CA2265878A1

CA2265878A1 - Porous structures and process for the manufacture thereof

Info

Publication number: CA2265878A1
Application number: CA002265878A
Authority: CA
Inventors: Wei-Chih Chen; Ronald V. Repetti; Jack Slovak
Original assignee: Individual
Current assignee: 3M Purification Inc
Priority date: 1996-09-10
Filing date: 1997-09-08
Publication date: 1998-03-19
Also published as: EP1484099A2; AU723880B2; WO1998010855A1; EP0951332A1; US5928588A; US5882517A; EP1484099A3; JP2001504398A; EP1484099B1; DE69739930D1; BR9712026A; EP0951332B1; KR20000036031A; JP4731642B2; DE69736009D1; AU4582697A; DE69736009T2

Abstract

A process of the manufacture of porous structures comprises forming a dry mixture comprising a component providing primary separation capability, a component providing green strength reinforcement capability and a component providing binding capability and selected from the group consisting of thermoplastic and thermosetting polymers; delivering the mixture to a suitable surface and building a desired thickness thereof; densifying the mixture into the form desired for the porous structure; removing the densified porous structure from the surface; binding the component providing the primary separation capability by melting the mixture to a temperature of up to about 20 ~C higher than the melting point of any thermoplastic component providing binding capability. Porous structures (100, 110, 120, 125, 140, 175) according to the present invention comprise from about 70 to about 90 parts by weight of a component providing primary separation capability (61, 62); from about one to about 15 parts by weight of a component providing green strength reinforcement capability (64, 65); and from about 8 to about 20 parts by weight of a component providing binding capability (67, 68) and selected from the group consisting of thermoplastic and thermosetting polymers.

