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WO1992001585A1 - Appareil et procede de recuperation de vapeur - Google Patents

Appareil et procede de recuperation de vapeur Download PDF

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Publication number
WO1992001585A1
WO1992001585A1 PCT/GB1991/001269 GB9101269W WO9201585A1 WO 1992001585 A1 WO1992001585 A1 WO 1992001585A1 GB 9101269 W GB9101269 W GB 9101269W WO 9201585 A1 WO9201585 A1 WO 9201585A1
Authority
WO
WIPO (PCT)
Prior art keywords
bed
adsorbent
canister
polymer
carbon
Prior art date
Application number
PCT/GB1991/001269
Other languages
English (en)
Inventor
Stephen Robert Tennison
Alan Ivor Foster
David Henry Nicholas
Richard Henry Weatherhead
Original Assignee
The British Petroleum Company Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The British Petroleum Company Plc filed Critical The British Petroleum Company Plc
Publication of WO1992001585A1 publication Critical patent/WO1992001585A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03—Fuel tanks
    • B60K15/035—Fuel tanks characterised by venting means
    • B60K15/03504—Fuel tanks characterised by venting means adapted to avoid loss of fuel or fuel vapour, e.g. with vapour recovery systems
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M25/00—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture
    • F02M25/08—Engine-pertinent apparatus for adding non-fuel substances or small quantities of secondary fuel to combustion-air, main fuel or fuel-air mixture adding fuel vapours drawn from engine fuel reservoir
    • F02M25/0854—Details of the absorption canister

