WO2006072889A1 - Activated carbons with molecular sieve membranes and their use as adsorbents in smoking articles - Google Patents

Activated carbons with molecular sieve membranes and their use as adsorbents in smoking articles Download PDF

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Publication number
WO2006072889A1
WO2006072889A1 PCT/IB2006/000296 IB2006000296W WO2006072889A1 WO 2006072889 A1 WO2006072889 A1 WO 2006072889A1 IB 2006000296 W IB2006000296 W IB 2006000296W WO 2006072889 A1 WO2006072889 A1 WO 2006072889A1
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WO
WIPO (PCT)
Prior art keywords
filter
composite
cigarette
substrate
smoking article
Prior art date
Application number
PCT/IB2006/000296
Other languages
French (fr)
Inventor
Zhaohua Luan
Jay A. Fournier
Shuzhong Zhuang
Timothy S. Sherwood
John B. Paine, Iii
Original Assignee
Philip Morris Products S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Philip Morris Products S.A. filed Critical Philip Morris Products S.A.
Publication of WO2006072889A1 publication Critical patent/WO2006072889A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/163—Carbon
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/166—Silicic acid or silicates

Definitions

  • activated carbon materials have been employed as sorbents in smoking articles to remove or reduce smoke constituents .
  • Activated carbons are useful sorbents and have a large capacity; however, they lack selectivity. While they are effective in removing targeted constituents from tobacco smoke, they also may remove volatile constituents which contribute to flavor, aroma and other desirable attributes . Further, activated carbon in a cigarette filter may be rapidly inactivated during storage by the adsorption of .volatile compounds , or by contact with various constituents of mainstream smoke .
  • Zeolite-type molecular sieves have also been used in smoking articles to selectively remove constituents of tobacco smoke .
  • Zeolite molecular sieve sorbents are capable of selectively removing one or more targeted constituents of mainstream smoke .
  • zeolites have minimal capacities and are quickly exhausted before removing a significant amount of the targeted constituent .
  • a smoking article which includes tobacco and a filter system comprising a composite composed of an activated carbon substrate and a zeolite-type membrane coated thereon . Also provided is a filter system, a method of making smoking articles containing said filter system and a method of selectively removing targeted constituents from tobacco smoke .
  • a filter is prepared containing .a composite made by the deposition of a molecular sieve membrane directly onto a carbon-containing substrate by hydrothermal synthesis of a given molecular sieve . Pre-treatment of the substrate may be desirable to achieve optimum adhesion and growth of the membrane on the substrate .
  • cigarettes are prepared which contain tobacco and the filter mentioned above .
  • a preferred smoking article is a traditional or non-traditional cigarette .
  • the aforementioned composite preferably is incorporated into a filter of a cigarette .
  • Another embodiment relates to a method of making a filter cigarette , comprising : ( i) providing a cut filler to a cigarette making machine and forming a tobacco column,- ( ii) placing a paper wrapper around the tobacco column and forming a tobacco rod; (iii) attaching a cigarette filter comprising the composite described above to the tobacco rod to form the cigarette .
  • a method is provided of treating mainstream smoke of a smoking article to preferentially remove one or more targeted constituents from mainstream smoke by contacting the mainstream smoke with a composite as described above .
  • Figure 1 is a view of a cigarette wherein folded paper containing a composite described above is inserted into a hollow portion of a tubular filter element of the cigarette .
  • Figure 2 is a view of another embodiment wherein a composite as described above is incorporated in folded paper and inserted into a hollow portion of a first free-flow sleeve of a tubular filter element next to a second free-flow sleeve .
  • Figure 3 is a view of another embodiment wherein a composite as described above is incorporated in a plug-space-plug filter element .
  • Figure 4 is a view of another embodiment wherein a composite is incorporated in a three-piece filter element having three plugs .
  • Figure 5 is a view of another embodiment wherein a- composite is incorporated in a four-piece filter element having a plug-space-plug arrangement and a hollow sleeve .
  • Figure 6 is a view of still another embodiment wherein a composite is incorporated in a three-part filter element having two plugs and a hollow sleeve .
  • Cigarette filters and smoking articles are provided preferably containing a porous composite comprising an activated carbon substrate and a zeolite molecular sieve membrane coated thereon and capable of selectively removing selected constituents from mainstream smoke .
  • Methods for making such cigarette filters and smoking articles , as well as a method of treating mainstream smoke are also provided.
  • sorption denotes filtration by adsorption and/or absorption and is intended to encompass interactions on the outer i surface of a sorbent , as well as interactions within the pores and channels thereof .
  • a " sorbent” is a substance that has the ability to condense or hold molecules of other substances on its surface and/or the ability to take up other substances , i . e . , through penetration of the other substances into its inner structure or into its pores .
  • sorbent refers to either an adsorbent , an absorbent , or a substance ' that can function as both an adsorbent and an absorbent .
  • the term "remove” as used herein refers to adsorption and/or absorption of at least some portion of a selected constituent . of o mainstream tobacco smoke .
  • mainstream smoke includes the mixture of gases and aerosolized condensed matter which passes down a tobacco column and issues through the filter end, i . e . , the amount of smoke issuing or drawn from the mouth end of a smoking article such as a cigarette 5 during smoking .
  • the mainstream smoke contains air that is drawn in through both the lit or heated region of the smoking article , as well as through the paper wrapper, and through any ventilation perforations that may be present .
  • Non-traditional cigarettes include , for example , smoking articles which include combustible heat sources such as that shown in commonly assigned,
  • the substrate portion of the aforementioned composite comprises an activated carbon .
  • Activated forms of carbon generally have strong physical sorption forces , and high volumes of sorbing porosity .
  • the activated carbon could be .manufactured by any suitable method. Such methods include the carbonization of coconut husk, coal , wood, pitch, cellulose fibers , or polymer fibers , for example . Carbonization is usually carried out at high temperatures , i . e .
  • the activated carbon used as the composite substrate could be in the form of carbon granules , beads , powder, fiber, fabric or shaped monoliths .
  • the substrate could also be an admixture of carbon and an inorganic material .
  • Suitable inorganic materials may comprise porous and/or catalytically active metal compounds such as oxides , hydroxides , silicates and phosphates .
  • Carbon-containing materials suitable as substrates may have a distribution of micropores , mesopores and macropores .
  • microporous generally refers to such materials having pore sizes of about 20A or less while the term “mesoporous” generally refers to such materials with pore sizes of about 2OA to 500A.
  • Macroporous materials have pore sizes above about 500A.
  • the relative amounts of micropores , mesopores and macropores in the carbon-containing substrate will depend upon the selected constituents from mainstream tobacco smoke that are to be targeted and removed . Thus , the pore sizes and pore distribution can be adjusted accordingly as needed for a certain application .
  • Another material in the filter system is a molecular sieve zeolite membrane .
  • molecular sieve refers to a porous structure composed of an inorganic silicate material .
  • Zeolites have channels or pores of uniform, molecular sized dimensions .
  • the size and shape of the channels or pores can significantly affect the properties of these materials with regard to adsorption and separation characteristics .
  • Zeolites can be used to separate molecules by size and shape possibly related to the orientation of the molecules in the channels or pores , and/or by differences in strength of sorption.
  • By using one or more zeolites having channels or pores larger than selected constituents of mainstream smoke only selected molecules that are small enough to pass through the pores of the molecular sieve material are able to enter the cavities and be sorbed by the zeolite .