Description

ï»¿1015202530CA 02265878 1999-03-09W0 98/10855 PCT/US97/15761POROUS STRUCTURES AND PROCESS FOR THEMANUFACTURE THEREOFTECHNICAL FIELDThis invention relates to porous structures for the separation of fluidsfrom unwanted constituents. Typically, media of this type contain filter aids andare manufactured in the form of hollow core cylindrical blocks or flat sheets. Inuse, fluid to be separated is directed through the porous filter structure, afterwhich it is withdrawn. The present invention additionally provides a process forthe manufacture of such porous structures.BACKGROUND or THE INVENTIONTypical separation medias include diatomaceous earth, perlite,activated carbon, zeolites and the like, to achieve filtration of adsorption effects.Use of such components in powdered form often generates high pressure dropand/or channeling. Accordingly, powdered filter aids are put into useful formsby a) incorporating them into thin media such as papers, or by depositing themas a thin pre-coat on a substrate to avoid high pressure drop; or b) combiningthem with a binder so they can subsequently be made into a useful porousstructure.Molded porous filter structures made from the typical separationsmedia could be improved if the amount of binder could be reduced from theusual 20 to 40 percent and if the molded object could be removed from the highpressure compression mold, i.e. if it had high green strength, and subsequentlythermally bonded in a self-supporting condition. Porous filter structures can bemade by an extrusion process, but such processes are slow and require a largenumber of extruders for commercial production. Moreover, such processes arelimited in the shape of useful filter structures that can be made.Filter structures can be made via wet or dry processing. An exampleof the wet process is U.S. Pat. No. 5,443,735 issued to Pall Corporation whichrelates to the manufacture of so-called immobilized carbon beds. Severalï»¿1015202530W0 98/10855CA 02265878 1999-03-09PCT/US97/ 15761methods are disclosed, one of which produces a radial flow pressed block filterby mixing a wet slurry of fibrous materials, activated carbon and an adhesive;pumping the slurry into a mold; pressing out the free water; removing the pressedblock from the mold and heating the block to remove moisture; and adding filtermaterials. Another produces an axial flow filter involving the mixing of carbonparticulate and fine powdered polyethylene resin; the mixture being subsequentlyheated to melt the polymer and join the carbon particles. The invention is basedupon the use of fine brass particles to aid in the inhibition of microbial growthin water.In the dry process, the components are first dry blended, followed bydensification and heating of the dry mixture into different forms and shapes. Thecurrent state of the dry process art is exemplified by the following patents. U.S.Pat. No. 4,664,683 issued to Pall Corporation teaches the use of molding carbonblocks with particle sizes from about 200 to 2000 microns. The maximummolding pressure is 400 psi. The particle size of the polyethylene powderedbinder employed is about 8 to 30 microns. The preferred binding pressure isfrom 0.3 to 10 psi. The binding temperature is about 50 to 90Â°F (28 to 50Â°C)above the Vicat softening temperature. These temperatures are equal to or belowthe melting temperature of the binder. The carbon and binder mixture is heatedwithin the mold and then pressed for 1 to 2 minutes. The cooled carbon blockis removed from the mold and found to be self-supporting. The filter blocks havepoor physical strength due to the lack of efficient binding between the binder andthe carbon particles.U.S. Pat. No. 4,859,386 issued to Amway Corporation teaches amethod for making a molded composite charcoal filter having two shells includingthe use of ultra-high molecular weight polyethylene as a binder, having a verylow melt flow index, on the order of S 1 gram/10 minutes, at a level of between20 and 35 percent by weight. Binders having a high melt flow index areproclaimed as causing blinding of the active sites of the activated carbon. Thepatent teaches that while the blocks are still in the mold, they are subjected toheat (175 to 205Â°C) and pressure (30 to 120 psi) to form a bonded integralï»¿10152025WO 98/10855CA 02265878 1999-03-09PCT/US97/ 15761composite filter. The drawback of this type of block is weak physical strengthdue to poor melt flow of the binder. At temperatures just a few degrees abovethe melting temperature (135 to 138Â°C), the block has very poor physicalstrength. The method relies on raising the temperature to 175 to 205Â°C toincrease melt flow, which is avoided in the first place, in order to improvebinding strength.U.S. Pat. No. 5,019,311 issued to KT Corporation teaches a similarprocess, which employs a blend of conventional binders having medium and highmelt flow index. These conventional binders are stretched out into a "continuousweb matrix" (CWM) by the shearing forces encountered during material blendingbefore extrusion without blocking the active sites, at a temperature substantiallyabove the softening point of the binder. As a result, the required amount ofbinder can be reduced significantly to about 8 to 20 percent by weight. Duringthe extrusion process, the media is in contact with the barrel and the screw. Theextruded media is very hot and soft and must be hardened by rapid cooling toallow for subsequent handling. The typical binder, ethylene-vinyl acetatecopolymer (EVA), used in this invention is sheared at a minimum of 145Â°C, whichis at least 30Â°C higher than the melting temperature (115Â°C). The binder isstretched and spread onto the carbon particles to give good binding strength.However, this process can blind off an excessive number of pores of the carbon.Moreover, the carbon adsorption capacity and efficiency are very sensitive to thetemperature variation and shear force of this process.Thus, while attempts have been made heretofore to manufactureporous structures containing fine particle size filter aids, the art has not provideda facile process by which to combine relatively low amounts of binder resin withfine particles to produce a block having good green strength and favorably lowpressure drop during fluid separation or filtration.ï»¿1015202530W0 98/ 10855CA 02265878 1999-03-09PCT/US97/ 15761SUMMARY or INVENTIONIt is therefore, an object of the present invention to provide a processfor the manufacture of porous structures.It is another object of the present invention to provide a process forthe manufacture of porous structures comprising fine fibrous and particulateseparation materials and binders.It is yet another object of the present invention to provide porousstructures comprising fine separation materials and binders.It is yet another object of the present invention to provide porousstructures providing adsorptive and non-adsorptive media.It is yet another object of the present invention to provide porousstructures comprising greater amounts of separation materials and respectivelylower amounts of binders, without sacrificing green strength.It is yet another object of the present invention to provide a processfor the manufacture of porous structures which have greater amounts ofseparation materials and respectively lower amounts of binders, withoutsacrificing green strength.At least one or more of the foregoing objects, together with theadvantages thereof over the known art relating to porous structures and processesfor the preparation thereof, which shall become apparent from the specificationwhich follows, are accomplished by the invention as hereinafter described andclaimed.In general, the present invention is directed toward a process for themanufacture of porous structures comprising forming a dry mixture comprisinga component providing primary separation capability, a component providinggreen strength reinforcement capability and, a component providing bindingcapability and selected from the group consisting of thermoplastic andthermosetting polymers; delivering the mixture to a suitable surface and buildinga desired thickness thereof; densifying the mixture into the form desired for theporous structure; removing the densified porous structure from the surface;binding the component providing the primary separation capability by heating theï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/ 15761mixture to a temperature of up to about 20Â° C. higher than the melting point ofany thermoplastic component providing binding capability.The present invention also provides porous structures comprising fromabout 70 to about 90 percent by weight of a component providing primaryseparation capability; from about one to about 15 percent by weight of acomponent providing green strength reinforcement capability; and, from abouteight to about 20 percent by weight of a component providing binding capabilityand selected from the group consisting of thermoplastic and thermosettingpolymers.BRIEF DESCRIPTION or THE DRAWINGSFigs. 1A-1D provide a series of steps depicting one means forcompressing components in the manufacture of porous structures, according tothe present invention;Figs. 2A-2C provide a series of steps schematically depicting anothermeans for compressing components in the manufacture of porous structures,according to the present invention;Figs. 3A-3B are block diagrams depicting various combinations of stepsfor the manufacture of porous structures according to the present invention;Fig. 4 is a diagrammatic depiction of various combinations ofcomponents and the processing steps for the manufacture of porous structuresaccording to the present invention;Figs. 5A-5B provide sequentially a schematic depiction of threecomponents combined for the manufacture of porous structures prior tocompression and heating in Fig. 5A and subsequent to compression and heatingin Fig. 58, according to the present invention;Figs. GA-6C provide sequentially a schematic depiction of twocomponents combined for the manufacture of porous structures prior tocompression and heating in Fig. 6A and subsequent to compression and heatingin Figs. 6B and 6C, according to the present invention;ï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/15761Figs. 7A-7B provide sequentially a schematic depiction of onecomponent for the manufacture of porous structures prior to compression andheating in Fig. 7A and subsequent to compression and heating in Fig. 78,according to the present invention;Fig. 8 is an enlarged cross-section, taken substantially along the lines8-8 of Fig. 7, of a multi-component polymer fiber which can be employed for themanufacture of porous structures according to the present invention;Fig. 9 depicts two multi-component polymer fibers employed for themanufacture of porous structures according to the present invention showing aportion of the outer polymer sheaths from each fiber melted together;Fig. 10 is a partial side elevation of a porous structure according to thepresent invention;Fig. 11 is an enlarged view of the area circled in Fig. 10;Fig. 12 is a partial side elevation of another porous structure accordingto the present invention;Fig. 13 is a partial side elevation of another porous structure accordingto the present invention;Fig. 14 is a side elevation, partially in section, depicting another porousstructure according to the present invention, having one closed end;Fig. 15 is a side elevation, partially in section, depicting a mold inconjunction with a plurality of removable sleeves for the manufacture of multi-layered cylindrical porous structures;Fig. 16 is a side elevation, partially in section, depicting a portion ofa multiâ|ayered cylindrical porous structure product, according to the presentinvention;Fig. 17A is a side elevation, partially in section, depicting a mold inconjunction with apparatus, schematically depicted for the manufacture of multi-layered cylindrical porous structures;Fig. 17B is a side elevation, partially in section, depicting a mold as inFig. 17A, partially filled;ï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/15761Fig. 17C is a side elevation, partially in section, depicting a mold as inFigs. 17A-B, depicting a densified multi-layered cylindrical porous structure;Fig. 18 is a schematic depiction of apparatus for manufacturing multi-layered flat sheet porous structures, according to the present invention; andFig. 19 is a cross-section through a portion of a mu|tiâlayered flat sheetporous structure product, according to the present invention;Fig. 20 is a perspective view of a non-fibrillated fiber component thatcan be employed as a component of the porous structures of the presentinvention;Fig. 22 is a perspective view of a fibrillated fiber component that canbe employed as a component of the porous structures of the present invention;andFig. 