative emission control canister has a canister sorbent-containing spatial area of 3.5 L or less, 3.0 L or less, 2.5 L or less, or 2.0 L or less. canister system.

Embodiment 129. A single canister sorbent- containing spatial region , the canister sorbent-containing spatial region comprising at least one chamber, wherein there is a canister sorbent material filled in the at least one chamber. and a single bleed discharge scrubber , wherein at least one bleed discharge scrubber includes a scrubber sorbent- containing spatial region , the scrubber sorbent- containing spatial region including a scrubber sorbent material, and A single bleed exhaust scrubber having a g-total BWC of less than about 2 grams and a canister sorbent- containing spatial area of about 1.5 L to about 2.0 L, the evaporative emission control canister comprising 135 beds 129. The evaporative emission control canister system of any of embodiments 1-128, having a 2-day diurnal breathing loss (DBL) of less than about 20 mg under the California Bleed Emission Test Protocol (BETP) at a purge volume of volume.

Embodiment 130. Any of embodiments 1-129, wherein the evaporative emission control canister has a 2-day diurnal respiratory loss (DBL) of less than about 10 mg under the California Bleed Emission Test Protocol (BETP) at a purge volume of 135 bed volumes. The evaporative emission control canister system described.

Embodiment 131. 131. The evaporative emission control canister system of any of embodiments 1-130, wherein the canister sorbent- containing spatial region comprises two chambers, with a canister sorbent material loaded within each chamber.

Embodiment 132. 132. The evaporative emission control canister system of any of embodiments 1-131, wherein the second sorbent- containing spatial region has an effective BWC of less than about 2 grams/dl.

Embodiment 133. 133. The evaporative emission control canister system of any of embodiments 1-132, wherein the second sorbent- containing spatial region has an effective BWC of from about 0.5 grams/dl to about 2 grams/dl.

Embodiment 134. 134. The evaporative emission control canister system of any of embodiments 1-133, wherein the second sorbent- containing spatial region has a g-total BWC of from about 0.1 grams to less than about 2 grams.

Embodiment 135. A single canister sorbent -containing spatial region , the canister sorbent- containing spatial region comprising at least one chamber in which a filled canister sorbent material resides. , a single bleed exhaust scrubber, and a canister sorbent -containing spatial area of about 2.5 L to about 3.0 L , wherein the evaporative emission control canister system has 80 bed volumes of 135. The evaporative emission control canister system of any of embodiments 1-134, having a 2-day diurnal breathing loss (DBL) of less than about 20 mg under California Bleed Emission Test Protocol (BETP) at purge volume.

Embodiment 136. 136. Any of embodiments 1-135, wherein the evaporative emission control canister has a 2-day diurnal respiratory loss (DBL) of less than about 10 mg under the California Bleed Emission Test Protocol (BETP) at a purge volume of 80 bed volumes. The evaporative emission control canister system described.

Embodiment 137. 137. The evaporative emission control canister system of any of embodiments 1-136, wherein the canister sorbent- containing spatial region comprises two chambers, and there is a charged canister sorbent material within each chamber.

Embodiment 138. 138. The evaporative emission control canister system of any of embodiments 1-137, wherein the second sorbent- containing spatial region has an effective BWC of less than about 2 grams/dl.

Embodiment 139. 139. The evaporative emission control canister system of any of embodiments 1-138, wherein the second sorbent- containing spatial region has an effective BWC of from about 0.5 grams/dl to about 2 grams/dl.

Embodiment 140. 140. The evaporative emission control canister system of any of embodiments 1-139, wherein the second sorbent- containing spatial region has a g-total BWC of from about 0.1 grams to less than about 2 grams.

These and other features, aspects and advantages of the present disclosure will become apparent upon reading the following detailed description in conjunction with the accompanying drawings briefly described below. Any combination of two, three, four or more of the above embodiments and any two, three, four or more features or elements described in this disclosure. , whether or not such features or elements are explicitly combined in the description of a particular embodiment herein. In this disclosure, distinct features or elements of the disclosed invention should be considered combinable in any of its various aspects and embodiments unless the context clearly indicates otherwise. If there is, it is intended to be read as a whole. Other aspects and advantages of the invention will become apparent below.

To provide an understanding of embodiments of the present invention, reference is made to the accompanying drawings. Reference numbers refer to components of exemplary embodiments of the invention. The drawings are examples only and should not be construed as limiting the invention. The disclosure described herein is illustrated by way of example and not by way of limitation in the accompanying figures. For simplicity and clarity of illustration, illustrated features are not necessarily drawn to scale. For example, the dimensions of some features may be exaggerated relative to other features for clarity. Further, where considered appropriate, reference labels have been repeated among the figures to indicate corresponding or analogous elements.

1 is a cross-sectional view of a bleed discharge scrubber provided according to a first embodiment; FIG. FIG. 4 is a cross-sectional view of a bleed discharge scrubber provided according to a second embodiment; FIG. 4 is a cross-sectional view of a bleed discharge scrubber provided according to a third embodiment; 1 is a schematic diagram of an evaporative emission control system including an evaporative emission control canister and a bleed emission scrubber provided according to one embodiment; FIG. FIG. 4 is a cross-sectional view of a bleed discharge scrubber provided according to a fourth embodiment; FIG. 4 is a graph showing cumulative pore volume measurements for pore widths of 4-10 Å for several particulate carbons; FIG. 1 is a graph showing cumulative pore volume measurements for pore widths from 1 to 30 Å for several particulate carbons. 1 is a graph showing butane isotherms for several particulate carbons; 1 is a graph showing butane isotherms for several particulate carbons; 1 is a graph showing butane isotherms for several particulate carbons; 1 is a graph showing butane adsorption for several particulate carbons. 1 is a graph showing butane affinities for several particulate carbons. 1 is a graph showing butane affinities for several particulate carbons. 1 is a graph showing butane breakthrough curves for several particulate carbons;

The present disclosure is directed to coated substrates adapted for hydrocarbon adsorption, and evaporative emission control articles and systems including coated substrates are provided. The disclosed coated substrates, articles, and systems are useful for controlling evaporative hydrocarbon emissions and can provide low diurnal breathing loss (DBL) emissions even under low purge conditions. The coated substrate removes evaporative emissions produced by internal combustion engines and/or associated fuel source components before the emissions can be released to the atmosphere. The coated substrates include activated carbons with novel pore size distributions compared to state-of-the-art activated carbons, providing higher adsorption capacities at relevant fugitive effluent concentrations and low over many adsorption/desorption cycles. Provides a heal build. Surprisingly, we have found that only certain combinations of surface area, pore volume distribution, and butane isotherm shape can qualify coating carbons to meet stringent emission regulations.

The invention will now be described more fully below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

Definitions Unless defined otherwise, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

The articles "a" and "an" herein refer to one or more (eg, at least one) of the grammatical object. All ranges cited herein are inclusive. The term "about" is used throughout to express and describe small variations. For example, “about” refers to numerical values of ±5%, ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.4%, ±0.3%, ±0 .2%, ±0.1%, or ±0.05%. All numerical values are modified with the term "about," whether or not explicitly indicated. Numeric values modified by the term "about" include the specific identified value. For example, "about 5.0" includes 5.0.

As used herein, the term "adsorbent material" refers to an adsorbent or adsorbent-containing material along the vapor flow path, which may be a bed, monolith, honeycomb, sheet, or It can consist of other materials.

The term "associated with," for example, means "comprising," "connected to," or "in communication with," e.g., "electrically connected to," or "in fluid communication with." means “connected” or connected in such a way as to perform a function. The term "related" can mean directly related or indirectly related, for example, through one or more other items or elements.

The term "micropore volume" refers to the volume of pores within particulate carbon having pore diameters between about 0.3 nm and about 1 nm.

The term "mesopore volume" refers to the volume of pores within particulate carbon having pore diameters between about 1 nm and about 30 nm.

As used herein, the term "substrate" refers to the material upon which the adsorbent material is disposed, typically in the form of a washcoat.

As used herein, the term "washcoat" has its ordinary meaning in the art of a thin, adherent coating of material applied to a substrate. Washcoating involves preparing a slurry containing an adsorbent with a specific solids content (eg, 10% to 50% by weight) in a liquid, which is then coated onto a substrate, dried, and washed. It is formed by providing a coating layer.

The term "vehicle" means any vehicle having an internal combustion engine, e.g., passenger cars, sport utility vehicles, minivans, vans, trucks, buses, garbage trucks, freight trucks, construction vehicles, heavy equipment, military vehicles. , agricultural vehicles, etc.

All parts and percentages are by weight unless otherwise specified. Unless otherwise specified, "weight percent (wt%)" is based on the total composition, ie, dry solids, without volatiles.

Coating Composition The coating comprises particulate carbon and a binder. Particulate carbon is activated carbon, which is highly porous carbon with a very high surface area, generally at least about 400 m ² /g. Activated carbon is well known in the art. See, for example, commonly assigned US Pat. No. 7,442,232. See also US Pat. No. 7,467,620.

Described herein are activated particulate carbon materials with unique adsorption properties. Plotting the pore volume of this particulate carbon as a function of pore radius, in addition to the peak just below 20 Å (2 nm), the particulate carbon exhibits significant It has a large amount of pore volume. Without wishing to be bound by theory, this feature of additional pore volume in the 30-80 Å range compares to state-of-the-art activated carbons used for hydrocarbon evaporative emission control in automotive applications. It is thought that the heal build will be lower. The particulate carbon is made from synthetic resin precursors by a process that can produce activated carbon with pore size distributions unattainable with other methods and precursors. Such particulate carbon is available from EnerG2 Technologies, Inc.; (100 NE Northlake Way, Seattle, WA 98105, USA; subsidiary of BASF) as P2-15.