  • Zeolite-type molecular sieves which are useful in the composites include crystalline aluminosilicates , silicoaluminophosphates (Ai?PO/SAPO) and mesoporous molecular sieves such as MCM-41 , MCM-48 and SBA-15.
  • This family of materials contains regular arrays of uniformly-sized channels and tunable internal active sites , and admits molecules below a certain size into their internal space which makes them useful as catalysts and sorbents where selectivity is critical .
  • Microporous and mesoporous molecular sieves are preferred. They are selected for use in the filter composites based on the particular constituent or constituents to be removed from the mainstream smoke .
  • microporous molecular sieves generally refers to molecular sieve materials having pore sizes of about 2OA or less .
  • the term “mesoporous molecular sieves” generally refers to such materials with pore sizes of about 2OA to 500A. Materials with pore sizes of about 50OA or larger may be referred to as “macroporous molecular sieves .
  • the composite preferably is prepared by a hydrothermal synthesis technique using zeolite precursor materials which form a coated membrane on the substrate . The hydrothermal synthesis of various zeolites can be accomplished by any • techniques which would generate in situ a zeolite membrane on the carbon-containing substrate .
  • the substrates are contacted with the zeolite precursors and a hydrothermal synthesis conducted whereby the zeolite membrane is coated upon and/or into the pores of the substrate . If the carbon- containing substrate has not been activated before synthesis of the zeolite membrane , known activation techniques may be employed to remove volatiles and produce the final activated composite .
  • the product is a composite filter system composed of a porous substrate of activated carbon having a zeolite membrane coated uniformly upon the surface and within the pores of the substrate .
  • sodium hydroxide may be used as the alkaline source .
  • Sodium aluminate (NaAlO 2 ) , aluminum nitrate (Al (NO 3 ) 3 9H 2 O) , aluminum sulfate (Al 2 (SO 4 ) 3 18H 2 O) , aluminum chloride (A1C1 3 6H 2 O) , aluminum hydroxide (Al (OH) 3 ) , aluminum alkoxide and alumina gel , etc . can be used as the source of alumina .
  • the factors affecting crystallization of aluminosilicate include the source of silica, the mole ratio of silica vs . alumina, pH, reaction temperature , reaction time , degree of aging in room temperature , presence of stirring, etc .
  • the morphology and nature of zeolite produced are directly linked to these variations .
  • An example of a method of preparing a molecular sieve compound is described in US 6 117 810 , the entire disclosure of which is incorporated herein by reference .
  • a sodium aluminate solution is made by adding a source of alumina to sodium hydroxide solution and stirring for about 20 to 60 minutes at about 70 0 C to 12O 0 C to dissolve completely .
  • the concentration of sodium hydroxide in solution is about 20 to 50 wt . % , especially about 30 to 40 wt . % .
  • a sodium silicate composition is produced by stirring the sodium hydroxide solution and the silica source at a temperature of about 25°C to 70 0 C . Thereafter, the sodium aluminate solution is admixed with a sodium silicate composition in SiO 2 /Al 2 O 3 mole ratios of about 2.0 to 40.0 , Na 2 O/SiO 2 mole ratios of about 0.4 to 2.0 and H 2 0/Na 2 0 mole ratios of about 15.0 to 70.0. Gelation is brought about by homogeneously stirring .
  • the gel composition is deposited onto and into the pores of the activated carbon substrate .
  • the mole ratio of SiO 2 /Al 2 O 3 is under 2.0 , some of the alumina component remains in the final product . If the mole ratio is greater than 40 , crystallization of the zeolite becomes difficult . If the mole ratio of Na 2 O/SiO 2 is under 0.4 , the activity of the silica component is low and it is slowly converted into zeolite . If the mole ratio is more than 2.0 , a crystalline aluminosilicate is produced having a very low activity .
  • the reaction mixture is allowed to age for about 2 to 96 hours at about 25°C to 60 0 C and crystallized at about 70 0 C to 120 0 C, preferably at 8O 0 C to 100 0 C, and most preferably at 9O 0 C to 100 0 C for 2 to 4 hours .
  • the slurry phase is separated, the final product washed with water, and dried for about 4 to 12 hours at about 100 0 C to 12O 0 C to provide the molecular sieve compound .
  • Preferred complex molecular sieve compounds produced are composed of microporous zeolites such as A, ZSM-5 , X or Y type finely distributed onto the surfaces of the activated carbon . Therefore , the composites have both hydrophilic and hydrophobic adsorption properties derived from the activated carbon and zeolite .
  • silanes are applied to the substrate followed by a heat treatment preferably in an oxidizing atmosphere .
  • Suitable silanes include alkoxysilanes such as tetraethoxysilane .
  • hydrophilic clays such as bentonite and montmorillonite may be admixed with the carbon- containing material before , during or after preparation of the substrate material .
  • the carbon-containing substrate includes activated carbon .
  • the substrate is not activated beforehand, it may be activated after deposition of the zeolite membrane such as by heating the composite which removes various volatiles used in the synthesis of the membrane while activating the substrate .
  • the composite is located in a filter portion of a cigarette .
  • about lOmg to about 300mg of the composite can be used in a cigarette filter .
  • amounts such as at least about 20mg, 30mg, 50mg, 75mg, lOOmg, 150mg, 200mg, or 250mg of the composite can be used in the cigarette filter .
  • Exemplary filter structures may be used to locate the composite .
  • Exemplary filter structures that can be used include, but are not limited to, a mono filter, a dual filter, a triple filter, a cavity filter, a recessed filter or a free-flow filter .
  • Mono filters typically contain cellulose acetate tow or cellulose paper materials .
  • Dual filters typically comprise a cellulose acetate mouthpiece filter plug and a second, different filter plug or segment .
  • the composite is preferably located closer to the smoking material or tobacco side of a cigarette . The length and pressure drop of the two segments of the dual filter can be adjusted to provide optimal adsorption, while maintaining acceptable draw resistance .
  • Triple filters can include mouth and smoking material or tobacco side segments , and a middle segment comprising a material or paper .
  • the aforementioned composite can be provided in the middle segment .
  • Cavity filters typically include two segments , e . g . , acetate-acetate , acetate-paper or paper-paper, separated by a cavity .
  • the composite can preferably be provided in the cavity .
  • Recessed filters include an open cavity on the mouth side , and the composite can be incorporated into the plug material .
  • the filters may also optionally be ventilated, and/or comprise additional sorbents (such as activated carbon, charcoal or magnesium silicate) , catalysts , flavorants or other additives .
  • Figure 1 illustrates a cigarette 2 having a tobacco rod 4 , a filter portion 6 , and a mouthpiece filter plug 8.
  • the composite can be loaded onto folded paper 10 inserted into a hollow cavity such as the interior of a free-flow sleeve 12 forming part of the filter portion 6.
  • Figure 2 shows a cigarette 2 having a tobacco rod 4 and " a filter portion 6 , wherein the folded paper 10 is located in the hollow cavity of a first free-flow sleeve 13 located between the mouthpiece filter 8 and a second free-flow sleeve 15.
  • the paper 10 can be used in forms other than as a folded sheet .
  • the paper 10 can be deployed as one or more individual strips , a wound roll , etc .
  • a desired amount of the composite can be provided in the cigarette filter portion by adjusting the amount per unit area of the paper and/or the total area of coated paper employed in the filter
  • the tobacco rod 4 and the filter portion 6 are j oined together with tipping paper 14.
  • the filter portion 6 may be held together by filter overwrap 11.
  • the composite can be incorporated into the filter paper in a number of ways .
  • particles or powders of the aforementioned composites can be mixed with water to form a slurry .
  • the slurry can then be coated onto preformed filter paper and allowed to dry.
  • the filter paper can then be incorporated into the filter portion of a cigarette in a manner shown in Figures 1 and 2.
  • the dried paper can be wrapped • into a plug shape and inserted into a filter portion of the cigarette .
  • the paper can be wrapped into a plug shape and inserted as a plug into the interior of a free-flow filter element such as a polypropylene or cellulose acetate sleeve .
  • the paper can be wrapped into a plug shape and inserted as a plug into the interior of a free-flow filter element such as a polypropylene or cellulose acetate sleeve .
  • the paper can be wrapped into a plug shape and inserted as a plug into the interior of a free-flow filter
  • the composite may be added to filter paper during the paper-making process .
