WO2004110188A2 - Papier effiloche a matiere de remplissage catalytique pour tabac de remplissage, et procedes de fabrication correspondants - Google Patents

Papier effiloche a matiere de remplissage catalytique pour tabac de remplissage, et procedes de fabrication correspondants Download PDF

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Publication number
WO2004110188A2
WO2004110188A2 PCT/IB2004/002217 IB2004002217W WO2004110188A2 WO 2004110188 A2 WO2004110188 A2 WO 2004110188A2 IB 2004002217 W IB2004002217 W IB 2004002217W WO 2004110188 A2 WO2004110188 A2 WO 2004110188A2
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WO
WIPO (PCT)
Prior art keywords
web
filler
catalyst
nanoparticle
smoking article
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/IB2004/002217
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English (en)
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WO2004110188A3 (fr
Inventor
Shalva Gedevanishvili
Firooz Rasouli
Mohammad R. Hajaligol
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Philip Morris Products SA
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Philip Morris Products SA
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Publication date
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Publication of WO2004110188A2 publication Critical patent/WO2004110188A2/fr
Publication of WO2004110188A3 publication Critical patent/WO2004110188A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/285—Treatment of tobacco products or tobacco substitutes by chemical substances characterised by structural features, e.g. particle shape or size
    • A24B15/286—Nanoparticles
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/281—Treatment of tobacco products or tobacco substitutes by chemical substances the action of the chemical substances being delayed
    • A24B15/282—Treatment of tobacco products or tobacco substitutes by chemical substances the action of the chemical substances being delayed by indirect addition of the chemical substances, e.g. in the wrapper, in the case
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24C—MACHINES FOR MAKING CIGARS OR CIGARETTES
    • A24C5/00—Making cigarettes; Making tipping materials for, or attaching filters or mouthpieces to, cigars or cigarettes
    • A24C5/005—Treatment of cigarette paper
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES OF CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D1/00—Cigars; Cigarettes
    • A24D1/02—Cigars; Cigarettes with special covers
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES OF CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D1/00—Cigars; Cigarettes
    • A24D1/02—Cigars; Cigarettes with special covers
    • A24D1/025—Cigars; Cigarettes with special covers the covers having material applied to defined areas, e.g. bands for reducing the ignition propensity

Definitions

  • Smoking articles such as cigarettes or cigars, produce both mainstream smoke during a puff and sidestream smoke during static burning.
  • One constituent of both mainstream smoke and sidestream smoke is carbon monoxide (CO).
  • CO carbon monoxide
  • the reduction of carbon monoxide in smoke is desirable.
  • Catalysts, sorbents, and/or oxidants for smoking articles are disclosed in the following: U.S. Patent No. 6,371,127 issued to Snider et al., U.S. Patent No. 6,286,516 issued to Bowen et al., U.S. Patent No. 6,138,684 issued to Yamazaki et al., U.S. Patent No. 5,671,758 issued to Rongved, U.S. Patent No. 5,386,838 issued to Quincy, III et al., U.S. Patent No. 5,211,684 issued to Shannon et al., U.S. Patent No. 4,744,374 issued to Deffeves et al., U. S.
  • Published applications WO 02/24005, WO 87/06104, WO 00/40104 and U.S. Patent Application Publication Nos. 2002/0002979 Al, 2003/0037792 Al and 2002/0062834 Al also refer to catalysts, sorbents, and/or oxidants.
  • Iron and/or iron oxide has been described for use in tobacco products (see e.g., U.S. Patent No. 4,197,861; 4,489,739 and 5,728,462). Iron oxide has been described as a coloring agent (e.g. U.S. Patent Nos. 4,119,104; 4,195,645; 5,284,166) and as a burn regulator (e.g. U.S. Patent Nos. 3,931,824; 4,109,663 and 4,195,645) and has been used to improve taste, color and/or appearance (e.g. U.S. Patent Nos. 6,095,152; 5,598,868; 5,129,408; 5,105,836 and 5,101,839).
