JPWO2019003157A5 - - Google Patents

Description

The present disclosure relates generally to hydrocarbon emission control systems. More particularly, the present disclosure provides substrates coated with hydrocarbon adsorptive coating compositions, evaporative emission control system components, and vaporization methods for controlling evaporative emissions of hydrocarbons from automotive engines and fuel systems. It relates to a gas emission control system.

Evaporative loss of gasoline fuel from the fuel system of automobiles driven by internal combustion engines is a major potential contributor to hydrocarbon air pollution. Using a canister system that uses activated carbon to adsorb fuel vapors emitted from the fuel system limits such evaporative emissions. All vehicles now have a fuel vapor canister containing activated carbon pellets to control evaporative emissions. Many fuel vapor canisters also contain additional control devices to capture fuel vapor exiting the carbon bed during the hot side of the diurnal temperature cycle. Current control devices for such emissions contain exclusively 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 reducing fuel vapor Regenerate the carbon for further adsorption. Exemplary US patents disclosing canister-based evaporative loss control systems include US Pat. Nos. 4,877,001, 4,750,465 and 4,308,841.

With strict regulations on hydrocarbon emissions allowances, there is an increasing demand for control over the amount of hydrocarbon emissions from vehicles, even during periods of non-use. During such periods (i.e., when parked), the vehicle's fuel system may be subjected to a warm environment, which increases the vapor pressure in the fuel tank and consequent potential evaporative loss of fuel to the atmosphere. leads to

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 the residue generally present on the adsorbent when the canister is in a purged or "clean" state, which can result in a reduction of the adsorption capacity of the adsorbent. refers to hydrocarbons. Effluent effluent, on the other hand, refers to effluent from the adsorbent. Efflux can occur, for example, when the equilibrium between adsorption and desorption is more heavily biased towards desorption than adsorption. Such emissions can occur when a vehicle is subjected to diurnal temperature changes over several days, commonly referred to as "all-day storage emissions." Certain regulations make it desirable for these diurnal breathing loss (DBL) emissions from the canister system to be maintained at very low levels. For example, the California Low Emission Vehicle Regulation (LEV-III) of March 22, 2012 requires that canister DBL emissions for 2001 and subsequent model automobiles must comply with the Bleedable Emissions Test Procedure (BETP). not exceed 20 mg based on

Tighter regulations on DBL emissions continue to drive the development of improved evaporative emission control systems, especially for use in reduced purge volume vehicles (ie, hybrid vehicles). Such vehicles can produce otherwise high DBL emissions due to the lower total purge volume and lower purge frequency equating to a higher residual hydrocarbon heel. Therefore, it is desirable to have an evaporative emission control system with low DBL emissions despite low volume and/or infrequent purge cycles.

A method for limiting hydrocarbon emissions under severe DBL conditions by routing fuel vapor through an initial sorbent- containing spatial region and then at least one subsequent sorbent- containing spatial region prior to venting to atmosphere. wherein the initial adsorbent- containing spatial region has a higher adsorption capacity than subsequent adsorbent- containing spatial regions . See US Pat. No. RE38,844.

It also has an initial and at least one subsequent sorbent- containing spatial region , effective butane processing capacity (BWC) of less than 3 g/dL, g total BWC of 2 grams to 6 grams, and applied after a 40 g/hr butane loading step. A high purge efficiency and moderate butane handling capacity evaporative emission control canister system device of 20 mg or less 2-day full-day storage discharge (DBL) discharge with a purge of about 210 liters or less has been previously disclosed. See US Patent Application Publication No. 2015/0275727.

Additional sources of fuel-derived hydrocarbon evaporative emissions include the engine, exhaust gas recirculation (EGR) system and air intake system. Large amounts of volatile hydrocarbons from several sources have been found to accumulate in the intake system of automobile engines after the engine has been shut down. Without evaporative emission capture technology, these hydrocarbons are vented to the atmosphere after the engine is shut down. Accordingly, reduction or elimination of hydrocarbon emissions in intake systems is desirable.

The majority of a vehicle's evaporative emissions are generated during the vehicle's off-cycle as a result of fuel injector leaks, paddle evaporation of residual fuel and blow-by gases from the positive crankcase ventilation (PCV) system. Ejected from the system. Ideally, hydrocarbon emissions are retained by the intake system until the powertrain is used again, where the emissions retention system emits hydrocarbons that are consumed and controlled through the normal emissions control system. be done.

Conventional solutions to control the outflow of hydrocarbon emissions from intake systems include careful shaping of ducting and filter boxes, incorporation of carbon adsorbents and filters into the intake system.

U.S. Pat. No. 4,877,001 U.S. Pat. No. 4,750,465 U.S. Pat. No. 4,308,841 U.S. Patent No. RE38,844 U.S. Patent Application Publication No. 2015/0275727

The challenges for creating a hydrocarbon emissions adsorption system for adsorption of emissions accumulated in the intake system are to minimize impact on intake air regulation, add little excess mass to the system, and still be suitable for a particular application. It is to provide sufficient adsorption capacity. Moreover, notwithstanding the previously disclosed devices for capturing evaporative hydrocarbon emissions from fuel systems, the required space and mass are reduced while reducing the amount of potential evaporative emissions under various conditions. A need exists for a highly efficient evaporative emission control system that further reduces emissions.

A coating substrate adapted for hydrocarbon adsorption, an air intake system configured to control evaporative emission and an evaporative emission control system are provided. The disclosed coated substrates, components and systems are useful in controlling evaporative hydrocarbon emissions and can provide low day storage emissions (DBL) emissions even under low purge conditions. The provided coating substrates remove evaporative emissions produced in internal combustion engines and/or associated fuel source components before the emissions can be released into the atmosphere.

In one aspect, a coated substrate adapted for hydrocarbon adsorption comprises a substrate comprising at least one surface having a hydrocarbon adsorbent coating thereon, the hydrocarbon adsorbent coating comprising particulate A coating substrate is provided comprising carbon and a binder, wherein the particulate carbon has a BET surface area of at least about 1400 m ² /g. The particulate carbon was equilibrated at room temperature, exposed to a 5% n-butane flow in 100 ml/min nitrogen for 20 min, purged with a 100 ml/min nitrogen flow for 25 min, and again 5% in 100 ml/min nitrogen. It has a second cycle n-butane adsorption capacity of at least about 9 wt% n-butane after exposure to % n-butane flow for 20 minutes.

In one embodiment, the particulate carbon has a BET surface area of at least about 1600 m ² /g. In one embodiment, the particulate carbon has a BET surface area of from about 1400 m ² /g to about 2500 m ² /g. In some embodiments, the particulate carbon has a BET surface area of about 1600 m ² /g to about 2500 m ² /g.

In some embodiments, the particulate carbon has a second cycle n-butane adsorption capacity of at least about 12 wt% n-butane. In some embodiments, the particulate carbon has a second cycle n-butane adsorption capacity of about 9 wt% to about 15 wt%.

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 selected from the group consisting of acrylic/styrene copolymer latexes, styrene-butadiene copolymer latexes, polyurethanes and mixtures thereof.

In one embodiment, 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, Selected from the group consisting of polyesters and polyurethanes. In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, helical coil, ribbon, structured media in extruded form, structured media in wound form, structured media in folded form, pleated is selected from the group consisting of structuring media in morphology, structuring media in corrugated morphology, structuring media in infusion morphology, structuring media in bonding morphology and combinations thereof;

In one embodiment, 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. Many such foams of varying porosity are commercially available from multiple sources and are well known in the art. Such foams can be made, for example, according to methods such as those described in U.S. Pat. Nos. 3,171,820 to Volz and 4,259,452 to Yukuta et al. both of which are incorporated herein by reference for their teachings of reticulated polyurethane foams.

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

In another aspect, an air intake system configured to control evaporative emissions from a motor vehicle having a combustion engine includes an air intake duct, an air filter chamber positioned to receive air from the air intake duct, and an air filter chamber positioned to receive air from the air intake duct. A system is provided that includes one or more clean air ducts in fluid communication with the air filter chamber and the combustion engine for transporting air from the filter chamber to the combustion engine. At least a portion of an inner surface of at least one of the intake duct, the air filter chamber and the clean air duct is in contact with a substrate that includes or is coated with a hydrocarbon adsorbent coating. , whereby the hydrocarbon adsorbent coating is brought into fluid contact with the path for entry of combustion air into the combustion engine of the vehicle. The hydrocarbon sorbent coating comprises particulate carbon and a binder, the particulate carbon having a BET surface area of at least about 1400 m ² /gram, the particulate carbon equilibrated at room temperature and containing 100 ml/min of nitrogen. After exposure to 5% n-butane in medium flow for 20 minutes, purged with 100 ml/min nitrogen flow for 25 minutes, and again exposed to 5% n-butane in 100 ml/min nitrogen flow for 20 minutes, at least about 9 It has a second cycle n-butane adsorption capacity of wt % n-butane. During the off-cycle of the engine, evaporative emissions that may escape the engine through the intake system to the atmosphere are adsorbed by the hydrocarbon adsorbent, thereby reducing evaporative emissions. During engine operation, atmospheric air is introduced into the air intake system and hydrocarbons already adsorbed by the hydrocarbon adsorbent are desorbed and circulated back to the engine for combustion through the air filter outlet duct.

In one embodiment, the particulate carbon has a BET surface area of at least about 1600 m ² /g. In one embodiment, the particulate carbon has a BET surface area of from about 1400 m ² /g to about 2500 m ² /g. In some embodiments, the particulate carbon has a BET surface area of about 1600 m ² /g to about 2500 m ² /g.

