(19)
(11)EP 3 337 589 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
13.05.2020 Bulletin 2020/20

(21)Application number: 16740994.5

(22)Date of filing:  14.07.2016
(51)Int. Cl.: 
B01D 39/16  (2006.01)
B01D 39/20  (2006.01)
B01D 39/18  (2006.01)
(86)International application number:
PCT/EP2016/066769
(87)International publication number:
WO 2017/032505 (02.03.2017 Gazette  2017/09)

(54)

FUEL-WATER SEPARATOR FOR REMOVING WATER FROM WATER-HYDROCARBON EMULSIONS HAVING IMPROVED EFFICIENCY

KRAFTSTOFF-WASSER-ABSCHEIDER ZUR ENTFERNUNG VON WASSER AUS WASSER-KOHLENWASSERSTOFF-EMULSION MIT VERBESSERTER EFFIZIENZ

SÉPARATEUR EAU/CARBURANT PERMETTANT D'ÉLIMINER L'EAU D'ÉMULSIONS EAU/HYDROCARBURES PRÉSENTANT UNE EFFICACITÉ AMÉLIORÉES


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 22.08.2015 US 201562208659 P

(43)Date of publication of application:
27.06.2018 Bulletin 2018/26

(73)Proprietor: Ahlstrom-Munksjö Oyj
00100 Helsinki (FI)

(72)Inventors:
  • GOODBY, Andrew
    Sturgis, KY 42459 (US)
  • JANA, Praveen
    Bear, Delaware 19701 (US)
  • ARRINGTON, Crawford
    Mount Juliet, Tennessee 37122 (US)
  • VENKATESWARAN, Ganga
    Worcester, MA 01604 (US)
  • HARMON, Aaron
    Owensboro, Kentucky 42301 (US)
  • SHIM, Jesse
    Daegu Metropolitan City (KR)
  • KWON, Ryan
    Daegu Metropolitan City (KR)
  • KIM, Kevin
    Daegu Metropolitan City (KR)
  • BAE, Jayden
    Daegu Metropolitan City (KR)
  • YEO, Patrick
    Chuncheon-si Gangwon-do (KR)

(74)Representative: Vossius & Partner Patentanwälte Rechtsanwälte mbB 
Siebertstrasse 3
81675 München
81675 München (DE)


(56)References cited: : 
WO-A2-02/20132
US-A1- 2007 074 628
US-A1- 2010 319 543
US-A1- 2006 137 318
US-A1- 2010 024 370
US-A1- 2011 168 647
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Technical field



    [0001] The present invention relates to a fuel water separator including a fuel water separation medium for removing water from water-hydrocarbon emulsions, a process for the preparation of the medium, and the use of the fuel water separator for removing water from water-hydrocarbon emulsions.

    Background



    [0002] There is an increasing demand for filter media that efficiently remove emulsified water from fuel. Specifically, an effectual fuel-water separation in new (bio-)diesel and gasoline engine systems requires media that are efficient in terms of water removal in order to avoid the known problems associated with a high amount of emulsified water in fuel. For instance, high amounts of water may considerably affect the performance of the carburetor, the fuel injection system and the engine itself due to lack of lubrication and/or corrosion protection caused by the water contamination. Ultimately, water contamination may result in increased wear and rust in the fuel system. Moreover, a blockage or damage of the carburetor and/or the fuel pump may occur.

    [0003] In addition to increasingly stricter emission regulations, there is also an increasing demand for smaller filters without considerably sacrificing the achieved water removal efficiency, thereby saving space/weight and consequently fuel. Less fuel consumption results in less carbon dioxide emission and is therefore desirable in order to meet the vehicle emission regulations.

    [0004] Some filter media of the prior art are saturated with water repellant additives for achieving a sufficiently high fuel-water separation efficiency, since these additives enhance the coalescence of water drops during the filtering process. Usually, these water repellant additives are silicone or fluorohydrocarbons which might not be desirable for environmental reasons.

    [0005] Known fuel water separator filter media, for example US 2011/168647 A1, typically contain a high percentage of synthetic fibers, such as meltblown synthetic fibers, or even consist of synthetic fibers only. However, these filter media are not pleateable or self-supporting as such, particularly when working under the harsh conditions in connection with a combustion engine. As a result, these media have to be co-pleated and reinforced with some sort of additional mechanical support layer, such as a plastic or wire mesh backing. Further, media made with high levels of synthetic fiber typically tend to exhibit drape and they lack sufficient stiffness and rigidity causing the pleats to collapse without an additional support. A 100 % synthetic media as disclosed in the prior art cannot maintain a grooving pattern like corrugation or a pleated structure due to the thermal and mechanical properties of the synthetic fibers. However, grooving patterns are typically important for increasing the surface of filter media, thereby being able to provide the desired high fuel-water removal efficiency of the filter media. Another issue to be addressed is that customers desire a longer service interval for filter media. This may be achieved when providing fuel water separation media that are able to remove water from water-fuel emulsions over a long period of time and with a high efficiency. Hence, a considerable loss of water removal efficiency over time due to e.g. clogging of the filter or wear is disadvantageous.

    [0006] It is thus an objective of the present invention to provide a fuel water separator with an improved filter medium for water removal from water-fuel emulsions which addresses the above issues.

    Summary of the Invention



    [0007] The following summary merely presents some concepts of the present invention in a simplified form as a prelude to a more detailed description of exemplifying embodiments of the present invention.

    [0008] The present invention relates to a fuel water separator with a fuel water separation medium for removing water from water-hydrocarbon emulsions comprising (A) a first layer comprising nanofibers; and (B) a second layer comprising a fibrous web wherein the fibrous web comprises cellulosic fibers and at least one binder resin. The nanofibers have an average fiber diameter of about 50-350 nm, such as about 100-300 nm. The fuel water separation medium has a basis weight of about 100-300 g/m2, such as about 150-300 g/m2, and is characterized by having a net change in water removal efficiency of preferably less than about 10 %, more preferably less than about 5 %. The net change in water removal efficiency is defined as the difference between the water removal efficiency measured after 165 min and after 15 min according to SAEJ1488.

    [0009] Without wishing to be bound by any particular theory, the Applicant surprisingly observed that by providing the inventive fuel water separation medium including, in combination:
    • a specific layer comprising nanofibers, wherein the nanofibers have a specific average fiber diameter; and
    • a specific fibrous web comprising cellulosic fibers; the fuel water separation medium also having:
      • a specific basis weight of about 100-300 gsm (g/m2); a better balance of the fuel water separation performance in terms of both water removal efficiency and long term effect may be achieved.

    Detailed Description of the Invention


    General Definitions:



    [0010] The verbs "to comprise" and "to include" are used herein as open limitations that neither exclude nor require the existence of un-recited features.

    [0011] The term "consisting essentially of" has the meaning that specific further component(s), which do not materially affect the essential characteristics of the layer or medium in question, may be present.

    [0012] The features recited in depending claims are freely combinable unless otherwise explicitly stated.

    [0013] Furthermore, it is to be understood that the use of "a" or "an", i.e. a singular form, used herein does not exclude the plural form.

    [0014] Unless stated otherwise, all percentages are expressed as percentages by weight.

    [0015] Unless otherwise indicated, the unit "um" corresponds to "µm" or micron(s).

    [0016] Within the framework of the present description and of the following claims, "cellulose fibers" or "cellulosic fibers" comprise naturally occurring cellulosic material such as Northern bleached softwood kraft pulp (NBSK), Southern bleached softwood kraft pulp (SBSK) and hardwood pulps, such as Eucalyptus pulp.

    [0017] "Synthetic Fibers" are manmade fibers including, but not limited to, thermoplastic fibers (such as polyether sulfone, polyester, PET, polyamide, polyvinylidene fluoride, polybutylene terephthalate), glass fibers and regenerated cellulose fibers.

    [0018] Within the framework of the present description and of the following claims, "nanofibers" are fibers having a diameter less than 1 um or 1 micron (1000 nm), particularly 50-350 nm such as 100-300 nm. The nanofibers are formed according to known methods such as via an electrospinning process using suitable polymeric material(s). In this disclosure, nanofibers preferably are formed from thermoplastic polymeric materials including, but not limited to, polyether sulfone (PES), polyamide (PA) such as nylon, fluoropolymers such as e.g. polyvinylidene fluoride (PVDF), polyacrylonitrile, polyamide, particularly nylon, or PVDF.