22 is a graph comparing the effect on the green strength of porousstructures, according to the present invention, with increasing amounts ofadditive polyethylene fiber.PREFERRED EMBODIMENT FOR CARRYING OUT THE INVENTIONThe present invention relates to the manufacture of porous structures,useful in separation, particularly filtration applications, and to a new and usefulform of blocks and other configurations thereof. The porous structures comprise1) a component providing primary separation capability, or primary media (PM);2) a component providing green strength reinforcement, or the green strengthagent (GSA); and, 3) a component providing binding capability or, binder (B).One or more types of each component can be combined. Optional components(4) include various additives, as will be described hereinbelow. The optionaladditives normally do not change the main functions of PM, GSA, and B.However, the additive can become part of the PM, GSA, and/or B when thecontribution of the additive is significant.With respect to the primary separation media, it can be one or severaltypes of particles or fibers in mixtures that function as the porous matrix.Preferably, the primary media is selected from the group consisting of carbonï»¿1015202530W0 98/ 10855CA 02265878 1999-03-09PCT/US97/15761particles, diatomaceous earth, perlite, activated alumina, silica, zeolites, naturalfibers, and man made fibers. Powdered carbon is typically selected to form acarbon block porous structure and comprises 10 to 400 microns particle size. Fora general description of suitable carbon, see U.S. Pat. No. 4,859,386, the subjectmatter of which is incorporated herein by reference. Activated carbon isavailable from Calgon, Barnebey and Sutcliffe, etc. Sizes for the other particulatemedia are generally well known to those skilled in the art and thus, do notconstitute a limitation to the practice of the present invention. Similarly, fiberdimensions, i.e., denier, length, diameter and the like can also be varied as isknown for the manufacture of various porous structures based upon fibrousmedia.Regarding fibers, the natural species include cellulose such as cottonand wood pulp, wool, jute, hemp and the man-made varieties include thepolyolefin fibers from monomers having from two to about five carbon atoms,such as polyethylene and polypropylene, as well as polyester, carbon, graphite,glass, acrylics, rayon, nylon and aramid fibers. In some instances, multi-component fibers having a polypropylene or polyester core and lower meltingpolyethylene sheath can be selected, as will be discussed hereinbelow. Suchfibers are commercially available and one example comprises a high densitypolyethylene (HDPE) sheath and a polypropylene (PP) core.The primary media can also include certain plastic powders, includingthe polyolefins, resulting from monomers having from two to about five carbonatoms, such as polyethylene and polypropylene, as well as polystyrene, polyvinylchloride, polycarbonate, polysulfone, nylon and polyester. As should now beapparent, some species of primary media are non-meltable, or at least do not meltduring manufacture of the porous structure, while other species can and do melt,partially or totally. Where the primary media does not melt, adsorptive porousmedia can be made; however, both adsorptive and non-adsorptive porous mediacan be made from both meltable and non-meltable primary media, which will beexplained in greater detail hereinbelow.ï»¿1015202530W0 98/10855CA 02265878 1999-03-09PCT/US97/15761Examples of adsorptive non-melting or non-melted primary mediainclude activated carbon, ion exchange resins, alumina and zeolites. Examplesof non-adsorptive non-melting or non-melted primary media include natural andsynthetic fibers. Examples of non-adsorptive media made from meltable primarymedia include multi-component fibers.As for the green strength agent, fibers and powders can be employed.While powders are less effective, fine fibers are more effective than coarse fibers.Straight or crimped fibers are less effective than fibrillated fibers. Soft fibers aremore effective than rigid fibers. The preferred fibers are fibrillated or micro-fibers, selected from the group consisting of polyolefin fibers, such aspolyethylene and polypropylene, polyesters, nylons, aramids and rayons. Thesefibers can function additionally as binders if melted, or as part of the porousmatrix, depending on their physical and chemical natures and porous condition.The preferred diameter of these types of fibers is less than 100 microns, but is notlimited. The amount of the green strength agent and the compressing pressuresare the processing variables for a specific formulation.Other types of green strength agents include liquid green strengthagents such as latexes and resin solutions. Styrene-butadiene, poly(ethylene-vinylacetate), and acrylate types of latexes are good candidates. Aqueous resinsolutions made of water soluble polymers, such as methyl-cellulose andhydroxypropyl methyl-cellulose, carboxymethyl cellulose, hydroxyethyl cellulose,polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyethylene oxide,polyethyleneimine, polyacrylamide, natural gums and their copolymers andderivatives can also be employed, separately or in mixtures. Even small amountsof water can be used to soften the dry powdered thermosetting binder resins,such as phenol-formaldehyde and melamine-formaldehyde resins, to improvegreen strength and thus, water can be employed as a green strength agent.The binder material can be in the form of powder or fibers or mixturesthereof, with thermoplastic and thermosetting plastics being preferred. Thefibrous binders may include multi-component and fibrillated fibers and may alsopossess some separation properties. The binder is preferred to have medium meltï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/1576110indices, in order to improve physical strength, reduce melt flow, and reduce thetime required for thermally bonding the media. The preferred melt index is > 1gram per 10 minutes (ASTM 1238 method) up to about 20 grams per 10 minutesfor adsorptive and absorptive media.More particularly, the powder materials are selected from the groupconsisting of polymeric powders, resulting from monomers having from two toabout five carbon atoms, such as the polyolefins e.g., polyethylene andpolypropylene; as well as epoxy, phenol-formaldehyde and melamine-formaldehyde resin powders. Such polymeric powders have particle sizes on theorder of 10 to 40 microns. The fibrous binders include polymeric fibers such assuch as the polyolefins, resulting from monomers having from two to about fivecarbon atoms, e.g., polyethylene and polypropylene and multi-component fibersof various geometries and polymer combinations. The length of such types offiber is usually less than 0.5 inch. The preferred length is less than 0.25 inch.The preferred fiber diameter is less than 200 microns.Additional thermoplastic polymers such as ethylene-vinyl acetate,polystyrene, polyvinyl chloride, polycarbonates, polysulfones, polyesters andnylons can be used as binders. The crystalline polymers usually give betterphysical strength and better defined melting temperatures. The amorphouspolymers do not have melting temperatures; the best way to select the bakingtemperature is to experiment from 5 to 20Â°C above the glass transitiontemperature. The melting temperatures and glass transition temperatures candetermined by using DSC or can be obtained from the suppliers.In addition to the foregoing components, the porous structures of thepresent invention can also include optional components or additives such ascationic charged resins, ion-exchange materials, perlite, diatomaceous earth,activated alumina, zeolites, resin solutions, latexes, metallic materials and fibers,cellulose, carbon particles, carbon fibers, rayon fibers, nylon fibers,polypropylene fibers, polyester fibers, glass fibers, steel fibers and graphite fibersand the like, including mixtures thereof to provide additional properties andfeatures or to reduce the cost of the product. Many fibers such as polypropylene,ï»¿1015202530W0 98/ 10855CA 02265878 1999-03-09PCT/US97/157611 1polyester, nylon, glass, carbon, steel and graphite are good candidates forimproving tensile and impact strength. Amounts of such optional componentsrange from about 0.1 to about 90 percent by weight, with an attendant decreasein the amount of primary media.While several of the optional components may also serve as primaryseparation media or green strength agents, and thus be present in mixtures fromwhich the porous structures are produced, as optional components they areemployed where the separation media or green strength agents employed are notthe same as for instance, where the separation media is diatomaceous earth andthe optional component is carbon fiber or, the green strength agent is apolyolefin fiber and the optional component is a glass fiber.Cationic charged resin can be sprayed directly onto the particulatemedia, such as diatomaceous earth and carbon. These treated media will adsorbsmall anionic particulates with greater efficiency in aqueous separation orfiltration. Such resins have been discussed in earlier patents owned by theAssignee of record, the subject matter of which is incorporated by referenceherein. They include for example, U.S. Pat Nos. 4,007,113 and 4,007,114relating to melamine formaldehyde cationic colloid modified media; No.4,305,782 relating to cationic colloidal silica modified fibrous and particulateelements and, No. 4,309,247 relating to epichlorohydrin-polyamine andpolyamide cationic resin treated cellulosic fiber and particulate media.The preferred process for practice of the invention is dry laying of thecomponents, as opposed to wet laying or wet processing. In the dry layingprocess, the components are first dry blended, followed by delivering the mixtureonto a suitable surface at ambient temperatures. The definition of "suitablesurface" as used herein includes depositing into a mold as well as onto anothersurface that permits building or establishing a desired thickness of the dry mixturefor subsequent processing. Where the mixture is deposited into a mold, thedesired thickness is obtained essentially by filling the mold. As will be explainedhereinbelow, the mixture can also be delivered to a flat surface, to a uniform andï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/1576112desired thickness. Accordingly, practice of the process of this invention is not tobe limited by whether or not a mold is employed.The definition of "dry" includes minimal amounts of liquid within theblend. This amount of liquid does not change the appearance and physicalhandling significantly to become a "wet" blend or process, which is defined tohave dripping liquid or require different handling. Thus, the process of thepresent invention does not involve the formation of a wet slurry of thecomponents; accordingly, vacuuming or other steps for the removal of liquid arenot necessary.The particle size distribution of the mixture can be kept very uniformby the presence of a fibrillated fiber component throughout the entire structure.In other words, fibrillated fibers hinder the separation or migration of the largeand small particles. The blend at this stage has no green strength.The next step in the process of the present invention, is densificationof the dry laid mixture into different forms and shapes. Such methods includecalendering, pressing, piston molding, injection molding, isostatic pressing, andextrusion. Where the mixture has been deposited into a mold, it is compressedand densified by piston molding, isostatic compression and the like. Similarly,where the mixture has been delivered to a flat surface, it can be compressed anddensified by calendering or other pressing operations, forming a flat sheet whichcan be used where flat sheet media is desired or, disk-shaped members can be cutfrom such sheets for ultimate use in appropriately configured porous structures.Isostatic compression includes either wet-bag or dry-bag processing.As is known, both methods employ a chamber filled with fluid which is appliedunder hydraulic pressure simultaneously and uniformly to all surfaces of the partbeing formed. The powdered material to be compacted is encapsulated in ashaped "membrane, known as "bag too|ing", which serves both as a mold for thepart and as barrier against the hydraulic liquid. The uniform pressure compactsthe powder from all directions into the exact shape of the bag tooling.In the wet-bag method, powder is loaded into a rubber mold. Afterloading, the mold is then sealed and hydraulic pressure is applied. Onceï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/1576113pressurizing is complete, the mold must be reopened and the compressed partremoved.In the dry-bag tooling method, the hydraulic pressurizing fluid is sealedby a master dry-bag inside of the pressure chamber and it is within this masterbag, that a separate tooling dry-bag is inserted. With this method, the materialis loaded into the tool bag, and then after pressurizing, the tool bag can beremoved from the pressure chamber. The dry-bag method simplifies operationsand increases the speed of production. Dry-bag compression is a preferred, albeitnon-limiting means to provide the step of densifying.With reference to Fig. 1A, the dry laid mixture of porous structureforming components 20 is fed into a rubber mold, bag 21, held within a pressurevessel 22. The vessel 22 provides a hydraulically activated chamber 23 tocompress the mold 21. In Fig. 18, the vessel is closed by a cover 24, via suitablemeans (not shown) and the rubber mold 21 is then compressed within thechamber 23 (Fig. 1C). Following compression the green product 25, has sufficientgreen strength to be self-supporting without an external mold and as depicted inFig. 1D, the pressure on bag 21 is released, the vessel 22 is opened and theproduct 25 is removed via suitable means, such as ram 26. Filling the rubbermold is accomplished with the aid of a hopper or similar filler apparatus,depicted generally by the numeral 28. Such apparatus must be capable of evenlydistributing the mixture of components 20 within the mold quickly and inmeasured amounts. Being within the ordinary skill of the art, such apparatusneed not be described more fully. Of course, the foregoing explanation as wellas Figs. 1A-1 D are merely schematic and have been simplified for presentation ofone type of operation.As noted hereinabove, the dry laid mixture of porous structure formingcomponents 20 can also be fed onto a flat surface. Alternatively and withreference to Fig. 2A, such a flat surface 30, can comprise a movable belt, suitablysupported and passing through a calender apparatus, generally 31. The mixtureis first deposited to provide a desired thickness, as depicted to the left of thecalender in Fig. 2A; it is then conveyed between opposed calender rolls 32 andï»¿1015202530W0 98/10855CA 02265878 1999-03-09PCT/US97/ 157611433 to form a densified sheet of green product 34. At this stage, the sheet 34 isremoved from the first surface 30 and transferred to a press 35, providing a lowersupport platen 36 and an upper die platen 38, as schematically depicted in Fig.2B. The latter provides a plurality of dies 39 which stamp or cut a like pluralityof smaller green porous media products, such as disks, or other suitablyconfigured media. The green disks 34 are then conveyed to an oven 40 forfurther processing into the porous media.Although a continuous process has been schematically depicted in Figs.2A and 2B, it is to be appreciated that the surface 30 could as well be the lowerplaten of a press. The calender 31 would be replaced by an upper platen (notshown) that would compress and densify the mixture of components 20 into thesheet of green product 34. Of course, subsequent cutting of the green productis dictated by the ultimate shape and dimensions of the porous media desired andthus, the sheet itself may be configured for use in plate and frame apparatus orthe like without being subjected to the cutting operation depicted in Fig. 2B.After, formation of the green product 25 or 34, the next step is to bindthe primary media by melting the binder within the porous structure to a temp-erature just above the melting point of the polymeric binder so that a self-supportcondition is maintained. This is again schematically depicted in Fig. 2C for thegreen disk products 34. The preferred temperature is up to 20Â°C above themelting point of the binder and most preferred is up to 10Â°C above the meltingpoint. For example, the bonding temperature and time for the FA700 (QuantumUS!) and 13040F (MiniFiber) high density polyethylene binders is about 140Â°C(~ 5 Â°C above melting temperature, and ~ 15 Â° above Vicat softening temperature)at 40 minutes, respectively. (The melting point of the binder is determined by adifferential scanning colorimeter at 5Â°C/min.) At this heating temperature, theporous structure gives the highest physical strength without causing a high meltflow problem, which is believed to reduce the capacity and efficiency by sealingoff the pores of the primary adsorptive separation media, such as activatedcarbon.