In some embodiments, the particulate carbon has a second cycle n-butane adsorption capacity of at least about 12 wt% n-butane. In some embodiments, the particulate carbon has a second cycle n-butane adsorption capacity of about 9 wt% to about 15 wt%.

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 selected from the group consisting of acrylic/styrene copolymer latexes, styrene-butadiene copolymer latexes, polyurethanes and mixtures thereof.

In one embodiment, 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, Selected from the group consisting of polyesters and polyurethanes.

In some embodiments, the thickness of the hydrocarbon sorbent coating on the substrate is less than about 500 microns.

In one embodiment, said portion of the inner surface of said air filter chamber is coated with a hydrocarbon adsorbent coating.

In other embodiments, the substrate is foam, monolithic material, nonwoven, fabric, sheet, paper, helical coil, ribbon, structured media in extruded form, structured media in wound form, structured media in folded form, pleated is selected from the group consisting of morphological structuring media, corrugated morphological structuring media, injection morphological structuring media, bonded structuring media, and combinations thereof.

In one embodiment, the substrate is a bonded nonwoven. In some embodiments, the bonded nonwoven is bonded to said portion of the inner surface of the air filter chamber.

In yet another aspect, an evaporative emission control system is provided that includes a fuel tank for fuel storage, an internal combustion engine adapted to consume the fuel, and an evaporative emission control canister system. The canister system includes an evaporative emission control canister and an effluent scrubber. The evaporative emission control canister includes a first sorbent- containing spatial region , a fuel vapor purge tube connecting the evaporative emission control canister to the engine, a fuel vapor inlet tube for venting the evaporative emission control canister from the fuel tank, and A vent tube is included for venting the evaporative emission control canister to atmosphere and for allowing purge air to enter the evaporative emission control canister system. The evaporative emission control canister system is routed from the fuel vapor inlet tube to the first sorbent- containing spatial region , by the fuel vapor flow path to the effluent scrubber to the vent tube, and from the vent tube to the effluent scrubber. , toward the first sorbent- containing spatial region and toward the fuel vapor purge tube. The effluent effluent scrubber includes at least a second sorbent- containing spatial region , the second sorbent- containing spatial region including a coating substrate adapted for hydrocarbon adsorption, the coating substrate comprising at least One side and a hydrocarbon sorbent coating on at least one side, the hydrocarbon sorbent coating comprising particulate carbon and a binder. Particulate carbon has a BET surface area of at least about 1400 m ² /gram. The particulate carbon was equilibrated at room temperature, exposed to a 5% n-butane flow in 100 ml/min nitrogen for 20 min, purged with a 100 ml/min nitrogen flow for 25 min, and again 5% in 100 ml/min nitrogen. It has a second cycle n-butane adsorption capacity of at least about 9 wt% n-butane after exposure to % n-butane flow for 20 minutes.

Fuel vapor exiting the fuel tank is removed by the sorbent in the canister system, thereby reducing the amount of fuel vapor released to the atmosphere. At the time of engine operation, atmospheric air is introduced into the canister system as a purge stream to desorb hydrocarbons already adsorbed by the hydrocarbon adsorbent and recirculated through the purge line to the engine for combustion.

In one embodiment, the particulate carbon has a BET surface area of at least about 1600 m ² /g. In one embodiment, the particulate carbon has a BET surface area of from about 1400 m ² /g to about 2500 m ² /g. In some embodiments, the particulate carbon has a BET surface area of about 1600 m ² /g to about 2500 m ² /g.

In some embodiments, the particulate carbon has a second cycle n-butane adsorption capacity of at least about 12 wt% n-butane. In some embodiments, the particulate carbon has a second cycle n-butane adsorption capacity of about 9 wt% to about 15 wt%.

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 selected from the group consisting of acrylic/styrene copolymer latexes, styrene-butadiene copolymer latexes, polyurethanes and mixtures thereof.

In one embodiment, 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, Selected from the group consisting of polyesters and polyurethanes.

In some embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, helical coil, ribbon, structured media in extruded form, structured media in wound form, structured media in folded form, pleated is selected from the group consisting of structuring media in morphology, structuring media in corrugated morphology, structuring media in infusion morphology, structuring media in bonding morphology and combinations thereof;

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 one embodiment, 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 one embodiment, the foam is polyurethane. In some embodiments, the foam is reticulated polyurethane. In some embodiments, polyurethanes are polyethers or polyesters.

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

In some embodiments, the second sorbent- containing spatial region of the evaporative emission control system is 390 1.6 L bed volume purges when subjected to a butane breakthrough test in a 29 x 100 mm sorbent- containing spatial region . It has a third cycle butane breakthrough time at a purge volume of less than 100 1.6 L bed volume that is within about 10% of the third cycle butane breakthrough time by volume. Third cycle butane breakthrough is the time (in seconds) at which the outlet concentration of butane from the adsorbent- containing spatial region reaches 100 ppm as measured by flame ionization detection during the third loading step of the butane breakthrough test. The butane breakthrough test was performed by placing the test sorbent- containing spatial region in the sample cell, filling the sample cell with a 1:1 butane/ _N2 gas mixture in an upward flow direction from the bottom to the top of the sample cell at 134 mL/ml. (10 g/h butane flow) for 45 min, purging the sample cell with _N2 for 10 min at 100 mL/min in the same flow direction, and rotating the sample cell in the opposite direction (top to bottom). ) at an air flow of 25 L/min for a time sufficient to reach the desired number of 1.6 L bed volumes, and the steps of loading, purging, and desorbing were repeated for 3 loading/purge/desorption cycles. includes repeating until the

In some embodiments, the second sorbent- containing spatial region of the evaporative emission control system is 390 1.6 L bed volume purges when subjected to a butane breakthrough test in a 29 x 100 mm sorbent- containing spatial region . It has a third cycle butane breakthrough time at a purge volume of less than 80 1.6 L bed volume that is within about 10% of the third cycle butane breakthrough time by volume. In some embodiments, the second sorbent- containing spatial region of the evaporative emission control system is 390 1.6 L bed volume purges when subjected to a butane breakthrough test in a 29 x 100 mm sorbent- containing spatial region . It has a third cycle butane breakthrough time at a purge volume of less than 60 1.6 L bed volume that is within about 10% of the third cycle butane breakthrough time by volume. In some embodiments, the second sorbent- containing spatial region of the evaporative emission control system is 390 1.6 L bed volume purges when subjected to a butane breakthrough test in a 29 x 100 mm sorbent- containing spatial region . It has a third cycle butane breakthrough time at a purge volume of less than 40 1.6 L bed volume that is within about 10% of the third cycle butane breakthrough time by volume. In some embodiments, the second sorbent- containing spatial region of the evaporative emission control system has a 100 1 It has a third cycle butane breakthrough time at a purge volume of less than 0.6 L bed volume.

In some embodiments, the effluent effluent scrubber further comprises a third sorbent- containing spatial region , the second sorbent- containing spatial region being a monolith substrate, the third sorbent- containing spatial region comprising It is a reticulated polyurethane foam.

In some embodiments, the evaporative emission control system has a two-day all-day storage emission (DBL) of less than about 20 mg under the California Bleed Emission Test Procedure (BETP).

The invention includes, without limitation, the following embodiments.

Embodiment 1: A coated substrate adapted for hydrocarbon adsorption, comprising a substrate comprising at least one surface having a hydrocarbon adsorbent coating thereon, wherein the hydrocarbon adsorbent coating is particulate Comprising carbon and a binder, the particulate carbon having a BET surface area of at least about 1400 m ² /g, the particulate carbon being equilibrated at room temperature and subjected to a 5% n-butane flow in nitrogen of 100 ml/min. 100 ml/min nitrogen flow for 25 min, again exposed to 5% n-butane in 100 ml/min nitrogen flow for 20 min, followed by a second cycle of at least about 9 wt% n-butane. A coated substrate having n-butane adsorption capacity.

Embodiment 2: The coating substrate of the preceding embodiments, wherein the particulate carbon has a BET surface area of at least about 1600 m ² /g.

Embodiment 3: The coating substrate of any preceding embodiment, wherein the particulate carbon has a BET surface area of from about 1400 m ² /g to about 2500 m ² /g.

Embodiment 4: The coating substrate of any preceding embodiment, wherein the particulate carbon has a BET surface area of from about 1600 m ² /g to about 2500 m ² /g.

Embodiment 5: The coating substrate of any preceding embodiment, wherein the particulate carbon has a second cycle n-butane adsorption capacity of at least about 12 wt% n-butane.

Embodiment 6: The coating substrate of any preceding embodiment, wherein the particulate carbon has a second cycle n-butane adsorption capacity of from about 9 wt% to about 15 wt%.

Embodiment 7: The coating substrate of any preceding embodiment, wherein the binder is present in an amount of about 10% to about 50% by weight relative to the particulate carbon.

Embodiment 8: The coating substrate of any preceding embodiment, wherein the binder is an organic polymer.

Embodiment 9: The coating substrate of any preceding embodiment, wherein the binder is selected from the group consisting of acrylic/styrene copolymer latexes, styrene-butadiene copolymer latexes, polyurethanes and mixtures thereof.

Embodiment 10: The coated substrate of any preceding embodiment, wherein the substrate is plastic.

Embodiment 11: The plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester and polyurethane The coating substrate of any preceding embodiment selected from the group consisting of:

Embodiment 12: The substrate is foam, monolithic material, nonwoven fabric, fabric, sheet, paper, spiral coil, ribbon, structured media in extruded form, structured media in wound form, structured media in folded form, or in pleated form. The coating substrate of any preceding embodiment selected from the group consisting of structured media, corrugated structured media, injected structured structured media, bonded structured structured media, and combinations thereof.

Embodiment 13: The coated substrate of any preceding embodiment, wherein the substrate is an extrusion medium.