    [0019] A "fluoropolymer" is a fluorocarbon-based polymer which typically has a high resistance to solvents, acids, and bases. Suitable fluoropolymers are PVF (polyvinylfluoride); PVDF (polyvinylidene fluoride); PTFE (polytetrafluoroethylene); PCTFE (polychlorotrifluoroethylene); PFA, MFA (perfluoroalkoxy polymer); FEP (fluorinated ethylene-propylene); SETFE (polyethylenetetrafluoroethylene); ECTFE (polyethylenechlorotrifluoroethylene); FFPM/FFKM (perfluorinated Elastomer); FPM/FKM (fluorocarbon [chlorotrifluoroethylenevinylidene fluoride]); FEPM (fluoroelastomer [tetrafluoroethylene-propylene]); PFPE (perfluoropolyether); PFSA (perfluorosulfonic acid); and/or perfluoropolyoxetane.

    [0020] A "fibrous web" as used herein includes a "nonwoven" or a "paper" and is a manufactured sheet or web of directionally or randomly oriented fibers bonded by friction, cohesion or adhesion. The fibers may be staple or continuous/substantially continuous or formed in situ and may be of natural or man-made materials.

    [0021] Within the framework of the present description and of the following claims, a "fine fiber layer" may comprise one or more fiber layer(s) that comprises continuous/substantially continuous fibers and may be of natural or man-made materials.

    [0022] "Staple fibers" are short cut fibers that may be typically not longer than about 45 mm.

    [0023] "Continuous fibers" are long fibers or filaments that may be typically longer than about 45 mm. The term "substantially continuous fibers" includes continuous fibers and fibers which might have been broken during formation and/or use.

    [0024] "Resins" or "binder resins" used in the inventive media may comprise phenolic, acrylic and epoxy resins. Resins can be applied or coated onto the substrate by any means know in the art. The resins can be applied to one side or both sides. The physical properties of the inventive media can be evaluated after it has been saturated and dried (SD) as well as after it has been saturated, dried and cured (SDC). The step of drying removes the solvent without crosslinking the resin.

    [0025] An "adhesive" or "glue" is a chemical compound that assists in holding together the specific layers of the medium such as the nanofiber layer to the fibrous web and/or the fine fiber layer, if present. The adhesive or glue is present in the form of a partial layer between the layers that shall be hold together.

    [0026] "Corrugations" (used interchangeably with "grooves" or "grooving") are added to a (preferably resin saturated) media in the machine direction to provide support for pleated media in the finished filter element.

    [0027] The term "substantially no glass fibers" means that no glass fibers, i.e. 0% by weight of glass fibers, are present in the corresponding layer, based on the total weight of the corresponding layer.

    [0028] The term "substantially no synthetic fibers" means that less than 10 % by weight, more preferably less than 5 % by weight, most preferably 0 % by weight, of synthetic fibers are present in the corresponding layer, based on the total weight of the corresponding layer.

    [0029] The term "substantially no fibrillated fibers" means that less than 10 % by weight, more preferably less than 5 % by weight, most preferably 0 % by weight, of fibrillated fibers are present in the corresponding layer, based on the total weight of the corresponding layer.

    [0030] The term "about" in the context of numerical values means that specific values may be modified by +/- 10%. As regards endpoints of ranges, the modifier "about" preferably means that the lower endpoint may be reduced by 10% and the upper endpoint may be increased by 10%. It is also contemplated that each numerical value or range disclosed in this application can be absolute, i.e. that the modifier "about" can be deleted.

    [0031] If a layer (L1) is "on an upstream side" (or "on top") of a layer (L2), this means that the layer (L1) is situated, relative to the layer (L2), closer to the inventive media's surface which is in contact with the unfiltered water-fuel emulsions. On the other hand, if a layer (L1) is "on a downstream side" of a layer (L2), this means that the layer (L1) is situated, relative to the layer (L2), farther from the inventive media's surface which is in contact with the unfiltered water-fuel emulsions. In the latter case, the layer (L1) is, relative to layer (L2), closer to the inventive media's surface which is in contact with the filtered water-fuel emulsions, i.e. to the surface of the inventive media from which the filtered and dried fuel exits the inventive media.

    [0032] The term "fuel" preferably refers to low sulphur diesel.

    [0033] The "dust holding capacity" refers to the added weight of trapped particles when the media reaches a target pressure drop or terminal differential pressure such as 85 KPa.

    [0034] The "water removal efficiency" in the context of the invention is the propensity of the inventive media to remove water from water-fuel emulsions, thereby producing dried fuel, as opposed to allowing the water-fuel emulsion to pass through the inventive media. Specifically, the "initial water removal efficiency" is the water removal efficiency directly after its preparation and not when being in usage, i.e. the filter is not loaded with particles or heavily soaked with water. In contrast, the "average water removal efficiency" means the mean water removal efficiency over time when being in usage.

    [0035] The "net change in water removal efficiency" is defined as the water removal efficiency measured according to SAEJ1488 after 165 min from which the water removal efficiency measured according to SAEJ1488 after 15 min is subtracted.

    Brief description of the Figures



    [0036] 

    Fig. 1: Construction of comparative and inventive filter media.

    Fig. 2: Overall water removal efficiency of an inventive medium as compared to comparative medium.


    The fuel water separation medium



    [0037] The fuel water separation medium according to the invention comprises, or consists (essentially) of, (A) at least one first layer comprising nanofibers and (B) at least one second layer comprising a fibrous web. Optionally, (C) at least one fine fiber layer as third layer and/or (D) at least one adhesive layer may be present. These specific layers are described in the following in more detail:

    (A) First layer (also referred to as "nanofiber layer")



    [0038] The first layer comprises, or consists (essentially) of, nanofibers, i.e. the first layer is a nanofiber layer. It is believed that this layer (possibly along with the second layer as defined below) provides efficient stripping of emulsified water and/or (surface) coalescence from water fuel emulsions. Specifically, emulsified water assembles/coalesces into larger droplets that may be efficiently stopped by the first layer, thereby reducing water saturation of the second layer which would deteriorate the second layer's water removal efficiency. Therefore, the first layer may be considered to be a water stripping and/or (surface) coalescing layer.

    [0039] The nanofibers of the first layer have an average fiber diameter of about 50 to about 350 nm, preferably about 100 to about 300 nm.

    [0040] In preferred embodiments, the nanofibers of the first layer may be electrospun directly onto the adjacent layer (like the second layer or, if present, an adhesive (coating) layer as defined below). Methods for preparing the nanofibers via electrospinning are known in the art. The obtained electrospun nanofibers are typically continuous or substantially continuous fibers.

    [0041] In other preferred embodiments, the nanofibers may be synthetic nanofibers prepared from the following thermoplastic polymeric materials: polyethersulfone (PES); polyacrylonitrile; polyamide (PA) such as nylon; fluoropolymers such as polyvinylfluoride (PVDF); and/or mixtures thereof. In more preferred embodiments, the nanofibers may be polyamide fibers or fluoropolymeric fibers. In most preferred embodiments, the nanofibers may be nylon fibers or polyvinylfluoride fibers.

    [0042] In other preferred embodiments, the first layer may consist, or consist essentially, of nanofibers as defined above.

    [0043] In some embodiments, the nanofibers may be prepared from an adhesive and polyethersulfone. Preferably, the adhesive is a diisocyanate. The adhesive is used in an amount of about 1 to about 5 % by weight and the PES is used in an amount of about 95 to about 99% by weight, based on the total weight of the corresponding composition. This composition is mixed and manufactured into nanofibers via electrospinning directly onto the second layer or, if present, on an adhesive (coating) layer on top of the second layer as defined below.

    (B) Second layer (also referred to as "substrate layer")



    [0044] The second layer comprises, or consists (essentially) of, at least one fibrous web. This fibrous web may be considered to be a substrate layer. The fibrous web comprises, or consists (essentially) of, cellulose fibers (also referred to as cellulosic fibers). The substrate layer is saturated with a binder resin including a water repellant additive like silicone or fluorocarbon. It is believed that the emulsified water from the water fuel emulsions does not easily wet the inventive media's surface and beads up on both the nanofiber layer's and the substrate layer's surfaces. The beads coalesce into larger drops which then fall into the collection bowl of the fuel water separator comprising the inventive media. Therefore, the substrate layer may be also considered to be a stripper media (and/or surface coalescer).

    [0045] In preferred embodiments, the cellulosic fibers may include about 0-100% by weight of softwood fibers and/or about 100-0% by weight of hardwood fibers based on the total weight of the second layer. More preferably, 40-10 % by weight of softwood fibers and 60-90 % by weight of hardwood fibers based on the total weight of the second layer may be present. Exemplary softwood fibers include fibers obtained from mercerized southern pine such as mercerized southern pine fibers or "HPZ fibers" or southern bleached softwood kraft such as Brunswick pine. Exemplary hardwood fibers include fibers obtained from Eucalyptus.