In some embodiments, the particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g at pore sizes of about 0.3 nm to about 1 nm. In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g.

In some embodiments, the particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g at pore sizes of about 1 nm to about 30 nm. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g.

In certain embodiments, the particulate carbon has a micropore volume greater than about 0.2 ml/g and a mesopore volume greater than about 0.5 ml/g. In certain specific embodiments, the particulate carbon has a micropore volume of about 0.3 ml/g and a mesopore volume of about 0.75 ml/g. In certain specific embodiments, the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g.

In some embodiments, particulate carbon has a BET surface area of at least about 1300 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2100 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g. As used herein, "BET surface area" has its ordinary meaning in relation to the Brunauer, Emmett, Teller method for determining surface area by _N2 adsorption. Pore size and pore volume can also be determined using BET-type _N2 adsorption or desorption experiments.

In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g.

In some embodiments, particulate carbon may be defined by its butane affinity. A material's "butane affinity" can be calculated by collecting butane isotherm measurements as described herein. From the butane isotherm measurements, a curve plotting the amount of butane adsorbed versus the absolute butane pressure in mmHg is obtained. The affinity of butane was then determined by setting the absolute partial pressure of butane to 760 mgHg (i.e., atmospheric pressure), which equals a "butane fraction" of 100%, and then plotting the amount of butane adsorbed versus butane fraction. Gender can be calculated. The data curve can be normalized by plotting the amount of butane adsorbed as a fraction of the amount of butane adsorbed at the 50% butane fraction. Butane affinities at 0.5% butane and 5% butane can then be determined from this plot by reading the fraction of butane adsorbed at 50% at these butane concentrations. In other words, the butane affinity of the material at 5% and 0.5% is 38 mmHg and It is the fraction of butane adsorbed by the material at a butane partial pressure of 3.8 mmHg.

In some embodiments, the particulate carbon has greater than 60% butane affinity at 5% butane, e.g., about 60% to about 100%, about 60% to about 99%, about 65% to about 95%, It has a butane affinity of about 70% to about 90%, or about 75% to about 85%. In some embodiments, the particulate carbon has a butane affinity of about 75% to about 80% at 5% butane. In some embodiments, the particulate carbon has a butane affinity greater than 35% at 0.5% butane, e.g. %, from about 45% to about 60%, or from about 45% to about 50%. In some embodiments, the particulate carbon has a butane affinity of greater than 60% at 5% butane and greater than 35% at 0.5% butane.

In some embodiments, the particulate carbon has a BET surface area of at least about 1300 m ² /g and a butane affinity greater than 60% at 5% butane. In some embodiments, the particulate carbon has a BET surface area of at least about 1300 m ² /g and a butane affinity greater than 35% at 0.5% butane. In some embodiments, the particulate carbon has a BET surface area of at least about 1300 m ² /g, a butane affinity of greater than 60% at 5% butane, and a butane affinity of greater than 35% at 0.5% butane. .

In some embodiments, the particulate carbon has a BET surface area of at least about 1300 m ² /g and greater than 60% butane affinity at 5% butane and greater than 35% butane affinity at 0.5% butane. or both, and have a micropore volume greater than about 0.2 ml/g, a mesopore volume greater than about 0.5 ml/g, or both. In some embodiments, the particulate carbon has a BET surface area of at least about 1300 m ² /g, greater than 60% butane affinity at 5% butane, greater than 35% butane affinity at 0.5% butane, about 0 It has a micropore volume greater than .2 ml/g and a mesopore volume greater than about 0.5 ml/g. Any possible combination of these features is therefore contemplated, provided that at least one of the features is present.

The hydrocarbon sorbent coating further includes an organic binder that adheres the sorbent coating to the substrate. When the coating is applied as a slurry and dried, the binder material secures the hydrocarbon adsorbent particles to themselves and to the substrate. In some cases, the binder can crosslink with itself to improve adhesion. This improves coating integrity, adhesion to the substrate, and provides structural stability under the vibration conditions experienced in automobiles. The binder can also contain additives to improve water resistance and improve adhesion. Typical binders for use in slurry formulation include: organic polymers; sols of alumina, silica, or zirconia; inorganic salts, organic salts, and/or hydrolysis products of aluminum, silica, or zirconium; hydroxides of aluminum, silica or zirconium; organosilicates hydrolyzable to silica; and mixtures thereof. Preferred binders are organic polymers. Organic polymers can be thermoset or thermoplastic polymers and can be plastics or elastomers. The binder can be, for example, an acrylic/styrene copolymer latex, a styrene-butadiene copolymer latex, polyurethane, or any mixture thereof. The polymeric binder may contain suitable stabilizers and anti-aging agents known in the polymer art. In some embodiments, the binder is a thermoset elastomeric polymer that is introduced into the sorbent composition as a latex, optionally as an aqueous slurry. Preferred are thermoset elastomeric polymers that are introduced into the sorbent composition as a latex, preferably as an aqueous slurry.

Useful organic polymer binder compositions include polyethylene, polypropylene, polyolefin copolymers, polyisoprene, polybutadiene, polybutadiene copolymers, chlorinated rubbers, nitrile rubbers, polychloroprene, ethylene-propylene-diene elastomers, polystyrenes, polyacrylates, polymethacrylates, Polyacrylonitrile, poly(vinyl ester), poly(vinyl halide), polyamide, cellulosic polymer, polyimide, acrylic, vinyl acrylic and styrene acrylic, polyvinyl alcohol, thermoplastic polyester, thermoset polyester, poly(phenylene oxide), poly( phenylene sulfide), fluorinated polymers such as poly(tetrafluoroethylene), polyvinylidene fluoride, poly(vinyl fluoride) and chloro/fluoro copolymers such as ethylene chlorotrifluoro-ethylene copolymers, polyamides, phenolics and epoxies Resins, polyurethanes, acrylic/styrene acrylic copolymer latexes and silicone polymers. In some embodiments, the polymeric binder is an acrylic/styrene acrylic copolymer latex, such as a hydrophobic styrene-acrylic emulsion. In some embodiments, the binder is selected from the group consisting of acrylic/styrene copolymer latexes, styrene-butadiene copolymer latexes, polyurethanes, and mixtures thereof.

Considerations regarding the compatibility of the components of slurries, including hydrocarbon adsorbent materials and polymeric binders such as latex emulsions, are known in the art. See, for example, commonly-owned US Patent Publication No. 2007/0107701. In some embodiments, the organic binder can have a low glass transition temperature (Tg). Tg is conventionally measured by Differential Scanning Calorimetry (DSC) by methods known in the art. An exemplary hydrophobic styrene-acrylic emulsion binder with a low Tg is Rhoplex™ P-376 (trademark of Dow Chemical; available from Rohm and Haas, Independence Mall West, Philadelphia, Pa., 19105). In some embodiments, the binder has a Tg of less than about 0°C. An exemplary binder having a Tg of less than about 0° C. is Rhoplex™ NW-1715K (trademark of Dow Chemical; also available from Rohm and Haas). In some embodiments, the binder is an ultra-low formaldehyde, styrenated acrylic emulsion free of alkylphenol ethoxylates (APEO). One such exemplary binder is Joncryl™ 2570. In some embodiments, the binder is an aliphatic polyurethane dispersion. One such exemplary binder is Joncryl™ FLX 5200. Joncryl(TM) is a trademark of BASF, Wyandotte, MI, 48192 and Joncryl(TM) products are available from BASF. In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon.

The hydrocarbon adsorbent coatings of the present invention, particularly those slurries containing polymer latexes, may contain conventional additives such as thickeners, dispersants, surfactants, biocides, antioxidants, and the like. can. The thickener makes it possible to achieve a sufficient amount of coating (and thus sufficient hydrocarbon adsorption capacity) on relatively low surface area substrates. Thickeners may also play a secondary role by enhancing slurry stability through steric hindrance of dispersed particles. It can also promote bonding of coating surfaces. Exemplary thickeners are xanthan gum thickeners or carboxymethylcellulose thickeners. Kelzan®, a product of CP Kelco, Cumberland Center II, 3100 Cumberland Boulevard, Suite 600, Atlanta GA, 30339, is an exemplary such xanthan thickener.

In some embodiments it is preferred to use a dispersant in combination with a binder. Dispersants can be anionic, nonionic, or cationic and are typically utilized in amounts of about 0.1 to about 10 weight percent, based on the weight of the material. Of course, the particular choice of dispersant is important. Suitable dispersants include polyacrylates, alkoxylates, carboxylates, phosphate esters, sulfonates, taurates, sulfosuccinates, stearates, laurates, amines, amides, imidazolines, sodium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, and mixtures thereof. In one embodiment, the dispersant is a low molecular weight polyacrylic acid in which many of the protons on the acid have been replaced with sodium. In some embodiments, the dispersant is a polycarboxylic acid ammonium salt. In some embodiments, the dispersant is a hydrophobic copolymer pigment dispersant. An exemplary dispersant is Tamol™ 165A (trademark of Dow Chemical, available from Rohm & Haas). Raising the pH of the slurry or adding an anionic dispersant alone can impart sufficient stability to the slurry mixture, but best results are obtained with an elevated pH and the use of an anionic dispersant. can. In some embodiments, the dispersant is a nonionic surfactant such as Surfynol® 420 (Air Products and Chemicals, Inc). In some embodiments, the dispersant is an acrylic block copolymer such as Dispex® Ultra PX 4575 (BASF).

In some embodiments it is preferred to use a surfactant that can act as an antifoaming agent. In some embodiments, the surfactant is a small molecule, non-anionic dispersant. An exemplary oil- and silicone-free defoamer surfactant is Rhodoline® 999 (Solvay). Another exemplary surfactant is a blend of a hydrocarbon and a nonionic surfactant such as Foammaster® NXZ (BASF).