Definitions

  • the present invention relates to the recovery of gasoline vapours from mixtures of gasoline vapour and air.
  • Gasoline vapour is emitted from motor vehicles powered by gasoline engines as a consequence of displacing gasoline vapour from the fuel tank during refuelling (refuelling losses). It is also emitted as a consequence of evaporation from the engine and fuel system either when the vehicle is in operation or when standing after use (diurnal losses). The emission of gasoline vapour is considered to be undesirable. Manufacturers already fit carbon canisters to eliminate the diurnal losses and such an arrangement is disclosed for instance in GB 1 416 336. The carbon adsorbs the vapour emitted when the engine is stationary after use.
  • the carbon canister is then regenerated by drawing air through the canister using the vacuum generated in the engine inlet manifold so that the gasoline vapour recovered from the canister is mixed with the normal air/fuel mixture to the engine.
  • the vapour emission when the vehicle is stationary is quite small so that a canister having a capacity of about 1 litre is thought to be satisfactory.
  • the vapours emitted are continuously returned to the engine.
  • Refuelling an almost empty tank involves displacing a large amount of gas (corresponding to the volume of the fuel tank if it is being completely refilled) saturated with gasoline vapour although this only occurs approximately once every 600 km. This is equivalent to approximately 150-200 g of vapour for a typical European car (60 L tank) depending on the composition of the vapour.
  • One approach to reducing the size of the canister is to use a carbon with a high adsorptive capacity.
  • carbons are not easily regenerated in use by drawing air through the carbon bed. They would adsorb a large quantity of gasoline vapour on the first cycle, but only small quantities thereafter.
  • the optimum active carbon the adsorption of gasoline vapours is one which has a high pore volume with pores in the small mesopore range (approximately 2 nm diameter). This maximises both the adsorption capacity of the carbon and the regenerability resulting in the largest possible working capacity.
  • the working capacity for typical gasolines is still limited to approximately 5% weight predominantly by the difficulty of regenerating the bed.
  • GB 1 416 336 discusses some of the disadvantages of the use of carbon and proposes to overcome them by replacing the carbon by a particulate macroreticular, substantially non-ionogenic, water-insoluble polymer having a specified surface area, porosity and average pore diameter.
  • polymers which may be used are polymers of divinyl benzene.
  • porous polymers are not satisfactory for use as gasoline adsorbents.
  • the porous polymers have a good saturation capacity for gasoline vapour and are easily regenerated.
  • a canister for attachment to a vehicle fuel tank comprising a body adapted to receive an adsorbent, and having a gas inlet adapted to be connected to a gasoline storage tank, a gas outlet adapted to be connected tc a gasoline engine, and a vent to the atmosphere, is characterised in that the canister contains a bed of adsorbent polymer and a bed of carbon arranged such that the vent opens into the bed of carbon and the gas inlet and gas outlet open into the bed of adsorbent polymer.
  • the present invention further provides a motor vehicle with a gasoline engine having a canister defined as above.
  • a method of adsorbing gasoline vapour from air comprises passing the mixture of air and gasoline vapour through a first bed of adsorbent polymer, and then through a bed of adsorbent carbon, and subsequently regenerating the adsorbent beds by passing a stripping gas first through the bed of adsorbent carbon and then through the bed of adsorbent polymer.
  • a process for operating a gasoline engine of a motor vehicle comprises passing 85 PCT/GB91/01269
  • the mixture of air and desorbed gasoline components will generally be blended will the normal gasoline/air fuel before the total mixture is passed to the engine.
  • the adsorbent carbon may be any of the conventional active carbons already proposed for use in gasoline engines. " However the use of the carbon in conjunction with the polymer adsorbent bed in the layered bed canister allows the use of a wider variety of active carbons where the requirement for the majority of pores to be small mesopores can be relaxed. Using conventional premium European gasoline the best results in the layered bed canister have been obtained with a highly microporous coconut shell carbon.
  • Polymers which are suitable adsorbent polymers for gasoline vapour adsorption are disclosed in GB 1 416 336. This discloses the use of -particulate macroreticular, substantially non-ionogenic, water-insoluble polymers having a specific surface area in the range- 10 to 10000 m g, a porosity of 25% to 85%, and an average pore diameter of 2 nm to 2000 nm.
  • specific polymers which may be used are those obtained by polymerising under macroreticular polymer producing conditions.
  • the monomer charge is composed of ethylenically unsaturated monomer or monomers and containing from 2% to 100% by weight, based on the weight of the charge, of 1 or more of divinyl benzene, trivinyl benzene, alkyl vinyl benzenes having from 1 to 4 methyl or ethyl groups substituted in the benzene nucleus, and alkyl divinyl benzenes having from 1 to 3 methyl or ethyl groups substituted in the benzene nucleus.
  • the surface area of the polymer is preferably in the range 200 to 2000 rn ⁇ /g, and that the polymer should contain a significant volume of pores in the range 1 nm to 50 nm for adsorption purposes, as well as larger pores for gas transfer.
  • a particularly preferred polymer is a copolymer of a mixture containing a major amount of divinyl benzene and a minor amount of ethyl styrene which is sold under the designation "Ambersorb XAD4" by Rohm & Haas Inc.
  • the quantities of adsorbent used will depend on the working adsorbing capacity of the polymer, the working adsorbing capacity of the active carbon, the quantity of gasoline vapour to be adsorbed between each regeneration period and the time available for regeneration.
  • the total volume of adsorbent may be in the range 500 ml to 5 litres.
  • the optimum amount of the two different adsorbents to be used will depend on the design of the canister.
  • the designated ratios refer to the volume of adsorbent between the gasoline vapour inlet and the vent to atmosphere. This can be seen by reference to figures 1 and 2.
  • the polymer:carbon ratio refers to the volume of adsorbent between the vapour inlet (2) and the vent to atmosphere (4).
  • the ratio refers to the total volume of adsorbent in the canister between the vapour inlet (12) and the vent to atmosphere (14).