    [0046] In preferred embodiments, the fibrous web may comprise cellulosic fibers in an amount of at least about 50 % by weight, preferably at least about 60% by weight or at least about 70 % by weight, more preferably at least about 80% by weight or 90% by weight based on the total weight of second layer. In most preferred embodiments, the fibrous web may consist (essentially) of cellulosic fibers. Due to the presence of cellulosic fibers, it is believed that the second layer may provide the stiffness that e.g. synthetic (such as meltblown) base sheets of the prior art will not be able to provide. However, if the substrate layer is not stiff enough, it may be very difficult to make a pleated and/or corrugated filter.

    [0047] Preferably, the second layer may have a Gurley stiffness of about 2-15 g, preferably about 3-8 g such as about 5.5 g. The Gurley stiffness indicates the bending resistance of the analyzed filter medium.

    [0048] In preferred embodiments, the fibrous web may comprise substantially no glass fibers. In other embodiments, the second layer may comprise about 70 to about 100 % by weight cellulosic fibers and about 0 to about 30 % by weight glass fibers, based on the total weight of the second layer.

    [0049] In other preferred embodiments, the fibrous web may comprise substantially no synthetic fibers. In other embodiments, the second layer may comprise about 50 to about 90 % by weight cellulosic fibers and about 50 to about 10 % by weight synthetic fibers, based on the total weight of the second layer.

    [0050] The average fiber diameter of the cellulose fibers in the second layer may be, for example, greater than or equal to about 0.5 microns, about 1 micron, about 5 microns, about 10 microns, about 20 microns, about 50 microns, or about 75 microns. In some instances, the average fiber diameter of the cellulose fibers may be less than or equal to about 75 microns, about 50 microns, about 20 microns, about 10 microns, about 5 microns, about 1 micron, or about 0.5 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to about 1 micron and less than or equal to about 5 microns). Preferably, the average fiber diameter is greater than or equal to about 0.5 mm and less than or equal to about 20 microns).

    [0051] In some embodiments, the cellulose fibers may have an average length of greater than or equal to about 0.5 mm, about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 10 mm, or about 20 mm. In some instances, the average length may be less than or equal to about 20 mm, about 10 mm, about 5 mm, about 4 mm, about 3 mm, about 2 mm, about 1 mm, or about 0.5 mm. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to about 1 mm and less than or equal to about 0.5 mm). Preferably, the average length may be greater than or equal to about 1 mm and less than or equal to about 7 mm.

    [0052] In some embodiments, (micro-)fibrillated fibers (like (micro-)fibrillated cellulosic fibers) may be present in the second layer such as up to about 30 % by weight of (micro-)fibrillated fibers, preferably up to 20 % by weight of (micro-)fibrillated fibers, more preferably up to 10 % by weight of (micro-)fibrillated fibers. In alternative and more preferred embodiments, substantially no (micro-)fibrillated cellulose fibers may be present in the second layer.

    [0053] In preferred embodiments, the second layer may have a basis weight in the range of 60-250 g/m2, preferably in the range of 100-170 g/m2.

    [0054] In some embodiments, the air permeability of the second layer (w/phenolic resin) may be greater than or equal to about 51 l/m2sec (10 cfm) and/or less than or equal to about 102 l/m2sec (20 cfm). Preferably, the air permeability may be greater than or equal to about 61 l/m2sec (12 cfm) and less than or equal to about 91 l/m2sec (18 cfm) such as e.g. 66 l/m2sec (13 cfm), 81 l/m2sec (16 cfm), or 86 l/m2sec (17 cfm).

    [0055] The second layer comprises at least one binder resin such as a phenolic resin, an acrylic resin, a melamine resin, a silicone resin, a fluorocarbon resin/fluoropolymer, an epoxy resin and/or mixtures thereof. Preferably, the second layer may be coated or impregnated/saturated with the binder resin. In preferred embodiments, the binder resin may have a concentration of from 10-30 % by weight, preferably 15-20 % by weight, of the second layer.

    [0056] The second layer may optionally include at least one additive which is common in the art. The at least one additive may be selected from a wet strength additive, a water repellant, a flame-retardant agent, a coloring agent, a hydrophobic agent, a hydrophilic agent, a wetting agent, an antimicrobial agent or an antistatic agent.

    [0057] In preferred embodiments, the second layer may not comprise a water repellant additive without sacrificing the obtained water removal efficiency.

    [0058] In some preferred embodiments, the second layer may be present on a downstream side of the first layer.

    [0059] In some alternative preferred embodiments, the second layer may be present on an upstream side of the first layer.

    (C) Optional at least one third layer (also referred to as "fine fiber layer")



    [0060] The at least one third layer is a fine fiber layer and may be optionally present in the inventive media. This at least one fine fiber layer serves to protect the downstream layers of the inventive media by capturing particulate impurities from the water-fuel emulsions to be filtered, thereby avoiding the clogging of the second layer's pores which would deteriorate the second layer's absorption performance and ultimately its water removal efficiency. Therefore, the fine fiber layer may be considered to be a protective layer.

    [0061] In one embodiment, the inventive medium may not include a protective fine fiber layer as third layer on an upstream side of the first layer.

    [0062] In an alternative embodiment, the inventive medium may comprise at least one fine fiber layer as protective layer, wherein the at least one fine fiber layer may be present on an upstream side of the first layer. In one embodiment, two fine fiber layers may be present, wherein one of the fine fiber layers may be present on an upstream side of the first layer and the other fine fiber layer may be present on a downstream side of the first layer.

    [0063] In preferred embodiments, the at least one third layer has a basis weight of about 10 to about 100 g/m2 such as about 15 to about 80 g/m2.

    [0064] In preferred embodiments, the fine fiber layer may comprise, or may consist (essentially) of, synthetic fibers. Synthetic fibers may include any suitable type of synthetic polymer fibers. Examples of suitable (thermoplastic) synthetic polymers fibers include, but are not limited to, fibers prepared from polyester; polyethylene terephthalate; polyolefin such as polyethylene or polypropylene; polybutylene terephthalate; polyamide; and/or mixtures thereof.

    [0065] Synthetic fibers may also include multi-component fibers, i.e. fibers having multiple compositions such as bicomponent fibers.

    [0066] In some embodiments, the synthetic fibers of the fine fiber layer may be formed via meltblowing, meltspinning, or spunbonding. These methods are known in the art. The obtained synthetic fibers are typically continuous and/or substantially continuous fibers.

    [0067] In preferred embodiments, the third layer may comprise, or may consist (essentially) of, two sub-layers: (i) a spunbond fine fiber layer, such as a PET layer having preferably a basis weight of about 8 to about 30 g/m2; and (ii) a meltblown fine fiber layer, such as a PBT layer having preferably a basis weight of about 25 to about 80 g/m2. Preferably, the spunbond fine fiber layer may be on an upstream side of the meltblown fine fiber layer and both sub-layers may be on an upstream side of the first and second layer. In some preferred embodiments, the meltblown layer may be present on a downstream side of the spunbond layer.

    [0068] In other preferred embodiments, the third layer may comprise, or may consist (essentially) of, one sub-layer: a spunbond fine fiber layer, such as a PP/PE layer having preferably a basis weight of about 10 to about 20 g/m2 such as 17 g/m2. Preferably, this spunbond fine fiber sub-layer may be on a downstream side of the first and second layer.

    [0069] The diameter range of the synthetic fibers of this meltblown fine fiber layer in the inventive media may be between about 0.1 to about 30 microns, more preferably between about 0.1 to about 5 microns for a majority of fibers such as e.g. 95 % or 98 % of the total number of meltblown fibers.

    [0070] The average diameter of the synthetic fibers of this spunbond layer in the inventive media may be, for example, greater than or equal to about 10 microns, about 20 microns, or about 30 microns. In some instances, these synthetic fibers may have an average diameter of less than or equal to about 30 microns, about 20 microns, about 10 microns. Preferred is an average fiber diameter of less than or equal to about 20 microns and greater than or equal to 0.5 or micron(s).

    (D) Optional adhesive layer(s)



    [0071] In preferred embodiments, the inventive medium may comprise at least one adhesive layer or adhesive coating between adjacent first, second or, if present, third layers as defined above. Specifically, in one preferred embodiment, the inventive medium may comprise at least one adhesive layer between the first and the second layer and/or between the first and the third layer, if present. In another preferred embodiment, the inventive medium may comprise at least one adhesive layer between the first and the second layer and/or between the second and the third layer, if present.

    [0072] The adhesive can be any adhesive that can be spray-coated onto the layer to be coated. Preferably, the adhesive is selected from a polyurethane; acrylate; PVA; polyolefin ethylene co-polymer; and/or rubber-based adhesive. Most preferred are polyamide hot melt adhesives, polyurethane hot melt adhesives or PVOH stabilized carboxylated vinyl acetate-ethylene copolymers. In preferred embodiments, the adhesive is applied to the layer to be coated in a manner such that it does not affect the permeability of the corresponding layer. That is, the adhesive is applied with a coat weight of less than about 5 gsm.