ï»¿1015W0 98/ 10855CA 02265878 1999-03-09PCT/US97/1576115In addition to the above features, the porous structures are self-supporting during the heating process. The green strength agents also provide hotstrength to the porous structures. The best combinations of time and temperatureare dependent on the type or mixtures of binders. The best condition is to givethe least melt flow and highest physical strength within the shortest amount oftime. Other thermal bonding processes such as microwave, radio frequency andinfrared heating can be used. Unlike the existing art, there is no shear forceapplied against the media during the baking step. Nor, are ultra-high molecularweight polymer binders employed.While heating the green product 25 sufficient to melt or react thebinder is a preferred step, the present invention also includes a process whereinthe product is finished after the compressing step and does not require baking orseparate heating. Examples of such products produced by compression alone arepresented herein below in Example Nos. 1 to 20.In Table I which follows, the differences between the processes taughtby the three patents summarized in the Background and the process of thepresent invention which has been assigned to Cuno, Inc., have been listed. Noneof the first three products of the prior art were self-supporting prior to and duringthermal bonding.ï»¿CA 02265878 1999-03-09PCT/US97/ 15761WO 98/1085516CEOQw:_:m.:om w:_:o&_.m.8_> :mm 5:. omÃ©mz Â£3: 2 .32m>oaw Uocm \w:_:o.a=m ~:w5E< w:w_>Â£w>_o._:85 oz -3 uomS-mm_ Em _.a E.$-oo~ .55E< rise .3: 2.3: as acsuSE02w=_Â§:8 .3: 3 .32~mu_> w>onm m:o::::oU .oE>_oQoUuocb <>m 6: $Â£8< _?_> 88 :m.So.m23% ._m_: .2 uomi oz\oz E. ociwom E: ..:a_E.o->_o._ - Z. .93 C.SE9.w:_:m:om mac: we >>o._ >E>:U_> u>onm :o_E_.umw_. o:w_.EÂ«u>_o._ owm.mmw.vuoomlsc oz 8: Em_o>> .32 E8.85 2:: uomowmt oz\o2 _2. Stem .Â§5E< ;w_:.Â£=: Snem Â§sE<9:32w.._5c8umu_> m>opm Â£w_â._ 3 .32uocï¬ï¬ 5:. N; E: o5_>.:m.->_o._ Sou m$..$3.._8._m 2:: uommwm: oz\oz ._a 8-2. :a5E< bias 23 53 95 :5.5625 U0 â.:.UZm=_hm mi; Â«M .._Sm_h ..=2m._. xuoz_ :52 I .m~_m .02 hZm~<._#0: 5:8 .._SE.F 02:5: howtzmmuc .9. .H_:mm=_._ UZ_x_<< DZ< 3:25 5u_:_<._ Â«W >Z<._S.OUEmzm uz_n:o2 ZO5_<Umzom:_<.Â§ou $505._ mzmÃ©.ommâSSUBSTITUTE SHEET (RULE 26)ï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCTIUS97/157611 7Multiple layers of separation media can be made with the calendering,pressing or isostatic compression processes. The blends of each layer can beadded and pressed sequentially to make the multi-layer porous structures atvarious pressing conditions. In the case of the isostatic process, the blends ofdifferent layers can be added simultaneously through a feeder equipped with aconcentric mouth. The feeder moves upward during filling without disturbing theseparate layers. Or, the filling process can be accomplished by removing thesleeves after the different components are added.The addition of as little as about 1% of high strength fibrous materialscan significantly improve the physical and impact strength. This type ofcomposite structure reduces cracking of products during shipping and handling,and improves reliability of the product. Many fibers such as, polypropylene,polyester, glass, carbon and graphite fibers are good candidates for such purpose.If the media becomes too fluffy and difficult to process when large amounts ofthe fibrous materials are used in the product, it is preferred to precompact themedia. The shape of the pre-compacted materials can be pressed into manyshapes such as sheet, rod, tube, pellet, and briquette.Another advantage of the isostatic compression process is to makevarious shapes or patterns of the porous structures. In particular, grooves indifferent shapes can be directly molded onto the surface of the porous structureswhen the bag tooling is designed to have opposite patterns. The surface groovesimprove the dirt holding capacity in separation applications. Furthermore, thisprocess can make porous structures, typically in cylindrical shape, with a hollowcenter core which can be sealed at one end when a shorter center pin is used.This kind of product eliminates the materials and process needed to put an endcap at the end of the structure in a typical cylindrical filter construction process.Densifying via isostatic compression provides as another benefit theformation of porous structures having L/ D (length to diameter) ratios greater than3:1 , in contrast to conventional means of axial compression that are as a practicalmatter limited to UD of 2 to 3:1, because of axial density gradients createdwithin the structure.ï»¿1015202530W0 98/10855CA 02265878 1999-03-09PCT/US97/1576118Summarizing, the major ingredients within the formulations of theporous structures are: 1) primary media (PM); 2) green strength agent (GSA); 3)binder (B) and, 4) optional additives. The optional additives normally do notchange the main functions of PM, GSA, and B. However, the additive canbecome part of the PM, GSA, and/or B when the contribution of the additive issignificant.Before proceeding with the examples to demonstrate practice of thepresent invention, it is necessary to recapitulate on the foregoing components.Accordingly, in some instances there are minimally three separate componentspresent, excluding optional components. These include the primary media PM,the green strength agent GSA and the binder B, as depicted in boxes 50 of Figs.3A and 3B. These components are initially mixed dry, and then compressed, box51 removed from the box 52 and either heated, Fig. 3A box 53 or not heated, asdepicted in Fig. 3B. Both processes produce non-adsorptive and adsorptiveporous structures e.g., filter, or separation media, boxes 54 and 55 respectivelyof Fig. 3A and boxes 56 and 58 respectively of Fig. 3B.Focusing on the method outlined per Fig. 3A and with reference to Fig.4, the primary media in box 60 can include both powders 61 and fibers 62. Thebinder materials in box 63 can also include both powders 64 and fibers 65.Finally, the green strength agents in box 66 can also include powders 67 andfibers 68. In the interest of simplifying the explanation at this stage, species ofcomponents that are non-powder and non-fiber, such as resin solutions, latexesand water, have not been depicted in Fig. 4 with the understanding that theirpresence is not necessarily precluded. The point to be considered in Fig. 4 is thatthe finished product 69 can result from the combination of powders and fibers,for example: PM powder, 61; B powder, 64 and GSA fibers, 68 as well asmixtures of three fibers: PM, 62; B, 65 and GSA, 68 and so forth.It must also be considered that PM powders and fibers are generallynon-melting, but can be selected from meltable materials. Likewise, while the Bpowders and fibers are meltable, the GSA powders and fibers are generally non-melting, but can be selected from meltable materials. Furthermore, it is notï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/157611 9always necessary to select three separate component materials to provide a PM,a B and a GSA. For instance, fiber selected for the PM can be employed as theGSA for a two-component product 69; or where the fiber selected for the PM isa multi-component fiber (HDPE/PP), it can be employed as the B and GSA, for aone component product 69 and so forth. In similar fashion, the present inventioncan be practiced with mixtures of more than one PM and/or more than one Band/or more than one GSA and thus, it is to be appreciated that the porousstructures 69 and processes of the present invention are not limited to thecombination of a single PM component, a single B component and a single GSAcomponent.Nevertheless, the porous structures of the present invention willcomprise between 70 and 90 percent by weight of PM; between eight and 20percent by weight of B; and between one and 15 percent by weight of GSA evenif two or three of the components are originally provided in the mixture by onecomponent. Where either 8 or GSA is a resin solution or the like, not depictedin Fig. 4, it is still possible to select powders and/or fibers for the PM and for atleast one other component, B or GSA.With reference next to Figs. 5-7, further explanation of the inventionis schematically depicted for three exemplary component mixtures. In Fig. 5A,the mixture of PM, indicated by 80; 8, indicated by 81; and GSA, indicated by 82is first depicted. In Fig. 5B, after the mixture has been compressed and heated,it will be noted that the product 83, only a segment of which is shown, comprisesidentifiable PM 80 and GSA 82, while the binder material 81 has melted and isholding the other two components together, to form the product 83. A typicalexample (Example 41) includes carbon particles as the PM; fibrillatedpolypropylene fiber as the GSA and polyethylene powder as the B. After thermalbonding, the polypropylene fiber acts to increase structural strength of the porousproduct 83.In Fig. 6A, the mixture comprises PM; indicated by 90 and a secondcomponent 91, which represents a fibrous component, serving as the GSA and B.In Fig. 6B, after this mixture has been compressed and heated, it will be notedï»¿1015202530W0 98/ 10855CA 02265878 1999-03-09PCT/US97/1576120that a portion of the fiber 91 has melted, forming the binder 92 to bind theremaining fibers (GSA) and PM together in the product 93. A typical exampleincludes carbon black as the PM and a fibrillated fiber e.g., PE, as the GSA andB (examples 17 to 20). Fig. 6C shows complete melting of the fiber 91, so thatthe primary media 90 and binder 92 remain. Depending upon the componentsselected, the product 93 can be that depicted by either Fig. 6B or Fig. 6C.In Fig. 7A, the mixture comprises only a fiber, such as the multi-component HDPE/PP fibers, indicated by the numeral 91. These fibers providePM, GSA and B (Example 47). In Fig. 7B, after these fibers have been compressedand heated, a portion of the fibers have melted, forming the binder 92 of product94, while the majority of the fibers are now PM 95, forming the fiber matrixnetwork of the product 94. A typical example is a product resulting from thecompression and heating of multi-component fibers, such as HDPE/PP. Suchfibers are depicted in Figs. 8 and 9 wherein the inner core 96 is PP and the outersheath 98 is HDPE. In Fig. 9 after these fibers 91 have been heated, portions ofthe sheaths 98 melt together to form a matrix of joined fibers which provide bothseparating capability and green strength.With reference now to Figs. 10-13, several of the types of products thatcan be manufactured according to the present invention are depicted. In Fig. 10,the product 100 comprises a cylindrical element or body 101 with a hollowcentral core 102. A plurality of annular grooves 103 are formed in the outermostsurface 104 to increase the effective surface area of the element. Preferably, thegrooves provided opposed tapered lands 105, as depicted in Figs. 10 and 11,which strengthen the respective grooves and ensure the clean separation of themold 21 from the element 101.While such annular grooves 103 can be machined into a cylindricalcartridge blank, this extra step and the attendant waste material are eliminatedby compressing the components in a mold, as described hereinabove. As anotheradvantage, it is equally possible to provide other exterior surfaces thancircumferential grooves. As an example, Fig. 12 depicts another product 110,providing a cylindrical body 111, with a hollow central core 112. The outermostï»¿1015202530W0 98/10855CA 02265878 1999-03-09PCT/US97/1576121surface 113 carries a plurality of longitudinal grooves 114, running axially overmost of the length of the body. Typically, the grooves terminate at each end 1 15,of the cartridge.As another example of exterior configuration, Fig. 1 3 depicts a product120 having a cylindrical body 121, a central hollow core 122 and provided witha plurality of inwardly truncated dimples 123, from the outer circumferentialsurface 124. Of course, it is to be appreciated that other exterior configurationsare readily possible as well as the fact that the overall configuration of theproduct is not limited to cylindrical, but could also be rectangular, square, orotherwise configured to accommodate the inner volume of a specific housing.Accordingly, it is to be appreciated that the present invention includes productshaving discontinuous exterior surfaces, provided without separate machiningsubsequent to manufacture, as well as smooth exterior surfaces i.e., uninterruptedcylindrical or other surfaces provided by a relatively smooth mold surface.It is also possible to formulate tubular products, having a hollow core,which are closed at one end, by densified the mixture of components in a closedend mold. Such a structure is depicted in Fig. 14 for the porous product 125,having a