Embodiment 14: The coated substrate of any preceding embodiment, wherein the extrusion medium is a honeycomb.

Embodiment 15: The coating substrate of any preceding embodiment, wherein the substrate is a foam.

Embodiment 16: The coating substrate of any preceding embodiment, wherein the foam has greater than about 10 pores per inch.

Embodiment 17: The coating substrate of any preceding embodiment, wherein the foam has greater than about 20 pores per inch.

Embodiment 18: The coating substrate of any preceding embodiment, wherein the foam has from about 15 to about 40 pores per inch.

Embodiment 19: The coating substrate of any preceding embodiment, wherein the foam is reticulated polyurethane.

Embodiment 20: The coated substrate of any preceding embodiment, wherein the coating thickness is less than about 500 microns.

Embodiment 21: The coated substrate of any preceding embodiment, wherein the substrate is a nonwoven.

Embodiment 22: An intake system configured to control evaporative emissions from a motor vehicle having a combustion engine, said system comprising an intake duct, an air cleaner positioned to receive air from the intake duct. a housing and one or more clean air ducts in fluid communication with the air cleaner housing and the combustion engine for transporting air from the air filter chamber to the combustion engine, said intake duct, said air cleaner housing and At least a portion of an inner surface of at least one of said clean air ducts is in contact with a substrate comprising or coated with a hydrocarbon sorbent coating, whereby the hydrocarbon sorbent coating is in fluid contact with a path for entry of combustion air into said combustion engine of said motor vehicle, said hydrocarbon adsorbent coating comprising particulate carbon and a binder, said particulate carbon comprising at least about 1400 m ² /gram of BET surface area, the particulate carbon was equilibrated at room temperature, exposed to a 5% n-butane in nitrogen flow of 100 ml/min for 20 minutes, and purged with a nitrogen flow of 100 ml/min for 25 minutes. , again having a second cycle n-butane adsorption capacity of at least about 9 wt.

Embodiment 23: The air intake system of any previous embodiment, wherein the particulate carbon has a BET surface area of at least about 1600 m ² /g.

Embodiment 24: The intake system of any preceding embodiment, wherein the particulate carbon has a BET surface area of from about 1400 m ² /g to about 2500 m ² /g.

Embodiment 25: The intake system of any preceding embodiment, wherein the particulate carbon has a BET surface area of from about 1600 m ² /g to about 2500 m ² /g.

Embodiment 26: The intake system of any preceding embodiment, wherein the particulate carbon has a second cycle n-butane adsorption capacity of at least about 12 wt% n-butane.

Embodiment 27: The air intake system of any preceding embodiment, wherein the particulate carbon has a second cycle n-butane adsorption capacity of from about 9 wt% to about 15 wt%.

Embodiment 28: The intake system of any preceding embodiment, wherein the binder is present in an amount of about 10% to about 50% by weight relative to the particulate carbon.

Embodiment 29: The intake system of any preceding embodiment, wherein the binder is an organic polymer.

Embodiment 30: The air intake system of any preceding embodiment, wherein the binder is selected from the group consisting of acrylic/styrene copolymer latexes, styrene-butadiene copolymer latexes, polyurethanes and mixtures thereof.

Embodiment 31: The air intake system of any preceding embodiment, wherein the base material is plastic.

Embodiment 32: The plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester and polyurethane The intake system of any preceding embodiment selected from the group consisting of:

Embodiment 33: The intake system of any preceding embodiment wherein the hydrocarbon sorbent coating thickness is less than about 500 microns.

Embodiment 34: 34. The intake system of any preceding embodiment, wherein said portion of the inner surface of said air filter chamber is coated with a hydrocarbon adsorbent coating.

Embodiment 35: The substrate is foam, monolithic material, nonwoven fabric, fabric, sheet, paper, spiral coil, ribbon, structured media in extruded form, structured media in wound form, structured media in folded form, or in pleated form. The intake system of any preceding embodiment selected from the group consisting of structural media, corrugated structural media, injected structural media, bonded structural media, and combinations thereof.

Embodiment 36: The air intake system of any preceding embodiment, wherein the substrate is a bonded nonwoven.

Embodiment 37: The air intake system of any preceding embodiment, wherein an adhesive nonwoven is adhered to said portion of the inner surface of the air filter chamber.

Embodiment 38: An evaporative emission control system comprising a fuel tank for fuel storage, an internal combustion engine adapted to consume the fuel, and an evaporative emission control canister system, wherein the canister system comprises the evaporative emission control canister and an effluent emission scrubber, the evaporative emission control canister having a first sorbent- containing spatial region , a fuel vapor purge tube connecting the evaporative emission control canister to the engine, and venting from the fuel tank to the evaporative emission control canister. and a vent tube for venting the evaporative emission control canister to atmosphere and for allowing purge air to enter the evaporative emission control canister system;
An evaporative emission control canister system is routed from the fuel vapor inlet tube to the first sorbent- containing spatial region , by a fuel vapor flow path to the effluent scrubber to the vent tube, and from the vent tube to the effluent scrubber. , a reciprocal airflow path toward the first sorbent- containing spatial region and toward the fuel vapor purge tube, the effluent scrubber including at least a second sorbent- containing region of space , the second sorbent- containing region of The spatial region comprises a coated substrate adapted for hydrocarbon adsorption, the coated substrate comprising at least one surface and a hydrocarbon adsorbent coating on the at least one surface, the hydrocarbon adsorbent coating comprising: comprising particulate carbon and a binder, the particulate carbon having a BET surface area of at least about 1400 m ² /gram, the particulate carbon equilibrated at room temperature and a 5% n-butane flow in nitrogen of 100 ml/min. for 20 minutes, purged with a nitrogen flow of 100 ml/min for 25 minutes, and again exposed to a 5% n-butane in 100 ml/min nitrogen flow for 20 minutes, followed by a second An evaporative emission control system having a two-cycle n-butane adsorption capacity.

Embodiment 39: The evaporative emission control system of any preceding embodiment, wherein the particulate carbon has a BET surface area of at least about 1600 m ² /g.

Embodiment 40: The evaporative emission control system of any preceding embodiment, wherein the particulate carbon has a BET surface area of from about 1400 m ² /g to about 2500 m ² /g.

Embodiment 41: The evaporative emission control system of any preceding embodiment, wherein the particulate carbon has a BET surface area of from about 1600 m ² /g to about 2500 m ² /g.

Embodiment 42: The evaporative emission control system of any preceding embodiment, wherein the particulate carbon has a second cycle n-butane adsorption capacity of at least about 12 wt% n-butane.

Embodiment 43: The evaporative emission control system of any preceding embodiment, wherein the particulate carbon has a second cycle n-butane adsorption capacity of from about 9 wt% to about 15 wt%.

Embodiment 44: The evaporative emission control system of any preceding embodiment, wherein the binder is present in an amount of about 10% to about 50% by weight relative to the particulate carbon.

Embodiment 45: The evaporative emission control system of any preceding embodiment, wherein the binder is an organic polymer.

Embodiment 46: The evaporative emission control system of Claim 38, wherein the binder is selected from the group consisting of acrylic/styrene copolymer latexes, styrene-butadiene copolymer latexes, polyurethanes and mixtures thereof.

Embodiment 47: The evaporative emission control system of any preceding embodiment, wherein the substrate is plastic.

Embodiment 48: The plastic is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride, polyester and polyurethane The evaporative emission control system of any preceding embodiment selected from the group consisting of:

Embodiment 49: The substrate is foam, monolithic material, nonwoven fabric, fabric, sheet, paper, spiral coil, ribbon, structured media in extruded form, structured media in wound form, structured media in folded form, or in pleated form. The evaporative emission control system of any preceding embodiment selected from the group consisting of structured media, corrugated structured media, injected structured structured media, bonded structured structured media, and combinations thereof.

Embodiment 50: The evaporative emission control system of any preceding embodiment, wherein the substrate is extrusion media.

Embodiment 51: The evaporative emission control system of any preceding embodiment, wherein the extrusion media is a honeycomb.

Embodiment 52: The evaporative emission control system of any preceding embodiment, wherein the substrate is a foam.

Embodiment 53: The evaporative emission control system of any preceding embodiment, wherein the foam has greater than about 10 pores per inch.

Embodiment 54: The evaporative emission control system of any preceding embodiment, wherein the foam has greater than about 20 pores per inch.

Embodiment 55: The evaporative emission control system of any preceding embodiment, wherein the foam has from about 15 to about 40 pores per inch.

Embodiment 56: The evaporative emission control system of any preceding embodiment, wherein the foam is reticulated polyurethane.

Embodiment 57: The evaporative emission control system of any preceding embodiment, wherein the coating thickness is less than about 500 microns.

Embodiment 58: 3rd cycle butane breakthrough at a purge volume of 390 1.6 L bed volume when the second sorbent- containing spatial area is subjected to a butane breakthrough test with a 29 x 100 mm sorbent- containing spatial area With a third cycle butane breakthrough time at a purge volume of less than 100 1.6 L bed volume that is within about 10% of the time, the third cycle butane breakthrough exiting the butane from the adsorbent- containing spatial region The time (in seconds) when the concentration reaches 100 ppm as measured by flame ionization detection during the third loading step of the butane breakthrough test, which places the test adsorbent- containing spatial region in the sample cell. loading the sample cell with a 1:1 butane/ _N2 gas mixture in an upward flow direction from the bottom to the top of the sample cell at a flow rate of 134 mL/min (10 g/h butane flow) for 45 min; Purge the sample cell with _N2 for 10 min at 100 mL/min in the same flow direction, then purging the sample cell in the opposite direction (top to bottom) to the desired number of 1.6 L bed volumes with 25 L/min air flow. and repeating the steps of loading, purging, and desorbing until three loading/purge/desorption cycles are completed. Any evaporative emission control system.