  • the composite can be mixed with bulk cellulose to form a cellulose pulp mixture .
  • the mixture can be then formed into filter paper .
  • the aforementioned composite may be incorporated into the fibrous material of the cigarette filter portion itself .
  • filter materials include , but are not limited to, fibrous filter materials including paper, cellulose acetate fibers , and polypropylene fibers .
  • Figure 3 shows a cigarette 2 comprised of a tobacco rod 4 and a filter portion 6 in the form of a plug-space-plug filter having a mouthpiece filter 8 , a plug 16 , and a space 18.
  • the plug 16 can comprise a tube or solid piece of material such as polypropylene or cellulose acetate fibers .
  • the tobacco rod 4 and the filter portion 6 are j oined together with tipping paper 14.
  • the filter portion 6 may- include a filter overwrap 11.
  • the filter overwrap 11 containing traditional fibrous filter material and the composite can be incorporated in or on the filter overwrap 11 such as by being coated thereon .
  • the composite can be incorporated in the mouthpiece 5 filter 8 , in the plug 16 , and/or in the space 18.
  • the composite can be incorporated in any element of the filter portion of a cigarette .
  • the filter portion may consist only of the mouthpiece filter 8 and the composite can be incorporated in the mouthpiece filter 8 and/or in the tipping paper 14.
  • Figure 4 shows a cigarette 2 comprised of a tobacco rod 4 and filter portion 6.
  • FIG. 1 This arrangement is similar to that of Figure 3 except the space 18 is filled with granules of composite or a plug 15 made of material such as fibrous polypropylene or cellulose acetate containing the composite .
  • the plug 16 s can be hollow or solid and the tobacco rod 4 and filter portion 6 are j oined together with tipping paper 14.
  • Figure 5 shows a cigarette 2 comprised of a tobacco rod 4 and a filter portion 6 wherein the filter portion 6 includes a mouthpiece o filter 8 , a filter overwrap 11 , tipping paper 14 to j oin the tobacco rod 4 and filter portion 6 , a space 18 , a plug 16 , and a hollow sleeve 20.
  • the composite can be incorporated into one or more elements of the filter portion 6.
  • the composite can be incorporated into the sleeve 20 or granules of the composite can be filled into the 5 space within the sleeve 20.
  • the plug 16 and sleeve 20 can be made of material such as fibrous polypropylene or cellulose acetate containing the composite .
  • the plug 16 can be hollow or solid.
  • FIG. 6 shows a further modification of the filter portion 6.
  • cigarette 2 is comprised of a tobacco rod 4 and filter portion 6.
  • the filter portion 6 includes a mouthpiece filter 8 , a filter overwrap 11 , a plug 22 , and a sleeve 20.
  • the composite can be incorporated in one or more of these filter elements .
  • the plug 22 can be solid or hollow.
  • the tobacco rod 4 and filter portion 6 are j oined 5 together by tipping paper 14.
  • Various techniques can be used to apply the composite to filter fibers or other substrate supports .
  • the composite can be added to the filter fibers before they are formed into a filter cartridge , e . g . , a tip for a cigarette .
  • the composite can be added to the filter fibers , for example , in the form of a dry powder or a slurry. If the composite is applied in the form of a slurry, the fibers are allowed to dry before they are formed into a filter cartridge .
  • the composite is employed in a hollow portion of a cigarette filter .
  • some cigarette filters have a plug/space/plug configuration in which the plugs comprise a fibrous filter material and the space is simply a void between the two filter plugs . That void can be filled with the aforementioned composite .
  • An example of this embodiment is shown in Figure 3.
  • the composite can be in granular form or can be loaded onto a suitable support such as a fiber or thread.
  • composite can be incorporated in various support materials .
  • the particles may have an average particle diameter of about 5 ⁇ m to lOO ⁇ m, preferably about lO ⁇ m to 50 ⁇ m.
  • larger particles may be used .
  • Such particles preferably have a mesh size from about 25 to 60 , and more preferably from about 35 to 60 mesh .
  • the amount of composite employed in the cigarette filter by way of incorporation on a suitable support such as filter paper and/or filter fibers depends on the amount of constituents in the tobacco smoke and the amount of constituents desired to be removed .
  • the filter paper and the filter fibers may contain from 10% to 50% by weight of the composite .
  • One embodiment relates to a method of making a filter .
  • the method comprises incorporating the aforementioned composite into a cigarette filter .
  • Most filters contain four main components : filter tow, plasticizer, plug wrap and adhesive .
  • the filter tow comprises a bundle of cellulose acetate fibers or papers , that are bound together using the plasticizer, which acts as a hardening agent .
  • the filter is contained in the plug wrap, usually a paper wrapper, which is secured using an adhesive . Any conventional or modified method of making cigarette filters may be used to incorporate the composite .
  • Another embodiment relates to methods for making cigarettes .
  • the method comprises : ( i) providing a cut filler to a cigarette making machine to form a tobacco rod; (ii ) placing a paper wrapper around the tobacco rod; and (iii) attaching a cigarette filter incorporating a composite to the tobacco rod to form the cigarette .
  • the composites may be used to prepare impregnated fibers .
  • Particles or powders of the composite are first mechanically mixed with the fiber in a closed volume .
  • the resulting impregnated fibers will thus have a Loading Factor (LF) , which term is defined as the ratio of the weight of material in the fiber micro cavities divided by the weight of the fiber itself .
  • LF Loading Factor
  • the Loading Factor may be expressed as a percentage or as a decimal number .
  • the Loading Factor may vary between about 1% and about 150% . More preferably, the Loading Factor is between about 20% and about 80% , e . g . , the Loading Factor can be about 40 -60% .
  • the fibers that are impregnated with the composite are formed into a cylindrical segment which is inserted in the space of a cigarette with a plug/space/plug filter configuration . Preferably, the segment is packed to a density to achieve a desired resistance to draw and contains an amount of the composite effective to filter out the selected smoke gas phase constituents . Tipping paper attaches the tobacco to the filter rod .
  • Activated carbons and zeolite-type molecular sieves when combined together can produce composite materials with tailored sorption capacity and selectivity for application in smoking articles to selectively reduce targeted smoke constituents .
  • the composite can be provided with a surface area effective to preferentially sorb selected constituents from cigarette smoke . While surface area is inversely proportional to particle size, sorbents having small particle size may pack together too densely to permit mainstream smoke to flow through the filter during smoking . If particle size is too large , there will be, less than desired surface area . Therefore , these factors should be considered in manufacturing a composite having a particular particle size .
  • the zeolite and activated carbon used in making the composite may ⁇ be chosen to target selected constituents in mainstream smoke , while prolonging the shelf life of the activated carbon during storage of smoking articles containing the composite .
  • the selection of starting materials permits the preferential removal of one or more selected constituents from mainstream smoke, while retaining other constituents , such as those relating to flavor .
  • smoke substituents relating to flavor of large size and/or molecular weight can pass through the filter to a greater extent than smaller smoke substituents , such as light gases , various aldehydes or other small molecules which may be targeted for removal .
  • the selectivity of the composite can be fine tuned, particularly by the selection of zeolites and activated carbons as well as the choice of particle sizes and pore sizes .
  • Selected constituents of mainstream smoke may be removed by the composite through one or more mechanisms such as molecular sieving, ion exchange , hydrophobic interactions , chelation, and/or chemical binding .
  • the selected constituents of mainstream smoke that are removed preferably are composed of at least one of a hydrocarbon, a polar organic and/or non-polar organic compound .
  • the selected constituent of mainstream smoke that is removed is an aldehyde, ketone, diene or aromatic compound.
  • constituents which may be removed include carbon monoxide , 1 , 3 -butadiene , isoprene , acrolein, acrylonitrile , hydrogen cyanide , o-toluidine , 2 - naphthylamine , nitrogen oxide, benzene , phenol , and/or catechol . More preferably, the constituent is an aldehyde or diene .