cylindrical body 126, a core 128 and a closed base 129. Typically,hollow tube products of this type, prepared from primary reinforcement mediaand a binder are hollow cylinders, open at both ends. By use of the process ofthe present invention, such limitations are no longer existent.It is also possible to prepare multi-layered cylindrical porous structuresaccording to the present invention. With reference to Fig. 15, a pressure vessel130 is depicted, provided with a rubber mold, bag 131, located within ahydraulically activated chamber 132. The chamber 132 is closed at the base bya ram 133 and at the top by a removable cover (not shown) received within moldopening 134. Located within the rubber mold are a plurality of cylindricalsleeves e.g., two 135 and 136, as well as a cylindrical central mandrel 138 whichforms a hollow core 139, for the porous structure 140 (Fig. 16).While use of a mandrel is not critical to manufacture of the porousstructures because the process of the present invention is suitable for theï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/1576122manufacture of solid porous structures, a mandrel will be used for making hollowstructures which are, in turn, employed where radial flow through the porousstructure is desired or necessary.As is evident from Fig. 15, the sleeves 135 and 136 are concentric withthe mandrel 138 and together allow for the addition of three differentcombinations of components 141, 142 and 143. The sleeves are initially placedwithin the rubber mold 131 so that three cylindrical shells of components can beformed after which the sleeves are withdrawn, the mold is closed and thecomponents are densified under pressure. The mold is subsequently opened andthe green product 140 is removed via the ram 133 for subsequent heating to meltthe binder materials.With reference to Fig. 16, a portion of the resulting product 140 isdepicted having an outer layer 141 of one type of media; an intermediate layer142 of another type of media and, an inner layer 143 of a media different fromthe intermediate layer 142, which can be the same media as the outer layer 141,or different. The advantages should be apparent considering the fact that theresulting product 140 can provide varying or gradient porosities, from coarse tofine or from fine to coarse. Additionally, different types of primary media canbe employed, such as particulate and fiber, as is true for the other twocomponents, the binder material and the green strength agent. Moreover, whilethe foregoing description relates to three distinguishable layers, it is to beappreciated that multi-layered products providing two layers or more than threelayers are possible according to the present invention.As an alternative, it is also possible to prepare multi-layered cylindricalporous structures without the use of sleeves. With reference to Fig. 17A, apressure vessel 130 is again depicted, provided with a rubber mold, bag 131,located within a hydraulically activated chamber 1 32. The chamber 132 is closedat the base by a ram 133 and at the top by a removable cover 145 (Fig. 17C)received within mold opening 135. When the mold is open, a filling apparatus,filler 146, is inserted which dispenses concentric layers of composite media asdescribed throughout herein.ï»¿1015202530W0 98/ 10855CA 02265878 1999-03-09PCT/US97/1576123Filler 146, as depicted provides an open base 148 and an upper funnel-like mouth 149. The filler 146 is supplied with a source of composite mixturesaccording to the present invention, in this instance two. It is to be understoodthat filler 146 has been depicted somewhat schematically in the interest ofsimplification and that means for delivering composite mixtures to the mouth andthrough the filler are within the skill of the art and need not be depicted. Thefiller 146 also provides an outer wall 150 and an internal sleeve 151, to providetwo separate concentric layers, 152 and 153, of composite mixtures. Of course,while only two layers are shown, it is to be understood that more layers arepossible.Filler 146 is initially placed within the bottom of the mold, as depictedin Fig. 17A, and the mixtures are carefully deposited into the mold so that thelayers 152, 153 remain separate and distinct. As it slowly withdrawn, (Fig. 178)the composites continue to flow into the mold and form, in essence, a layeredpre-product, prior to densification. When the filler 146 has completed itsdeposition, the flow is shut off (by suitable means, not shown), it is removed andthe cover 145 is placed, following which the mixtures are subjected to isostaticcompressing. After pressing, the product 155 appears as in Fig. 17C and iswithdrawn from the mold 130, similar to the procedure described hereinabove.Again, while a mandrel 138 has been depicted for a hollow structure, solid,layered structures can be manufactured by omitting the mandrel.It is to be appreciated that one could also form multi-layered productswith two or more zones or layers of different character by sequentiallycompressing an added layer over a previously made structure of cylindrical shapeor other. While this embodiment has not been depicted in the drawings, basedupon the foregoing description herein, it is within the skill of the art to form aporous structure in this manner and accordingly, is an alternative included withinthe scope of this invention. Sequential compressing can be practiced by addingan additional layer or layers of composite materials to the compressed structure155, before it has been removed from the mold or, after such removal in whichinstance the structure could be placed in other apparatus or returned to the mold.ï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCTIUS97/1576124Additionally, flat sheet or layer materials can also be formed,particularly where the mixture of components is calendered or otherwisedensified to provide such shapes. Moreover, it is possible to formulate bi- andmulti-layered flat sheet products by adding subsequent layers of componentmï¬maomomemï¬hwnlnmkmmmmï¬ï¬umgmhuï¬mmmmemmmdsfrom different mixtures of the basic components, each layer having a specificblend of one or more of the component elements as provide primary separation,reinforcement and binding capabilities. The specific blend can be the same asanother layer in the product or different. Also, such layers can have smoothexterior e.g., upper and lower, surfaces or, they can be provided with grooves orother configurations, as described hereinabove.With reference to Fig. 18, an apparatus 160 is depicted schematicallywhich comprises a movable belt 161, providing a flat surface 162, the belt beingdriven by a motor 163. Above the surface 162, is a first hopper 164 whichdispenses a first type of media 165, which is uniformly laid out by a doctor bladeor roller 166. A second hopper 168 is provided downstream from the first, todispenses an intermediate layer of media 169, which is again uniformly laid outby a roller 166. Further downstream, is third hopper 170 which dispenses a thirdtype of media 171, which is also uniformly laid out by a roller 166. As a result,a product is formed which can be densified on the belt by means not shown toform the green product 172, or subsequently densified.In Fig. 19, a portion of the multi-layered flat product 175 is depictedin cross-section, providing a first layer 165 of one type of media; an intermediatelayer 169 of another type of media and, an third layer 171 of a media differentfrom the intermediate layer 169, which can be the same media as the first layer165, or different. As for the cylindrical layered product 140, the resultingproduct 175 can provide varying or gradient porosities, from coarse to fine orfrom fine to coarse. Additionally, different types of primary media, bindermaterial and/or green strength agent can be employed. Again, while theforegoing description relates to three distinguishable layers, it is to be appreciatedthat multi-layered products providing two layers or more than three layers areï»¿10152025WO 98/10855CA 02265878 1999-03-09PCT/US97/1576125possible according to the present invention. Similar to the explanation providedwith respect to Figs. 28 and 2C, the green flat sheet product 172 can be die cutinto a plurality of disks or other configured media.It is again to be appreciated that one could also form multi-layeredproducts with two or more zones or layers of different character by sequentiallycompressing an added layer over a previously made flat structure. To do sowould merely require the step of feeding a subsequent layer of another mediacomposite, prior to heating, followed by densification of all the layers. Additionallayers could be added in this fashion or, several layers of media could be addedand densified in one step, depending upon the design of the apparatus beingemployed.From the foregoing explanation of fibrous components, it is to beappreciated that the fibers can be monofilamentary, as is depicted by the fiber180 in Fig. 20, or they can be fibrillated, as depicted by the fiber 181 in Fig. 21.Fibrillated fibers 181 provide fibrils 182 extending outwardly from strands 183.Fibrillated fibers are useful as the PM, as the GSA and as the binder B, wheresome melting occurs.According to the preferred process of the present invention, a varietyof porous structures can be manufactured under several different pressing andheating conditions based on whether the primary media is non-adsorptive oradsorptive (or absorptive). The various combinations for manufacture aredepicted diagrammatically in Figs. 3A and 3B. There are nine (9) major cases formaking the non-adsorptive and four (4) major cases for making the adsorptiveporous structures presented in Table II when different PM, GSA, and B materialcombinations are compressed and heated.ï»¿1015202530CA 02265878 1999-03-09WO 98/10855 PCT/US97/ 1576126TABLE IICASES FOR COMPRESSING AND HEATING or COMPONENTSADSORPTIVE NON-ADSORPTIVECASE PM GSA B MEDIA MEDIAA1 0 O M Yes YesA2 0 M M Yes YesA3 M O M - YesA4 M M M - YesA5 0 - M Yes YesA6 0 M - Yes YesA7 M M - - YesA8 M O - - YesA9 M - - - YesThe O symbol indicates the presence of the ingredient and it does notfunction as a binder. The M symbol indicates the presence of the ingredient andit melts or reacts as a binder.Case A1: The primary media and green strength agent do not melt orreact. Only the binder melts or reacts. (Example 41).Case A2: The primary media does not melt or reacts. Both of thegreen strength agent and binder melt or react. (Examples 21-23).Case A3: The green strength agent does not melt. Primary media andbinder both melt or react. (Example 42).Case A4: Primary media, green strength agent, and binder all melt.(Example 43).Case A5: Either primary or binder works as green strength agent.Only the binder melts or reacts. (Example 44).Case A6: The green strength agent melts or reacts. No binder needed.(Examples 17-20, if the PE is melted).Case A7: Both the primary media and green strength agent melt orreact. (Example 45).ï»¿10152025W0 98/ 10855CA 02265878 1999-03-09PCT/US97/1576127Case A8: The primary media melts or reacts. No binder is necessary.(Example 46).Case A9: The primary media functions as green strength agent andbinder. (Example 47).Another example, the multi-component polyethylenesheath/polypropylene core fiber can be used as a primary media, however, if thepolyethylene sheath melts by heating, then it works as a binder. If there is notbinder present, either PM and/or GSA must melt or react (Case A6, A7, A8, andA9). Formulations with more than one kind of PM, GSA, and B are covered bythe combinations of the nine basic cases shown in the Table II. In the case ofadsorptive porous structures, the primary media does not melt or react with otheringredients, therefore, only four (4) different cases can be found for differentcombinations (Table II).The adsorptive porous structures, i.e., activated carbon media, shouldbe made with minimum amounts of binder to reduce blinding the useful surfaces.However, non-adsorptive media does not have these restrictions. Normally, it ispreferred to have higher physical strength at high flow rates. The amount ofbinders for non-adsorptive media can be significantly higher than the amountused for the adsorptive media, if higher physical strength is required.If the media does not require binding force by melting or reacting thebinder, the green strength agent is then required to hold the porous structuretogether to give the final strength. The primary media (PM) and/or the greenstrength agent (GSA) should be responsible for contributing the strength. Theporous structure is held together by the entangled or deformed fibers andparticles. For each of the non-adsorptive and adsorptive media there are two (2)cases listed in Table I ll. Typical fine metal fibers and particles are idealcandidates to provide the physical strength.ï»¿1015202530W0 98/10855CA 02265878 1999-03-09PCT/US97/1576128TABLE IIICASES FOR NO-BINDER FORMULATIONCASE PM GSA ADSORPTIVE NON-ADSORPTIVEMEDIA MEDIAB1 0 0 Yes YesB2 0 Yes YesThe O symbol indicates the presence of the ingredient and it does notfunction as a binder.In order to demonstrate practice of the present invention, a series offilter blocks were prepared as detailed in the examples hereinbelow. All parts arepresented by weight percent, unless otherwise noted.Examples No. 1-20The contribution of fibrillated fiber, namely polyethylene (PE), on greenstrength of the carbon block was demonstrated by formulating carbon, PE fiberand PE powder utilizing the following ingredients:85% Carbon: Barnebey & Sutcliffe Type 3049 carbon, 80x325 mesh4-15% PE fiber: (Minifiber, 13040F)5-11% PE powder: (Quantum Chemical, FASP007)As will be seen, the relative amounts of powder and fiber, totalling 15percent of polyethylene (PE) by weight, were varied among Examples 1 to 20. Allof the blocks formed were 55 grams and each was molded into blocks with ametal piston mold under various pressures. The mold employed was 1.75 inchO.D. and 0.375 inch |.D. and dwell time was 15 seconds. The length variedslightly by about 2 to 5 percent, depending upon the molding pressure and wasabout 2.4 inches. The green strength was measured by compressing the porousstructures perpendicular to the block axis at a rate of 0.0238 inches/sec. Theeffects of molding pressure and the amount of PE fiber on the green strength haveï»¿CA 02265878 1999-03-09WO 98/10855 PCT/US97/1576129been provided in Table IV and Fig. 22. The four curves of Fig. 22 are plots of thedata points presented in Table IV, each curve beginning at 4 percent PE fiber andincreasing to 15 percent. Respective green strengths can be read from the curvesand compared.