Embodiment 59: 3rd cycle butane breakthrough at a purge volume of 390 1.6 L bed volume when the second sorbent- containing spatial area is subjected to butane breakthrough test with 29 x 100 mm sorbent- containing spatial area The evaporative emission control system of any preceding embodiment having a third cycle butane breakthrough time at a purge volume of less than 80 1.6 L bed volume that is within about 10% of the time.

Embodiment 60: 3rd cycle butane breakthrough at a purge volume of 390 1.6 L bed volume when the second sorbent- containing spatial area is subjected to a butane breakthrough test with a 29 x 100 mm sorbent- containing spatial area The evaporative emission control system of any preceding embodiment having a third cycle butane breakthrough time at a purge volume of less than 60 1.6 L bed volume that is within about 10% of the time.

Embodiment 61: 3rd cycle butane breakthrough at a purge volume of 390 1.6 L bed volume when the second sorbent- containing spatial area is subjected to butane breakthrough test with 29 x 100 mm sorbent- containing spatial area The evaporative emission control system of any preceding embodiment having a third cycle butane breakthrough time at a purge volume of less than 40 1.6 L bed volume that is within about 10% of the time.

Embodiment 62: When the second sorbent- containing spatial region is subjected to a butane breakthrough test with a 29 x 100 mm sorbent- containing spatial region , at a purge volume of less than 100 1.6 L bed volumes for at least about 800 seconds. The evaporative emission control system of any preceding embodiment having a third cycle butane breakthrough time of .

Embodiment 63: The effluent effluent scrubber further comprises a third sorbent- containing spatial region , wherein the second sorbent- containing spatial region is a monolith substrate, and the third sorbent- containing spatial region is a reticulated polyurethane The evaporative emission control system of any preceding embodiment, which is a foam.

Embodiment 64: The evaporative emission control system of any preceding embodiment, wherein the 2-day full storage emissions (DBL) of the system is less than about 20 mg under the California Effluent Emissions Test Procedure (BETP).

These and other features, aspects and advantages of the present disclosure will become apparent from a reading of the following detailed description in conjunction with the accompanying drawings briefly described below. The invention encompasses any combination of two, three, four or more of the above-described embodiments, and whether such features or elements are expressly combined in the descriptions of specific embodiments herein. including any combination of two, three, four or more features or elements shown in this disclosure. The present disclosure, in any of its various aspects and embodiments, contemplates that any separable feature or element of the disclosed invention can be combined unless the context clearly dictates otherwise. Intended to be read holistically as it should be regarded as intended.

The above aspects, embodiments and other features of the present disclosure are explained in the following description in conjunction with the drawings attached hereto.

1 is a schematic diagram of an intake system of an internal combustion engine; FIG. 1 is a schematic diagram of a fuel system including an evaporative emission control system including an evaporative emission control canister system provided in accordance with one embodiment; FIG. 1 is a cross-sectional view of an efflux scrubber provided in accordance with one embodiment; FIG. 1 is a cross-sectional view of an efflux scrubber provided in accordance with one embodiment; FIG. 1 is a cross-sectional view of an efflux scrubber provided in accordance with one embodiment; FIG. 1 is a cross-sectional view of an efflux scrubber provided in accordance with one embodiment; FIG.

The articles "a" and "an" are used herein to refer to one or more than one (i.e., at least one) of the grammatical objects of the article. used. By way of example, "an element" means at least one element and may include more than one element.

"About" is flexible to the extreme values of a numerical range by stating that a given value can be "slightly above" or "slightly below" the extreme value without affecting the desired result. used to bring about sexuality.

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.

As used herein, the term "adsorbent" refers to an adsorbent or adsorbent containing material along the vapor flow path, such as a bed of particulate material, monolith, honeycomb, sheet or other material. can consist of

I. Coated Substrate for Hydrocarbon Adsorption In one aspect, a coated substrate adapted for hydrocarbon adsorption comprises a substrate comprising at least one surface having a coating thereon, wherein the coating is particulate. A coating substrate is provided that includes carbon and a binder. The particulate carbon has a BET surface area of at least about 1400 m ² /g and a second cycle n-butane adsorption capacity of at least about 9 wt% n-butane. "Second cycle n-butane adsorption capacity" is the exposure of a particulate carbon, coated substrate or article to a flow of 5% n-butane in nitrogen at 100 ml/min for 20 minutes to obtain a stable mass; The substrate or article is purged with a 100 ml/min nitrogen flow for 25 minutes, and again the particulate carbon, the coated substrate or article is exposed to a 100 ml/min 5% n-butane in nitrogen flow for 20 minutes, and the particulate carbon , means grams of butane adsorbed per gram of carbon, expressed as a mass %, as determined by weighing the coated substrate or article to obtain the mass of butane adsorbed.

Particulate carbon is activated carbon, which is highly porous carbon having 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. In one embodiment, the particulate carbon has a BET surface area of at least about 1600 m ² /g. In one embodiment, the particulate carbon has a BET surface area of from about 1400 m ² /g to about 2500 m ² /g. In some embodiments, the particulate carbon has a BET surface area of about 1600 m ² /g to about 2500 m ² /g. As used herein, the term "BET surface area" has its ordinary meaning referring 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 a second cycle n-butane adsorption capacity of at least about 12 wt% n-butane. In some embodiments, the particulate carbon has a second cycle n-butane adsorption capacity of about 9 wt% to about 15 wt%.

As used herein, the term "substrate" refers to the material upon which the adsorbent, typically in the form of a washcoat, is disposed. Washcoating involves preparing a slurry containing a specific solids content (eg, 10-50% by weight) of adsorbent in a liquid, which is then coated onto a substrate and dried to form a washcoat layer. is formed by providing As used herein, the term "washcoat" has its ordinary meaning in the art of a thin, adherent coating of material applied to a substrate material. In some embodiments, the coating thickness of the dry washcoat layer is less than about 500 microns.

In some embodiments, the substrate is part of an air introduction system configured to control evaporative emissions from a motor vehicle having a combustion engine, a component of an evaporative emissions control system, or both. In some embodiments, the substrate is plastic. In some embodiments, the substrate is polypropylene, nylon-6, nylon-6,6, aromatic nylon, polysulfone, polyethersulfone, polybutylene terephthalate, polyphthalamide, polyoxymethylene, polycarbonate, polyvinyl chloride , polyesters and polyurethanes.

In one or more embodiments, the substrate is a foam, monolithic material, nonwoven, fabric, sheet, paper, helical coil, ribbon, structured media in extruded form, structured media in wound form, structured media in folded form. , a pleated form of structural medium, a corrugated form of structural medium, an injection form of structural medium, a bonded form of structural medium and combinations thereof.

As used herein, the term "monolithic substrate" refers to fine parallel gas particles extending from the inlet or outlet face of the substrate therethrough such that the passageways are open to fluid flow therethrough. It is a type of substrate that has channels. The passageway, which can be an essentially straight path from its fluid inlet to its fluid outlet, or which can be a patterned path (e.g., zigzag, herringbone pattern, etc.), is coated with the sorbent material as a washcoat, resulting in a passageway is defined by a wall through which the gas flowing through contacts the adsorbent. The channels of the monolithic substrate are thin-walled channels that can be of any suitable cross-sectional shape and size, such as trapezoidal, rectangular, square, sinusoidal, hexagonal, elliptical, circular, and the like. Such structures may contain from about 60 to about 900 or more gas inlet openings (ie, cells) per square inch of cross-sectional area. Monolithic substrates can be, for example, metals, ceramics, plastics, papers, impregnated papers, and the like.

In one embodiment, the substrate is an extrusion medium. In some embodiments, the extrusion media are honeycombs. Honeycombs can be of any geometry including, but not limited to, circles, cylinders or squares. Furthermore, the cells of the honeycomb substrate can be of any geometry. Uniform cross-sectional area honeycombs for flow-through passages, such as square honeycombs with square cross-sectional cells or spirally wound honeycombs in corrugated form, are used in orthogonal matrices resulting in adjacent passages with varying cross-sectional areas and thus equally non-purged passages. It may work better than a circular honeycomb with square cross section cells.

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.

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 itself and to the substrate. In some cases, the binder crosslinks with itself to improve adhesion. This enhances the integrity of the coating, its adhesion to the substrate, and provides structural stability under the vibration conditions encountered in automobiles. The binder may also contain additives to improve water resistance and improve adhesion. Typical binders for use in slurry formulations include organic polymers, alumina, silica or zirconia sols, inorganic salts, organic salts and/or hydrolysis products of alumina, silica or zirconium, alumina, silica or zirconium hydroxides, organosilicates that are 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 introduced into the sorbent composition as a latex, optionally as an aqueous slurry. Thermosetting elastomeric polymers introduced into the sorbent composition as latexes, preferably as aqueous slurries, are preferred.

Useful organic polymeric 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, cellulose 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, phenolic resins and Epoxy 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 slurry components, including hydrocarbon adsorbents such as latex emulsions and polymeric binders, are known in the art. See, for example, co-assigned 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 alkylphenol ethoxylate (APEO)-free ultra-low formaldehyde styrenated acrylic emulsion. One such exemplary binding agent 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 and Joncryl(TM) products are available from BASF; Wyandotte, MI, 48192. In some embodiments, the binder is present in an amount of about 10% to about 50% by weight of the particulate carbon.