    [0073] Alternatively, the inventive medium may comprise no adhesive layer between the first and the second layer and/or between the first and the third layer, if present, but these layers are laminated or adhered to by any commonly known technique(s).

    Specific embodiments of the fuel water separation medium



    [0074] In one embodiment, the inventive medium may comprise the second layer on a downstream side of the first layer.

    [0075] In preferred embodiments, the inventive medium may not include the protective fine fiber layer as third layer on an upstream side of the first layer.

    [0076] In an alternative embodiment, the inventive medium may comprise the second layer on an upstream side of the first layer.

    [0077] In some other preferred embodiments, the inventive medium may comprise the third fine fiber layer on an upstream side of the first layer.

    [0078] In other preferred embodiments, the inventive medium may comprise, or consist (essentially) of, the second layer on a downstream side of the first layer and the third (fine fiber) layer is on an upstream side of the first layer.

    [0079] In other preferred embodiments, the inventive medium may comprise, or consist (essentially) of, a first fine fiber layer on an upstream side of the second layer, the second layer on an upstream side of the first layer and a second fine fiber layer on a downstream side of the first layer.

    [0080] In most preferred embodiments, the inventive medium may therefore comprise, or consist (essentially) of, the following layers from downstream to upstream: (B) the second layer; (D1) a first adhesive layer on top of the second layer; (A) the first layer on top of the first adhesive layer; (D2) a second adhesive layer on top of the first layer; and (C) a fine fiber layer on top of the second adhesive layer. Preferably, the fine fiber layer may comprise, or consist (essentially) of, two sub-layers, namely a meltblown (such as PBT) and a spunbond (such as PET) fine fiber layer.

    [0081] In other preferred embodiments, the inventive medium may therefore comprise, or consist (essentially) of, the following layers from downstream to upstream: (B) the second layer; (A) the first layer on top of the second layer; and (C) a first fine fiber layer on top of the first layer.

    [0082] In other preferred embodiments, the inventive medium may therefore comprise, or consist (essentially) of, the following layers from downstream to upstream: (B) the second layer; (D) an adhesive layer on top of the second layer; and (A) the first nanofiber layer on top of the adhesive layer.

    [0083] In most preferred embodiments, the inventive medium may therefore comprise, or consist (essentially) of, the following layers from downstream to upstream: (C1) a first fine fiber layer; (A) the first layer on top of the first fine fiber layer; (D1) a first adhesive layer on top of the first layer; (B) the second layer; (D2) a second adhesive layer on top of the second layer; and (C2) a second fine fiber layer on top of the second layer. Preferably, the first fine fiber layer may comprise, or consist (essentially) of, two sub-layers, namely a meltblown (such as PBT) and a spunbond (such as PET) fine fiber layer, and the second fine fiber layer may comprise, or consist (essentially) of, a spunbond fine fiber layer such as bicomponent PE/PP.

    [0084] In other preferred embodiments, the inventive medium may therefore comprise, or consist (essentially) of, the following layers from downstream to upstream: (C1) a first fine fiber layer; (A) the first layer on top of the first fine fiber layer; (B) the second layer; and (C2) a second fine fiber layer on top of the second layer.

    [0085] The inventive medium has a basis weight of about 100-300 g/m2, preferably about 150-300 g/m2.

    [0086] The inventive medium is characterized by having a net change in water removal efficiency being preferably less than about 10 %, more preferably less than about 5 %. Specifically, the net change in water removal efficiency is defined as follows:
    net change in water removal efficiency = (water removal efficiency after 165 min) - (water removal efficiency after 15 min);
    wherein the water removal efficiency is measured according to SAEJ1488.

    [0087] It has been found that the inventive medium may have excellent mechanical properties. In particular, the inventive medium may preferably show at least one of the following properties:
    • a basis weight of about 150-300 g/m2 when tested according to TAPPI Standard T 410 om-02; and/or
    • an overall fuel-water separation efficiency of at least about 55% after 15 minutes when tested according to SAEJ1488; and/or
    • an overall fuel-water separation efficiency of at least about 60% after 165 minutes when tested according to SAEJ1488; and/or
    • a TSI aerosol penetration of less than or equal to about 15 %; and/or
    • a TSI resistance to flow of about 49 - 735 Pa (5 -75 mm H2O) ; and/or
    • an air permeability of about 15 - 102 l/m2sec (3 - 20 cfm) when tested
      according to TAPPI Standard T 251 cm-85; and/or
    • a mean flow pore size of about 2-10 um when tested according to ASTM 316-03 (2011); and/or
    • a leakage-corrected Frazier of 15 - 102 l/m2sec (3 - 20 cfm) when tested
      according to TAPPI Standard T 251 cm-85.


    [0088] Further, it was found that the inventive media is also suitable for use as a particle removal filter medium for removing particles from fuel or oil.

    Process for the preparation of the filter medium



    [0089] The process for the preparation of the inventive medium comprises the steps of
    • providing a first homogeneous slurry;
    • supplying the first slurry onto a dewatering screen to form a first deposit;
    • removing the water from the deposit to form a wet fibrous web;
    • drying the wet fibrous web while heating to form the second layer;
    • saturating the thus obtained second layer with at least a binder resin;
    • optionally coating of a first adhesive layer on top of the thus obtained second layer;
    • applying the first layer on top of the second layer or on top of the first adhesive layer coated onto the second layer, wherein the applying is preferably performed using electrospinning;
    • optionally coating of a second adhesive layer (i) on top of the first layer or (ii) on top of the second layer; and
    • optionally applying the third layer (iii) on top of the first layer, (iv) on top of the second adhesive layer coated onto the first layer, if present, (v) on top of the second layer or (vi) on top of the second adhesive layer coated onto the second layer, if present, wherein the applying is preferably performed by meltblowing a first fine fiber (sub-)layer and spunbonding a second fine fiber layer on top of the first fine fiber (sub-) layer;
    wherein the first slurry comprises water and cellulosic fibers.

    [0090] In this process, a first homogenous slurry is provided which may be prepared according to methods known in the art such as by adding and mixing the cellulosic fibers in water.

    [0091] Once the first homogeneous slurry is prepared, it is applied onto a dewatering screen in order to prepare the second layer. This screen can be any screen commonly used in a paper making process. Preferably, this screen is a dewatering endless screen. Upon supplying the first slurry onto the dewatering screen, a first deposit is formed on the screen. During or after deposition of the slurry, water is removed to form a wet fibrous mat or sheet. Subsequently, the wet fibrous mat or sheet is dried while heating.

    [0092] Impregnation of the thus obtained layer with a binder resin is carried out followed by drying, and/or a first adhesive layer may be (spray-)coated on top of the thus prepared dried fibrous mat or sheet which corresponds to the second layer as defined above. The binder resin and the adhesive can be any one as defined above.

    [0093] Next, nanofibers are applied on top of the second layer or on top of the first adhesive layer, if present, wherein the application is preferably performed using electrospinning. Methods for electrospinning of the nanofibers are known in the art.

    [0094] Optionally, a second adhesive layer may be (spray-)coated (i) on top of the thus prepared nanofiber layer or (ii) on top of the second layer. In the latter case, the nanofiber layer is present on the side opposite to the second adhesive layer, i.e. the second layer has a nanofiber layer on a downstream side and the second adhesive layer on an upstream side of the second layer.

    [0095] Optionally, a fine fiber layer may be applied (iii) on top of the first layer, (iv) on top of the second adhesive layer coated onto the first layer, if present, (v) on top of the second layer or (vi) on top of the second adhesive layer coated onto the second layer, if present. The application is preferably performed by meltblowing a first fine fiber (sub-)layer and spunbonding a second fine fiber layer on top of the first fine fiber (sub-)layer as defined above.

    Examples



    [0096] The invention will now be described in further detail by way of the following examples:

    Test methods:



    [0097] Basis Weight: The basis weight is measured according to TAPPI Standard T 410 om-02 and reported in grams per square meter (gsm or g/m2).

    [0098] Caliper or Thickness: The caliper or thickness of the media is determined according to TAPPI Standard T 411 om-05 using a Thwing Albert 89-100 Thickness Tester.

    [0099] Corrugation Depth: The corrugation depth is the difference between the caliper of the flat sheet of media and the thickness of the sheet after corrugating the media.

    [0100] Air Permeability (Frazier): The air permeability is determined according to TAPPI Standard T 251 cm-85. Specifically, the air permeability of the filter medium as defined by airflow was measured in cubic feet per minute per square foot (cfm/sf or also referred to as cfm or CFM) at a pressure drop of 125 Pascal (0.5" water column) using a Textest FX 3300 Air Permeability Tester, a calibration plate as supplied by Textest, Ltd., Zurich, Switzerland and a thin plastic film - GBC Heatseal letter-size laminating pouch or equivalent plastic film under controlled atmospheric conditions. The units "cfm" and "cfm/sf" are interchangeable. Air permeability may also be referred to porosity, Frazier or Textest.