ï»¿1015202530CA 02265878 1999-03-09WO 98110855 PCT/US97/1576130TABLE IVEFFECT or MOLDING PRESSURE ANDPE FIBER CONTENT ON GREEN STRENGTHEXAMPLE % % MOLDING GREENNo. OF PE or PE FORCE, STRENGTH,FIBER POWDER LB LB1 4 11 2000 11.852 4 11 4000 24.103 4 11 6000 36.304 4 1 1 8000 42.305 5 10 2000 19.256 5 10 4000 42.257 5 10 6000 57.908 5 10 8000 76.509 6 9 2000 29.5510 6 9 4000 56.4411 6 9 6000 68.851 2 6 9 8000 93.501 3 10 5 2000 41.6514 10 5 4000 74.701 5 1 0 5 6000 1 07.9016 10 5 8000 131.0517 15 0 2000 55.7018 15 0 4000 90.801 9 V 15 0 6000 135.9020 15 0 8000 153.95As should be apparent from Table IV, the higher molding pressuresprovided greater green strength and, the green strengths were higher when thePE fiber was increased, for blocks comprising 85 percent carbon. For purposesï»¿101520W0 98/ 10855CA 02265878 1999-03-09PCT/US97/1576131of subsequent processing, acceptable green strength for these blocks is about 20poundsExamples No. 21-24Three porous structures (carbon blocks) were manufactured utilizingthe following ingredients:4% PE fiber 13040F11% PE powder FASP00785% Carbon: Barnebey & Sutcliffe Type 3049 carbon, 80x325 meshThe same size mold employed for Examples No. 1-20 was used, molding forcewas 8000psi, and dwell time was 15 seconds to produce blocks 2.25 inches inlength except Example 24 which was a 9.75 inch block manufactured by KXCorporation and subsequently cut to 2.25 inch blocks. The KX Corporation blockcomprised 85 percent carbon and 15 percent binder. A collapse test wasconducted on 0.625 inch slices, cut from the 2.25 inch blocks, by compressingat a rate of 0.0238 inch/sec. The blocks had 1.75 inch O.D. and 0.375 inch l.D.Examples 21-23 were baked at 139Â°C for the period cited in Table V. Methylenechloride reduction evaluations were conducted to evaluate efficiency of thevarious blocks. To a feed flow stream of 300 ml/min of Meriden, Connecticutcity water, methylene chloride was injected to a concentration of 300 ppb.Breakthrough concentration was set to be 15 ppb. After the experiment, collapsetests were conducted on 0.625 inch slices, cut from the 2.25 inch blocks, bycompressing perpendicular to the axis at a rate of 0.0238 inch/sec. The resultsof both tests are presented in Table V.ï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/157613 2TABLE VCARBON BLOCK METHYLENE CHLORIDE REDUCTION AND COLLAPSE TESTINGEXAMPLE BAKING TIME THROUGHPUT AT 15 COLLAPSE FORCENO. MIN. PPB, GALLON or 0.625 INCHSLICE, LB21 25 20 6722 45 26 11023 55 14 9424 (KX) N/A 24 79Examples No. 25-29The same formulation employed for Examples 21-23 was scaled up tomake 290 gram blocks, 12 inches in length with a 1.75 inch 0.D. and a 0.375inch l.D.embodiment, was employed utilizing a rubber mold and compressed by hydraulicThe isostatic compression process according to the preferredpressure at 2500 psi for 20 seconds. The blocks were subsequently baked forvarious times at 142Â° to 143Â°C, and then cut to 9.75 inch lengths for testing. ACfine test dust (ACFTD) was employed for three tests: gram life; turbidityreduction efficiency and, percentage particulate reduction at 0.6GPM. Two 9.75inch products of KX Corporation from different lots were evaluated (Examples NO.28 and 29). Collapse force tests were also conducted and have been reported inTable VI, with the other test results.The definitions of the terms used in Table VI are as follows:a. AP; Differential pressure (psid) across the filter at 0.6 GPM flowrate.b. Gram life, ACFTD: The cumulative weight (in grams) of the AC finetest dust (ACFTD) fed to the filter when the differential pressure increased by 20psi at 0.6 GPM flow rate.c. Turbidity, NTU: Nephelometric turbidity units. Turbidity is afunction of concentration and particle size of the suspended solids in water.ï»¿CA 02265878 1999-03-09W0 98/ 10855 PCT/U S97! 1576133d. Percentage reduction of number of particles between 1-5 pm. TheNSF (National Sanitation Foundation) Standard 42 is using minimum 85%reduction of this particle range for particulate reduction Class II rating.ï»¿CA 02265878 1999-03-09PCT/U S97/ 15761WO 98/1085534m H 3 <\Z Â¢m.mm-am.ow _.R-m.E 36 3.: 00: an 3M H 3. <\Z ow.mm-em.mm m.nm-w.Â¢a ON.m O06 003 anm H S cm S.mm-mm.wm m.wm-m..$ 3.Â». sad ANm H cm me om.ma.mv.R q.R-_.mm â_..m cod @NA H on 3 _m.$-mm.mm m.wm-m...:.. mg 3.~ mm3.5 .Â§_Â£ ..\.. .>uzm_uEmmm._<:ou .z__2 52:. as .2: m-_ zo_U38~_ zo_C:B~_ U .n_Eu< SE0 9:wuzm :uz_ Qm 5.5 m533U_E<._ Spzv >:o:==F E: 25.0 E .2 .._< .02 502.53 m_m._<:oU oz< n_EU< V505 205:0_> Em<pSUBSTITUTE SHEET (RULE 26) ï»¿10CA 02265878 1999-03-09W0 98/10855 PCT/US97/1576135Example 30-33Four porous structures (carbon blocks) were manufactured utilizing thefollowing ingredients shown in Table VII. The length was about 2.42 inch, theO.D. was 1.75 inch and the l.D. was 0.375 inch. The blocks were molded at6,000 lb force, and baked at 141 Â°C for 45 minutes. The radial air flow resistancewas measured at constant flow of air at the rate of 135 SCFH through a 0.625inch slice of filter donuts. In these examples, both PE fiber and powder meltedas binder materials and the effect of PP fiber reinforcement can be seen bycomparing Example Nos. 31 to 33 (1 to 3% fiber) with No. 30 containing nofiber, namely, approximately a 50 to 60 percent increase in final productstrength, as indicated by the collapse force test.ï»¿CA 02265878 1999-03-09PCT/US97/15761W0 98/ 10855368. mm mm C q M mmS. 3 mm : e N am3; no em ââ V â E3 mm mm : V s am2 5.: cf 52. .5352. mac... :uz_ mam... zo$_<u 595..go 5:0â. mo 5z<EmE was 5 :3 ma noc._m<a Em: ma Eu: .5 Em:_z_2ma,_<:ou >5: ~=< avom 5 ea u_o 4.. 339 go as 52. X 3.23 m go ..\o .02 5$_:m._o~_._ DZ< mzzsm 505 ZOm~_<U__> 393oâSUBSTITUTE SHEET (RULE 26)W. ï»¿1015202530CA 02265878 1999-03-09WO 98110855 PCT/US97/1576137Example No. 34A 55 gram block was manufactured in a metal mold 2.4 inch O.D.,0.75 inch I.D., utilizing a molding force of 2000 lbs and the following ingredients:85% diatomaceous earth (Grefco, Dicalite 6000)6% PE fiber 13040F9% PE powder FASP007The block was baked at 142Â°C for 45 minutes.Example No. 35The formulation and mold specifications of Example No. 34 wererepeated for Example 35 except an additional 2.00 grams of resin Kymene 557H(Hercules, 12.5 percent solids) was added. The porous structure was baked at142Â°C for 45 minutes.Example No. 36A 55 gram block was manufactured in a metal mold 2.40 inch O.D.,0.75 inch I.D., utilizing a molding force of 2000 lbs and the following ingredients:80% diatomaceous earth (Grefco, Dicalite 6000)5% Polypropylene (PP) fiber (MiniFiber Y600F)6Â°/o PE fiber 13040F9% PE powder FASP007The block was baked at 142Â°C for 45 minutes.Example No. 37A 55 gram block was manufactured in a metal mold 2.40 inch O.D.,0.75 inch I.D., utilizing a molding force of 6000 lbs and the following ingredients:65% Carbon type 30494% PE fiber 13040F11% PE powder FASP00720% Diatomaceous earth (Grefco, Dicalite 6000)The block was baked at 142Â°C for 45 minutes.ï»¿10152025CA 02265878 1999-03-09W0 98/10855 PCT/US97/1576138Example No. 38A 55 gram block was manufactured in a metal mold 2.40 inch O.D.,0.75 inch |.D., utilizing a molding force of 5000 lbs and the following ingredients:85% Cuno MicroK|ean grind dust composed of cured resinous binderand cellulosic fiber, sieved to 120-400 mesh8% PE fiber 13040F7% PE powder FASP007The block was baked at 143Â°C for 50 minutes.Example No. 39A 20 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch |.D., utilizing a molding force of 4000 lbs and thefollowing ingredients:23.5% Polypropylene fiber (Hercules, type T-153, 3 denier, 3mm)15.5% PE fiber 13040F1.5% PE powder FA700 (Quantum)59.5% Carbon Type 3049The porous structure was baked at 140Â°C for 50 minutes.Example No. 40A 15 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch l.D., utilizing a molding force of 6000 lbs and thefollowing ingredients:6.25% of PE powder FA70031.25% of PE fiber 1304F62.5% of polypropylene fiber (Microfibers, NAT)The porous structure was baked at 141Â°C for 45 minutes.ï»¿1015202530WO 98/10855CA 02265878 1999-03-09PCT/US97/1576139Example No. 41A 55 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch |.D., utilizing a molding force of 6000 lbs and thefollowing ingredients:80% Carbon type 30498% PP fiber (MiniFiber Y600F)12% PE powder FA700The porous structure was baked at 141 Â°C for 45 minutes.Example No. 42A 20 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch l.D., utilizing a molding force of 6000 lbs and thefollowing ingredients:50% HDPE sheath/PP core multi-component fiber (BASF, B1657)30% PP fiber (MiniFiber, Y600F)20% PE powder FA700The porous structure was baked at 141Â°C for 45 minutes.Example No. 43A 20 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch l.D., utilizing a molding force of 6000 lbs and thefollowing ingredients:65% HDPE sheath/PP core multi-component fiber (BASF, B1657)25% PE fiber 13040F10% PE powder FA700The porous structure was baked at 141Â°C for 45 minutes.Example No. 44A 15 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch |.D., utilizing a molding force of 2000 lbs and thefollowing ingredients:ï»¿10152025CA 02265878 1999-03-09W0 98/10855 PCT/US97/157614070Â°/o PP fiber (Y600F)30% PE powder FA700The porous structure was baked at 141 Â°C for 45 minutes.Example No. 45A 20 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch I.D., utilizing a molding force of 6000 lbs and thefollowing ingredients:85% HDPE sheath/PP core multi-component fiber (BASF, B1657)15% PE fiber 13040FThe porous structure was baked at 141 Â°C for 45 minutes.Example No. 46A 20 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch I.D., utilizing a molding force of 6000 lbs and thefollowing ingredients:80% HDPE sheath/PP core multi-component fiber (BASF, B1657)20% Polypropylene fiber Y600F (MiniFiber)The porous structure was baked at 141 Â°C for 45 minutes.Example No. 47A 20 gram porous structure was manufactured in a metal mold 2.40inch O.D., and 0.75 inch I.D., utilizing a molding force of 6000 lbs and thefollowing ingredients:100% HDPE sheath/PP core multi-component fiber (BASF, B1657)The porous structure was baked at 141Â°C for 45 minutes.ï»¿1015202530W0 98/10855CA 02265878 1999-03-09PCTlUS97/ 157614 1Example No. 48A 55 gram porous structure was manufactured in a metal mold 2.40inch O.D. and 0.75 inch |.D., utilizing a molding force of 6000 lb and thefollowing ingredients:84% Carbon type 30494% PE fiber (1304F)1Â°/o PP fiber (MiniFiber Y600F)11% PE powder FA700The porous structure was baked at 141Â°C for 45 minutes.Example No. 49A formulation of 66.5g of Calgonâs TOGC carbon (80X325 mesh), 28.5gof Georgia Pacific GP 5485 phenolic resin powder, and 3 g of water were mixedwith a Osterizer blender at the lowest speed for 30 seconds. Then 13 g of themixture was molded into a block of 1.75 inch O.D., 0.375 inch l.D., 7/16 inchthick, and baked at 130Â°C for 2 hours.Example No. 50Donut shaped 55 g filters were manufactured in a metal mold 2.40inch O.D. and 0.75 inch l.D., utilizing a molding force of 4000 lb and thefollowing ingredients:60% Cuno MicroK|ean grind dust composed of curedresinous binder and cellulosic fiber, sieved through 200mesh39.6% BTL Melamine-formaldehyde resin powder, grade 4120.4% citric acid (solids), 8% solutionThe porous structure was baked at 141 Â°C for 45 minutes.The porous structures representing Examples No. 34 to 50 were testedagainst a slice of KX 1M carbon block and are reported in Table VIII. The radialair flow resistance was measured at constant flow of air at the rate of 50 SCFHthrough a 0.625 inch slice of filter donuts.ï»¿CA 02265878 1999-03-09W0 98/10855 PCT/US97ll576l42The air flow resistance and collapse force measured for Examples 34through 50 are presented in Table VIII.ï»¿1015202530CA 02265878 1999-03-09W0 98/10855 PCT/US97/1576143TABLE VI"EXAMPLE No. AIR FLOW RESISTANCE,INCH H20 COLLAPSE FORCE, LB34 49 12.935 51.1 26.336 48.2 25.637 30.6 36.538 22.6 15.939 10.9 64.240 10.8 106KX 1M Block 56.5 5941 25.3 93.742 2.9 62.343 8.3 192.744 61 162.145 4.7 171.946 1.7 40.547 0.9 54.848 50 14749 - 9050 11.2 143Thus it should be evident that the process of the present invention ishighly effective in the manufacture of porous structures. The invention isparticularly suited for the production of carbon block structures e.g., filters,having high separation (filter) media weight and relatively low binder weight, butis not necessarily limited thereto. The process of the present invention can beemployed with a variety of equipment, and component materials. Similarly, theseparation media made according to the process need not be limited to powderedcarbon media. Nor, is shape of form of the porous structures a limitation of thepresent invention inasmuch as flat sheets; flat structures; cylindrical structures,open at both ends or closed at one end and, virtually any geometrically shapedï»¿1015W0 98/10855CA 02265878 1999-03-09PCT/US97l1576144structures, solid as well as hollow, can be formed. Moreover, the exteriorsurfaces of the porous structures can be widely varied.Based upon the foregoing disclosure, it should now be apparent thatthe use of the process described herein will carry out the objects set forthhereinabove. It is, therefore, to be understood that any variations evident fallwithin the scope of the claimed invention and thus, the selection of specificcomponent materials can be determined without departing from the spirit of theinvention herein disclosed and described. In particular, porous structuresaccording to the present invention are not necessarily limited to those based oncarbon; nor, are the blocks necessarily limited to the preferred hollow corecylindrical shapes. Similarly, layered products are also included, derived frommore than one component mixture and which provide at least two differentseparation properties or characteristics. Thus, the scope of the invention shallinclude all modifications and variations that may fall within the scope of theattached claims.