In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon. In some embodiments the binder is an organic polymer. In some embodiments, the binder is an acrylic/styrene copolymer latex.

Substrate In one or more embodiments, the coating composition is disposed on a substrate. Articles including coated substrates, such as bleed emission scrubbers, can be part of an evaporative emission control system in some embodiments. The substrate is three-dimensional and has length, diameter, and volume similar to a cylinder. The shape does not necessarily have to be the same shape as the cylinder. Length is the axial length defined by the inlet and outlet ends. The diameter is the maximum cross-sectional length, eg, the maximum cross-section if the shape is not exactly conformal to a cylinder. In one or more embodiments, the substrate is a monolith as described herein below.

As used herein, the term "monolithic substrate" refers to microscopic substrates extending from an inlet or outlet surface of the substrate therethrough such that passageways are open to fluid flow therethrough. A type of substrate with parallel gas channels. The channels, which may be essentially straight paths or patterned paths (e.g., zig-zag, herringbone, etc.) from their fluid inlets to their fluid outlets, allow gas to flow through the channels. is defined by a wall coated with adsorbent material as a washcoat such that the is in contact with the adsorbent material. The channels of the monolithic substrate are thin-walled channels, which can be of any suitable cross-sectional shape and size, such as trapezoidal, rectangular, square, triangular, serpentine, hexagonal, elliptical, circular, etc. can. Such structures may contain from about 60 to about 900 or more gas inlet openings (ie, cells) per square inch of cross-section. Monolithic substrates can be composed of, for example, metals, ceramics, plastics, papers, impregnated papers, and the like. In some embodiments, the substrate is a carbon monolith.

In one or more embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted helix, ribbon, structured media in extruded form, structured media in wound form, folded The structural medium is selected from the group consisting of a structural medium in form, a structural medium in pleated form, a structural medium in corrugated form, a structural medium in injection form, a structural medium in bonded form, and combinations thereof.

In one embodiment, the substrate is an extrusion medium. In some embodiments, the extrusion media are honeycombs. Honeycombs can be of any geometric shape including, but not limited to, circular, cylindrical, or square. Additionally, the cells of the honeycomb substrate can be of any shape.

In one embodiment, the substrate is foam. In some embodiments, the foam has greater than about 10 pores per inch. In some embodiments, the foam has greater than about 20 pores per inch. In some embodiments, the foam has about 15 to about 40 pores per inch. In some embodiments, the foam is polyurethane. In some embodiments, the foam is reticulated polyurethane. In some embodiments, polyurethanes are polyethers or polyesters. In some embodiments, the substrate is a nonwoven.

In some embodiments, the substrate is plastic. In some embodiments, the substrate is a thermoplastic polyolefin. In some embodiments, the substrate is glass or a thermoplastic polyolefin containing inorganic fillers. In some embodiments, the substrate is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, A plastic selected from the group consisting of polyester and polyurethane.

In certain alternative embodiments, particulate carbon may be combined with additional materials and extruded to form an adsorptive porous monolith. Such porous monoliths thus represent sorbent articles that are free of substrates and sorbent coatings and can be utilized, for example, in bleed exhaust scrubbers as described below. To prepare such porous monoliths, the particulate carbon described herein may generally be combined with, for example, ceramic-forming materials, flux materials, binders, and water to form an extrudable mixture. . The extrudable mixture can then be extruded through an extrusion die to form a monolith having a honeycomb structure. After extrusion, the extruded honeycomb monolith can be dried and then fired at a temperature and time sufficient to form a monolith with particulate carbon dispersed throughout the structure. Suitable methods for preparing such extruded porous monoliths are disclosed, for example, in US Pat. No. 5,914,294 to Park et al., the disclosure of which is incorporated herein by reference for such methods. incorporated herein by.

Article - Bleed Exhaust Scrubber In one aspect of the present disclosure, a bleed exhaust scrubber is provided, the scrubber comprising a sorbent-containing spatial region adapted for hydrocarbon adsorption comprising a coated substrate as described herein. wherein the coated substrate comprises a substrate having at least one surface and a coating on the at least one surface, the coating comprising particulate carbon as described herein and wherein the particulate carbon has a BET surface area of at least about 1300 m ² /g and (i) greater than 60% butane affinity at 5% butane, (ii) 0.5% (iii) a micropore volume greater than about 0.2 ml/g and a mesopore volume greater than about 0.5 ml/g; In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g.

In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2500 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g.

In some embodiments, particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g. In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g.

In some embodiments, particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g.

In some embodiments, the particulate carbon has a BET surface area of about 1400 m ² /g, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g.

In some embodiments, the sorbent- containing spatial region has a g-total butane working capacity (BWC) of less than about 2 grams. As used herein, "g-total BWC" refers to the amount of butane purged under standard test conditions (eg, ASTM D5228). In some embodiments, the sorbent- containing spatial region is about 0.2 grams to about 1.6 grams, such as about 0.2 grams, about 0.3 grams, about 0.4 grams, about 0.5 grams grams, about 0.6 grams, about 0.7 grams, about 0.8 grams, about 0.9 grams, or about 1 gram, about 1.1 grams, about 1.2 grams, about 1.3 grams, Have a g-total BWC of up to about 1.4 grams, about 1.5 grams, or about 1.6 grams.

In some embodiments, the sorbent- containing spatial region has an effective butane working capacity (BWC) of less than 3 g/dL. As used herein, "effective butane work capacity" refers to g-total BWC divided by effective adsorbent -containing spatial area . Effective adsorbent- containing spatial area compensates for voids, air gaps, and other non-adsorbable volumes. Measurement of effective BWC is disclosed, for example, in US Patent Application Publication No. 2015/0275727, which is incorporated herein by reference.

FIG. 1A illustrates an embodiment of a bleed discharge scrubber 1, where the coated substrate is structured media (2a) in pleated form. FIG. 1B illustrates an embodiment in which the coated substrate is foam 2b. In one embodiment, foam 2b has greater than about 10 pores per inch. In some embodiments, foam 2b has more than about 20 pores per inch. In some embodiments, foam 2b has about 15 to about 40 pores per inch. In one embodiment, foam 2b is polyurethane. In some embodiments, foam 2b is reticulated polyurethane. In some embodiments, polyurethanes are polyethers or polyesters.

FIG. 1C illustrates an embodiment in which the coated substrate is extrusion media 2c. In some embodiments, extrusion media 2c is a honeycomb. Honeycomb adsorbents can be of any geometric shape including, but not limited to, circular, cylindrical, or square. Additionally, the cells of the honeycomb adsorbent can be of any shape. Uniform cross-sectional area honeycombs for flow-through channels, such as square honeycombs with square cross-section cells, or corrugated spiral wound honeycombs, provide a range of cross-sectional areas for adjacent channels As such, they may perform better than circular honeycombs with square cross-sectional cells in a rectangular matrix that provide equally non-purged flow paths. Without being bound by theory, the more uniform the cell cross-sectional area across the honeycomb face, the more uniform the flow distribution in the scrubber during both the adsorption and purge cycles, thus reducing the diurnal respiration from the scrubber. Loss (DBL) emissions are expected to be lower.

Surprisingly, the sorbent -containing spatial regions of the bleed discharge scrubbers disclosed herein may, in some embodiments, have a lower butane working capacity (BWC) than that of competing monoliths, Nonetheless, it has been found to effectively control hydrocarbon emissions from evaporative emission control canisters under low purge conditions.

In particular, the foam substrates disclosed herein exhibit lower butane workability than competing monoliths, yet control emissions more efficiently under low purge volumes. Without wishing to be bound by theory, this may be due to the low thickness of the sorbent coating and/or the high turbulence of the gas flow through the foam. , can provide more rapid purging than bulk monoliths used in competitive products.

In certain embodiments, the sorbent- containing spatial region does not comprise a coated substrate, but instead comprises a porous extruded monolith comprising particulate carbon as described herein.

Evaporative Emission Control Canisters and Canister Systems The coated substrates for hydrocarbon adsorption disclosed herein can be used as components in evaporative emission control canister systems. Thus, in yet another aspect, an evaporative emission control comprising an evaporative emission control canister comprising at least one canister sorbent- containing spatial region comprising a canister sorbent material, and an evaporative emission control canister comprising at least one bleed out scrubber. A canister system, wherein at least one bleed discharge scrubber includes a scrubber sorbent- containing spatial region , the scrubber sorbent- containing spatial region including a scrubber sorbent material and having a g-total BWC of less than about 2 grams. , a bleed emission scrubber in fluid communication with the evaporative emission control canister, the evaporative emission control canister allowing fuel vapor to continuously contact the canister sorbent- containing spatial region and the scrubber sorbent- containing spatial region; and the evaporative emission control canister system was tested under the California Bleed Emission Test Protocol (BETP) under the following test conditions: 2.5 L total canister sorbent in the evaporative emission control canister and 80 beds Has a 2-day diurnal breathing loss (DBL) of less than about 20 mg when tested under test conditions of 100000000000000000000000000000000000000000000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,100,000 and 1,000,000. In some embodiments, the evaporative emission control canister system was tested under the following test conditions: total canister sorbent material volume in a 2.5 L evaporative emission control canister and a purge volume of 80 bed volumes. When having a 2-day diurnal respiratory loss (DBL) of less than about 20 mg under the California Breed Emission Test Protocol (BETP). In some embodiments, the evaporative emission control canister system was tested under the following test conditions: total canister sorbent material volume in 1.9 L evaporative emission control canister and purge volume of 135 bed volumes. When having a 2-day diurnal respiratory loss (DBL) of less than about 20 mg under the California Breed Emission Test Protocol (BETP).