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)

Abstract

A composite for use in smoking articles such as cigarettes is described comprising a zeolite membrane coated upon an activated carbon-containing substrate. The substrate may be a fiber, fabric, particle, granule or monolith. The composite is prepared by contacting zeolite precursors with the substrate and hydrothermally synthesizing the membrane upon the substrate. The substrate may be pretreated to provide activation sites for adhesion and growth of the membrane. By selection of the zeolite components, the the composite may be tailored to selectively remove constituents of tobacco smoke while simultaneously controlling access to the substrate thereby prolonging the shelf life of the activated carbons.

Description

ACTIVATED CARBONS WITH MOLECULAR SIEVE MEMBRANES AND THEIR USE AS ADSORBENTS IN SMOKING ARTICLES
BACKGROUND Various activated carbon materials have been employed as sorbents in smoking articles to remove or reduce smoke constituents . Activated carbons are useful sorbents and have a large capacity; however, they lack selectivity. While they are effective in removing targeted constituents from tobacco smoke, they also may remove volatile constituents which contribute to flavor, aroma and other desirable attributes . Further, activated carbon in a cigarette filter may be rapidly inactivated during storage by the adsorption of .volatile compounds , or by contact with various constituents of mainstream smoke .
Zeolite-type molecular sieves have also been used in smoking articles to selectively remove constituents of tobacco smoke . Zeolite molecular sieve sorbents are capable of selectively removing one or more targeted constituents of mainstream smoke . However, zeolites have minimal capacities and are quickly exhausted before removing a significant amount of the targeted constituent .
There is interest in a filter system for use in smoking- articles which can readily be manufactured in various shapes from commercially available activated carbons and zeolite materials and can be tailored to produce components which selectively remove or reduce the concentration of various smoke constituents while retaining desirable flavor constituents and having an extended shelf life .
SUMMARY
A smoking article is provided which includes tobacco and a filter system comprising a composite composed of an activated carbon substrate and a zeolite-type membrane coated thereon . Also provided is a filter system, a method of making smoking articles containing said filter system and a method of selectively removing targeted constituents from tobacco smoke . In one embodiment , a filter is prepared containing .a composite made by the deposition of a molecular sieve membrane directly onto a carbon-containing substrate by hydrothermal synthesis of a given molecular sieve . Pre-treatment of the substrate may be desirable to achieve optimum adhesion and growth of the membrane on the substrate .
In another embodiment , cigarettes are prepared which contain tobacco and the filter mentioned above . A preferred smoking article is a traditional or non-traditional cigarette . The aforementioned composite preferably is incorporated into a filter of a cigarette .
Another embodiment relates to a method of making a filter cigarette , comprising : ( i) providing a cut filler to a cigarette making machine and forming a tobacco column,- ( ii) placing a paper wrapper around the tobacco column and forming a tobacco rod; (iii) attaching a cigarette filter comprising the composite described above to the tobacco rod to form the cigarette .
In another embodiment , a method is provided of treating mainstream smoke of a smoking article to preferentially remove one or more targeted constituents from mainstream smoke by contacting the mainstream smoke with a composite as described above .
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a view of a cigarette wherein folded paper containing a composite described above is inserted into a hollow portion of a tubular filter element of the cigarette .
Figure 2 is a view of another embodiment wherein a composite as described above is incorporated in folded paper and inserted into a hollow portion of a first free-flow sleeve of a tubular filter element next to a second free-flow sleeve .
Figure 3 is a view of another embodiment wherein a composite as described above is incorporated in a plug-space-plug filter element .
Figure 4 is a view of another embodiment wherein a composite is incorporated in a three-piece filter element having three plugs .
Figure 5 is a view of another embodiment wherein a- composite is incorporated in a four-piece filter element having a plug-space-plug arrangement and a hollow sleeve .
Figure 6 is a view of still another embodiment wherein a composite is incorporated in a three-part filter element having two plugs and a hollow sleeve . DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Cigarette filters and smoking articles are provided preferably containing a porous composite comprising an activated carbon substrate and a zeolite molecular sieve membrane coated thereon and capable of selectively removing selected constituents from mainstream smoke . Methods for making such cigarette filters and smoking articles , as well as a method of treating mainstream smoke , are also provided.
The term "sorption" denotes filtration by adsorption and/or absorption and is intended to encompass interactions on the outer i surface of a sorbent , as well as interactions within the pores and channels thereof . A " sorbent" is a substance that has the ability to condense or hold molecules of other substances on its surface and/or the ability to take up other substances , i . e . , through penetration of the other substances into its inner structure or into its pores . The
; term "sorbent " as used herein refers to either an adsorbent , an absorbent , or a substance ' that can function as both an adsorbent and an absorbent .
The term "remove" as used herein refers to adsorption and/or absorption of at least some portion of a selected constituent . of o mainstream tobacco smoke .
The term "mainstream smoke" includes the mixture of gases and aerosolized condensed matter which passes down a tobacco column and issues through the filter end, i . e . , the amount of smoke issuing or drawn from the mouth end of a smoking article such as a cigarette 5 during smoking . The mainstream smoke contains air that is drawn in through both the lit or heated region of the smoking article , as well as through the paper wrapper, and through any ventilation perforations that may be present .
Smoking articles , such as cigarettes , cigarillos and cigars , as 0 well as non-traditional cigarettes , are provided. Non-traditional cigarettes include , for example , smoking articles which include combustible heat sources such as that shown in commonly assigned,
US 4 966 171 , and cigarettes for electrical smoking systems as described in commonly-assigned US 6 026 820 ; US 5 988 176 ; 5 US 5 915 387 ; and US 5 499 636. The substrate portion of the aforementioned composite comprises an activated carbon . Activated forms of carbon generally have strong physical sorption forces , and high volumes of sorbing porosity . The activated carbon could be .manufactured by any suitable method. Such methods include the carbonization of coconut husk, coal , wood, pitch, cellulose fibers , or polymer fibers , for example . Carbonization is usually carried out at high temperatures , i . e . , 2000C-IOOO0C in an inert atmosphere, followed by activation. The activated carbon used as the composite substrate could be in the form of carbon granules , beads , powder, fiber, fabric or shaped monoliths . The substrate could also be an admixture of carbon and an inorganic material . Suitable inorganic materials may comprise porous and/or catalytically active metal compounds such as oxides , hydroxides , silicates and phosphates .
Carbon-containing materials suitable as substrates may have a distribution of micropores , mesopores and macropores . The term "microporous " generally refers to such materials having pore sizes of about 20A or less while the term "mesoporous " generally refers to such materials with pore sizes of about 2OA to 500A. "Macroporous " materials have pore sizes above about 500A. The relative amounts of micropores , mesopores and macropores in the carbon-containing substrate will depend upon the selected constituents from mainstream tobacco smoke that are to be targeted and removed . Thus , the pore sizes and pore distribution can be adjusted accordingly as needed for a certain application . Another material in the filter system is a molecular sieve zeolite membrane . The term "molecular sieve" as used herein refers to a porous structure composed of an inorganic silicate material . Zeolites have channels or pores of uniform, molecular sized dimensions . There are many known unique zeolite structures having different sized and shaped channels or pores . The size and shape of the channels or pores can significantly affect the properties of these materials with regard to adsorption and separation characteristics . Zeolites can be used to separate molecules by size and shape possibly related to the orientation of the molecules in the channels or pores , and/or by differences in strength of sorption. By using one or more zeolites having channels or pores larger than selected constituents of mainstream smoke, only selected molecules that are small enough to pass through the pores of the molecular sieve material are able to enter the cavities and be sorbed by the zeolite .