Slurries containing the hydrocarbon adsorbent coatings, particularly polymer latexes, of the present invention may contain conventional additives such as thickeners, dispersants, surfactants, biocides, antioxidants, and the like. 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 can also serve a secondary role by increasing slurry stability through steric hindrance of dispersed particles. It can also help bond the coating surface. Exemplary thickeners are xanthan gum thickeners or carboxymethyl-cellulose thickeners. Kelzan® CC, a product of CP Kelco, Cumberland Center II, 3100 Cumberland Boulevard, Suite 600, Atlanta GA, 30339, is one such exemplary xanthan thickener.

In some embodiments it is preferred to use a dispersant in conjunction with the binder. Dispersants may 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 specific 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 of these may be mentioned. In one embodiment, the dispersant is a low molecular weight polyacrylic acid in which many of the acid protons have been replaced with sodium. In some embodiments, the dispersant is a polycarboxylate 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). Although increasing the pH of the slurry or adding an anionic dispersant alone can sufficiently stabilize a slurry mixture, the best results are obtained when both increasing the pH and an anionic dispersant are used. 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 surfactants, which can also act as defoamers. In some embodiments, the surfactant is a small molecule non-anionic dispersant. An exemplary oil-free and silicone-free antifoam surfactant is Rhodoline® 999 (Solvay). Another exemplary surfactant is a blend of hydrocarbon and nonionic surfactants, such as Foammaster® NXZ (BASF).

II. Air Intake System for Controlling Evaporative Emissions A coating substrate for hydrocarbon adsorption as disclosed above is a component of an air intake system configured to control evaporative emissions from a motor vehicle having a combustion engine. can be used as Thus, in another aspect, an air intake duct, an air purifier housing positioned to receive air from the air intake duct, and fluid communication with the air filter chamber and the combustion engine for transporting air from the air filter chamber to the combustion engine. An air intake system is provided that includes one or more clean air ducts.

Intake system components typically include a three-dimensional hollow interior space or chamber defined at least in part by a molded planar material, such as a molded thermoplastic olefin. "Molded planar material" means a material that has two dimensions substantially greater than a third dimension and that has been molded or otherwise formed into a three-dimensional shape. "Hollow" means a cavity substantially filled with a fluid such as air or exhaust gas. The planar material includes an inner surface, which is the side facing the hollow inner chamber, and an outer surface, which is the side facing away from the inner chamber.

The intake system of the present invention can be more readily appreciated by reference to FIG. 1 which is merely exemplary in nature and is in no way intended to limit the invention or its application or method of use. FIG. 1 is a schematic diagram of an intake system 1. FIG. System 1 includes an opening 6 in air intake duct 4 in fluid communication with air cleaner housing 2, which defines, at least in part, a hollow interior space in which air cleaner 10 is located. The air cleaner housing 2 is shown in a rectilinear configuration, but may be of any shape, such as oval or circular. The air purifier 10 may be present in the ambient air, dividing the air purifier housing into a dirty air portion 8 located upstream of the air purifier 10 and a clean air portion 11 located downstream from the air purifier 10 . It functions to absorb other particulate matter (eg dust particles). It should be appreciated that the air cleaner may be of any shape and size. The air cleaner housing 2 is connected to an air duct 12 which is connected to a throttle body 13 containing a throttle valve 14 . An intake manifold 16 including a surge tank 18 connects the slot body to an engine 20 including fuel injector and piston assemblies 22 and a crankcase 24 . A hose 26 containing a PCV valve 28 communicates with both the crankcase 24 and surge tank 18 . Parts of the intake system can be made of metal, plastic or plastic-metal composite.

When the engine 20 is running, the intake system 2 draws air from the environment through the intake duct 4 . Air is drawn through the opening 6 of the intake duct 4 into the dirty air portion 8 of the interior space of the air purifier housing 2 and through the air purifier 10 contained therein into the clean air portion 11 of the interior space. The air purifier 10 collects dirt and other particulate matter that may be present in the ambient air and produces a clean airflow. The clean air flow exits clean air section 11 via clean air duct 12 . Clean airflow passes through a throttle body 13 with its throttle body valve 14 and enters an intake manifold 16 containing a surge tank 18 . Clean air is transported to engine 20 which includes crankcase 24 and portion 22 containing fuel injectors and piston assemblies for use in combustion. Crankcase combustion gases are fed back to intake manifold 16 via a breather tube 26 containing a positive crankcase ventilation (PCV) valve 28 .

A hydrocarbon sorbent coating or an adherent hydrocarbon sorbent coating substrate can be applied to one or more of several possible locations within the intake system. It can be applied to the inner surface of the intake duct 4 . It can be applied to the inner surface of the air cleaner housing 2 where the inner surface is in contact with the contaminated air portion 8 . This position has the advantage that coating loss is captured by the air filter 10 and protects the engine 20 from potential damage. The disadvantage is that this location must withstand large amounts of dust and other contaminants. The sorbent coating or coating substrate can be applied to the inner surface of the air cleaner housing 2 with the inner surface contacting the clean air portion 11 . A coating or coating substrate can also be applied to the inner surface of the clean air duct 12, the inner wall of the throttle body 13 and/or the intake manifold 16 through which the clean air travels. These positions on the clean side of the air filter have the advantage of being protected from external contaminants. However, the coating or coating substrate can still be exposed to contaminants such as from engine oil. Adhesion requirements are stringent at these locations as it is undesirable to have coating loss flowing into the engine. Throttle body 12 is typically metal and has a very low surface area. The intake manifold 16 has the disadvantage of exposure to high temperatures and high concentrations of fuel vapors and pollutants due to the large drop in hydrocarbon concentration from the engine side of the throttle body to the other. The coating or coating substrate can be applied at a single location or at multiple locations within the intake system. A given location may be completely coated with the adsorbent, or may be partially coated. A given location may be fully coated or partially coated with the adhesive coating substrate. The coating or coating substrate may be of substantially the same thickness over locations or throughout the intake system, or may be of varying thickness, resulting in more coating at one location. The amount of adsorbent is increased compared to another position where the thickness is thinner.

Evaporative emissions from the engine are adsorbed by the hydrocarbon adsorbent coating or coating substrate during engine off-time. During engine operation, ambient air is introduced into the intake system, desorbs hydrocarbons already adsorbed by the hydrocarbon adsorbent, and is cycled back to the engine for combustion through clean air duct 12 .

According to some embodiments of the present invention, at least a portion of the inner surface of at least one of intake duct 4, air cleaner housing 2 and clean air duct 12 is coated with a hydrocarbon sorbent coating as disclosed herein. comprising or in contact with a substrate coated with a hydrocarbon sorbent coating as disclosed herein, whereby the hydrocarbon sorbent coating is for entry of combustion air into a combustion engine of said motor vehicle; is in fluid contact with the path of Hydrocarbon adsorbent coatings and coating substrates are as presented and described in the previous section (I. Coating substrates for hydrocarbon adsorption).

In some embodiments, at least a portion of the inner surface of air cleaner housing 2 is coated with a hydrocarbon adsorbent coating. In some embodiments, the thickness of the coating layer is less than about 500 microns.

In some embodiments, the substrate is a bonded nonwoven. In some embodiments, the thickness of the coating layer on the nonwoven is less than about 500 microns. In some embodiments, the contact nonwoven adheres to at least a portion of the inner surface of one or more of the air intake duct 4 , air cleaner housing 2 or clean air duct 12 . In some embodiments, the bonded nonwoven is bonded to at least a portion of the inner surface of the air filter chamber.

III. Evaporative Emission Control Systems for Fuel Storage Coated substrates for hydrocarbon adsorption as disclosed above can be used as components of evaporative emission control systems for fuel storage. Accordingly, in yet another aspect, an evaporative emission control system is provided that includes a fuel tank for fuel storage, an internal combustion engine adapted to consume the fuel, and an evaporative emission control canister system. The canister system includes an evaporative emission control canister and an effluent scrubber. The evaporative emission control canister includes a first sorbent- containing spatial region , a fuel vapor purge tube connecting the evaporative emission control canister to the engine, a fuel vapor inlet tube for venting the evaporative emission control canister from the fuel tank, and A vent tube is included for venting the evaporative emission control canister to atmosphere and for allowing purge air to enter the evaporative emission control canister system. The evaporative emission control canister system is routed from the fuel vapor inlet tube to the first sorbent- containing spatial region , by the fuel vapor flow path to the effluent scrubber to the vent tube, and from the vent tube to the effluent scrubber. , toward the first sorbent- containing spatial region and toward the fuel vapor purge tube. Effluent effluent scrubbers, as presented herein (I. Coating substrates for hydrocarbon adsorption), comprise at least a second sorbent- containing spatial region , the second sorbent- containing spatial region comprising , a coating substrate adapted for hydrocarbon adsorption, the coating substrate comprising at least one side and a coating on the at least one side, the coating comprising particulate carbon and a binder.

Evaporative emissions from the fuel tank are adsorbed by the evaporative emissions control system during engine off-time. During engine operation, atmospheric air is introduced into the evaporative emission control system and hydrocarbons already adsorbed by the sorbent- containing spatial region are desorbed and circulated back to the engine for combustion. Evaporative emission control system canisters typically include a three-dimensional hollow interior space or chamber defined at least in part by a molded planar material, such as a molded thermoplastic olefin. The evaporative emission control system of the present invention can be more readily appreciated by referring 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, and an evaporative emission control canister system. 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 one embodiment of the invention, the evaporative emission control canister system includes an evaporative emission control canister 46 and an effluent scrubber 58 . Evaporation control canister 46 includes a first sorbent- containing spatial region (represented by 48), a fuel vapor purge tube 66 connecting evaporative emission control canister 46 to engine 32, and evaporative emission control from fuel tank 38. A fuel vapor inlet tube 42 for venting the canister 46 and vent tubes 56, 59, 60 for venting the evaporative emission control canister 46 to atmosphere and for allowing purge air to enter the evaporative emission control canister system. include.