  • U.S. Patent Nos. 6,095,152; 5,598,868; 5,129,408; 5,105,836 and 5,101,839 Despite the developments to date, there remains a need for improved and more efficient methods and compositions for reducing the amount of carbon monoxide in the mainstream smoke of a smoking
  • a preferred embodiment of a smoking article comprises a cigarette tobacco rod including a wrapper surrounding a tobacco column, the tobacco column containing a cut filler and a catalytic paper including a web, a web-filler material, and a nanoparticle carbon monoxide catalyst, the web-filler material supporting said nanoparticle catalyst.
  • the nanoparticle carbon monoxide catalyst comprises a nanoparticle iron oxide catalyst supported by calcium carbonate.
  • a preferred method of making a smoking article comprises (i) optionally supporting a nanoparticle carbon monoxide catalyst on a web-filler material to form a catalyst modified web-filler, (ii) making catalytic paper including the catalyst modified web-filler, (iii) forming a tobacco column, the tobacco column including the catalytic paper and a cut filler, (iv) placing a wrapper around the tobacco column to form the smoking article.
  • a preferred smokeable material for a cigarette tobacco rod comprises shredded tobacco and a catalytic paper, the catalytic paper including a web, a web- filler material, and a catalyst modified web-filler, the catalyst modified web-filler including a nanoparticle carbon monoxide catalyst supported on the web-filler material.
  • a preferred method of making a smokeable material for a tobacco rod comprises adding catalytic paper to shredded tobacco, the catalytic paper including a web, a web-filler material and a nanoparticle carbon monoxide catalyst supported on the web-filler material.
  • FIG. l(a) shows an exemplary smoking article with a composition of tobacco including cut filler and a catalytic paper containing a nanoparticle carbon monoxide catalyst.
  • FIG. l(b) shows an expanded view of the composition of tobacco.
  • FIG. 2 shows a schematic of a papermaking machine wherein the chalk box may contain a catalyst modified web-filler.
  • Catalytic paper in cut filler compositions and smoking articles and methods for making smoking articles which involve the use of shredded paper with nanoparticle additives in cut filler compositions are capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide.
  • the nanoparticle additives reduce the amount of carbon monoxide in mainstream smoke.
  • mainstream smoke refers to the mixture of gases passing down the tobacco rod and issuing through the filter end, i.e. the amount of smoke issuing or drawn from the mouth end of a cigarette during smoking of the cigarette.
  • the mainstream smoke contains smoke that is drawn in through both the lighted region, as well as through the cigarette paper wrapper.
  • Carbon monoxide (CO) oxidation catalysts such as nanoparticle iron oxide catalysts of the preferred embodiments, can be incorporated into the tobacco cut filler formed into tobacco rods for smoking articles, such as cigarettes. Subsequently, the smoking article is consumed during smoking. While not wishing to be bound by theory, it is believed that during smoking, the incorporated -A-
  • nanoparticle catalyst catalyzes a constituent gas component in the gas stream, e.g., the carbon monoxide catalyst catalyzes CO to reduce the level of CO in the mainstream and sidestream cigarette smoke by reaction with oxygen (O 2 ) in the gas stream of the smoking article to form carbon dioxide (CO 2 ) following equation 1 :
  • FIG. l(a) shows an exemplary smoking article with a cigarette tobacco rod that includes a nanoparticle carbon monoxide catalyst.
  • the preferred smoking article 100 has a tobacco rod portion 90 and filtering tip 92.
  • the tobacco rod portion 90 comprises a cigarette tobacco column 102 of a composition of tobacco 104 surrounded by a wrapper 106. As shown in the magnified view of FIG.
  • the composition of tobacco 104 contains a cut filler 108 and a catalytic paper 110 including a web of fibrous cellulosic material 112 in which is dispersed particles of web-filler material 114, such as calcium carbonate (CaCO 3 ).
  • web-filler material 114 serves as an agent for determining the permeability of the catalytic paper 110 (measured typically in units of CORESTA, which is defined as the amount of air, measured in cubic centimeters, that passes through one square centimeter of material in one minute at a pressure drop of 1.0 kilopascals) and also serves as a support for nanoparticles of carbon monoxide catalyst, preferably nanoparticles of iron oxide.
  • the catalytic paper 110 can optionally include a catalyst-free web-filler material 116.
  • the web- filler material is a filler material utilized in production for the wrapper 104.
  • the filtering tip can comprise one or more plugs of cellulose tow and optionally could include an adsorbent such as carbon.