Claims

What is claimed is:

1. A process for the manufacture of porous structures comprising:
forming a dry mixture comprising a component providing primary separation capability, a component providing green strength reinforcement capability and, a component providing binding capability and selected from the group consisting of thermoplastic and thermosetting polymers;
delivering said mixture to a suitable surface and building a desired thickness thereof;
densifying said mixture into the form desired for said porous structure;
removing said densified porous structure from said surface;
binding said component providing said primary separation capability by heating said mixture to a temperature of up to about 20° C. higher than the melting point of any said thermoplastic component providing binding capability.

2. A process for the manufacture of porous structures, as set forth in claim 1, wherein said step of forming includes the step of selecting first, second and third components, each said component providing one of said three capabilities.

3. A process for the manufacture of porous structures, as set forth in claim 1, wherein said step of forming includes the step of selecting two of said three components, which together provide said three capabilities.

4. A process for the manufacture of porous structures, as set forth in claim 1, wherein said step of forming includes the step of selecting one component providing said primary separation capability, said green strength reinforcement capability and said binding capability.

5. A process for the manufacture of porous structures, as set forth in claim 1, wherein said steps of delivering and densifying are conducted via compression tooling.

6. A process for the manufacture of porous structures, as set forth in claim 1, wherein said step of delivering includes the step of filling a mold with said mixture and said step of densifying is conducted by isostatic compression of said mixture into the shape of the porous structure, having sufficient green strength to be self-supporting.

7. A process for the manufacture of porous structures, as set forth in claim 6, including the additional step of providing a mandrel in said mold prior to said step of filling.

8. A process for the manufacture of porous structures, as set forth in claim 7, wherein said shape of the porous structure is cylindrical and said porous structure is hollow.

9. A process for the manufacture of porous structures, as set forth in claim 8 wherein said shape has a L/D ratio of at least about 3:1.

10. A process for the manufacture of porous structures, as set forth in claim 6,including the additional steps of filling said mold with at least a second dry mixture of said components around said porous structure; and isostatically compressing said second mixture around said porous structure, thereby providing a layered porous structure having sufficient green strength to be self-supporting.

11. A process for the manufacture of porous structures, as set forth in claim 10, wherein said additional steps are conducted after said step of removing and including the further step of returning said porous structure to said mold prior to said additional steps.

12. A process for the manufacture of porous structures, as set forth in claim 6,wherein said shape of the porous structure is cylindrical and including the additional steps of providing a mandrel within said mold and at least one cylindrical sleeve, concentric with said mandrel, said sleeve and said mandrel defining separate volumes and wherein said step of delivering includes the steps of filling the volume defined between the mold and said sleeve with a first dry mixture of components and filling the volume defined between said sleeve and said mandrel with a second dry mixture of components, different from said first; and removing said sleeve from said mold prior to said step of densifying.

13. A process for the manufacture of porous structures, as set forth in claim 12, including the additional steps of providing one or more additional cylindrical sleeves, concentric with said mandrel, said sleeves additional defining separate volumes and wherein said step of delivering includes the step of filling the volume defined between adjacent sleeves with a second dry mixture of components; and removing said sleeves from said mold prior to said step of densifying.

14. A process for the manufacture of porous structures, as set forth in claim 6,wherein said shape of the porous structure is cylindrical and including the additional steps of providing a mandrel within said mold; and filling the volume defined between the mold and said mandrel with at least first and second dry mixtures of components in concentric layers around said mandrel, prior to said step of densifying, said second dry mixture of components being different from said first.

15. A process for the manufacture of porous structures, as set forth in claim 14, including the additional steps of filling said mold with at least a third dry mixture of said components around said porous structure; and isostatically compressing said second mixture around said porous structure, thereby providing a layered porous structure having sufficient green strength to be self-supporting.

16. A process for the manufacture of porous structures, as set forth in claim 15, wherein said additional steps are conducted after said step of removing and including the further step of returning said porous structure to said mold prior to said additional steps.

17. A process for the manufacture of porous structures, as set forth in claim 1,wherein said step of delivering includes the step of applying said mixture onto a flat support surface and said step of densifying includes the step of pressing said delivered mixture into a sheet of reduced thickness, having sufficient green strength to be self-supporting.

18. A process for the manufacture of porous structures, as set forth in claim 17, including the additional step of applying at least a second dry mixture of components onto said first delivered mixture, prior to said step of densifying.

19. A process for the manufacture of porous structures, as set forth in claim 17, including the additional steps of applying at least a second mixture, different from said delivered mixture, onto said densified sheet and pressing said second delivered mixture and said densifed sheet into a layered sheet of reduced thickness, having sufficient green strength to be self-supporting.

20. A process for the manufacture of porous structures, as set forth in claim 19, including the additional step of cutting desired shapes of porous structures from said sheet of reduced thickness.