Zeolite-type molecular sieves which are useful in the composites include crystalline aluminosilicates , silicoaluminophosphates (Ai?PO/SAPO) and mesoporous molecular sieves such as MCM-41 , MCM-48 and SBA-15. This family of materials contains regular arrays of uniformly-sized channels and tunable internal active sites , and admits molecules below a certain size into their internal space which makes them useful as catalysts and sorbents where selectivity is critical . Microporous and mesoporous molecular sieves are preferred. They are selected for use in the filter composites based on the particular constituent or constituents to be removed from the mainstream smoke .
The term "microporous molecular sieves" generally refers to molecular sieve materials having pore sizes of about 2OA or less . The term "mesoporous molecular sieves" generally refers to such materials with pore sizes of about 2OA to 500A. Materials with pore sizes of about 50OA or larger may be referred to as "macroporous molecular sieves . " The composite preferably is prepared by a hydrothermal synthesis technique using zeolite precursor materials which form a coated membrane on the substrate . The hydrothermal synthesis of various zeolites can be accomplished by any • techniques which would generate in situ a zeolite membrane on the carbon-containing substrate . Methods for the preparation of zeolite membranes on activated porous carbon monoliths and porous carbon membranes are disclosed in the following articles : "Preparation of hollow-fibre composite carbon-zeolite membranes , " Smith, S . P . J. ; Linkov, V.M; Sanderson, R .D . ; Petrik, L . F . ; O ' Connor, C . T . ; Keiser, K. , Microporous Materials , 1995 , 4 , pp .385- 390 ; "Preparation of an MFI zeolite coating on activated carbon, "van der Vaart , ' R. ; Bosch, H. ; Keizer, K. ; Reith, T . , Microporous Materials , 1997 , 9 , pp . 203 -207 , the entire disclosures of both articles incorporated herein in their entirety . In general , the substrates are contacted with the zeolite precursors and a hydrothermal synthesis conducted whereby the zeolite membrane is coated upon and/or into the pores of the substrate . If the carbon- containing substrate has not been activated before synthesis of the zeolite membrane , known activation techniques may be employed to remove volatiles and produce the final activated composite . The product is a composite filter system composed of a porous substrate of activated carbon having a zeolite membrane coated uniformly upon the surface and within the pores of the substrate .
In the hydrothermal synthesis of crystalline aluminosilicates , sodium hydroxide may be used as the alkaline source . Sodium aluminate (NaAlO2) , aluminum nitrate (Al (NO3) 39H2O) , aluminum sulfate (Al2 (SO4) 318H2O) , aluminum chloride (A1C136H2O) , aluminum hydroxide (Al (OH) 3) , aluminum alkoxide and alumina gel , etc . can be used as the source of alumina . Colloidal silica, fumed silica, water glass (sodium silicate aqueous solution) , silica gel , etc . can be used as the silica source . The factors affecting crystallization of aluminosilicate include the source of silica, the mole ratio of silica vs . alumina, pH, reaction temperature , reaction time , degree of aging in room temperature , presence of stirring, etc . The morphology and nature of zeolite produced are directly linked to these variations . An example of a method of preparing a molecular sieve compound is described in US 6 117 810 , the entire disclosure of which is incorporated herein by reference . A sodium aluminate solution is made by adding a source of alumina to sodium hydroxide solution and stirring for about 20 to 60 minutes at about 700C to 12O0C to dissolve completely . The concentration of sodium hydroxide in solution is about 20 to 50 wt . % , especially about 30 to 40 wt . % . A sodium silicate composition is produced by stirring the sodium hydroxide solution and the silica source at a temperature of about 25°C to 700C . Thereafter, the sodium aluminate solution is admixed with a sodium silicate composition in SiO2/Al2O3 mole ratios of about 2.0 to 40.0 , Na2O/SiO2 mole ratios of about 0.4 to 2.0 and H20/Na20 mole ratios of about 15.0 to 70.0. Gelation is brought about by homogeneously stirring .
Following gelation, the gel composition is deposited onto and into the pores of the activated carbon substrate . In the above process , if the mole ratio of SiO2/Al2O3 is under 2.0 , some of the alumina component remains in the final product . If the mole ratio is greater than 40 , crystallization of the zeolite becomes difficult . If the mole ratio of Na2O/SiO2 is under 0.4 , the activity of the silica component is low and it is slowly converted into zeolite . If the mole ratio is more than 2.0 , a crystalline aluminosilicate is produced having a very low activity .
If the mole ratio of H20/Na20 is under 15 , alkalinity in solution is so high that side reactions can easily occur . If the ratio is more than 70.0 , higher pressures and temperatures are required for the synthesis reaction .
The reaction mixture is allowed to age for about 2 to 96 hours at about 25°C to 600C and crystallized at about 700C to 1200C, preferably at 8O0C to 1000C, and most preferably at 9O0C to 1000C for 2 to 4 hours . Upon completion of crystallization, the slurry phase is separated, the final product washed with water, and dried for about 4 to 12 hours at about 1000C to 12O0C to provide the molecular sieve compound .
Preferred complex molecular sieve compounds produced are composed of microporous zeolites such as A, ZSM-5 , X or Y type finely distributed onto the surfaces of the activated carbon . Therefore , the composites have both hydrophilic and hydrophobic adsorption properties derived from the activated carbon and zeolite .
To facilitate adhesion and growth of the zeolite membrane on the carbon-containing substrate, it may be desirable to pretreat the substrate to provide sufficient nucleation sites . Preferably, silanes are applied to the substrate followed by a heat treatment preferably in an oxidizing atmosphere . Suitable silanes include alkoxysilanes such as tetraethoxysilane . Alternatively, hydrophilic clays such as bentonite and montmorillonite may be admixed with the carbon- containing material before , during or after preparation of the substrate material . Preferably, the carbon-containing substrate includes activated carbon . As indicated above , if the substrate is not activated beforehand, it may be activated after deposition of the zeolite membrane such as by heating the composite which removes various volatiles used in the synthesis of the membrane while activating the substrate . In a preferred embodiment , the composite is located in a filter portion of a cigarette . Typically, about lOmg to about 300mg of the composite can be used in a cigarette filter . For example , amounts such as at least about 20mg, 30mg, 50mg, 75mg, lOOmg, 150mg, 200mg, or 250mg of the composite can be used in the cigarette filter .
Various filter constructions may be used to locate the composite . Exemplary filter structures that can be used include, but are not limited to, a mono filter, a dual filter, a triple filter, a cavity filter, a recessed filter or a free-flow filter . Mono filters typically contain cellulose acetate tow or cellulose paper materials . Dual filters typically comprise a cellulose acetate mouthpiece filter plug and a second, different filter plug or segment . The composite is preferably located closer to the smoking material or tobacco side of a cigarette . The length and pressure drop of the two segments of the dual filter can be adjusted to provide optimal adsorption, while maintaining acceptable draw resistance .
Triple filters can include mouth and smoking material or tobacco side segments , and a middle segment comprising a material or paper . The aforementioned composite can be provided in the middle segment . Cavity filters typically include two segments , e . g . , acetate-acetate , acetate-paper or paper-paper, separated by a cavity . The composite can preferably be provided in the cavity . Recessed filters include an open cavity on the mouth side , and the composite can be incorporated into the plug material . The filters may also optionally be ventilated, and/or comprise additional sorbents (such as activated carbon, charcoal or magnesium silicate) , catalysts , flavorants or other additives .
Figure 1 illustrates a cigarette 2 having a tobacco rod 4 , a filter portion 6 , and a mouthpiece filter plug 8. The composite can be loaded onto folded paper 10 inserted into a hollow cavity such as the interior of a free-flow sleeve 12 forming part of the filter portion 6.
Figure 2 shows a cigarette 2 having a tobacco rod 4 and" a filter portion 6 , wherein the folded paper 10 is located in the hollow cavity of a first free-flow sleeve 13 located between the mouthpiece filter 8 and a second free-flow sleeve 15. The paper 10 can be used in forms other than as a folded sheet . For instance , the paper 10 can be deployed as one or more individual strips , a wound roll , etc . In whichever form, a desired amount of the composite can be provided in the cigarette filter portion by adjusting the amount per unit area of the paper and/or the total area of coated paper employed in the filter
(e .g . , higher amounts of composite can be provided simply by using larger pieces of coated paper) . In the cigarettes shown in Figures 1 and 2 , the tobacco rod 4 and the filter portion 6 are j oined together with tipping paper 14. In both cigarettes , the filter portion 6 may be held together by filter overwrap 11.
The composite can be incorporated into the filter paper in a number of ways . For examples , particles or powders of the aforementioned composites can be mixed with water to form a slurry . The slurry can then be coated onto preformed filter paper and allowed to dry. The filter paper can then be incorporated into the filter portion of a cigarette in a manner shown in Figures 1 and 2. Alternatively, the dried paper can be wrapped • into a plug shape and inserted into a filter portion of the cigarette . For example , the paper can be wrapped into a plug shape and inserted as a plug into the interior of a free-flow filter element such as a polypropylene or cellulose acetate sleeve . In another arrangement , the paper can