In some embodiments, the evaporative emission control canister includes a fuel vapor purge tube for connecting the evaporative emission control canister to the engine, a fuel vapor inlet conduit for venting the fuel tank to the evaporative emission control canister, and an evaporative emission control canister. and a vent conduit for venting the control canister to atmosphere and for admitting purge air into the evaporative emission control canister.

In some embodiments, the canister sorbent material is the group consisting of activated carbon, carbon charcoal, zeolites, clays, porous polymers, porous alumina, porous silica, molecular sieves, kaolin, titania, ceria, and combinations thereof. is selected from In some embodiments, the activated carbon is wood, wood dust, wood flour, cotton linters, peat, coal, coconut, lignite, carbohydrates, petroleum pitch, petroleum coke, coal tar pitch, fruit seeds, fruit kernels, nuts. husks, nut seeds, sawdust, palms, vegetables, synthetic polymers, natural polymers, lignocellulosic materials, and combinations thereof.

In some embodiments, the scrubber sorbent material comprises particulate carbon, the particulate carbon having a BET surface area of at least about 1300 m ² /g, and (i) 60% in 5% butane (ii) greater than 35% butane affinity at 0.5% butane; (iii) greater than about 0.2 ml/g micropore volume and greater than about 0.5 ml/g mesopore volume; have

In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g.

In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2500 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g.

In some embodiments, particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g. In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g.

In some embodiments, particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g.

In some embodiments, the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.75 ml/g.

In some embodiments, a bleed discharge scrubber includes a substrate. In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted helix, ribbon, structured media in extruded form, structured media in wound form, folded form. structure media, pleated structure media, corrugated structure media, infused structure media, bonded structure media, and combinations thereof. In some embodiments, the substrate is co-molded, formed, or extruded with a mixture comprising the scrubber sorbent material. In some embodiments, the substrate comprises a coating, and the coating comprises a scrubber adsorbent material and a binder. In some embodiments, the substrate is a monolith. In some embodiments, the monolith is ceramic. In some embodiments, the substrate is plastic. In some embodiments, the plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester , and polyurethane.

In some embodiments, the coating thickness is less than about 500 microns.

In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon. In some embodiments the binder is an organic polymer. In some embodiments, the binder is an acrylic/styrene copolymer latex.

In some embodiments, the second sorbent- containing spatial region has an effective BWC of less than about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region has an effective BWC from about 0.5 grams/dl to about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region is from about 0.5, about 0.6, about 0.7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0 grams It has an effective BWC up to /dL. In some embodiments, the second sorbent- containing spatial region has a g-total BWC from about 0.1 grams to less than about 2 grams. In some embodiments, the second sorbent- containing spatial region is about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.5. 7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about Have a g-total BWC of up to 1.7, about 1.8, or about 1.9 grams.

In some embodiments, the evaporative emission control canister has a canister sorbent- containing spatial area of 3.5 L or less, 3.0 L or less, 2.5 L or less, or 2.0 L or less.

In some embodiments, the evaporative emission control canister system is a single canister sorbent- containing spatial region , the canister sorbent- containing spatial region comprising at least one chamber, and filled within the at least one chamber. a single canister sorbent- containing spatial region and a single bleed discharge scrubber, wherein at least one bleed discharge scrubber includes a scrubber sorbent- containing spatial region , the scrubber A single bleed discharge scrubber and about 1.5 L to about 2.0 L of canister sorbent containing space, wherein the sorbent containing space region comprises a scrubber sorbent material and has a g-total BWC of less than about 2 grams. and wherein the evaporative emission control canister system has a 2-day diurnal breathing loss (DBL) of less than about 20 mg under the California Bleed Emission Test Protocol (BETP) at a purge volume of 135 bed volumes. In some embodiments, the evaporative emission control canister has a 2-day diurnal respiratory loss (DBL) of less than about 10 mg under the California Breed Emission Test Protocol (BETP).

In some embodiments, the canister sorbent- containing spatial region comprises two chambers, with a canister sorbent material charged within each chamber. In some embodiments, the second sorbent- containing spatial region has an effective BWC of less than about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region has an effective BWC from about 0.5 grams/dl to about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region is from about 0.5, about 0.6, about 0.7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0 grams It has an effective BWC up to /dL. In some embodiments, the second sorbent- containing spatial region has a g-total BWC from about 0.1 grams to less than about 2 grams. In some embodiments, the second sorbent- containing spatial region is about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.5. 7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about Have a g-total BWC of up to 1.7, about 1.8, or about 1.9 grams.

In some embodiments, the evaporative emission control canister is a single canister sorbent -containing spatial region , the canister sorbent- containing spatial region comprising at least one chamber, wherein the at least one chamber contains a single canister sorbent-containing spatial region in which the filled canister sorbent material resides; a single bleed discharge scrubber; The control canister has a 2-day diurnal respiratory loss (DBL) of less than about 20 mg under the California Bleed Emission Test Protocol (BETP) at a purge volume of 80 bed volumes. In some embodiments, the evaporative emission control canister has a 2-day diurnal respiratory loss (DBL) of less than about 10 mg under the California Breed Emission Test Protocol (BETP).

In some embodiments, the canister sorbent- containing spatial region comprises two chambers, with a canister sorbent material charged within each chamber. In some embodiments, the second sorbent- containing spatial region has an effective BWC of less than about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region has an effective BWC from about 0.5 grams/dl to about 2 grams/dl. In some embodiments, the second sorbent- containing spatial region is from about 0.5, about 0.6, about 0.7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, or about 2.0 grams It has an effective BWC up to /dL. In some embodiments, the second sorbent- containing spatial region has a g-total BWC from about 0.1 grams to less than about 2 grams. In some embodiments, the second sorbent- containing spatial region is about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.5. 7, about 0.8, or about 0.9 to about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about Have a g-total BWC of up to 1.7, about 1.8, or about 1.9 grams.

Evaporative Emission Control System Evaporative emission control canister systems as disclosed herein can be used as a component of an evaporative emission control system for fuel storage. Thus, in yet another aspect, an evaporative emission control system is provided, the evaporative emission control system comprising a first sorbent- containing spatial region contained within a first canister and connecting the first canister to an engine. a fuel vapor inlet conduit for venting the fuel tank to the first canister; and a vent for venting the first canister to the atmosphere and allowing purge air into the first canister. and a second sorbent-containing spatial region including a bleed discharge scrubber as disclosed herein, the second sorbent- containing spatial region being in fluid communication with the first sorbent volume. a bleed exhaust scrubber housed in the first canister or housed in the second canister, the evaporative emission control system causing the fuel vapor to separate the first sorbent- containing spatial region and the second is configured to allow continuous contact with the sorbent- containing spatial region of the . In some embodiments, the evaporative emission control system includes a fuel tank for fuel storage and an internal combustion engine adapted to consume the fuel, the evaporative emission control system receiving from the fuel vapor inlet conduit bounded by a fuel vapor flow path to the first canister to the second sorbent volume and to the vent conduit, and from the vent conduit to the second sorbent- containing spatial region to the first canister; and defined by an inter-air flow path to the fuel vapor purge pipe.

Evaporative emissions from the fuel tank are absorbed by the evaporative emission control system during engine shutdown. Fuel vapor that bleeds from the fuel tank is removed by the sorbent in the canister system, thereby reducing the amount of fuel vapor emitted to the atmosphere. During engine operation, atmospheric air is introduced as a purge stream into the canister system and the bleed exhaust scrubber to desorb hydrocarbons already adsorbed by the hydrocarbon adsorbent and through the purge line for combustion. is recirculated to the engine.

Evaporative emission control canisters of evaporative emission control systems typically include a three-dimensional hollow interior space or chamber defined at least in part by a shaped planar material such as a molded thermoplastic olefin. In some embodiments, a bleed exhaust scrubber is positioned within the first sorbent -containing spatial region of the evaporative emission control canister. In some embodiments, the bleed exhaust scrubber is located in a separate canister in fluid communication with the evaporative emission control canister. The evaporative emission control system of the present invention according to embodiments in which the bleed emission scrubber is located in a separate canister can be more readily understood with reference to FIG. FIG. 2 schematically illustrates an evaporative emission control system 30 according to one embodiment of the invention. Evaporative emission control system 30 includes a fuel tank 38 for fuel storage, an internal combustion engine 32 adapted to consume fuel, an evaporative emission control canister 46 and a bleed emission scrubber 1 . Engine 32 is preferably an internal combustion engine controlled by controller 34 . Engine 32 typically burns gasoline, ethanol, and other volatile hydrocarbon fuels. Controller 34 may be a separate controller or may form part of an engine control module (ECM), powertrain control module (PCM), or any other vehicle controller.

According to an embodiment of the present invention, the evaporative emission control canister 46 includes a first sorbent -containing spatial region (indicated by 48), a fuel vapor purge line 66 connecting the evaporative emission control canister 46 system to the engine 32, a fuel a fuel vapor inlet conduit 42 for venting the tank 38 to the evaporative emission control canister 46, and vent conduits 56, 59 for venting the evaporative emission control canister 46 to atmosphere and allowing purge air into the evaporative emission control canister system; 60 and

The evaporative emission control canister system is provided by a fuel vapor flow path from the fuel vapor inlet conduit 42 through the vent conduit 56 to the first sorbent containing spatial region 48 towards the bleed exhaust scrubber 1 and to the vent conduits 59,60. and through vent conduits 56 to first adsorbent- containing spatial region 48 and to fuel vapor purge pipe 66 to bleed exhaust scrubber 58. , is further defined. The bleed discharge scrubber 1 includes at least a second sorbent- containing spatial region , the second sorbent- containing spatial region adapted for hydrocarbon adsorption as provided and described herein. It contains a coated substrate 2 .