  • the optimum ratio of polymer to carbon will vary with the type of gasoline to be used but may be in the range 3:7 to 7:3, or preferably in the range 4:6 to 6:4, more preferably 4.5:5.5 to 5.5:4.5.
  • the relative volumes of the two adsorbents may be adjusted to optimise the performance of the canister system for different types of gasoline used in different regions of the world. For the higher volatility fuels typically used in Europe a volume ratio of polymer to carbon of about 1:1 is preferred. For lower volatility fuels it is believed that polymer to carbon volume ratios of greater than 1:1 (ie larger relative amounts of polymer) will be desirable.
  • the ratios described above may correspond to a canister having a relatively large bed of adsorbent polymer and a
  • Figure 1 is a diagramatic cross-sectional view of one form of a gasoline adsorbing canister for use in the present invention
  • Figure 2 is a cross-sectional diagramatic view of an alternative form of gasoline canister according to the invention.
  • a cylindrical canister (1) is provided with a gas inlet (2) extending downwardly into the body of the canister and opening into the canister through slots at its lower end.
  • a vapour outlet (3) is provided at the top of the canister.
  • vent (4) which may allow air to both enter or leave the canister is provided at the lower end.
  • a perforated plate (5) is mounted above springs (6) which serves to urge the plate (5) upwards so as to keep any adsorbent material in the upper part of the canister compressed into its packed state.
  • the upper part of the canister between the connection to the vehicle inlet manifold (3) and the vapour inlet (2) is filled with a bed (7) of adsorbent polymer particles.
  • the lower part of the canister is filled with two layers.
  • the upper layer (1) is of the porous polymeric adsorbent whilst the lower layer (8), closest to the atmospheric vent (4) is filled with carbon adsorbent such that the volume ratio of the volume of bed (1) to bed (8) is most preferably in the ratio 4.5:5.5 to 5.5:4.5.
  • the inlet (2) is connected by piping and appropriate valves to the vehicle's fuel tank connected by piping and appropriate valves to the vehicles fuel tank and to the vents from the vehicles fuel inlet system and crankcase.
  • the outlet (3) is connected by piping and an appropriate valve to the engine, for example it may be connected as a bleed to a carburettor.
  • the vent (4) provides for the inlet or outlet of gas to the outside air.
  • Figure 2 shows an alternative design of canister for use particularly in reducing emissions during the refueling of motor vehicles.
  • the canister (11) is provided with a gas inlet (12) and a gas outlet (13) together with a vent (14). These are all provided at the top of the canister.
  • a metal divider (15) covered with an asbestos insulating sheet (16) divides canister (11) so that an elongated flow path is provided between the inlet (12) and outlet (13) on the one hand and the vent (14) on the other.
  • the canister is filled with two types of adsorbent material, namely a bed of adsorbent polymer (17), and a similar bed of adsorbent carbon (18). Wire mesh or perforated plates (19) and glass fibre (20) hold the adsorbent particles in position.
  • the relative quantities of gasoline-adsorbing polymer and absorbent carbon were 3:1 by packed volume.
  • the working capacity of the mixture was determined as the mean of six cycles of the operation with a standard deviation of 3.54 g. The result is given in the Table.
  • the two adsorbent beds (1 and 2) were contained in steel vessels that could be separated and weighed individually after each adsorption and desorption cycle. Each vessel was 4 cm in diameter and could hold up to 80 ml of adsorbent held in place between plugs of glass wool. The two beds were contained in a water bath maintained at 53C.
  • the adsorption cycle was simulated by passing gasoline vapour, produced by bubbling 83 ml min of nitrogen through 200 ml Eurograde unleaded 95/85 gasoline held at 200C in a water bath, through the polymer bed and then the carbon bed in series.
  • Desorption was carried out by reversing the nitrogen flow through the two beds. An average flow rate of 485 ml/minutes was used for a fixed time of 40 minutes for the desorption cycle. Aft the 40 minutes the two beds were again removed from the water bath and weighed.
  • Tests C and D are not according to the present invention and show the breakthrough time in minutes and the workin capacity in both % weight and g/litre for the tests where both vessels contained either 80 ml of the porous polymer, XAD4 (test C) or 80 mis of a typical extrudate active carbon recommended for use in evaporative loss canisters (test D) .
  • Examples 2 to 7 are not according to the present invention and show the breakthrough time in minutes and the workin capacity in both % weight and g/litre for the tests where both vessels contained either 80 ml of the porous polymer, XAD4 (test C) or 80 mis of a typical extrudate active carbon recommended for use in evaporative loss canisters (test D) . Examples 2 to 7
  • Examples 2 to 7 demostrate the dramatic improvements in both the time to breakthrough and the working capacity when the first bed is filled with 80 ml of the porous polymer, XAD4, and the second bed with 80 ml of activated carbon.
  • the carbo is the recommended extrudate active carbon used in comparative test D. It can be seen from a comparison of tables 1 and 2 that the increase in the working capacity compared to both the polymer/polymer bed and the carbon/carbon beds is almost identical to that found in the vehicle tests whilst the actual working capacities are slightly higher for the laboratory test probably due to slight differences in the breakthrough criterion. This demonstrates the validity of the laboratory test method.
  • Examples 3 to 7 demonstrate the use of different activated carbons in the second adsorbent bed. These materials were not selected using the normal criterion for evaporative emission canister carbons of maximising the small mesopore (2nm) volume but were typical microporous active carbons. It can be seen that the best perforance for the dual bed system was achieved with Sutcliffe Speakman AC610C, a highly microporous active carbon. The relative performance of the activated carbons in the dual bed system correlates better with the saturation butane capacity of the carbon than the working capacity which are also shown in table 2. These results demonstrate a second benefit of the dual bed canister, namely that the carbon component can now be selected to maximise the butane adsorption capacity without the generally poorer regeneration capability of the microporous carbons influencing the working capacity.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Transportation (AREA)
  • General Engineering & Computer Science (AREA)
  • Supplying Secondary Fuel Or The Like To Fuel, Air Or Fuel-Air Mixtures (AREA)