Alternatively, the composite may be added to filter paper during the paper-making process . For example , the composite can be mixed with bulk cellulose to form a cellulose pulp mixture . The mixture can be then formed into filter paper .
In another embodiment , the aforementioned composite may be incorporated into the fibrous material of the cigarette filter portion itself . Such filter materials include , but are not limited to, fibrous filter materials including paper, cellulose acetate fibers , and polypropylene fibers . This embodiment is illustrated in Figure 3 , which shows a cigarette 2 comprised of a tobacco rod 4 and a filter portion 6 in the form of a plug-space-plug filter having a mouthpiece filter 8 , a plug 16 , and a space 18. The plug 16 can comprise a tube or solid piece of material such as polypropylene or cellulose acetate fibers . The tobacco rod 4 and the filter portion 6 are j oined together with tipping paper 14. The filter portion 6 may- include a filter overwrap 11. The filter overwrap 11 containing traditional fibrous filter material and the composite can be incorporated in or on the filter overwrap 11 such as by being coated thereon . Alternatively, the composite can be incorporated in the mouthpiece 5 filter 8 , in the plug 16 , and/or in the space 18. Moreover, the composite can be incorporated in any element of the filter portion of a cigarette . For example , the filter portion may consist only of the mouthpiece filter 8 and the composite can be incorporated in the mouthpiece filter 8 and/or in the tipping paper 14. o Figure 4 shows a cigarette 2 comprised of a tobacco rod 4 and filter portion 6. This arrangement is similar to that of Figure 3 except the space 18 is filled with granules of composite or a plug 15 made of material such as fibrous polypropylene or cellulose acetate containing the composite . As in a previous embodiment , the plug 16 s can be hollow or solid and the tobacco rod 4 and filter portion 6 are j oined together with tipping paper 14. There is also a filter overwrap 11.
Figure 5 shows a cigarette 2 comprised of a tobacco rod 4 and a filter portion 6 wherein the filter portion 6 includes a mouthpiece o filter 8 , a filter overwrap 11 , tipping paper 14 to j oin the tobacco rod 4 and filter portion 6 , a space 18 , a plug 16 , and a hollow sleeve 20. The composite can be incorporated into one or more elements of the filter portion 6. For instance , the composite can be incorporated into the sleeve 20 or granules of the composite can be filled into the 5 space within the sleeve 20. If desired, the plug 16 and sleeve 20 can be made of material such as fibrous polypropylene or cellulose acetate containing the composite . As in the previous embodiment , the plug 16 can be hollow or solid.
Figure 6 shows a further modification of the filter portion 6. 0 In Figure 6 , cigarette 2 is comprised of a tobacco rod 4 and filter portion 6. The filter portion 6 includes a mouthpiece filter 8 , a filter overwrap 11 , a plug 22 , and a sleeve 20. The composite can be incorporated in one or more of these filter elements . The plug 22 can be solid or hollow. The tobacco rod 4 and filter portion 6 are j oined 5 together by tipping paper 14. Various techniques can be used to apply the composite to filter fibers or other substrate supports . For example, the composite can be added to the filter fibers before they are formed into a filter cartridge , e . g . , a tip for a cigarette . The composite can be added to the filter fibers , for example , in the form of a dry powder or a slurry. If the composite is applied in the form of a slurry, the fibers are allowed to dry before they are formed into a filter cartridge .
In another embodiment , the composite is employed in a hollow portion of a cigarette filter . For example , some cigarette filters have a plug/space/plug configuration in which the plugs comprise a fibrous filter material and the space is simply a void between the two filter plugs . That void can be filled with the aforementioned composite . An example of this embodiment is shown in Figure 3. The composite can be in granular form or can be loaded onto a suitable support such as a fiber or thread.
As explained above, composite can be incorporated in various support materials . When the composite is used in filter paper, the particles may have an average particle diameter of about 5μm to lOOμm, preferably about lOμm to 50μm. When the composite is used in filter fibers or other mechanical supports , larger particles may be used . Such particles preferably have a mesh size from about 25 to 60 , and more preferably from about 35 to 60 mesh .
The amount of composite employed in the cigarette filter by way of incorporation on a suitable support such as filter paper and/or filter fibers depends on the amount of constituents in the tobacco smoke and the amount of constituents desired to be removed . As an example , the filter paper and the filter fibers may contain from 10% to 50% by weight of the composite . One embodiment relates to a method of making a filter . The method comprises incorporating the aforementioned composite into a cigarette filter . ■ Most filters contain four main components : filter tow, plasticizer, plug wrap and adhesive . Often the filter tow comprises a bundle of cellulose acetate fibers or papers , that are bound together using the plasticizer, which acts as a hardening agent . The filter is contained in the plug wrap, usually a paper wrapper, which is secured using an adhesive . Any conventional or modified method of making cigarette filters may be used to incorporate the composite .
Another embodiment relates to methods for making cigarettes . For example , the method comprises : ( i) providing a cut filler to a cigarette making machine to form a tobacco rod; (ii ) placing a paper wrapper around the tobacco rod; and (iii) attaching a cigarette filter incorporating a composite to the tobacco rod to form the cigarette .
The composites may be used to prepare impregnated fibers . Particles or powders of the composite are first mechanically mixed with the fiber in a closed volume . The resulting impregnated fibers will thus have a Loading Factor (LF) , which term is defined as the ratio of the weight of material in the fiber micro cavities divided by the weight of the fiber itself . The Loading Factor may be expressed as a percentage or as a decimal number .
The Loading Factor may vary between about 1% and about 150% . More preferably, the Loading Factor is between about 20% and about 80% , e . g . , the Loading Factor can be about 40 -60% . The fibers that are impregnated with the composite are formed into a cylindrical segment which is inserted in the space of a cigarette with a plug/space/plug filter configuration . Preferably, the segment is packed to a density to achieve a desired resistance to draw and contains an amount of the composite effective to filter out the selected smoke gas phase constituents . Tipping paper attaches the tobacco to the filter rod .
Activated carbons and zeolite-type molecular sieves when combined together can produce composite materials with tailored sorption capacity and selectivity for application in smoking articles to selectively reduce targeted smoke constituents . The composite can be provided with a surface area effective to preferentially sorb selected constituents from cigarette smoke . While surface area is inversely proportional to particle size, sorbents having small particle size may pack together too densely to permit mainstream smoke to flow through the filter during smoking . If particle size is too large , there will be, less than desired surface area . Therefore , these factors should be considered in manufacturing a composite having a particular particle size .
The zeolite and activated carbon used in making the composite may¬ be chosen to target selected constituents in mainstream smoke , while prolonging the shelf life of the activated carbon during storage of smoking articles containing the composite . The selection of starting materials permits the preferential removal of one or more selected constituents from mainstream smoke, while retaining other constituents , such as those relating to flavor . For example , smoke substituents relating to flavor of large size and/or molecular weight can pass through the filter to a greater extent than smaller smoke substituents , such as light gases , various aldehydes or other small molecules which may be targeted for removal . The selectivity of the composite can be fine tuned, particularly by the selection of zeolites and activated carbons as well as the choice of particle sizes and pore sizes . Mixtures of molecular sieves with varying compositions and geometries can be employed to tailor the removal of selected constituents of tobacco smoke while controlling access to the pores of the activated carbon substrate . Selected constituents of mainstream smoke may be removed by the composite through one or more mechanisms such as molecular sieving, ion exchange , hydrophobic interactions , chelation, and/or chemical binding . The selected constituents of mainstream smoke that are removed preferably are composed of at least one of a hydrocarbon, a polar organic and/or non-polar organic compound . Preferably, the selected constituent of mainstream smoke that is removed is an aldehyde, ketone, diene or aromatic compound. Specific constituents which may be removed include carbon monoxide , 1 , 3 -butadiene , isoprene , acrolein, acrylonitrile , hydrogen cyanide , o-toluidine , 2 - naphthylamine , nitrogen oxide, benzene , phenol , and/or catechol . More preferably, the constituent is an aldehyde or diene .
Variations and modifications of the ' foregoing embodiments will be apparent ' to those skilled in the- art . Such variations and modifications are to be considered within the purview and scope of the claims appended hereto .