Vaporized hydrocarbon-containing fuel vapor from fuel tank 38 may pass from fuel tank 38 through vapor inlet conduit 42 to first sorbent -containing spatial region 48 within canister 46 . Evaporative emission control canister 46 may be formed from any suitable material. For example, molded thermoplastic polymers such as nylon are typically used.

As the temperature of the gasoline in the fuel tank 38 increases, the fuel vapor pressure increases. Without the evaporative emission control system 30 of the present invention, the fuel vapor would be emitted untreated to the atmosphere. However, according to the present invention, the fuel vapor is treated by the evaporative emission control canister 46 and by the bleed emission scrubber 1 located downstream of the evaporative emission control canister 46 .

When vent valve 62 is open and purge valve 68 is closed, fuel vapor passes under pressure from fuel tank 38 through evaporative vapor inlet conduit 42, canister vapor inlet 50, and into evaporative emission control device 46. It sequentially flows through the contained first adsorbent -containing spatial region 48 . Fuel vapor not adsorbed by the first sorbent -containing spatial region subsequently exits evaporative emission control canister 46 via vent conduit opening 54 and vent conduit 56 . The fuel vapor then enters the bleed exhaust scrubber 1 for further adsorption. After passing through the bleed exhaust scrubber 1, the remaining fuel vapor exits the bleed exhaust scrubber 1 via conduit 59, vent valve 62 and vent conduit 60 and is released to the atmosphere.

Over time, the hydrocarbon adsorbent material contained in both the evaporative emission control canister 46 and the second adsorbent -containing spatial region of the bleed exhaust scrubber 1 becomes loaded with hydrocarbons adsorbed from the fuel vapor. Once the hydrocarbon sorbent is saturated with fuel vapors and thus hydrocarbons, the hydrocarbons must be desorbed from the hydrocarbon sorbent in order to continue to control the exhausted fuel vapors from the fuel tank 38 . During engine operation, engine controller 34 commands valves 62 and 68 to open via signal leads 64 and 70 respectively, thereby creating an air flow path between the atmosphere and engine 32 . By opening the purge valve 68, clean air can be drawn into the bleed exhaust scrubber 1 and subsequently from the atmosphere via vent conduit 60, vent conduit 59 and vent conduit 56 to the evaporative emission control canister 46. . Clean air, or purge air, flows through clean air vent conduit 60, through bleed exhaust scrubber 1, through vent conduit 56, through vent conduit opening 54, and into evaporative emission control canister 46. do. The clean air flows through and/or past the hydrocarbon adsorbents contained within the bleed exhaust scrubber 1 and emission control canisters 46 to desorb hydrocarbons from the saturated hydrocarbon adsorbents within each volume. The purge air and hydrocarbon flow then exits evaporative emission control canister 46 through purge opening outlet 52 , purge line 66 and purge valve 68 . Purge air and hydrocarbons flow through purge line 72 to engine 32 where the hydrocarbons are subsequently combusted.

In some embodiments, the particulate carbon has an n-butane adsorption capacity of at least about 40 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon has an n-butane adsorption capacity of about 40 ml/g to about 80 ml/g at an n-butane pressure of about 3 mmHg. In some embodiments, the particulate carbon is about 40 ml/g, about 45 ml/g, about 50 ml/g, about 55 ml/g, about 60 ml/g, or about 65 ml/g at an n-butane pressure of about 3 mmHg. n-butane adsorption capacity from about 70 ml/g, about 75 ml/g, or about 80 ml/g. In some embodiments, particulate carbon has a BET surface area from about 1300 m ² /g to about 2500 m ² /g. In some embodiments, particulate carbon has a BET surface area from about 1400 m ² /g to about 1600 m ² /g. In some embodiments, particulate carbon has a micropore volume of about 0.20 ml/g to about 0.35 ml/g. In some embodiments, the particulate carbon is about 0.20 ml/g, about 0.21 ml/g, about 0.22 ml/g, about 0.23 ml/g, about 0.24 ml/g, or about 0 from .25 ml/g to about 0.26 ml/g, about 0.27 ml/g, about 0.28 ml/g, about 0.29 ml/g, about 0.30 ml/g, about 0.31 ml/g, about 0 .32 ml/g, about 0.33 ml/g, about 0.34 ml/g, or up to about 0.35 ml/g. In some embodiments, particulate carbon has a mesopore volume of about 0.5 ml/g to about 0.8 ml/g. In some embodiments, the particulate carbon is from about 0.5 ml/g, about 0.55 ml/g, or about 0.60 ml/g to about 0.65 ml/g, about 0.70 ml/g, about It has a mesopore volume of up to 0.75 ml/g, or about 0.8 ml/g. In some embodiments, the particulate carbon has a BET surface area of about 1400 m ² /gram, a micropore volume of about 0.3 ml/g, and a mesopore volume of about 0.7 ml/g. In some embodiments, the particulate carbon has a BET surface area of at least about 1300 m ² /g and (i) greater than 60% butane affinity at 5% butane, (ii) 35% at 0.5% butane. (iii) a micropore volume greater than about 0.2 ml/g; and a mesopore volume greater than about 0.5 ml/g.

In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted helix, ribbon, structured media in extruded form, structured media in wound form, folded form. structure media, pleated structure media, corrugated structure media, infused structure media, bonded structure media, and combinations thereof. In some embodiments, the substrate is a monolith. In some embodiments, the monolith is ceramic. In some embodiments, the substrate is plastic. In some embodiments, the plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester , and polyurethane. In some embodiments, the coating thickness is less than about 500 microns. In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon. In some embodiments the binder is an organic polymer. In some embodiments, the binder is an acrylic/styrene copolymer latex.

In some embodiments, the bleed discharge scrubber is contained in the first canister. In some embodiments, the bleed discharge scrubber is housed in a second canister.

In some embodiments, the second sorbent -containing spatial region within the bleed exhaust scrubber has a useful butane working capacity (BWC) of less than about 3 g/dL and a g-total BWC of less than about 2 grams. In some embodiments, the second sorbent- containing spatial region has a g-total BWC from about 0.2 grams to about 1.999 grams.

In some embodiments, the second sorbent -containing spatial region further comprises a third sorbent- containing spatial region , the third sorbent- containing spatial region having a BWC of at least about 0.05 grams. . In some embodiments, the third sorbent- containing spatial region comprises reticulated polyurethane foam. Figure 3 schematically illustrates a bleed discharge scrubber 1 in which the substrate comprising the second sorbent -containing spatial region is extruded media 2a and the third sorbent-containing spatial region is reticulated polyurethane foam 2b. including a substrate comprising

The second sorbent- containing spatial region (and any additional sorbent- containing spatial regions ) may contain a volumetric diluent. Non-limiting examples of volumetric diluents can include, but are not limited to spacers, inert gaps, foams, fibers, springs, or combinations thereof. Additionally, the evaporative emission control canister system may contain empty volumes anywhere within the system. As used herein, the term "empty volume" refers to a volume that contains no adsorbent. Such volumes may contain any non-adsorbents including, but not limited to, air gaps, foam spacers, screens, or combinations thereof.

In some embodiments, the 2-day diurnal breathing loss (DBL) of the evaporative emission control system is less than about 20 mg under the California Breed Emission Test Protocol (BETP).

In some embodiments, the first sorbent- containing spatial area is about 1.9 to about 3.0 liters and the 2-day diurnal breathing loss (DBL) is with the following test conditions: total canister sorbent material volume in a 1.9 L evaporative emission control canister and a purge volume of 135 bed volumes, or total canister sorbent material volume in a 2.5 L evaporative emission control canister and 80 Less than about 20 mg when tested under test conditions of bed volume purge volume.

In some embodiments, the evaporative emission control system maintains a 2-day DBL of less than about 20 mg under California BETP and the second absorbent volume has a g-total BWC of less than about 2 grams. .

Those skilled in the relevant art will appreciate that suitable modifications and adaptations to the compositions, methods, and uses described herein can be made without departing from the scope of any embodiment or aspect thereof. would be readily apparent. The compositions and methods provided are exemplary and are not intended to limit the scope of the claimed embodiments. All of the various embodiments, aspects and options disclosed herein can be combined in all variations. The scope of compositions, formulations, methods and processes described herein includes all actual or potential combinations of embodiments, aspects, options, examples and preferences herein. be All patents and publications cited in this specification are herein incorporated by reference for their specific teachings as indicated, unless specifically provided otherwise. be

The invention is more fully illustrated by the following examples, which are set forth to illustrate the invention and should not be construed as limiting the invention. Unless otherwise specified, all parts and percentages are by weight and all weight percentages are expressed on a dry basis, i.e. excluding moisture content unless otherwise specified.

Example 1: Preparation of coated monoliths using Carbon 1.
A 1.4% Kelzan CC aqueous solution was prepared one day before use. Water (310 ml) was combined with 21 ml Kelzan CC thickener solution, 0.65 g Surfynol 420 dispersant, and 0.5 g Foammaster NXZ antifoam and the combination was thoroughly mixed. To this mixture, 100 g of a high surface area activated carbon adsorbent (P2-15 from EnerG2 Technologies, Inc., "Carbon 1" in Table 1, embodiment of the invention) was added with stirring. The resulting carbon dispersion was added with stirring to a second vessel containing 40 g of Joncryl 2570 binder (50% solution). Additional Kelzan CC thickener solution was added until the viscosity of the slurry was sufficient for coating purposes.

A 29 x 100 mm size (width x length) cylindrical ceramic monolith substrate (230 cells per square inch) was dipped into the slurry. Excess slurry was removed by cleaning the channel using an air knife operating at 15 psig pressure. The substrate was dried at 110°C for 2 hours. This procedure was repeated until the desired carbon loading was achieved.