The evaporative emission control canister system provides a fuel vapor flow path from the fuel vapor inlet pipe 42 to the first sorbent containing space region 48 through the vent pipe 56 to the effluent scrubber 58 to the vent pipes 59,60. and from the vent pipes 60 , 59 to the effluent scrubber 58 , through the vent pipe 56 to the first adsorbent- containing spatial region 48 to the fuel vapor purge tube 66 . Effluent effluent scrubber 58 includes at least a second sorbent- containing spatial region , which is presented and described herein (I. Coating substrates for hydrocarbon adsorption). As noted, it includes a coating substrate 74 adapted for hydrocarbon adsorption.

In one embodiment, evaporative emissions control canister 46 is in fluid communication with effluent scrubber 58 via vent tube 56 and with engine 32 via fuel vapor purge tube 66 , purge valve 68 and purge line 72 . there is In this embodiment, the vent pipes for venting the evaporative emission control canister system to atmosphere and for allowing purge air to enter the evaporative emission control canister system comprise several vent pipe segments 56, 59, 60 and valves. 62 included. In one embodiment, the evaporative emission control canister system provides an effluent exhaust from the fuel vapor inlet tube 42 through the canister vapor inlet 50 to the first sorbent- containing spatial region 48 via the canister vapor outlet 54 and vent tube 56. to the effluent scrubber 58, by the fuel vapor flow path to the vent pipes and valves (59, 60 and 62) and from the vent pipes and valves (60, 62 and 59) to the effluent scrubber 58, the vent pipes 56 and It is defined by a reciprocal air flow path through the canister vapor outlet 54 to the first sorbent- containing spatial region 48 to the fuel vapor purge outlet 66 .

During engine operation, gasoline is delivered from the fuel tank 38 by the fuel pump through the fuel line to the fuel injectors, all represented schematically by line 40 . The timing and operation of the fuel injectors and the amount of fuel injected are governed by controller 34 via signal line 36 . Fuel tank 38 is typically a closed container, except for evaporative fuel vapor inlet tube 42 and fill tube 44 . The fuel tank 38 is often made of blow molded high density polyethylene with one or more gasoline impermeable inner layers.

In one embodiment, fuel tank 38 includes an evaporative fuel vapor inlet tube 42 that extends from fuel tank 38 to first sorbent- containing spatial region 48 of evaporative emission control canister 46 . Vaporized hydrocarbon-containing fuel vapor from fuel tank 38 may pass from fuel tank 38 through evaporative vapor inlet tube 42 to first sorbent- containing spatial region 48 within canister 46 . Evaporative emission control canister 46 may be formed of any suitable material weight. For example, molded thermoplastic polymers such as nylon are typically used.

Fuel vapor pressure increases as the temperature of the gasoline in fuel tank 38 increases. Without the evaporative emission control system 30 of the present invention, the fuel vapor would be released to the atmosphere untreated. However, in accordance with the present invention, the fuel vapor is treated by the evaporative emission control canister 46 and by an effluent scrubber 58 located downstream of the evaporative emission control canister 46 .

When vent valve 62 is open and purge valve 68 is closed, fuel vapor is contained under pressure from fuel tank 38 through evaporative vapor inlet tube 42, canister vapor inlet 50 and subsequently into evaporative emission control canister 46. through the first adsorbent- containing spatial region 48. Fuel vapor that is not adsorbed by the first sorbent- containing spatial region then exits evaporative emission control canister 46 through vent tube opening 54 and vent tube 56 . The fuel vapor then enters the effluent scrubber 58 for further adsorption. After passing through the effluent scrubber 58, the remaining fuel vapor exits the effluent scrubber 58 via pipe 59, vent valve 62 and vent pipe 60, thereby being vented to the atmosphere.

Over time, the hydrocarbon adsorbents contained in both the evaporative emission control canister 46 and the adsorbent- containing spatial region of the effluent scrubber 58 become loaded with hydrocarbons adsorbed from the fuel vapor. When the hydrocarbon sorbent becomes saturated with fuel vapors, and therefore with hydrocarbons, the hydrocarbons must be desorbed from the hydrocarbon sorbent for continued control of the fuel vapors exiting the fuel tank 38 . During engine operation, engine controller 34 sends commands to open valves 62 and 68 via signal leads 64 and 70 respectively, thereby creating an airflow path between the atmosphere and engine 32 . Opening purge valve 68 allows clean air to be drawn from the atmosphere through vent pipe 60 , vent pipe 59 and vent pipe 56 to effluent scrubber 58 and subsequently to evaporative emission control canister 46 . Become. Clean air or purge air flows through clean air vent tube 60 , through effluent scrubber 58 , through vent tube 56 , through vent tube opening 54 and to evaporative emission control 46 . Clean air flows through and/or through hydrocarbon adsorbents contained within effluent effluent scrubber 58 and emission control canister 46 to desorb hydrocarbons from the saturated hydrocarbon adsorbents within each volume. The purge air and hydrocarbon streams then exit 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, coating substrate 74 is an extrusion medium. In some embodiments, the extrusion media are honeycombs. FIG. 3 illustrates an embodiment of an efflux scrubber 58 in which the coating substrate 74 is structured media 74a in pleated form. FIG. 4 illustrates an embodiment in which coating substrate 74 is foam 74b. In one embodiment, foam 74b has more than about 10 pores per inch. In some embodiments, foam 74b has greater than about 20 pores per inch. In some embodiments, foam 74b has about 15 to about 40 pores per inch. In one embodiment, foam 74b is polyurethane. In some embodiments, foam 74b is reticulated polyurethane. In some embodiments, polyurethanes are polyethers or polyesters.

FIG. 5 illustrates an embodiment in which coating substrate 74 is extrusion media 74c. In some embodiments, extrusion media 74c is a honeycomb. Honeycomb adsorbents can be of any geometry including, but not limited to, circles, cylinders or squares. Additionally, the cells of the honeycomb adsorbent can be of any geometry. Uniform cross-sectional area honeycombs for flow-through passages, such as square honeycombs with square cross-sectional cells or spirally wound honeycombs in corrugated form, are used in orthogonal matrices resulting in adjacent passages with varying cross-sectional areas and thus equally non-purged passages. It may work better than a circular honeycomb with square cross section cells. Without wishing to be 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, and thus during all-day storage from the canister system. Emissions of emissions (DBL) are reduced. In some embodiments, the system can achieve low all-day storage emissions (DBL, less than 20 mg per BETP protocol) that represent an effective control device for hydrocarbon emissions.

Surprisingly, as disclosed herein, the sorbent- containing spatial region of the effluent scrubber has, in some embodiments, a lower butane handling capacity (BWC) than that of competing monoliths. and still be able to effectively control hydrocarbon emissions from the evaporative emission control canister under low purge conditions.

In some embodiments, the second sorbent- containing spatial area is subjected to a butane breakthrough test with a 29 x 100 mm sorbent- containing spatial area for a third cycle at a purge volume of 390 1.6 L bed volume. It has a third cycle butane breakthrough time at a purge volume of less than 100 1.6 L bed volume that is within about 10% of the butane breakthrough time. Third cycle butane breakthrough is the time (in seconds) at which the outlet concentration of butane from the adsorbent- containing spatial region reaches 100 ppm as measured by flame ionization detection during the third loading step of the butane breakthrough test. The butane breakthrough test was performed by placing the test sorbent- containing spatial region in the sample cell, filling the sample cell with a 1:1 butane/ _N2 gas mixture in an upward flow direction from the bottom to the top of the sample cell at 134 mL/ml. (10 g/h butane flow) for 45 min, purging the sample cell with _N2 for 10 min at 100 mL/min in the same flow direction, and rotating the sample cell in the opposite direction (top to bottom). ) desorbing with an air flow of 25 L/min for a time sufficient to reach the desired number of 1.6 L bed volumes, and the steps of loading, purging, and desorbing for three loading/purge/desorption cycles; Including repeating until done. In some embodiments, the second sorbent- containing spatial region is less than 80 1.6 L bed volumes within about 10% of the third cycle butane breakthrough time at a purge volume of 390 1.6 L bed volumes. with a third cycle butane breakthrough time at a purge volume of . In some embodiments, the second sorbent- containing spatial region is less than 60 1.6 L bed volumes, which is within about 10% of the third cycle butane breakthrough time at a purge volume of 390 1.6 L bed volumes. with a third cycle butane breakthrough time at a purge volume of . In some embodiments, the second sorbent- containing spatial region is less than 40 1.6 L bed volumes, which is within about 10% of the third cycle butane breakthrough time at a purge volume of 390 1.6 L bed volumes. with a third cycle butane breakthrough time at a purge volume of . In some embodiments, the second sorbent- containing spatial region is within about 10% of the third cycle butane breakthrough time at a purge volume of less than 100 1.6 L bed volume of at least about 800 seconds. It has a 3rd cycle butane breakthrough time at a purge volume of less than 80 1.6 L bed volume.

In particular, foam substrates as disclosed herein exhibit lower butane throughput than competing monoliths while still controlling emissions more effectively under low purge volumes. Without wishing to be bound by theory, this suggests that the thickness of the sorbent coating is thinner and/or that the sorbent coating through the foam, which may result in faster purging than bulk monoliths used in competitive products. It can be attributed to the high turbulence of the gas flow.