    [0101] The Standard Textest procedure is as follows: Saturated/Dried paper is to be cured for 5 minutes at 175°C (Solvent Based Systems) or 2 minutes at 175°C (Water Based Systems) prior to testing. Saturated/Cured paper may be given an abbreviated cycle at an elevated temperature, since it is only necessary to drive off any moisture present. Unsaturated (Raw) paper samples may be tested Off Machine; drying is not necessary. Test Pressure: 125 Pa (or 0.5" w.c.). Place a sample to be measured felt side up between the clamping arm and the test head. Push the clamping arm down until it clicks, and locks into place, starting the test. Then note and record the displayed reading. Release the clamping arm by pressing down until it clicks a second time, stopping the test. All subsequent readings should be taken in the same fashion.

    [0102] The Textest clamp leakage test procedure is as follows: Textest leakage is determined by using a thin plastic film sheet over the grooved media under the clamping mechanism on the textest machine. Test the sample according to the above standard textest test procedure and then note and record the small leakage measurement.

    [0103] Mean Flow Pore Size (MFP): The size of the pores in the medium was determined using a bubble point method according to ASTM 316-03 (2011) utilizing a Porometer G3 Series (Quantachrome Instruments) and is reported in microns (µm or um).

    [0104] Gurley stiffness: The stiffness of the medium was determined according to TAPPI 543om-05 using a Gurley-type tester. The Gurley stiffness analyzes the ability of a sample to resist an applied bending force (i.e. the sample's bending resistance). The unit of the Gurley stiffness is gf (gram force) which is herein sometimes also referred to as gms or g.

    [0105] TSI penetration: The TSI penetration was determined using a TSI Incorporated Automated Filter Tester (Model 8130) to generate a salt (NaCl) or oil (DEHS) aerosol with particles of 0.3 micron diameter (modified EN 143 procedure). The particles in the upstream aerosol are counted and then the aerosol is used to challenge a flat sheet test sample (100 cm2) at a flow rate of 32 L/min. The particles in the aerosol are then counted again after passing completely through the test sample. The ratio between the quantities of particles counted before (upstream) and after (downstream) filtering is reported as the percent penetration, i.e. the downstream count is divided by the upstream count and multiplied by 100.

    [0106] TSI Resistance to Flow (mm H2O): TSI Resistance to flow is a measure of the pressure drop across the filter media. The higher the TSI resistance to flow, the greater the pressuredrop across the media. TSI Resistance is measured via an electronic pressure transducer and reported alongside the penetration number and the test flow rate. The measurement range of the instrument is 0-150mm H2O (0-1470 Pa) with an accuracy of 2% of the scale (TSI tester system: Model 8127 8130 Automated filter Tester).

    [0107] Fuel Filter Water Separation Efficiency: The filter medium was analyzed according to the SAEJ1488 test standard using a diesel-water emulsion (ultra-low sulfur diesel containing 2500 ppm water). Water removal is tested by taking samples upstream and downstream of the filter medium. The amount of water in the upstream and downstream samples is tested via Karl Fischer titration according to known methods.

    [0108] Example 1 (comparative): The base substrate is a 100 % cellulosic wet laid nonwoven comprising 28.5% NBSK and 71.4% Eucalyptus pulp having a basis weight of 128 gsm and a flat 25 sheet caliper of 0.36 mm (4 mils). The substrate is saturated with 17% phenolic resin. The substrate (w/phenolic resin) has an air permeability of 81 l/m2sec (16 cfm). This sample does not include a water repellant additive.

    [0109] Example 2: The base substrate is the same as in Example 1, but has an additional layer of polyether sulfone nanofibers electrospun directly onto the substrate at an add-on of 2 gsm for a total basis weight of 130 gsm and caliper of 0.38 mm (15 mils) (instructions for manufacturer; only theoretical values). The nanofibers have an average fiber diameter of 100-300 nm.

    [0110] Example 3 (comparative): The base substrate has a total basis weight of 114 gsm and is a wet-laid nonwoven consisting of 100 % cellulosic fibers (81.6 % by weight cellulosic fibers in the medium). The substrate is saturated with 18% by weight phenolic resin including 1-3 % by weight silicone as H2O repellant additive and 0.4 % by weight wet strength additive. The substrate (w/phenolic resin) has an air permeability of 66 l/m2sec (13 cfm).

    [0111] The base substrate has an additional adhesive layer (hot melt additive) on an upstream side and an additional protective fine fiber layer of meltblown PET (55 gsm) and spunbond PBT (15 gsm) on an upstream side directly onto the adhesive layer at an add-on of 70 gsm. The resulting filter medium is then corrugated. Example 4: The base substrate has a total basis weight of 144 gsm and is a wet-laid nonwoven consisting of 100 % cellulosic fibers (81.6 % by weight cellulosic fibers in the medium). The substrate is saturated with 18% by weight phenolic resin including 1-3 % by weight silicone as H2O repellant additive and 0.4 % by weight wet strength additive. The substrate (w/phenolic resin) has an air permeability of 66 l/m2sec (13 cfm).

    [0112] The base substrate has an adhesive layer (PVOH stabilized, carboxylated vinyl acetate-ethylene copolymer)) on an upstream side and a layer of nylon nanofibers electrospun directly onto the adhesive layer on an upstream side. An additional adhesive layer (hot melt additive) on an upstream side directly onto the nanofiber layer is present. The nylon nanofibers' diameter is 90-340 nm. An additional protective fine fiber layer of meltblown PET (55 gsm) and spunbond PBT (15 gsm) on an upstream side directly onto the additional adhesive layer at an add-on of 70 gsm is present. The resulting filter medium is then corrugated.

    [0113] Table I shows the structures of examples 3 and 4 (see also Figure 1):
    Table I
     Example 3Example 4
     (base paper A-fine fiber)(base paper A -nylon nano-fine fiber)
    5 Base paper Base paper
    Weight: 114gsm Weight: 114gsm
      18% Phenolic Resin with silicone additive, 18% Phenolic Resin with silicone additive,
    0.4% Wet-strength additive,
    0.4% Wet-strength additive, 81.6% Cellulose Fibers
    81.6% Cellulose Fibers  
    Corrugated Corrugated
    4 N/A Adhesive layer
    3 N/A Nanofiber Layer (Nylon)
    2 Adhesive layer
    1 70 gsm Fine-fiber Layer
    55gsm layer of PBT meltblown
    15gsm PET spunbond


    [0114] Example 5 (comparative): The base substrate has a total basis weight of 150 gsm and is a wet-laid nonwoven consisting of 100 % cellulosic fibers (84 % by weight cellulosic fibers in the medium). The substrate is saturated with 16% by weight phenolic resin including 1-3 % by weight fluorocarbon as H2O repellant additive and 0.6 % by weight wet strength additive. The substrate (w/phenolic resin) has an air permeability of 85.3 l/m2sec (16.8 cfm).

    [0115] The base substrate has an additional protective fine fiber layer of meltblown PET (55 gsm) and spunbond PBT (15 gsm) on an upstream side directly onto the substrate layer at an add-on of 70 gsm. The resulting filter medium is then corrugated.

    [0116] Example 6: The base substrate has a total basis weight of 150 gsm and is a wet-laid nonwoven consisting of 100 % cellulosic fibers (84 % by weight cellulosic fibers in the medium). The substrate is saturated with 16% by weight phenolic resin including 1-3 % by weight fluorocarbon as H2O repellant additive and 0.6 % by weight wet strength additive. The substrate (w/phenolic resin) has an air permeability of 86 l/m2sec (17 cfm).

    [0117] The base substrate has an additional adhesive layer (polyurethane, heat activated water dispersion) on an upstream side. In addition, a layer of polyamide nanofibers electrospun directly onto the adhesive layer on an upstream side and an additional adhesive layer (polyurethane, hot melt adhesive) on an upstream side directly onto the nanofiber layer are present. The polyamide nanofibers' average diameter is about 130-200 nm. An additional protective fine fiber layer of meltblown PET (55 gsm) and spunbond PBT (15 gsm) on an upstream side directly onto the adhesive layer at an add-on of 70 gsm is further present. The resulting filter medium is corrugated.

    [0118] Example 7: The base substrate has a total basis weight of 150 gsm and is a wet-laid nonwoven consisting of 100 % cellulosic fibers (84.0 % by weight cellulosic fibers in the medium). The substrate is saturated with 16.0% by weight phenolic resin including 1-3 % by weight fluorocarbon as H2O repellant additive and 0.6 % by weight wet strength additive. The substrate (w/phenolic resin) has an air permeability of 86 l/m2sec (17 cfm).