Claims

CLAIMS :
1. A smoking article comprising tobacco and a filter component comprising a composite comprising at least one activated carbon- containing substrate coated with at least one zeolite molecular sieve layer .
2. The smoking article of claim 1 , wherein said substrate comprises a fiber, fabric , particle, granule or monolith.
3. The smoking article of claim 1 , wherein the zeolite comprises a crystalline alumino-silicate , a silicoaluminophosphate or a micro- or meso-porous molecular sieve .
4. The smoking article of claim 3 , wherein the zeolite comprises a molecular sieve selected from ZSM-5 , X, Y or A type zeolites .
5. The smoking article of claim 1 , wherein the substrate is pretreated to provide nucleation sites .
6. The smoking article of claim 5 , wherein the pretreatment comprises reaction with a silane .
7. The smoking article of claim 1 , wherein the activated carbon of the substrate has a distribution of micropores , mesopores and macropores .
8. The smoking article of claim 1 , wherein the filter component is a mono filter, a dual filter, a triple filter, a cavity filter, a recessed filter or a free-flow filter .
9. The smoking article of claim 1 , wherein the filter component comprises cellulose acetate tow, cellulose paper, polypropylene fiber or combinations thereof .
10. The smoking article of claim 1 , wherein the smoking article is a cigarette and the composite is incorporated into at least one cigarette filter part selected from a shaped paper inset , a plug, a space, cigarette filter paper or a free-flow sleeve .
5
11. A smoking article comprising a filter component composed of a composite comprising at least one activated porous carbon substrate and at least one zeolite molecular sieve membrane coated on the surface of and/or in the pores of the substrate .
10
12. A smoking article comprising tobacco cut filler, cigarette paper and cigarette filter material , further including a composite capable of selectively removing components from cigarette smoke , wherein the composite comprises at least one activated carbon substrate coated is with at least one zeolite membrane adhered to the substrate .
13. The smoking article of claim 12 , wherein said composite is prepared by hydrothermally synthesizing a zeolite molecular sieve layer on a carbon-containing substrate .
20
14. A method of making a smoking article comprising : preparing a composite comprising a porous activated carbon substrate having a zeolite membrane adhered thereon; and i incorporating the composite into cigarette filter material .
25
15. A method of smoking the smoking article of claim 1 , wherein the smoking article is a cigarette , comprising lighting the cigarette to form tobacco smoke and drawing the tobacco smoke through the cigarette , wherein during the smoking the composite reduces the amount
30 of selected constituents in the tobacco smoke .
16. The method of claim 15 , wherein the composite is located in a filter component of the cigarette .
35 17. A cigarette comprising tobacco and a filter element , wherein the filter element includes a composite comprising an activated porous carbon substrate having a zeolite molecular sieve membrane coated upon and within the pores of the substrate .
18. The cigarette of claim 17 , wherein the tobacco is contained in a tobacco rod attached to the filter with tipping paper .
19. A method of manufacturing a cigarette filter, comprising incorporating into a cigarette filter a composite comprising a porous activated carbon-containing substrate and a zeolite molecular sieve membrane coated upon and within the pores thereof , the composite being loaded on a support , or incorporated in a support , or incorporated with a support, in a plug-space-plug arrangement , in bead form, and/or in monolith form.
20. A method of treating mainstream smoke of a smoking article of claim 17 , by contacting mainstream smoke with the porous composite , wherein during the smoking of the cigarette , the porous composite selectively removes at least one selected component from mainstream smoke .
21. The method of claim 20 , wherein said selected component removed is at least one of an aldehyde , ketone , hydrocarbon, aromatic , HCN, a nitrile , CO, a polar or non-polar organic compound or mixtures thereof .
PCT/IB2006/000296 2005-01-05 2006-01-05 Activated carbons with molecular sieve membranes and their use as adsorbents in smoking articles WO2006072889A1 (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012064294A1 (en) 2010-11-09 2012-05-18 KAYA, Selçuk Reduction of harmful smoke constituents, including a tobacco column and a filter element
US9259031B2 (en) 2011-06-06 2016-02-16 British American Tobacco (Investments) Limited Filter for a smoking article
CN107568790A (en) * 2017-10-23 2018-01-12 上海聚华科技股份有限公司 Cigarette filter tip and cigarette containing zeolite perfume (or spice) pearl zeolite perfume (or spice) pearl preparation method
US10375996B2 (en) 2014-10-22 2019-08-13 British American Tobacco (Investments) Limited Inhalator and cartridge thereof
US10420375B2 (en) 2014-04-30 2019-09-24 British American Tobacco (Investments) Limited Aerosol-cooling element and arrangements for use with apparatus for heating a smokable material
US10426199B2 (en) 2015-02-27 2019-10-01 British American Tobacco (Investments) Limited Cartridge, components and methods for generating an inhalable medium
US11511056B2 (en) 2015-10-02 2022-11-29 Nicoventures Trading Limited Apparatus for generating an inhalable medium
US11672276B2 (en) 2016-11-02 2023-06-13 British American Tobacco (Investments) Limited Aerosol provision article
US11865246B2 (en) 2015-02-27 2024-01-09 Nicoventures Trading Limited Apparatus for generating an inhalable medium