In some embodiments, the effluent scrubber further comprises a third sorbent- containing spatial region . FIG. 6 shows that the second sorbent- containing spatial region comprises a coated substrate 74 as disclosed above and the third sorbent- containing spatial region comprises a coated substrate as disclosed above. , illustrates an embodiment in which the substrate is foam (74b). In some embodiments, the second sorbent- containing spatial region is a monolithic substrate. In some embodiments, the third sorbent- containing spatial region is a reticulated polyurethane foam. In some embodiments, foam 74b has more than about 10 pores per inch. In some embodiments, foam 74b has greater than about 20 pores per inch. In some embodiments, foam 74b has about 15 to about 40 pores per inch. In some embodiments, foam 74b is polyurethane. In some embodiments, foam 74b is reticulated polyurethane. In some embodiments, polyurethanes are polyethers or polyesters. In some embodiments, the coated monolith substrate is combined with a downstream coated foam substrate to achieve a low It is particularly effective in controlling hydrocarbon emissions under purge conditions.

As previously discussed, FIGS. 2-6 are merely exemplary embodiments of the disclosed evaporative emission control system, and those skilled in the art may envision additional embodiments without departing from the scope of the present disclosure. obtain.

The second sorbent- containing spatial region (and any further sorbent- containing spatial regions ) may contain a volume diluent. Non-limiting examples of volume 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 does not contain adsorbent. Such volumes may contain any non-adsorbent including, but not limited to, air gaps, foam spacers, screens or combinations thereof.

Those skilled in the relevant art will readily appreciate that suitable modifications and adaptations to the compositions, methods and applications described herein can be made without departing from any embodiment or aspect thereof. becomes clear. The compositions and methods presented are exemplary and are not intended to limit the scope of the disclosed 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 encompasses all actual or possible combinations of embodiments, aspects, options, examples and preferences herein. include. All patents and publications referenced herein are hereby incorporated by reference for their specific teachings as set forth, unless other specific statements of incorporation are specifically provided. .

The following examples are provided by way of illustration and not by way of limitation.

[Example 1]
Adsorbent Selection Several commercially available carbon materials were tested using the following protocol for thermogravimetric analysis (TGA). The material to be tested was equilibrated at room temperature and exposed to a 5% n-butane flow in nitrogen of 100 ml/min for 20 minutes to obtain the total butane adsorption capacity of the material. After mass stabilization, the sample was purged with a nitrogen flow of 100 ml/min for 25 minutes. The butane adsorption was repeated to obtain the butane treat capacity. This is reported as 2nd Cycle % Butane Adsorption which reflects the mass % value of grams of butane/gram of carbon.

Nitrogen pore size distribution and surface area analyzes were performed on a Micromeritics TriStar 3000 series instrument. The material to be tested was degassed in a Micromeritics SmartPrep degasser for a total of 6 hours (heated to 300° C. in 2 hours, then held at 300° C. for 4 hours under dry nitrogen flow). Let the nitrogen BET surface area be . It was determined using 5 partial pressure points from 08 to 0.20. Nitrogen pore size was determined using BJH calculations and 33 desorption points. The BET surface area and adsorption capacity results are shown in Table 1.

Based on the adsorption capacities listed in Table 1, several carbon materials provided higher second cycle butane adsorption capacities than commercial hydrocarbon traps or commercial hydrocarbon adsorption carbon canisters.

[Example 2]
Preparation of Carbon Slurries for Coating Substrates Formulation A
A solution of 1.4% Kelzan CC in water was prepared one day prior to 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 activated carbon adsorbent (“Carbon 1” in Table 1) was added with stirring. The resulting carbon dispersion was added to a second vessel containing 40 g of Joncryl 2570 binder (50% solution) with stirring. Additional Kelzan CC thickener solution was added until the slurry was sufficiently viscous for coating.

Formulation B
Water (193 ml) was combined with 2.96 g of Dispex Ultra PX 4575 dispersant and 0.37 g of Foammaster NXZ defoamer and the combination was thoroughly mixed. To this mixture, 76 g of activated carbon adsorbent (“Carbon 1” in Table 1) was added with stirring. The resulting carbon dispersion was added to a second vessel containing 14.8 g of Joncryl 2570 binder (50% solution) with stirring. The resulting carbon slurry was added with stirring to a third vessel containing 37 g of Joncryl FLX 5200 binder (40% solution). Rheovis 1152 thickener was added until the slurry was sufficiently viscous for coating.

[Example 3]
Coating of Foam Substrate Cylindrical foam pieces (10 ppi polyurethane) sized 29 x 100 mm (width x length) were dipped into Formulation B slurry. The foam was then squeezed to remove excess slurry. The pores of the foam were cleaned using an air knife operating at 15 psig pressure. The foam was dried at 110°C for 2 hours. The procedure was repeated until the desired carbon loading was achieved.

[Example 4]
Coating of Monolith Substrates A cylindrical ceramic monolith substrate (230 cells per square inch) sized 29 x 100 mm (width x length) was dipped into Formulation A slurry. Excess slurry was removed by clearing the channel using an air knife operating at 15 psig pressure. The substrate was dried at 110° C. for 2 hours. The procedure was repeated until the desired carbon loading was achieved.

[Example 5]
Adsorption capacity and desorption time in simulated canister applications Commercially available carbon monoliths and several coated monoliths and foams prepared as in Examples 3 and 4 were tested in a butane adsorption-desorption setup. A cylindrical sample with a size of 29×100 mm was placed inside a vertically oriented cylindrical sample cell. The sample cell was then loaded with a 1:1 butane/ _N2 test gas at a flow rate of 134 mL/min (10 g/h butane flow) for 45 minutes. The direction of flow was upward from the bottom to the top of the sample cell. The gas composition of the exit stream from the sample cell was monitored by FID (Flame Ionization Detector). After the 45 min butane adsorption step, the sample cell was purged with _N2 in the same flow direction at 100 mL/min for 10 min. The sample was then desorbed in the opposite direction (top to bottom) with an air flow of 25 L/min for 25 minutes. The adsorption-purge-desorption sequence was repeated a total of three times.

The relative effective butane adsorption capacity can be correlated with the time required for butane breakthrough through the sample to occur. Butane breakthrough is defined as the time when the outlet concentration of butane from the sample cell reaches 100 ppm. In this test setup, when a blank 10 ppi foam piece with no adsorbent coating applied was placed in the sample cell, it took 636 seconds for butane breakthrough to occur on the third adsorption cycle (Table 2). Breakthrough times for 10 ppi, 20 ppi, 30 ppi and 40 ppi foam pieces coated with 2.43 g, 2.19 g, 2.37 g and 2.24 g of activated carbon slurry (taken dry, Formulation B of Example 2) were breakthrough times of 857, 833, 854 and 842 seconds, respectively. The increase in breakthrough time compared to the blank foam (636 seconds) correlates with the relative effective butane adsorption capacity of the adsorbent coating. These results demonstrate an increase in butane content proportional to the amount of coating added to the foam, independent of the foam's cell density. A commercial carbon monolith was tested by this method and had a breakthrough time of 1452 seconds, averaging over three tests. These results indicate that the above coated foam has about 25% butane content of the commercial carbon monolith.

Additional tests were performed on commercial carbon monoliths with desorption times varied from 45 minutes to 2.5 minutes. The flow rate was kept constant at 25 L/min. The effect of butane breakthrough time for the third adsorption cycle is shown in Table 3 below. These results indicate that desorption of a butane-saturated commercial carbon monolith for less than 5 minutes fails to completely regenerate, resulting in a drop in its butane capacity in subsequent desorption cycles. Desorption times of 5 minutes and 2.5 minutes correspond to purges of 125 L and 62.5 L (or 78 and 39 bed volumes), respectively, for a 1.6 L fuel vapor canister.

Coated samples of 10 ppi and 40 ppi foam were also tested under reduced desorption times (5 minutes and 2.5 minutes). The effect of butane breakthrough time for the third adsorption cycle is shown in Table 4 below. These test results indicate that the reduction in desorption time has a similar effect for the 10 ppi piece of foam compared to the commercial carbon monolith, but the reduction in effective butane capacity for the 40 ppi piece of coated foam is significantly proves to be less. The results indicate that the 40 ppi coated foam pieces are more completely desorbed under low purge conditions.

[Example 6]
Airbox Coating A hydrocarbon adsorbent was coated on the inside surface of an air purifier housing (airbox) of a commercial air intake system. The air freshener housing was made of automotive grade glass-filled polypropylene, which was primed with a commercial adhesion promoter prior to coating. The adsorbent was Carbon 1 (Example 1). The sorbent coating composition was as described in Example 2 (Formulation A). The coating was applied as an aqueous slurry (28% solids in water) using a spray gun and then dried at 110°C for 30 minutes.

[Example 7]
Nonwoven Substrate Coating and Incorporation A piece of Nomex nonwoven (11″×11″) having a mass of 86 g/m ² was taped around the edges of a flat rigid substrate using heat resistant tape. A sample of the carbon slurry (55.8 g, prepared according to Example 2, Formulation A (27% solids)) was poured onto the non-woven fabric and evenly distributed to achieve complete coverage. The spatula was manually moved back and forth over the fabric to form a uniform coating that penetrated the fabric well. The treated fabric-substrate combination was then placed in a drying oven at 110° C. and dried to a dry touch. It was then removed from the oven, the tape removed, the coated nonwoven fabric peeled from the substrate and returned to the drying oven until completely dry. A sheet of coated nonwoven fabric, made as described, was cut using scissors to a size that would approximately fit inside a commercial air box. A correctly sized coated non-woven fabric sheet was properly secured in the airbox using epoxy.