Abstract

Une boîte métallique destinée à être fixée au réservoir de carburant d'un véhicule afin de réduire les émissions d'hydrocarbures comprend une entrée des gaz, une sortie des gaz et une mise à l'évent, et contient un lit d'un polymère adsorbant et un lit de carbone. La mise à l'évent débouche dans le lit de carbone et l'entrée des gaz et la sortie des gaz débouchent dans le lit polymère.
PCT/GB1991/001269 1990-07-26 1991-07-26 Appareil et procede de recuperation de vapeur WO1992001585A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9016419.5 1990-07-26
GB909016419A GB9016419D0 (en) 1990-07-26 1990-07-26 Vapour recovery

Publications (1)

Publication Number Publication Date
WO1992001585A1 true WO1992001585A1 (fr) 1992-02-06

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PCT/GB1991/001269 WO1992001585A1 (fr) 1990-07-26 1991-07-26 Appareil et procede de recuperation de vapeur

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AU (1) AU8281391A (fr)
GB (1) GB9016419D0 (fr)
WO (1) WO1992001585A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997033765A1 (fr) * 1996-03-13 1997-09-18 Filterwerk Mann+Hummel Gmbh Filtre d'adsorption variable
EP0822004A3 (fr) * 1996-07-31 1998-07-15 Seibu Giken Co., Ltd. Un adsorbant
WO1999049236A1 (fr) * 1998-03-20 1999-09-30 Courtney, William Amortisseur elastomere perfectionne a amortissement visqueux
WO2001062367A1 (fr) * 2000-02-22 2001-08-30 Norit Nederland B.V. Procede servant a effectuer l'adsorption de vapeurs organiques depuis des melanges de gaz les contenant
US6540815B1 (en) 2001-11-21 2003-04-01 Meadwestvaco Corporation Method for reducing emissions from evaporative emissions control systems
US6773491B1 (en) * 1999-10-29 2004-08-10 Daimlerchrysler Ag Activated carbon filter
EP1852596A1 (fr) * 2006-05-03 2007-11-07 Delphi Technologies, Inc. Récipient de rétention de vapeur
US9732649B2 (en) 2012-10-10 2017-08-15 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US10960342B2 (en) 2012-10-10 2021-03-30 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US11732680B2 (en) 2017-06-19 2023-08-22 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
WO2024052872A1 (fr) * 2022-09-08 2024-03-14 Delphi Technologies Ip Limited Absorbeur de vapeurs de carburant doté de carbone en couches

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3838673A (en) * 1972-10-04 1974-10-01 Chevron Res Two-stage cold start and evaporative control system and apparatus for carrying out same
US3844739A (en) * 1972-10-05 1974-10-29 Dow Chemical Co Apparatus and method for the prevention of evaporative loss of mixed organic liquids
GB1416336A (en) * 1971-11-30 1975-12-03 Rohm & Haas Adsorption process
US4289513A (en) * 1978-03-27 1981-09-15 The Mead Corporation Activated sorbtion paper and products produced thereby
US4308841A (en) * 1977-02-02 1982-01-05 General Motors Corporation Emission control system with integrated evaporative canister purge
US4684382A (en) * 1986-02-28 1987-08-04 General Motors Corporation Evaporative fuel control canister containing EPDM foam filter
EP0330864A2 (fr) * 1988-02-27 1989-09-06 Adam Opel Aktiengesellschaft Dispositif de contrôle de l'évaporation du carburant dans des véhicules
DE3842994A1 (de) * 1988-12-21 1990-07-05 Audi Ag Aktivkohlefilter zum auffangen von kraftstoffdaempfen