    [0119] The base substrate has an additional adhesive layer (polyurethane, heat activated water dispersion) on an upstream side. In addition, a layer of polyvinylidenefluoride (PVDF) nanofibers electrospun directly onto the adhesive layer on an upstream side and an additional adhesive layer (polyurethane, hot melt additive) on an upstream side directly onto the nanofiber layer are present. The polyamide nanofibers' average diameter is about 130-200 nm. An additional protective fine fiber layer of meltblown PET (55 gsm) and spunbond PBT (15 gsm) on an upstream side directly onto the adhesive layer at an add-on of 70 gsm is further present. The resulting filter medium is corrugated.

    [0120] Example 8 (comparative): The base substrate has a total basis weight of 150 gsm and is a wet-laid nonwoven consisting of 100 % cellulosic fibers (84 % by weight cellulosic fibers in the medium). The substrate is saturated with 16% by weight phenolic resin including 1-3 % by weight fluorocarbon as H2O repellant additive and 0.6 % by weight wet strength additive. The substrate (w/phenolic resin) has an air permeability of 85.3 l/m2sec (16.8 cfm).

    [0121] The resulting filter medium is then corrugated.

    [0122] Example 9: The base substrate has a total basis weight of 150 gsm and is a wet-laid nonwoven consisting of 100 % cellulosic fibers (84 % by weight cellulosic fibers in the medium). The substrate is saturated with 16% by weight phenolic resin including 1-3 % by weight fluorocarbon as H2O repellant additive and 0.6 % by weight wet strength additive. The substrate (w/phenolic resin) has an air permeability of 86 l/m2sec (17 cfm).

    [0123] The base substrate has an additional adhesive layer (polyurethane, heat activated water dispersion) on an upstream side. In addition, a layer of polyamide nanofibers electrospun directly onto the adhesive layer on an upstream side is present. The polyamide nanofibers' average diameter is about 130-200 nm. The resulting filter medium is corrugated.

    [0124] Example 10: The base substrate has a total basis weight of 150 gsm and is a wet-laid nonwoven consisting of 100 % cellulosic fibers (84.0 % by weight cellulosic fibers in the medium). The substrate is saturated with 16.0% by weight phenolic resin including 1-3 % by weight fluorocarbon as H2O repellant additive and 0.6 % by weight wet strength additive. The substrate (w/phenolic resin) has an air permeability of 86 l/m2sec (17 cfm).

    [0125] The base substrate has an additional adhesive layer (polyurethane (PU), heat activated water dispersion) on an upstream side. In addition, a layer of polyvinylidenefluoride (PVDF) nanofibers electrospun directly onto the adhesive layer on an upstream side is present. The polyamide nanofibers' average diameter is about 130-200 nm. The resulting filter medium is corrugated.

    [0126] Table II-III show the furnish compositions of Examples 1-10 and Tables IV-VI show the properties of the thus obtained filter media: The conversion in SI units for these Tables are 1 cfm = 5.08 l/m2sec and 1 mm H2O = 9.8 Pa.











    [0127] Tables IV-VI and Figure 2 show that the initial and average water removal efficiency performance of the inventive media with nanofiber coating (Examples 2, 4, 6, 7, 9 and 10) is higher than the one of the same control media without nanofiber coating (Examples 1, 3, 5 and 8). Moreover, the control medium without nanofiber coating (Examples 1, 3, 5 and 8) loses its fuel-water efficiency over time to a much greater extent than the same inventive medium with nanofiber coating (Examples 2, 4, 6, 7, 9 and 10). The negative NET change in water removal efficiency is indicative for enhanced water removal efficiency over time (see Examples 9 and 10). Thus, the water removal performance of the inventive media remains consistent or is even increased over time compared to the control media without nanofiber coating.

    [0128] Moreover, a comparison between Examples 6 and 9 (or Examples 7 and 10) illustrates that the presence of a protective fine fiber layer as third layer on an upstream side from the nanofiber layer is not essential for achieving the desired initial and average water removal efficiency and/or the desired NET change in water removal efficiency which is indicative for the long term performance of the fuel water separation medium or its life time cycle. In addition, the water removal efficiency (initial, average, NET change) obtained for the inventive media of Examples 4, 6, 7, 9 and 10 illustrates that nanofibers formed from polyamide or PVDF are particularly preferred.


    Claims

    1. A fuel water separator for removing water from water-hydrocarbon emulsions comprising a fuel water separation medium comprising

    (A) a first layer comprising nanofibers,

    (B) a second layer comprising a fibrous web, wherein the fibrous web comprises cellulosic fibers and at least one binder resin;
    wherein the nanofibers have an average fiber diameter of about 50-350 nm, such as about 100-300 nm;
    wherein the fuel water separation medium has a basis weight of about 100-300 g/m2, such as about 150-300 g/m2;
    wherein the fuel water separation medium is characterized by having a net change in water removal efficiency measured according to SAEJ1488 being preferably less than about 10 %, more preferably less than about 5 %; and
    wherein the net change in water removal efficiency is defined as follows:
    net change in water removal efficiency = water removal efficiency after 165 min - water removal efficiency after 15 min.


     
    2. The fuel water separator according to claim 1, wherein the filter medium is characterized by a mean flow pore size of about 2-10 microns.
     
    3. The fuel water separator according to any of the preceding claims, wherein the fibrous web of the second layer is a wet-laid fibrous web.
     
    4. The fuel water separator according to any of the preceding claims, wherein the nanofibers are synthetic nanofibers selected from polyethersulfone (PES); polyacrylonitrile; polyamide (PA) such as nylon; and fluoropolymer such as polyvinylfluoride (PVDF); and/or mixtures thereof.
     
    5. The fuel water separator according to claim 4, wherein the nanofibers are polyamide nanofibers or fluoropolymeric nanofibers.
     
    6. The fuel water separator according to any of the preceding claims, wherein the second layer has a basis weight of about 60-250 g/m2.
     
    7. The fuel water separator according to any of the preceding claims, wherein the second layer has a Gurley stiffness of about 2-15 g.
     
    8. The fuel water separator according to any of the preceding claims, wherein the second layer comprises substantially no glass fibers.
     
    9. The fuel water separator according to any of the preceding claims, wherein the second layer comprises substantially no synthetic fibers.
     
    10. The fuel water separator according to any of the preceding claims, wherein the second layer comprises cellulosic fibers in an amount of at least about 50 % by weight such as at least about 60% by weight or at least about 80 % by weight, based on the total weight of second layer.
     
    11. The fuel water separator according to any of the preceding claims, wherein the nanofibers of the first layer, which are preferably prepared from an adhesive, which is preferably used in an amount of about 1 to about 5 % by weight, and a polyethersulfone which is preferably used in an amount of about 95 to about 99% by weight, based on the total weight of the nanofibers, are electrospun directly onto the second layer.
     
    12. The fuel water separator according to any of the preceding claims, wherein the first layer consists essentially of nanofibers.
     
    13. The fuel water separator according to any of the preceding claims, wherein the second layer is on a downstream side of the first layer.
     
    14. The fuel water separator according to any one of claims 1-13, wherein the medium comprises a third layer on an upstream side of the first layer, the third layer being a protective fine fiber layer.
     
    15. The fuel water separator according to claim 14, wherein the protective fine fiber layer comprises, or consists of, synthetic fibers such as synthetic fibers selected from polyester, polyethylene terephthalate, polyolefin, polybutylene terephthalate and/or polyamide.
     
    16. The fuel water separator according to claims 14 or 15, wherein the third layer has a basis weight of about 10 to about 200 g/m2 such as about 15 to about 100 g/m2.
     
    17. The fuel water separator according to any of claims 14-16, wherein the second layer is on a downstream side of the first layer and the third layer is on an upstream side of the first layer.
     
    18. The fuel water separator according to any of the preceding claims, wherein the medium comprises an adhesive layer between the first and the second layer.
     
    19. The fuel water separator according to any of claims 14-18, wherein the medium comprises an adhesive layer between the first and the third layer.
     
    20. The fuel water separator according to any one of claims 18-19, wherein said adhesive layer(s) comprise(s) an adhesive selected from polyurethane; acrylate; PVA; polyolefin ethylene co-polymer; and/or rubber-based adhesive.
     
    21. The fuel water separator according to any of the preceding claims, wherein the filter medium is characterized by a basis weight of about 150-300 g/m2 when tested according to TAPPI Standard T 410 om-02.
     
    22. The fuel water separator according to any of the preceding claims, wherein the filter medium is characterized by an air permeability of about 15-102 l/m2 sec (3-20 cfm) when tested according to TAPPI Standard T 251 cm-85.
     