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100972657B1 (en) 2007-12-27 2010-07-27 박진학 Filtering media for smoking containing the montmorillonite and cigarette filter comprising the same
CN101828769B (en) * 2010-04-16 2011-08-31 云南正邦生物技术有限公司 Preparation method of cigarette flavor compensating particles
US9399110B2 (en) 2011-03-09 2016-07-26 Chong Corporation Medicant delivery system
EP3178510B1 (en) * 2011-03-09 2018-08-01 Chong Corporation Medicant delivery system
CA2829043C (en) * 2011-04-22 2019-09-03 Chong Corporation Medicant delivery system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6047670A (en) * 1983-08-23 1985-03-15 日水製薬株式会社 Adsorbing element for tobacco filter
EP1029461A2 (en) * 1999-02-17 2000-08-23 Dieter Meyer Filter material for reducing harmful substances in tobacco smoke
US6117810A (en) * 1996-06-11 2000-09-12 Korea Research Institute Of Chemical Technology Manufacturing method of complex molecular sieve compound
EP1238594A2 (en) * 2001-03-05 2002-09-11 Ivo Pera Tobacco smoke filter and relative composition made of antioxidant and mineral substances
US20030000538A1 (en) * 2000-11-10 2003-01-02 Bereman Robert D. Method and product for removing carcinogens from tobacco smoke
US20030154993A1 (en) * 2002-01-09 2003-08-21 Paine John B. Cigarette filter with beaded carbon

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3734770A (en) * 1970-12-14 1973-05-22 Motorola Inc Nitrogen nucleation process for the chemical vapor deposition of polycrystalline silicon from sici4
US5288619A (en) * 1989-12-18 1994-02-22 Kraft General Foods, Inc. Enzymatic method for preparing transesterified oils
US5618435A (en) * 1992-03-31 1997-04-08 Inrad Synthesis of inorganic membranes including metals
US5672388A (en) * 1994-07-08 1997-09-30 Exxon Research & Engineering Company Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition
US5968366A (en) * 1994-07-08 1999-10-19 Exxon Research And Engineering Company Zeolite containing composition with a selectivity enhancing coating
US5871650A (en) * 1994-07-08 1999-02-16 Exxon Research And Engineering Company Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer
US5716527A (en) * 1994-07-08 1998-02-10 Exxon Research & Engineering Company Zeolite membrane with a selectivity enhancing coating
CA2198128A1 (en) * 1994-09-20 1996-03-28 Graham John Bratton Improved membrane
FR2742071B1 (en) * 1995-12-08 1998-01-09 Inst Francais Du Petrole PROCESS FOR PRODUCING ZEOLITE MEMBRANES SUPPORTED BY POROUS GLASS
KR100481611B1 (en) * 1996-01-25 2005-05-16 엑손 리써치 앤드 엔지니어링 컴파니 Separation process in which a membrane is used
US6471745B1 (en) * 1996-06-28 2002-10-29 University Of Delaware Nanoporous carbon catalytic membranes and method for making the same
US6077436A (en) * 1997-01-06 2000-06-20 Corning Incorporated Device for altering a feed stock and method for using same
WO1998036830A1 (en) * 1997-02-21 1998-08-27 Engelhard Corporation Composite material based on zeolite and active carbon, preparation and use thereof in water treatment
US6037292A (en) * 1998-07-02 2000-03-14 Exxon Research And Engineering Co. Compositions having two or more zeolite layers
JP3686262B2 (en) * 1998-07-27 2005-08-24 三井造船株式会社 Mixture separation membrane
DE19853971B4 (en) * 1998-11-23 2011-06-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Inorganic / organic polysiloxane hybrid polymers and their use
US6500490B1 (en) * 2000-03-23 2002-12-31 Honeywell International Inc. Hydrophilic zeolite coating
US6494326B1 (en) * 2000-06-15 2002-12-17 Sandia Corporation Composite zeolite membranes
US6626980B2 (en) * 2001-09-21 2003-09-30 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Mixed matrix membranes incorporating chabazite type molecular sieves
US6814786B1 (en) * 2003-04-02 2004-11-09 Philip Morris Usa Inc. Filters including segmented monolithic sorbent for gas-phase filtration

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6047670A (en) * 1983-08-23 1985-03-15 日水製薬株式会社 Adsorbing element for tobacco filter
US6117810A (en) * 1996-06-11 2000-09-12 Korea Research Institute Of Chemical Technology Manufacturing method of complex molecular sieve compound
EP1029461A2 (en) * 1999-02-17 2000-08-23 Dieter Meyer Filter material for reducing harmful substances in tobacco smoke
US20030000538A1 (en) * 2000-11-10 2003-01-02 Bereman Robert D. Method and product for removing carcinogens from tobacco smoke
EP1238594A2 (en) * 2001-03-05 2002-09-11 Ivo Pera Tobacco smoke filter and relative composition made of antioxidant and mineral substances
US20030154993A1 (en) * 2002-01-09 2003-08-21 Paine John B. Cigarette filter with beaded carbon

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012064294A1 (en) 2010-11-09 2012-05-18 KAYA, Selçuk Reduction of harmful smoke constituents, including a tobacco column and a filter element
US9259031B2 (en) 2011-06-06 2016-02-16 British American Tobacco (Investments) Limited Filter for a smoking article
US10420375B2 (en) 2014-04-30 2019-09-24 British American Tobacco (Investments) Limited Aerosol-cooling element and arrangements for use with apparatus for heating a smokable material
US10779577B2 (en) 2014-04-30 2020-09-22 British American Tobacco (Investments) Limited Aerosol-cooling element and arrangements for use with apparatus for heating a smokable material
US10375996B2 (en) 2014-10-22 2019-08-13 British American Tobacco (Investments) Limited Inhalator and cartridge thereof
US11324254B2 (en) 2014-10-22 2022-05-10 Nicoventures Trading Limited Inhalator and cartridge thereof
US10426199B2 (en) 2015-02-27 2019-10-01 British American Tobacco (Investments) Limited Cartridge, components and methods for generating an inhalable medium
US11865246B2 (en) 2015-02-27 2024-01-09 Nicoventures Trading Limited Apparatus for generating an inhalable medium
US11511056B2 (en) 2015-10-02 2022-11-29 Nicoventures Trading Limited Apparatus for generating an inhalable medium
US11672276B2 (en) 2016-11-02 2023-06-13 British American Tobacco (Investments) Limited Aerosol provision article
CN107568790A (en) * 2017-10-23 2018-01-12 上海聚华科技股份有限公司 Cigarette filter tip and cigarette containing zeolite perfume (or spice) pearl zeolite perfume (or spice) pearl preparation method

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