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1416336A (en) * 1971-11-30 1975-12-03 Rohm & Haas Adsorption process
US3838673A (en) * 1972-10-04 1974-10-01 Chevron Res Two-stage cold start and evaporative control system and apparatus for carrying out same
US3844739A (en) * 1972-10-05 1974-10-29 Dow Chemical Co Apparatus and method for the prevention of evaporative loss of mixed organic liquids
US4308841A (en) * 1977-02-02 1982-01-05 General Motors Corporation Emission control system with integrated evaporative canister purge
US4289513A (en) * 1978-03-27 1981-09-15 The Mead Corporation Activated sorbtion paper and products produced thereby
US4684382A (en) * 1986-02-28 1987-08-04 General Motors Corporation Evaporative fuel control canister containing EPDM foam filter
EP0330864A2 (fr) * 1988-02-27 1989-09-06 Adam Opel Aktiengesellschaft Dispositif de contrôle de l'évaporation du carburant dans des véhicules
DE3842994A1 (de) * 1988-12-21 1990-07-05 Audi Ag Aktivkohlefilter zum auffangen von kraftstoffdaempfen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 9, no. 103 (M-377)(1826) 8 May 1985 & JP,A,59 226 263 ( TOYOTA ) 19 December 1984 see abstract *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997033765A1 (fr) * 1996-03-13 1997-09-18 Filterwerk Mann+Hummel Gmbh Filtre d'adsorption variable
EP0822004A3 (fr) * 1996-07-31 1998-07-15 Seibu Giken Co., Ltd. Un adsorbant
WO1999049236A1 (fr) * 1998-03-20 1999-09-30 Courtney, William Amortisseur elastomere perfectionne a amortissement visqueux
US6773491B1 (en) * 1999-10-29 2004-08-10 Daimlerchrysler Ag Activated carbon filter
WO2001062367A1 (fr) * 2000-02-22 2001-08-30 Norit Nederland B.V. Procede servant a effectuer l'adsorption de vapeurs organiques depuis des melanges de gaz les contenant
US6866699B2 (en) 2000-02-22 2005-03-15 Norit Nederland B.V. Process for the adsorption of organic vapours from gas mixtures containing them
US6540815B1 (en) 2001-11-21 2003-04-01 Meadwestvaco Corporation Method for reducing emissions from evaporative emissions control systems
WO2003046362A1 (fr) * 2001-11-21 2003-06-05 Meadwestvaco Corporation Procede de reduction des emissions provenant des systemes de controle des emissions de vapeurs de carburant
USRE38844E1 (en) 2001-11-21 2005-10-25 Meadwestvaco Corporation Method for reducing emissions from evaporative emissions control systems
KR100762051B1 (ko) * 2001-11-21 2007-09-28 미드웨스트바코 코포레이션 연료증발가스 배출 억제 시스템에서의 배출량 감소 방법
CN100416073C (zh) * 2001-11-21 2008-09-03 米德韦斯特瓦科公司 减少蒸发排放控制系统中排放物的方法
EP1852596A1 (fr) * 2006-05-03 2007-11-07 Delphi Technologies, Inc. Récipient de rétention de vapeur
US9732649B2 (en) 2012-10-10 2017-08-15 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US11506097B2 (en) 2012-10-10 2022-11-22 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US10323553B2 (en) 2012-10-10 2019-06-18 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US10422261B2 (en) 2012-10-10 2019-09-24 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US10960342B2 (en) 2012-10-10 2021-03-30 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US11286823B2 (en) 2012-10-10 2022-03-29 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US11448109B2 (en) 2012-10-10 2022-09-20 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US10280820B2 (en) 2012-10-10 2019-05-07 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US11536178B2 (en) 2012-10-10 2022-12-27 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US11976581B2 (en) 2012-10-10 2024-05-07 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US11846221B2 (en) 2012-10-10 2023-12-19 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US11732680B2 (en) 2017-06-19 2023-08-22 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
US12152554B2 (en) 2017-06-19 2024-11-26 Ingevity South Carolina, Llc Evaporative fuel vapor emission control systems
WO2024052872A1 (fr) * 2022-09-08 2024-03-14 Delphi Technologies Ip Limited Absorbeur de vapeurs de carburant doté de carbone en couches

Also Published As

Publication number Publication date
GB9016419D0 (en) 1990-09-12
AU8281391A (en) 1992-02-18

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