The g-total BWC of this sample was measured to be 1.29 g and its effective BWC was determined to be 1.95 g n-butane/dL.

Example 2: Preparation of coated monoliths using carbon 2 (comparative).
A 1.4% Kelzan CC aqueous solution was prepared one day before use. Water (483 ml) was combined with 84.58 g Kelzan CC thickener solution, 1.33 g Surfynol 420 dispersant, and 1.03 g Foammaster NXZ antifoam and the combination was thoroughly mixed. To this mixture, 205.06 g of activated carbon adsorbent (“Carbon 2” in Table 1, comparison) was added with stirring. The resulting carbon dispersion was added with stirring to a second vessel containing 79.93 g of Joncryl 2570 binder (50% solution).

A 29 x 100 mm size (width x length) cylindrical ceramic monolith substrate (230 cells per square inch) was dipped into the slurry. Excess slurry was removed by cleaning the channel using an air knife operating at 15 psig pressure. The substrate was dried at 110°C for 2 hours. This procedure was repeated until the desired carbon loading was achieved.

The g-total BWC of this sample was measured to be 1.28 g and its effective BWC was determined to be 1.94 g n-butane/dL.

Example 3: Preparation of coated monoliths using carbon 3 (comparative).
A 1.4% Kelzan CC aqueous solution was prepared one day before use. Water (475 ml) was combined with 31.4 ml Kelzan CC thickener solution, 0.98 g Surfynol 420 dispersant, and 0.75 g Foammaster NXZ antifoam and the combination was thoroughly mixed. To this mixture, 50 g of activated carbon adsorbent (“Carbon 3” in Table 1, comparison) was added with stirring. 92.6 g of Joncryl FLX5020 binder (50% solution) was added to the carbon dispersion with stirring. 4.9 g of 30% ammonium hydroxide solution was added to the slurry to adjust the pH to 8.5. 100 g of a second activated carbon (“Carbon 1” in Table 1) was added to the slurry with stirring. Water was added as needed until the rheology of the slurry was sufficient for coating purposes.

A 29 x 100 mm size (width x length) cylindrical ceramic monolith substrate (230 cells per square inch) was dipped into the slurry. Excess slurry was removed by cleaning the channel using an air knife operating at 15 psig pressure. The substrate was dried at 110°C for 2 hours. This procedure was repeated until the desired carbon loading was achieved.

The g-total BWC of this sample was measured to be 1.24 and its effective BWC was determined to be 1.88 g of n-butane/dL.

Comparative Examples In the following tests, in addition to Examples 1-3, an Ingevity bleed exhaust trap of size 29 x 100 mm and 230 cells per square inch was tested. The carbon content was determined to be 31.8 wt% by LOI up to 1000°C. The total weight of the monolith was approximately 28 g. This carbon content was used to correct the surface area, pore volume, and butane adsorption capacity measured in the examples below. The surface area and pore volume properties of this comparative carbon are shown in Table 1 (Comparative Example).

The g-total BWC of this sample was measured to be 2.21 g and its effective BWC was determined to be 3.35 g n-butane/L.

Example 4 Surface Area and Pore Size Distribution Measurements Nitrogen pore size distribution and surface area analyzes were performed on Micromeritics TriStar 3000 series instruments. The materials to be tested were degassed in a Micromeritics SmartPrep degasser for a total of 6 hours (2 hours ramp to 300° C., then 4 hour hold at 300° C. under dry nitrogen flow). Nitrogen BET surface areas were determined using five partial pressure points between 0.08 and 0.20. The nitrogen pore size was determined using BJH calculations and 33 desorption points (Figs. 4 and 5).

Example 5 Measurement of Butane Isotherms Butane isotherms were obtained for several adsorbent materials. A butane isotherm measurement measures the amount of adsorption of butane in a sample sorbent material as a function of the partial pressure of butane at constant temperature.

A butane isotherm was collected according to the following procedure. Butane gas was slowly introduced into the evacuated sample to reach equilibrium and the mass adsorbed was measured. Specifically, a sample of the material (approximately 0.1 g) was degassed under vacuum at 120° C. for 960 minutes and the butane isotherm was measured using a 3Flex high resolution high throughput surface characterizer. The adsorption test gas used was butane. A circulating bath of water/ethylene glycol mixture maintained a temperature of 298°K during the analysis. The low pressure dose was 0.5 cc butane gas per gram of sample (cc/g) up to 0.000000100 P/Po and up to 0.001 P/Po at 3.0 cc/g. A 30 second equilibration interval was used up to 0.001 P/Po and a 10 second equilibration interval was used for the remaining isotherms. The comparative example data was divided by the carbon content (31.8%) to obtain the carbon only capacity. Adsorbent materials tested by this procedure are listed in Table 2 below.

Carbons 4, 5, and 6 were used as further comparative examples. Carbon 4 and carbon 5 were commercially available activated carbons marketed for use as canister carbon. These materials were received as extruded pellets and ground into powder with a mortar and pestle prior to testing. Carbon 6 was an extruded honeycomb activated carbon used in evaporation canister scrubber applications. The scrubber was ground into powder with a mortar and pestle prior to testing. The test results were normalized by the carbon content of the scrubber material, which was measured as 31.8% by LOI up to 1000°C.

Butane Isotherm Results The results of butane isotherm measurements for these samples (Carbons 1, 4, 5, and 6; Carbon 6 are referred to as “Comparative” in FIGS. 6A-F) are provided in FIG. 6A. do. Data are plotted in mmHg against absolute pressure of butane. This data defines the absolute partial pressure of butane (i.e., atmospheric pressure) at 760 mg Hg equal to the "butane percentage" of "100% butane" and the butane adsorption versus butane fraction as shown in Figure 6B. Plotting can be correlated with evaporative emission applications. The butane concentration typically used to measure the BWC of evaporative emission control devices (e.g., ASTM D5528, USCAR02) is 50% butane, so the data are plotted up to 50% butane percentage, It represents an important butane fraction for evaporative emission control applications. A plot of the same data normalized with respect to the amount of butane adsorbed by the material as a fraction of the total butane adsorbed at 50% butane is provided as FIG. 6C.

At lower percentages of butane, the relative amount of butane adsorbed by these materials is the hydrocarbon adsorber used to reduce evaporative emissions generated from vehicle air intake systems (AIS) during SHED testing. It is more relevant to certain evaporative emissions applications such as (HCA). An estimated vapor concentration that a typical HCA would encounter during SHED testing is around 5% butane, depending on the size of the air cleaner housing. The vapor concentration encountered by the scrubber during the daytime of the BETP test is on the order of 0.5% butane. Thus, while not wishing to be bound by theory, it is initially relatively steep at low butane proportions up to 5% butane and more flat between butane proportions of 5% butane and 50% butane. A more isothermal shaped material is expected to perform better in these applications.

Figure 6D shows the amount of butane adsorbed by these materials at 50% butane as measured by the butane isotherm. These values were determined by reading the values for each material in Panel B at 50% butane.

Figures 6E and 6F provide the relative amount that these materials adsorb at 5% and 0.5% butane as a fraction of the amount that the material adsorbs at 50% butane. These values were defined as the butane affinity for these materials at butane concentrations of 5% and 0.5% respectively. The butane affinity for each material was determined by reading the values for each material at 5% and 0.5% butane concentrations from Figure 6C. Specifically, the absolute partial pressure of butane, which equals a "butane fraction" of 100%, was set at 760 mgHg (i.e., atmospheric pressure), and then the amount of butane adsorbed versus butane The butane affinity was calculated by plotting the ratio of . The data curves were normalized by plotting the amount of butane adsorbed as a fraction of the amount of butane adsorbed at the 50% butane fraction, as shown in FIG. 6C. Butane affinities at 0.5% butane and 5% butane were then determined from this plot by reading the fraction of butane adsorbed at 50% at these butane concentrations. In other words, the butane affinities of the materials at 5% and 0.5%, respectively, compared to the amount of butane adsorbed by the material at 380 mmHg, as determined by butane isotherm measurements. and the fraction of butane adsorbed at a butane partial pressure of 3.8 mmHg.

Based on the data in FIG. 6D alone, carbon 1 would not be expected to have particularly advantageous performance in AIS and scrubber applications as it has a butane adsorption capacity comparable to or lower than other carbons. . However, as shown in Figures 6E and 6F, butane affinity at both 5% butane and 0.5% butane indicates that this material is superior to other materials used for evaporative emission control. Indicated. The butane affinity at 5% above 60% (indicated by carbon 1 in FIG. 6E) is unique and unexpected when compared to standard evaporative sorbent materials and is expected to improve evaporative emissions capture efficiency. . The butane affinity at 0.5% greater than 35% (indicated by carbon 1 in FIG. 6F) is unique and unexpected when compared to standard evaporative sorbent materials and is expected to improve evaporative emission capture efficiency. be done. Therefore, the utilization of such materials in these applications is expected to provide better evaporation performance than standard sorbents, or comparable performance at lower levels of such materials. Yo.

Example 6 Measurement of Butane Adsorption Capacity A commercial carbon monolith (comparative example) and several coated monoliths (Examples 1-3) were tested in a butane adsorption-desorption setup.

Cylindrical samples of size 29×100 mm were placed in a vertically oriented cylindrical sample cell. The sample cell was filled with a 1:1 butane/ _N2 test gas flow rate of 134 mL/min (10 g/hr butane flow rate) for 45 minutes. The direction of flow was upward from the bottom to the top of the sample cell. The gas composition of the outlet flow from the sample cell was monitored by an FID (Flame Ionization Detector).