    23. The fuel water separator according to any of the preceding claims, wherein the filter medium is characterized by a leakage-corrected Frazier of 15-102 l/m2 sec (3-20) cfm when tested according to TAPPI Standard T 251 cm-85.
     
    24. The fuel water separator according to any one of claims 1-23, wherein the filter medium is pleated.
     
    25. The fuel water separator according to any one of claims 1-23, wherein the filter medium is corrugated.
     
    26. The fuel water separator according to any one of claims 1-23, wherein the filter medium includes a wire mesh supporting layer co-pleated with the filter medium.
     
    27. Process for the preparation of the fuel water separation medium of the fuel water separator according to any of claims 1 to 26, the process comprising the steps of

    • providing a first homogeneous slurry;

    • supplying the first slurry onto a dewatering screen to form a first deposit;

    • removing the water from the deposit to form a wet fibrous web;

    • drying the wet fibrous web while heating to form the second layer;

    • saturating the thus obtained second layer with at least a binder resin;

    • optionally coating of a first adhesive layer on top of the thus obtained second layer;

    • applying the first layer on top of the second layer or on top of the first adhesive layer coated onto the second layer, wherein the applying is preferably performed using electrospinning;

    • optionally coating of a second adhesive layer (i) on top of the first layer or (ii) on top of the second layer; and

    • optionally applying the third layer (iii) on top of the first layer, (iv) on top of the second adhesive layer coated onto the first layer, if present, (v) on top of the second layer or (vi) on top of the second adhesive layer coated onto the second layer, if present;

    wherein the first slurry comprises water and cellulosic fibers.
     
    28. Use of the fuel water separator according to claims 1-26 for separating water from water-hydrocarbon emulsions.
     


    Ansprüche

    1. Ein Kraftstoff-Wasser-Abscheider zur Entfernung von Wasser aus Wasser-Kohlenwasserstoff-Emulsionen umfassend ein Kraftstoff-Wasser-Abscheidemedium, umfassend

    (A) eine erste Schicht umfassend Nanofasern,

    (B) eine zweite Schicht umfassend ein Faservlies, wobei das Faservlies Cellulosefasern und mindestens ein Bindemittelharz umfasst;

    wobei die Nanofasern einen mittleren Faserdurchmesser von etwa 50-350 nm aufweisen, wie etwa 100-300 nm;
    wobei das Kraftstoff-Wasser-Abscheidemedium ein Grundgewicht von etwa 100-300g/m2, wie beispielsweise etwa 150-300 g/m2 aufweist;
    wobei das Kraftstoff-Wasser-Abscheidemedium dadurch gekennzeichnet ist, dass es eine Nettoänderung in der Wasserentfernungseffizienz gemessen gemäß SAEJ1488 von bevorzugt weniger als etwa 10%, stärker bevorzugt von weniger als etwa 5% aufweist; und
    wobei die Nettoänderung in der Wasserentfernungseffizienz wie folgt definiert ist:


     
    2. Der Kraftstoff-Wasser-Abscheider gemäß Anspruch 1, wobei das Filtermedium durch eine mittlere Flussporengröße von etwa 1-10 Mikron gekennzeichnet ist.
     
    3. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei das Faservlies der zweiten Schicht ein nass gelegtes Faservlies ist.
     
    4. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei die Nanofasern synthetische Nanofasern, ausgewählt aus der Gruppe bestehend aus Polyethersulfon (PES); Polyacrylnitril; Polyamid (PA) wie Nylon; und Fluorpolymer wie Polyvinylfluorid (PVDF); und/oder Gemischen davon sind.
     
    5. Der Kraftstoff-Wasser-Abscheider gemäß Anspruch 4, wobei die Nanofasern Polyamid-Nanofasern oder Fluorpolymer-Nanofasern sind.
     
    6. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei die zweite Schicht ein Grundgewicht von etwa 60-250 g/m2 aufweist.
     
    7. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei die zweite Schicht eine Gurley-Steifheit von etwa 2-15 g aufweist.
     
    8. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei die zweite Schicht im Wesentlichen keine Glasfasern umfasst.
     
    9. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei die zweite Schicht im Wesentlichen keine synthetischen Fasern umfasst.
     
    10. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei die zweite Schicht Cellulosefasern in einer Menge von mindestens etwa 50 Gew.-% wie mindestens etwa 60 Gew.-% oder mindestens etwa 80 Gew.-% umfasst, bezogen auf das Gesamtgewicht der zweiten Schicht.
     
    11. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei die Nanofasern der ersten Schicht, welche bevorzugt aus einem Klebstoff hergestellt sind, welcher bevorzugt in einer Menge von etwa 1 bis etwa 5 Gew.% verwendet wird, und einem Polyethersulfon, welches bevorzugt in einem Anteil von etwa 95 bis etwa 99 Gew.-% verwendet wird, bezogen auf das Gesamtgewicht der Nanofasern, direkt auf die zweite Schicht elektrogesponnen sind.
     
    12. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei die erste Schicht im Wesentlichen aus Nanofasern besteht.
     
    13. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei sich die zweite Schicht auf einer stromabwärts gelegenen Seite der ersten Schicht befindet.
     
    14. Der Kraftstoff-Wasser-Abscheider gemäß einem der Ansprüche 1 bis 13, wobei das Medium eine dritte Schicht auf einer stromaufwärts gelegenen Seite der ersten Schicht umfasst, wobei die dritte Schicht eine schützende Feinfaserschicht ist.
     
    15. Der Kraftstoff-Wasser-Abscheider gemäß Anspruch 14, wobei die schützende Feinfaserschicht synthetische Fasern wie synthetische Fasern ausgewählt aus der Gruppe bestehend aus Polyester, Polyethylenterephthalat, Polyolefin, Polybutylenterephthalat und/oder Polyamid, umfasst, oder daraus besteht.
     
    16. Der Kraftstoff-Wasser-Abscheider gemäß Anspruch 14 oder 15, wobei die dritte Schicht ein Grundgewicht von etwa 10 bis etwa 200 g/m2 wie etwa 15 bis etwa 100 g/m2 aufweist.
     
    17. Der Kraftstoff-Wasser-Abscheider gemäß einem der Ansprüche 14 bis 16, wobei die zweite Schicht auf einer stromabwärts gelegenen Seite der ersten Schicht angeordnet ist und die dritte Schicht auf einer stromaufwärts gelegenen Seite der ersten Schicht angeordnet ist.
     
    18. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei das Medium eine Klebeschicht zwischen der ersten und der zweiten Schicht umfasst.
     
    19. Der Kraftstoff-Wasser-Abscheider gemäß einem der Ansprüche 14 bis 18, wobei das Medium eine Klebeschicht zwischen der ersten und der dritten Schicht umfasst.
     
    20. Der Kraftstoff-Wasser-Abscheider gemäß einem der Ansprüche 18 bis 19, wobei die Klebeschicht(en) einen Klebstoff ausgewählt aus Polyurethan; Acrylat; PVA; Polyolefm-Ethylen-Copolymer; und/oder einen Gummi-basierten Klebstoff umfasst (umfassen).
     
    21. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei das Filtermedium durch ein Grundgewicht von etwa 150-300 g/m2 bei einer Testmethode gemäß TAPPI Standard T 410 om-02 gekennzeichnet ist.
     
    22. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei das Filtermedium durch eine Luftdurchlässigkeit von etwa 15 - 102 l/m2sec (3-20 cfm) bei einer Testmethode gemäß TAPPI Standard T 251 cm-85 gekennzeichnet ist.
     
    23. Der Kraftstoff-Wasser-Abscheider gemäß einem der vorhergehenden Ansprüche, wobei das Filtermedium durch einen Leck-korrigierten Frazier-Wert von etwa 15 - 102 l/m2 sec (3-20 cfm) bei einer Testmethode gemäß TAPPI Standard T 251 cm-85 gekennzeichnet ist.
     
    24. Der Kraftstoff-Wasser-Abscheider gemäß einem der Ansprüche 1 bis 23, wobei das Filtermedium plissiert ist.
     
    25. Der Kraftstoff-Wasser-Abscheider gemäß einem der Ansprüche 1 bis 23, wobei das Filtermedium gewellt ist.
     
    26. Der Kraftstoff-Wasser-Abscheider gemäß einem der Ansprüche 1 bis 23, wobei das Filtermedium eine Drahtgeflecht-Trägerschicht, welches mit dem Filtermedium coplissiert ist, umfasst.
     