[Example 8]
Adsorption Capacity and Desorption Time in Application Simulations Coatings as described in Examples 6 and 7 and nonwoven-applied coatings were tested in a butane adsorption-desorption setup using an airflow tube from a commercial automotive airbox. tested. The airflow tube is the part of the airbox that is positioned at the clean side inlet of the airbox. The airflow tube was received with commercially available carbon paper lining the inner surface. This carbon paper was removed prior to application of the coating or coated nonwoven. The area of the inner surface of the airflow tube covered by the coating or nonwoven was the same as the area covered by the commercial carbon paper. A blank airflow tube and one with commercial carbon paper instead were also tested. The airflow tube was mounted in a sample cell consisting of a sealed box with an inlet and an outlet such that flow through the airbox from the inlet passed through the airflow tube. The sample cell was loaded with a 1:1 mixture of butane/ _N2 as the test gas at a flow rate of 134 mL/min (10 g/h butane flow) for 30 minutes. The gas composition of the outlet stream from the airbox was monitored by FID (Flame Ionization Detector). After the butane adsorption step, the sample cell was purged with _N2 in the same flow direction at 100 mL/min for 10 minutes. The samples were then desorbed with an airflow of 150 L/min in the opposite direction for either 25 or 75 minutes. The adsorption-purge-desorption sequence was repeated a total of 6 times.

The relative effective butane adsorption capacity can be correlated with the time required for butane breakthrough through the sample to occur. Butane breakthrough is defined as the average time for 54 mg of butane to breakthrough through the sample cell as monitored by FID (during the second of 6 adsorption cycles). The results of the tests are shown in Table 5 below. The increase in breakthrough time compared to the blank (1113 seconds) correlates with the relative effective butane adsorption capacity of the adsorbent coating. Using a 25 minute desorption time, the airflow tube with the 3.3 g coating has a lower effective butane adsorption than the airflow tube with the commercial carbon paper, but using a 75 minute desorption time, the butane Adsorption capacity is slightly higher. Both the airflow tubes with 5.5g and 4.0g coatings on the nonwoven have more effective butane adsorption capacities than the airflow tubes with commercial carbon paper under both desorption times.

Those skilled in the relevant art will readily appreciate that suitable modifications and adaptations to the compositions, methods and applications described herein can be made without departing from any embodiment or aspect thereof. becomes clear. The compositions and methods presented are exemplary and are not intended to limit the scope of the disclosed embodiments. All of the various embodiments, aspects and options disclosed herein can be combined in all variations. The scope of compositions, formulations, methods and methods described herein includes all actual or possible combinations of embodiments, aspects, options, examples and preferences herein. All patents and publications referenced herein are hereby incorporated by reference for their specific teachings as set forth, unless other specific statements of incorporation are specifically provided. .

Claims (27)

A coating substrate adapted for hydrocarbon adsorption, comprising:
A substrate comprising at least one surface having a hydrocarbon sorbent coating thereon, the hydrocarbon sorbent coating comprising particulate carbon and a binder, wherein the particulate carbon is at least 1400 m ² /g has a BET surface area of
The particulate carbon was equilibrated at room temperature, exposed to a 5% n-butane flow in 100 ml/min nitrogen for 20 min, purged with a 100 ml/min nitrogen flow for 25 min, and again 5% in 100 ml/min nitrogen. % having a second cycle n-butane adsorption capacity of at least 9 % by weight n-butane after 20 minutes of exposure to n-butane flow;
coating substrate. The coating substrate of claim 1, wherein the particulate carbon has a BET surface area of 1 400 m ² /g to 2 500 m ² /g. The coating substrate of claim 1, wherein the particulate carbon has a second cycle n-butane adsorption capacity of 9 wt% to 15 wt%. 2. The coating substrate of claim 1, wherein the binder is present in an amount of 10% to 50% by weight relative to the particulate carbon. A coating substrate according to claim 1, wherein the binder is an organic polymer. The coating substrate of claim 1, wherein the binder is selected from the group consisting of acrylic/styrene copolymer latexes, styrene-butadiene copolymer latexes, polyurethanes and mixtures thereof. 2. The coated substrate of claim 1, wherein the substrate is plastic. 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. 8. A coating substrate according to claim 7 , selected. The substrate is foam, monolithic material, non-woven fabric, fabric, sheet, paper, helical coil, ribbon, structural media in extruded form, structural media in wound form, structural media in folded form, structural media in pleated form, corrugated 2. The coating substrate of claim 1 selected from the group consisting of morphological structuring media, injection structuring media, bonded structuring media and combinations thereof. 2. The coated substrate of claim 1, wherein the substrate is an extrusion medium. 11. The coated substrate of claim 10, wherein the extrusion medium is a honeycomb. 2. The coating substrate of claim 1, wherein the substrate is a foam. 13. The coating substrate of claim 12, wherein the foam has 15 to 40 pores per inch. 13. The coating substrate of claim 12, wherein the foam is reticulated polyurethane. 2. The coated substrate of claim 1, wherein the coating thickness is less than 500 microns. 2. The coated substrate of claim 1, wherein the substrate is a nonwoven. An air intake system configured to control evaporative emissions from a motor vehicle having a combustion engine, comprising:
an air intake duct, an air cleaner housing positioned to receive air from the air intake duct, and in fluid communication with the air cleaner housing and the combustion engine for transporting air from the air filter chamber to the combustion engine; or including a plurality of clean air ducts,
17. At least a portion of an inner surface of at least one of the intake duct, the air cleaner housing and the clean air duct comprises a hydrocarbon sorbent coating according to any one of claims 1 to 16, or the carbonized air duct. in contact with a substrate coated with a hydrogen sorbent coating such that the hydrocarbon sorbent coating is in fluid contact with a pathway for entry of combustion air into said combustion engine of said motor vehicle; intake system. 18. The air intake system of claim 17, wherein said portion of the interior surface of said air filter chamber is coated with a hydrocarbon adsorbent coating. 18. The air intake system of claim 17, wherein the substrate is a bonded non-woven fabric adhered to said portion of the inner surface of the air filter chamber. fuel tanks for fuel storage,
An evaporative emission control system comprising: an internal combustion engine adapted to consume fuel; and an evaporative emission control canister system, the canister system comprising:
Evaporative Emission Control Canister, and Effluent Emission Scrubber, including Evaporative Emission Control Canister,
a first sorbent containing spatial region , a fuel vapor purge tube connecting the evaporative emission control canister to the engine, a fuel vapor inlet tube for venting from the fuel tank to the evaporative emission control canister, and from the evaporative emission control canister to the atmosphere. including a vent tube for venting the evaporative emission control canister system and for allowing purge air to enter the evaporative emission control canister system;
An evaporative emission control canister system is routed from the fuel vapor inlet tube to the first sorbent- containing spatial region , by the fuel vapor flow path to the effluent scrubber to the vent tube, and from the vent tube to the effluent scrubber. , towards the first sorbent-containing spatial region and towards the fuel vapor purge tube, defined by a reciprocal airflow path;
Evaporative emissions, wherein an effluent effluent scrubber comprises at least a second sorbent- containing spatial region , the second sorbent- containing spatial region comprising a coated substrate according to any one of claims 1 to 16 Emission control system. When the second adsorbent- containing spatial area was subjected to butane breakthrough testing with an adsorbent- containing spatial area of 29×100 mm, the third cycle butane breakthrough time at a purge volume of 390 1.6 L bed volume of 1 0 %, with a third cycle butane breakthrough time at a purge volume of less than 100 1.6 L bed volume, wherein the third cycle butane breakthrough is such that the exit concentration of butane from the adsorbent- containing spatial region is less than butane breakthrough. The time (in seconds) to reach 100 ppm as measured by flame ionization detection during the third loading step of the overtest, the butane breakthrough test consists of placing the test sorbent- containing spatial region in the sample cell, Loading the cell with a 1:1 butane/N ₂ gas mixture in an upward flow direction from the bottom to the top of the sample cell at a flow rate of 134 mL/min (10 g/h butane flow) for 45 min; At ₂ , purge at 100 mL/min for 10 minutes in the same flow direction, the sample cell was then purging in the opposite direction (top to bottom) with 25 L/min airflow to reach the desired number of 1.6 L bed volumes. 21. The evaporative emission control system of claim 20, comprising desorbing for a sufficient time and repeating the steps of loading, purging and desorbing until three loading/purge/desorption cycles are completed. When the second adsorbent- containing spatial area was subjected to butane breakthrough testing with an adsorbent- containing spatial area of 29×100 mm, the third cycle butane breakthrough time at a purge volume of 390 1.6 L bed volume of 1 0 21. The evaporative emission control system of claim 20, having a third cycle butane breakthrough time at a purge volume of less than 80 1.6 L bed volume that is within %. When the second adsorbent- containing spatial area was subjected to butane breakthrough testing with an adsorbent- containing spatial area of 29×100 mm, the third cycle butane breakthrough time at a purge volume of 390 1.6 L bed volume of 1 0 21. The evaporative emission control system of claim 20, having a third cycle butane breakthrough time at a purge volume of less than 60 1.6 L bed volume that is within %. When the second adsorbent- containing spatial area was subjected to butane breakthrough testing with an adsorbent- containing spatial area of 29×100 mm, the third cycle butane breakthrough time at a purge volume of 390 1.6 L bed volume of 1 0 21. The evaporative emission control system of claim 20, having a third cycle butane breakthrough time at a purge volume of less than 40 1.6 L bed volume that is within %. When the second adsorbent- containing spatial area was subjected to a butane breakthrough test with an adsorbent- containing spatial area of 29×100 mm, the second 21. The evaporative emission control system of claim 20, having a 3-cycle butane breakthrough time. The effluent effluent scrubber further comprises a third sorbent- containing spatial region , the second sorbent- containing spatial region being a monolith substrate, and the third sorbent- containing spatial region being a reticulated polyurethane foam. 21. The evaporative emission control system of claim 20. 21. The evaporative emission control system of claim 20, wherein the system has a 2-day full-day storage emissions (DBL) of less than 20 mg under the California Bleeding Emissions Test Procedure (BETP).