After the 45 min butane adsorption step, the sample cell was purged with _N2 at 100 ml/min for 10 min in the same flow direction. The sample was then desorbed in the opposite direction (top to bottom) with an air flow of 10 L/min for 15 minutes. In the next step, the gas composition was switched to a 0.5% butane/ _N2 mixture at 134 ml/min (0.1 grams of butane per hour) and the filling step was repeated. A breakthrough curve was recorded using the FID described above and the signal plotted against the cumulative mass of butane flowing.

The relative effective butane adsorption capacity can be related to the time it takes for butane breakthrough through the sample to occur. Butane breakthrough was defined as the time when the exit concentration of butane from the sample cell reached 25% of the saturation concentration. In this test setup, only Example 1 (using carbon 1) was found to provide similar adsorption capacity to the commercial standard (comparative example) (Figure 7). These results demonstrated the dependence of the butane isotherm on surface area, micropore volume, and shape.

Of the materials tested (Examples 1-3 and Comparative Example), only Example 1 exhibited a breakthrough point equal to or better than the Comparative Example. Without wishing to be bound by theory, this is achieved by a combination of high micropore volume at 0.3-1 nm pore size and high mesopore volume at 1-30 nm pore size. was thought to have been Relevant parameters are summarized in Table 3. The desired combination of high micropore volume, high mesopore volume, and high adsorption capacity at low partial pressures of butane was achieved only with the carbon of Example 1 (Carbon 1). The breakthrough point obtained was the highest for this carbon.

Example 7: BETP Testing of Evaporative Emission Control Canisters with Scrubbers Prepared According to Example 1 BETP Testing on 1.9 L Canisters Two 1.9 L, automotive canisters were subjected to the California Bleed Emission Procedure. Emission Test Procedure (BETP). These canisters contained two separate carbon beds. Both beds in this canister were filled with Ingevity BAX 1500 carbon. The first carbon bed was about twice the capacity of the second carbon bed. The canister also had an internal chamber for a scrubber. Prior to testing, a scrubber prepared according to Example 1 was placed in the scrubber chamber of one canister while the scrubber chamber of the other canister was left empty.

BETP test procedure:
Published Procedure "USCAR Advanced Powertrain Technical Leadership Council: Advanced Evaporative Technical Partnership; USCAR LEVIII/Tier 4 BETP Recommended Procedure Based on P Published Regulations” (5/23/2014) was used. Fill each canister with gasoline fuel vapor (EPA test fuel) and dry nitrogen (1:1 fuel vapor/ _N2 ratio) at a fill rate of 40 g/hr until 2 g of fuel vapor breakthrough is detected; This was followed by a dry air purge of 22.7 L/min at 300 bed volumes. This procedure was repeated for a total of 10 fill/purge cycles. The canister was then filled with butane (1:1 in nitrogen) to 2 g breakthrough and soaked for 1 hour. The canister was then purged with 22.7 L/min of 40% RH air at 25° C. until the canister lost a mass of 76.8 g, corresponding to 135 bed volumes. The canister was then connected to a 14.5 gallon fuel tank filled 40% with CARB Phase III fuel and soaked at 65° F. for 6 hours. The canister purge port was capped and the system was soaked at 65° F. for 12 hours. The system was then cycled from 65° F. to 105° F. with a ramp time of 12 hours for a total of two daytime cycles (48 hours total). The canister outlet was open to an evaporative emissions measurement enclosure to monitor evaporative emissions that escaped the canister. The highest hydrocarbon emissions were reported every 24 hours.

The highest daily daytime emissions were 275 mg for canisters without scrubbers, but only 9 mg for canisters with scrubbers prepared according to Example 1. The second day had the highest shedding in both canisters. This result demonstrated that the scrubber prepared according to Example 1 was capable of passing the carbon automotive canister to the California Breed Emissions Test Procedure (BETP) emission limit of less than 20 mg.

BETP Testing on 2.5 L Canisters 2.5 L canisters for automobiles were tested according to the California Breed Discharge Procedure (BETP). This canister contained two separate carbon beds. Both beds in this canister were filled with Ingevity BAX 1500 carbon. The first carbon bed was about twice the capacity of the second carbon bed. The canister did not have an internal chamber for the scrubber. To include the scrubber in this canister, the scrubber prepared according to Example 1 was placed in a separate housing, attached to the vent side port of the canister with a hose clamp, and leak tested to ensure a tight seal. . The canisters were tested according to the BETP test procedure described above, except that the canisters were purged with 80 bed volumes of air after the butane filling step. The highest daily diurnal release for this canister was 3 mg. The second day had the highest emissions. This result demonstrated that the scrubber prepared according to Example 1 was capable of passing the carbon automotive canister to the California Breed Emissions Test Procedure (BETP) emission limit of less than 20 mg.

Claims (72)