    27. Verfahren zur Herstellung des Kraftstoff-Wasser-Abscheidemediums des Kraftstoff-Wasser-Abscheiders gemäß einem der Ansprüche 1 bis 26, wobei das Verfahren die Schritte

    • Bereitstellen einer ersten homogenen Aufschlämmung;

    • Überführen der ersten Aufschlämmung auf ein Entwässerungssieb um eine erste Ablagerung zu bilden;

    • Entfernen des Wasser von der Ablagerung um ein nasses Faservlies zu bilden;

    • Trocknen des nassen Faservlieses unter Erwärmen um die zweite Schicht zu bilden;

    • Sättigen der so erhaltenen zweiten Schicht mit mindestens einem Bindemittelharz;

    • gegebenenfalls Beschichten einer ersten Klebstoffschicht auf die so erhaltene zweite Schicht;

    • Auftragen der ersten Schicht auf die zweite Schicht oder auf die erste, auf die zweite Schicht beschichtete, Klebstoffschicht, wobei das Auftragen bevorzugt mittels Elektrospinnen durchgeführt wird;

    • gegebenenfalls Beschichten einer zweiten Klebstoffschicht (i) auf die erste Schicht oder (ii) auf die zweite Schicht; und

    • gegebenenfalls Auftragen der dritten Schicht (iii) auf die erste Schicht, (iv) auf die zweite, auf die erste Schicht beschichtete, Klebstoffschicht, sofern vorhanden, (v) auf die zweite Schicht oder (vi) auf die zweite, auf die zweite Schicht beschichtete, Klebstoffschicht, sofern vorhanden;

    umfasst;
    wobei die erste Aufschlämmung Wasser und Cellulosefasern umfasst.
     
    28. Verwendung eines Kraftstoff-Wasser-Abscheiders gemäß einem der Ansprüche 1 bis 26 zum Abscheiden von Wasser aus Wasser-Kohlenwasserstoff-Emulsionen.
     


    Revendications

    1. Séparateur carburant-eau pour éliminer l'eau des émulsions eau-hydrocarbure comprenant un milieu de séparation carburant-eau comprenant

    (A) une première couche comprenant des nanofibres,

    (B) une seconde couche comprenant une toile fibreuse, où la toile fibreuse comprend des fibres cellulosiques et au moins une résine liante ;

    dans lequel les nanofibres ont un diamètre de fibre moyen d'environ 50-350 nm, comme d'environ 100-300 nm ;
    dans lequel le milieu de séparation carburant-eau a un poids de base d'environ 100-300 g/m2, comme d'environ 150-300 g/m2 ;
    dans lequel le milieu de séparation carburant-eau est caractérisé en ce qu'il a une variation nette d'efficacité d'élimination d'eau, mesurée selon SAEJ1488, de préférence inférieure à environ 10 %, plus préférablement inférieure à environ 5 % ; et
    dans lequel la variation nette d'efficacité d'élimination d'eau se définit comme suit :


     
    2. Séparateur carburant-eau selon la revendication 1, dans lequel le milieu de filtre est caractérisé par une taille de pore à écoulement moyen d'environ 2-10 microns.
     
    3. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel la toile fibreuse de la seconde couche est une toile fibreuse déposée par procédé humide.
     
    4. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel les nanofibres sont des nanofibres synthétiques choisies parmi la polyéthersulfone (PES) ; un polyacrylonitrile ; polyamide (PA) tel que le Nylon ; et un fluoropolymère tel que le polyfluorure de vinyle (PVF) ; et/ou leurs mélanges.
     
    5. Séparateur carburant-eau selon la revendication 4, dans lequel les nanofibres sont des nanofibres de polyamide ou des nanofibres fluoropolymères.
     
    6. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel la seconde couche a un poids de base d'environ 60-250 g/m2.
     
    7. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel la seconde couche a une rigidité de Gurley d'environ 2-15 g.
     
    8. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel la seconde couche ne contient sensiblement aucune fibre de verre.
     
    9. Séparateur carbure-eau selon l'une quelconque des revendications précédentes, dans lequel la seconde couche ne contient sensiblement aucune fibre synthétique.
     
    10. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel la seconde couche comprend des fibres cellulosiques en une quantité d'au moins environ 50 % en poids, comme d'au moins environ 60% en poids ou d'au moins environ 80 % en poids, sur la base du poids total de la seconde couche.
     
    11. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel les nanofibres de la première couche, qui sont de préférence préparées à partir d'un adhésif, qui est de préférence utilisé en une quantité d'environ 1 à environ 5 % en poids, et d'une polyéthersulfone qui est de préférence utilisée en une quantité d'environ 95 à environ 99 % en poids, sur la base du poids total des nanofibres, sont directement déposées par électrofilage sur la seconde couche.
     
    12. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel la première couche est principalement constituée de nanofibres.
     
    13. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel la seconde couche se situe côté aval de la première couche.
     
    14. Séparateur carburant-eau selon l'une quelconque des revendications 1 à 13, dans lequel le milieu comprend une troisième couche côté amont de la première couche, la troisième couche étant une couche protectrice à fibres fines.
     
    15. Séparateur carburant-eau selon la revendication 14, dans lequel la couche protectrice à fibres fines comprend, ou est constituée par, des fibres synthétiques telles que des fibres synthétiques choisies parmi le polyester, le polyéthylène téréphtalate, une polyoléfine, le polybutylène téréphtalate et/ou un polyamide.
     
    16. Séparateur carburant-eau selon les revendications 14 ou 15, dans lequel la troisième couche a un poids de base d'environ 10 à environ 200 g/m2 comme d'environ 15 à environ 100 g/m2.
     
    17. Séparateur carburant-eau selon l'une quelconque des revendications 14 à 16, dans lequel la deuxième couche se situe côté aval de la première couche et la troisième couche se situe côté amont de la première couche.
     
    18. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel le milieu comprend une couche adhésive entre la première et la seconde couche.
     
    19. Séparateur carburant-eau selon l'une quelconque des revendications 14 à 18, dans lequel le milieu comprend une couche adhésive entre la première et la troisième couche.
     
    20. Séparateur carburant-eau selon l'une quelconque des revendications 18 à 19, dans lequel ladite ou lesdites couches adhésives comprend/comprennent un adhésif choisi parmi le polyuréthane ; l'acrylate ; le PVA ; un copolymère de polyoléfine/éthylène ; et/ou un adhésif à base de caoutchouc.
     
    21. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel le milieu de filtre est caractérisé par un grammage, mesuré selon la norme TAPPI T 410 om-02, de 150-300 g/m2.
     
    22. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel le milieu de filtre est caractérisé par une perméabilité à l'air, mesurée selon la norme TAPPI T 251 cm-85, de 15-102 l/m2 sec (3-20 cfm).
     
    23. Séparateur carburant-eau selon l'une quelconque des revendications précédentes, dans lequel le milieu de filtre est caractérisé par un Frazier fuite-corrigé, mesuré selon la norme TAPPI T 251 cm-85, de 15-102 l/m2 sec (3-20 cfm).
     
    24. Séparateur carburant-eau selon l'une quelconque des revendications 1 à 23, dans lequel le milieu de filtre est plissé.
     
    25. Séparateur carburant-eau selon l'une quelconque des revendications 1 à 23, dans lequel le milieu de filtre est ondulé.
     
    26. Séparateur carburant-eau selon l'une quelconque des revendications 1 à 23, dans lequel le milieu de filtre comprend une couche supportant un treillis plissée conjointement avec le milieu de filtre.
     
    27. Procédé de préparation du milieu de séparation carburant-eau du séparateur carburant-eau selon l'une quelconque des revendications 1 à 26, le procédé comprenant les étapes de

    • fourniture d'une première suspension épaisse homogène ;

    • alimentation de la première suspension épaisse sur un écran de déshydratation pour former un premier dépôt ;

    • élimination de l'eau du dépôt pour former une toile fibreuse humide ;

    • séchage de la toile fibreuse humide sous chauffage pour former la seconde couche ;

    • saturation de la seconde couche ainsi obtenue à l'aide d'au moins une résine liante ;

    • éventuellement application d'une première couche adhésive au dessus de la seconde couche ainsi obtenue ;

    • application de la première couche au dessus de la seconde couche ou au dessus de la première couche adhésive appliquée sur la seconde couche, où l'application est de préférence réalisée par électrofilage ;

    • éventuellement application d'une seconde couche adhésive (i) au dessus de la première couche ou (ii) au dessus de la seconde couche ; et

    • éventuellement application de la troisième couche (iii) au dessus de la première couche, (iv) au dessus de la seconde couche adhésive appliquée sur la première couche, si présente, (v) au dessus de la seconde couche ou (vi) au dessus de la seconde couche adhésive appliquée sur la seconde couche, si présente ;
    dans lequel la première suspension épaisse comprend de l'eau et des fibres cellulosiques.


     
    28. Utilisation du séparateur carburant-eau selon les revendications 1 à 26 pour séparer l'eau contenue dans des émulsions eau-hydrocarbure.
     




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    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description