21. A process for the manufacture of porous structures, as set forth in claim 1, wherein said component providing primary separation capability is selected from the group consisting of carbon particles, diatomaceous earth, perlite, activated alumina, silica, zeolites, natural fibers, and man-made fibers.

22. A process for the manufacture of porous structures, as set forth in claim 21, wherein said natural fibers are selected from the group consisting of cellulose, wool, jute, hemp and said man-made varieties are selected from the group consisting of fibers made of polyolefins, polyesters, carbon, graphite, glasses, acrylics, rayons, nylons, aramids, multi-component fibers and mixtures thereof.

23. A process for the manufacture of porous structures, as set forth in claim 1, wherein said component providing green strength reinforcement is a fiber selected from the group consisting of polyolefins, polyesters, nylons, aramids, rayons and mixtures thereof and liquid green strength agents.

24. A process for the manufacture of porous structures, as set forth in claim 23, wherein said liquid green strength agents are selected from the group consisting of styrene-butadiene, poly(ethylene-vinyl acetate), and acrylate latexes; methyl-celluloseand hydroxypropyl methyl-cellulose, carboxymethyl cellulose, hydroxyethyl cellulose; polyvinyl alcohol; polyvinyl pyrrolidone;
polyacrylic acid; polyethylene oxide; polyethyleneimine; polyacrylamide;
natural gums and copolymers thereof; water and mixtures with one or more of the foregoing liquid green strength agents.

25. A process for the manufacture of porous structures, as set forth in claim 1,wherein said thermoplastic and thermosetting polymer component providing binding capability is selected from the group consisting of polyolefin, epoxy, phenol-formaldehyde and melamine-formaldehyde resin powders and polyolefin fibers.

26. A process for the manufacture of porous structures, as set forth in claim 1,including the additional step of adding an optional component selected from the group consisting of cationic charged resins, ion-exchange materials, perlite, diatomaceous earth, activated alumina, zeolites, resin solutions, latexes, metallic materials and fibers, cellulose, carbon particles, carbon fibers, rayon fibers, nylon fibers, polypropylene fibers, polyester fibers, glass fibers, steel fibers and graphite fibers, including mixtures thereof in an amount ranging from about 0.1 to about 90 percent by weight, with an attendant decrease in the amount of primary media.

27. A process for the manufacture of porous structures, as set forth in claim 1, including the additional step of cationically charging said optional component selected from the group consisting of perlite, diatomaceous earth, activated alumina, zeolites, cellulose, rayon fibers, nylon fibers and carbon particles.

28. A process for the manufacture of porous structures, as set forth in claim 27, wherein said step of cationically charging said optional component is conducted prior to said step of forming and including the additional step of adding said cationically charged component to said mixture.

29. A process for the manufacture of porous structures, as set forth in claim 1,wherein the desired form created by said step of densifying said mixture is a flat layer.

30. A process for the manufacture of porous structures, as set forth in claim 29, including the additional steps of forming at least a second mixture of said components; densifying said second mixture to form a flat layer and combining said layers to form a multiple layered product.

31. Porous structures comprising:
from about 70 to about 90 percent by weight of a component providing primary separation capability;
from about one to about 15 percent by weight of a component providing green strength reinforcement capability; and, from about eight to about 20 percent by weight of a component providing binding capability and selected from the group consisting of thermoplastic and thermosetting polymers.

32. Porous structures, as set forth in claim 31, further comprising an optional component selected from the group consisting of cationic charged resins, ion-exchange materials, perlite, diatomaceous earth, activated alumina, zeolites, resin solutions, latexes, metallic materials and fibers, cellulose, carbon particles, carbon fibers, rayon fibers, nylon fibers, polypropylene fibers, polyester fibers, glass fibers, steel fibers and graphite fibers, including mixtures thereof in an amount ranging from about 0.1 to about 90 percent by weight, with an attendant decrease in the amount of primary media.

33. Porous structures, as set forth in claim 31, having a first, second and third component, each said component providing one of said three capabilities.

34. Porous structures, as set forth in claim 31, wherein said step of forming includes the step of selecting two of said three components, which together provide said three capabilities.

35. Porous structures, as set forth in claim 31, wherein one said component provides said primary separation capability, said green strength reinforcement capability and said binding capability.

36. Porous structures, as set forth in claim 31, wherein said component providing primary separation capability is selected from the group consisting of carbon particles, diatomaceous earth, perlite, activated alumina, silica, zeolites, natural fibers, and man-made fibers.

37. Porous structures, as set forth in claim 36, wherein said natural fibers areselected from the group consisting of cellulose, wool, jute, hemp and the man-made varieties are selected from the group consisting of fibers made of polyolefins, polyesters, carbon, graphite, glasses, acrylics, rayons, nylons,aramids, multi-components fibers and mixtures thereof.

38. Porous structures, as set forth in claim 37, wherein said component providing green strength reinforcement is a fiber selected from the group consisting of polyolefins, polyesters, nylons, aramids, rayons and mixtures thereof and liquid green strength agents.

39. Porous structures, as set forth in claim 38, wherein said liquid green strength agents are selected from the group consisting of styrene-butadiene, poly(ethylene-vinyl acetate), and acrylate latexes; methyl-cellulose and hydroxypropyl methyl-cellulose, carboxymethyl cellulose, hydroxyethyl cellulose; polyvinyl alcohol; polyvinyl pyrrolidone; polyacrylic acid;
polyethylene oxide; polyethyleneimine; polyacrylamide; natural gums and copolymers thereof; water and mixtures with one or more of the foregoing liquid green strength agents.

40. Porous structures, as set forth in claim 39, wherein said thermoplastic and thermosetting polymer component providing binding capability is selected from the group consisting of polyolefin, epoxy, phenol-formaldehyde and melamine-formaldehyde resin powders and polyolefin fibers.

41. Porous structures, as set forth in claim 40, wherein said component providing primary separation capability comprises carbon particles; said components providing green strength reinforcement comprises polyolefin fibers and wherein said thermoplastic and thermosetting polymer components providing binding capability comprises polyolefin powders and only said component providing binding capability is melted.

42. Porous structures, as set forth in claim 40, wherein said component providing primary separation capability comprises carbon particles; said component providing green strength reinforcement comprises polyolefin fibers and wherein said thermoplastic and thermosetting polymer component providing binding capability comprises polyolefin powders and only both said components providing green strength reinforcement and binding capability are melted.

43. Porous structures, as set forth in claim 40, wherein said component providing primary separation capability comprises multi-component fibers;
said component providing green strenght reinforcement comprises polyolefin fibers and wherein said thermoplastic and thermosetting polymer component providing binding capability comprises polyolefin powders and both said components providing primary separation capability and binding capability are melted.

44. Porous structures, as set forth in claim 40, wherein said component providing primary separation capability comprises multi-component fibers;
said component providing green strength reinforcement comprises polyolefin fibers and wherein said thermoplastic and thermosetting polymer component providing binding capability comprises polyolefin powders and all three of said components are melted.

45. Porous structures, as set forth in claim 40, having a first and second component, said first component providing said primary separation and green strength reinforcement capabilities and said second component providing said binding capability, wherein said first component comprises polyolefin fibers; and wherein said second component comprises polyolefin powders and only said second component is melted.

46. Porous structures, as set forth in claim 40, having a first and second component, said first component providing said primary separation capability, and said second component providing said green strength reinforcement and binding capabilities wherein said first component comprises carbon particles and wherein said second component comprises polyolefin fibers and only said second component is melted.

47. Porous structures, as set forth in claim 40, having a first and second component, said first component providing said primary separation and binding capabilities and said second component providing said green strength reinforcement wherein said first component comprises a multi-component fiber; and wherein said second component comprises polyolefin fibers and both said first and second components are melted.

48. Porous structures, as set forth in claim 40, having a first and second component, said first component providing said primary separation and binding capabilities and said second component providing said green strength reinforcement, wherein said first component comprises a multi-componentfiber; and wherein said second component comprises polyolefin fibers and only said first component is melted.

49. Porous structures, as set forth in claim 40, having a first component, said first component providing said primary separation, said green strength reinforcement and said binding capabilities; wherein said first component comprises multi-component fibers; and wherein said first component is melted.

50. Porous structures, as set forth in claim 49, further comprising at least oneoptional component selected from the group consisting of cationic charged resins, ion-exchange materials, perlite, diatomaceous earth, activated alumina, zeolites, resin solutions, latexes, metallic materials and fibers, cellulose, carbon particles, carbon fibers, rayon fibers, nylon fibers, polypropylene fibers, polyester fibers, glass fibers, steel fibers and graphite fibers, including mixtures thereof in an amount ranging from about 0.1 to about 90 percent by weight, with an attendant decrease in the amount of primary media.

51. Porous structures, as set forth in claim 50, wherein said optional componentselected from the group consisting of perlite, diatomaceous earth, activated alumina, zeolites, cellulose, rayon fibers, nylon fibers and carbon particles is cationically charged.

52. Porous structures, as set forth in claim 31, comprising a flat layer.

53. Porous structures, as set forth in claim 52, comprising multiple flat layers, each said layer having a specific blend of said components.

54. Porous structures, as set forth in claim 31, comprising hollow, shaped structures.

55. Porous structures, as set forth in claim 54, having a L/D ratio of at least about 3:1.

56. Porous structures, as set forth in claim 31, comprising shaped structures having a plurality of concentric layers, each said layer having a specific blend of said components.

57. Porous structures, as set forth in claim 56, wherein said shaped structures are hollow, and have a L/D ratio of at least about 3:1.

58. Porous structures, as set forth in claim 31, comprising hollow, shaped structures, closed at one end.

59. Porous structures, as set forth in claim 31, comprising smooth exterior surfaces.

60. Porous structures, as set forth in claim 31, comprising discontinuous exterior surfaces, provided without separate machining following manufacture.

61. Porous structures, as set forth in claim 31, being fiber reinforced and having improved green strength over comparable porous structures devoid of said component providing green strength reinforcement.

62. Porous structures, as set forth in claim 31, being fiber reinforced and having improved final product strength over comparable porous structures devoid of such reinforcement.