A coated substrate adapted for hydrocarbon adsorption, comprising:
at least one surface and a coating on said at least one surface, said coating comprising particulate carbon and a binder, said particulate carbon having a BET surface area of at least 1 300 m ² /g. and
i. >60% butane affinity at 5% butane,
ii. >35% butane affinity at 0.5% butane;
iii . 0 . micropore volume greater than 2 ml/g and 0.2 ml/g. A coated substrate having a mesopore volume greater than 5 ml/g and at least one of said i, ii and iii . The coated substrate of claim 1, wherein said particulate carbon has an n-butane adsorption capacity of at least 40 ml/g at an n-butane pressure of 3 mmHg. The coated substrate of claim 1, wherein said particulate carbon has an n-butane adsorption capacity of 40ml/g to 80ml /g at an n-butane pressure of 3 mmHg. The particulate carbon is 40 ml/g , 45 ml/g , 50 ml/g , 55 ml/g , 60 ml/g, or 65 ml/g to 70 ml at an n-butane pressure of 3 mmHg. 2. The coated substrate of claim 1, having an n-butane adsorption capacity of up to /g , 75 ml/g, or 80 ml/g. The coated substrate of claim 1 , wherein said particulate carbon has a BET surface area of 1 300 m ² /g to 2 500 m ² /g. The coated substrate of claim 1 , wherein said particulate carbon has a BET surface area of 1 400 m ² /g to 1 600 m ² /g. The particulate carbon is less than 0 . 20 ml/g ~0 . A coated substrate according to any preceding claim, having a micropore volume of 35 ml/g. The particulate carbon is less than 0 . 20 ml/g , 0.20 ml/g. 21 ml/g , 0.21 ml/g. 22 ml/g , 0.22 ml/g. 23 ml/g , 0.23 ml/g. 24 ml/g, or 0.24 ml/g. 25 ml/g to 0.25 ml/g. 26 ml/g , 0.26 ml/g. 27 ml/g , 0.27 ml/g. 28 ml/g , 0.28 ml/g; 29 ml/g , 0.29 ml/g; 30 ml/g , 0.30 ml/g. 31 ml/g , 0.31 ml/g. 32 ml/g , 0.32 ml/g. 33 ml/g ,0 . 34 ml/g, or 0.34 ml/g. A coated substrate according to any preceding claim, having a micropore volume of up to 35 ml/g. The particulate carbon is less than 0 . 5 ml/g ~0 . A coated substrate according to any preceding claim, having a mesopore volume of 8 ml/g. The particulate carbon is less than 0 . 5 ml/g , 0.5 ml/g. 55 ml/g, or 0.55 ml/g. From 60 ml/g to 0.5 ml/g. 65 ml/g, 0.70 ml/g , 0.70 ml/g. 75 ml/g, or 0.75 ml/g. A coated substrate according to any preceding claim, having a mesopore volume of up to 8 ml/g. The particulate carbon has a BET surface area of 1 400 m ² /gram , 0 . 3 ml/g micropore volume, and 0 . A coated substrate according to claim 1, having a mesopore volume of 75 ml/g. The substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted spiral, ribbon, structured media in extruded form, structured media in rolled form, structured media in folded form, pleated form. 2. The coated substrate of claim 1, wherein the coated substrate is selected from the group consisting of: structuring medium in corrugated form, structuring medium in injection form, structuring medium in bonded form, and combinations thereof. The coated substrate of claim 1, wherein said substrate is a monolith. 14. The coated substrate of claim 13, wherein said monolith is ceramic. The coated substrate of claim 1, wherein said substrate is plastic. The group consisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester, and polyurethane. 16. The coated substrate of claim 15, selected from 2. The coated substrate of claim 1 , wherein said coating has a thickness of less than 500 microns. The coated substrate of claim 1, wherein said binder is present in an amount of 10 % to 50 % by weight relative to particulate carbon. A coated substrate according to claim 1, wherein the binder is an organic polymer. A coated substrate according to claim 1, wherein said binder is an acrylic/styrene copolymer latex. A bleed discharge scrubber, said scrubber comprising:
An adsorbent-containing spatial region comprising a coated substrate adapted for hydrocarbon adsorption, said coated substrate comprising at least one surface and a coating on said at least one surface. , said coating comprises particulate carbon and a binder, said particulate carbon having a BET surface area of at least 1 300 m ² /gram; and
i. >60% butane affinity at 5% butane,
ii. >35% butane affinity at 0.5% butane;
iii . 0 . micropore volume greater than 2 ml/g and 0.2 ml/g. A bleed discharge scrubber having a mesopore volume greater than 5 ml/g and at least one of said i, ii and iii . 22. The bleed exhaust scrubber of claim 21, wherein said particulate carbon has an n-butane adsorption capacity of at least 40 ml/g at an n-butane pressure of 3 mmHg. 22. A bleed exhaust scrubber according to claim 21, wherein said particulate carbon has a BET surface area between 1 300 m ² /g and 2 500 m ² /g. The particulate carbon is less than 0 . 20 ml/g ~0 . 22. A bleed discharge scrubber according to claim 21, having a micropore volume of 35 ml/g. The particulate carbon is less than 0 . 5 ml/g ~0 . 22. A bleed discharge scrubber according to claim 21, having a mesopore volume of 8 ml/g. The particulate carbon is less than 0 . 5 ml/g , 0.5 ml/g. 55 ml/g, or 0.55 ml/g. From 60 ml/g to 0.5 ml/g. 65 ml/g , 0.65 ml/g. 70 ml/g , 0.70 ml/g. 75 ml/g, or 0.75 ml/g. 22. A bleed discharge scrubber according to claim 21, having a mesopore volume of up to 8 ml/g. The particulate carbon has a BET surface area of 1 400 m ² /gram , 0 . 3 ml/g micropore volume, and 0 . 22. A bleed discharge scrubber according to claim 21, having a mesopore volume of 75 ml/g. 22. The bleed discharge scrubber of claim 21, wherein said sorbent- containing spatial region has a g-total butane working capacity (BWC) of less than 2 grams. The adsorbent- containing spatial region is 0 . 2 grams to 1 . A bleed discharge scrubber according to any of claims 21, having a g-total BWC of 6 grams. The substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted spiral, ribbon, structured media in extruded form, structured media in rolled form, structured media in folded form, pleated form. 22. The bleed discharge scrubber of claim 21, wherein the bleed discharge scrubber is selected from the group consisting of: structuring media in corrugated form, structuring media in injection form, structuring medium in bonded form, and combinations thereof. 22. A bleed discharge scrubber according to claim 21, wherein said substrate is a monolith. 32. A bleed discharge scrubber according to claim 31, wherein said monolith is ceramic. 32. A bleed discharge scrubber according to claim 31, wherein said substrate is plastic. The group consisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester, and polyurethane. 34. The bleed discharge scrubber of claim 33, selected from: 22. A bleed exhaust scrubber according to claim 21, wherein said coating has a thickness of less than 500 microns. 22. The bleed discharge scrubber of claim 21, wherein said binder is present in an amount of 10% to 50 % by weight relative to said particulate carbon. 22. A bleed discharge scrubber according to claim 21, wherein said binder is an organic polymer. 22. A bleed discharge scrubber according to claim 21, wherein said binder is an acrylic/styrene copolymer latex. An evaporative emission control canister system comprising:
a first sorbent- containing spatial region contained within a first canister; a fuel vapor purge line for connecting said first canister to an engine; and for venting said fuel tank to said first canister. a fuel vapor inlet conduit for venting said first canister to atmosphere and for admitting purge air into said first canister;
a second adsorbent-containing spatial region comprising a bleed discharge scrubber according to any one of claims 21 to 38;
The second sorbent -containing spatial region is in fluid communication with the first sorbent -containing spatial region , and the bleed exhaust scrubber is contained within the first canister or in a second canister. housed within
wherein the evaporative emission control system is configured to allow continuous contact of the first sorbent -containing spatial region and the second sorbent- containing spatial region by the fuel vapor; Control canister system. 40. The evaporative emission control canister system of claim 39, wherein said particulate carbon has an n-butane adsorption capacity of at least 40 ml/g at an n-butane pressure of 3 mmHg. 40. The evaporative emission control canister system of claim 39, wherein said particulate carbon has an n-butane adsorption capacity of 40ml/g to 80ml /g at an n-butane pressure of 3 mmHg. The particulate carbon is 40 ml/g , 45 ml/g , 50 ml/g , 55 ml/g , 60 ml/g, or 65 ml/g to 70 ml at an n-butane pressure of 3 mmHg. 40. The evaporative emission control canister system of claim 39, having an n-butane adsorption capacity of up to /g , 75 ml/g, or 80 ml/g. 40. The evaporative emission control canister system of claim 39, wherein said particulate carbon has a BET surface area of between 1300m2 ^/ g and 2500m2 ^/ g. 40. The evaporative emission control canister system of claim 39, wherein said particulate carbon has a BET surface area between 1400 ^m2 /g and 1600 ^m2 /g. The particulate carbon is less than 0 . 20 ml/g ~0 . 40. The evaporative emission control canister system of claim 39, having a micropore volume of 35 ml/g. The particulate carbon is less than 0 . 20 ml/g , 0.20 ml/g. 21 ml/g , 0.21 ml/g. 22 ml/g , 0.22 ml/g. 23 ml/g , 0.23 ml/g. 24 ml/g, or 0.24 ml/g. 25 ml/g to 0.25 ml/g. 26 ml/g , 0.26 ml/g. 27 ml/g , 0.27 ml/g. 28 ml/g , 0.28 ml/g; 29 ml/g , 0.29 ml/g; 30 ml/g , 0.30 ml/g. 31 ml/g , 0.31 ml/g. 32 ml/g , 0.32 ml/g. 33 ml/g ,0 . 34 ml/g, or 0.34 ml/g. 40. The evaporative emission control canister system of claim 39, having a micropore volume of up to 35 ml/g. The particulate carbon is less than 0 . 5 ml/g ~0 . 40. The evaporative emission control canister system of claim 39, having a mesopore volume of 8 ml/g. The particulate carbon is less than 0 . 5 ml/g , 0.5 ml/g. 55 ml/g, or 0.55 ml/g. From 60 ml/g to 0.5 ml/g. 65 ml/g , 0.65 ml/g. 70 ml/g , 0.70 ml/g. 75 ml/g, or 0.75 ml/g. 40. The evaporative emission control canister system of claim 39, having a mesopore volume of up to 8 ml/g. The particulate carbon has a BET surface area of 1 400 m ² /gram , 0 . 3 ml/g micropore volume, and 0 . 40. The evaporative emission control canister system of claim 39, having a mesopore volume of 7 ml/g. 40. The evaporative emission control canister system of claim 39, wherein said bleed emission scrubber is housed in said first canister. 40. The evaporative emission control canister system of claim 39, wherein said bleed exhaust scrubber is housed in said second canister. 40. The evaporative emission control canister system of claim 39, wherein said second sorbent- containing spatial region has an effective butane working capacity (BWC) of less than 3 g/dL and a g-total BWC of less than 2 grams. . The second adsorbent- containing spatial region is 0 . 2 grams to 1 . 40. The evaporative emission control canister system of claim 39, having a g-total BWC of 999 grams. Said second sorbent- containing spatial region further comprises a third sorbent- containing spatial region , said third sorbent- containing spatial region being at least 0 . 40. The evaporative emission control canister system of claim 39, having 05 grams of g-total BWC. The substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, twisted spiral, ribbon, structured media in extruded form, structured media in rolled form, structured media in folded form, pleated form. 40. The evaporative emission control canister system of claim 39, wherein the evaporative emission control canister system is selected from the group consisting of: structured media in corrugated form, structured media in injected form, structured medium in bonded form, and combinations thereof. 40. The evaporative emission control canister system of claim 39, wherein said substrate is a monolith. 57. The evaporative emission control canister system of claim 56, wherein said monolith is ceramic. 57. The evaporative emission control canister system of claim 56, wherein said substrate is plastic. The group consisting of polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester, and polyurethane. 59. The evaporative emission control canister system of claim 58, selected from: 40. The evaporative emission control canister system of claim 39, wherein said coating has a thickness of less than 500 microns. 40. The evaporative emission control canister system of claim 39, wherein said binder is present in an amount of 10% to 50 % by weight relative to said particulate carbon. 40. The evaporative emission control canister system of claim 39, wherein said binder is an organic polymer. 40. The evaporative emission control canister system of claim 39, wherein said binder is an acrylic/styrene copolymer latex. 55. The evaporative emission control canister system of claim 54, wherein said third sorbent -containing spatial region comprises reticulated polyurethane foam. The first adsorbent- containing spatial region comprises : 1 . 9 to 3 . 0 liters and a 2-day diurnal respiratory loss (DBL) under the California Breed Exhaust Test Protocol (BETP) under the following test conditions:
i. said first adsorbent- containing spatial region has a purge volume of 2.5 L and 80 bed volumes, or ii. 40. The evaporative emission control canister system of claim 39, wherein said first sorbent- containing spatial region is less than 20 mg when tested under test conditions of 1.9 L and a purge volume of 135 bed volumes. a fuel tank for fuel storage;
an internal combustion engine adapted to consume said fuel;
said evaporative emission control canister system defined by a fuel vapor flow path from said fuel vapor inlet conduit to said first canister to said second sorbent- containing spatial region and to said vent conduit; 40. The evaporative emission control canister system of claim 39 defined by a reciprocal air flow path from a vent conduit to said second sorbent- containing spatial region toward said first canister and toward said fuel vapor purge pipe. . 67. The evaporative emission control canister system of claim 66, wherein said bleed exhaust scrubber is housed in said first canister. 67. The evaporative emission control canister system of claim 66, wherein said bleed exhaust scrubber is contained in said second canister. 67. The evaporative emission control canister system of claim 66, wherein said second sorbent- containing spatial region has an effective butane working capacity (BWC) of less than 3 g/dL and a g-total BWC of less than 2 grams. . The second adsorbent- containing spatial region is 0 . 2 grams to 1 . 67. The evaporative emission control canister system of claim 66, having a g-total BWC of 999 grams. Said second sorbent- containing spatial region further comprises a third sorbent- containing spatial region , said third sorbent- containing spatial region being at least 0 . 67. The evaporative emission control canister system of claim 66, having 05 grams of g-total BWC. The first adsorbent- containing spatial region comprises : 1 . 9 to 3 . 0 liters and the 2-day diurnal respiratory loss (DBL) under the California Breed Exhaust Test Protocol (BETP) under the following test conditions:
i. said first adsorbent- containing spatial region has a purge volume of 2.5 L and 80 bed volumes, or ii. 67. The evaporative emission control canister system of claim 66, wherein said first sorbent- containing spatial region is less than 20 mg when tested under test conditions of 1.9 L and a purge volume of 135 bed volumes.