  • nanoparticles is meant that the particles have an average particle diameter of less than a micron.
  • the nanoparticle catalyst preferably has an average particle diameter of less than about 500 nm, further preferably less than about 300 to 400 nm, more preferably from 1 to 50 nm, even more preferably 1 to 10 nm, and most preferably less than about 5 nm.
  • a bulk density of the nanoparticle catalyst is preferably less than 0.25 g/cc, preferably about 0.05 g/cc.
  • the Brunauer, Emmett, and Teller (BET) surface area of preferred nanoparticle catalyst is about 20 m 2 /g to 400 m 2 /g, more preferably about 200 m 2 /g to about 300 m 2 /g.
  • An example of a high temperature nanoparticle carbon monoxide catalyst includes nanoparticle iron oxide catalyst.
  • a preferred nanoparticle iron oxide catalyst is NANOCATO Superfine Iron Oxide, available from Mach I, Inc., of King of Prussia, PA.
  • the nanoparticle iron oxide catalyst can comprise FeOOH, Ot-Fe 2 O 3 , 7-Fe 2 O 3 , or mixtures thereof.
  • the nanoparticle carbon monoxide catalyst is incorporated into the composition of tobacco by directly mixing the nanoparticle carbon monoxide catalyst with the tobacco cut filler and/or by incorporating the nanoparticle carbon monoxide catalyst into a web-filler material of a catalytic paper, reducing the size of the catalytic paper (by, for example, shredding), and mixing the reduced catalytic paper with the tobacco cut filler in the composition of the tobacco.
  • the nanoparticle carbon monoxide catalyst is incorporated into a web-filler material by fixing the nanoparticle carbon monoxide catalyst to web-filler material utilized as web-filler material in the production of cigarette wrapping paper.
  • the web-filler material can include an oxide, a carbonate, or a hydroxide of a Group II, Group III or Group IV metal, or the web-filler material can be selected from the group consisting of CaCO 3 , TiO 2 , silicates such as SiO 2 , Al 2 O 3 , MgCO 3 , MgO and Mg(OH) 2 .
  • the web-filler material is CaCO 3 or other conventional web- filler material used in cigarette paper manufacture.
  • the catalytic paper can include web-filler materials which do not include the nanoparticle carbon monoxide catalyst.
  • the nanoparticle iron oxide catalytic particle includes FeOOH, 0-Fe 2 O 3 , 7-Fe 2 O 3 , or mixtures thereof.
  • the nanoparticle iron oxide catalytic particle is supported on a web-filler material selected from the group consisting of CaCO 3 , TiO 2 , silicates such as SiO 2 , Al 2 O 3 , MgCO 3 , MgO and Mg(OH) 2 to form a catalyst modified web-filler.
  • An average particle size of the catalyst modified web-filler is 0.1 to 10 microns, preferably less than or equal to 1.5 microns.
  • a total amount of nanoparticle carbon monoxide catalyst in the smoking article is an amount effective to convert at least some CO to CO 2 .
  • a preferred amount of catalyst per cigarette is 1 to 100 mg, 1 to 50 mg or 50 to 100 mg, 2 to 25 mg or 25 to 50 mg, 1 to 15 mg or 15 to 40 mg, or 4 to 10 mg or 10 to 30 mg.
  • the nanoparticle carbon monoxide catalyst such as nanoparticle iron oxide catalytic particles
  • web-filler material such as CaCO 3
  • the CaCO 3 used in this process can be the same as the filler material used in the papermaking process, such as ALBACAJRD 5970 commercially available from Specialty Minerals of Bethlehem, Pennsylvania.
  • the slurry is spread, by, for example, spreading the slurry with a doctors blade, and then dried to evaporate the water leaving behind a solid.
  • One method to dry the slurry includes exposure in air while heated by a heat source, such as a radiation lamp at 75EC, although other methods such as vacuum filtering followed by drying can also be used.
  • the catalyst and filler can be provided in any desired amount, e.g., 10 to 90% catalyst and 90 to 10% web-filler.
  • the solid is either a powdery substance or a self-supporting solid mass, depending on the nanoparticle carbon monoxide catalyst loading of the slurry. For example, for a slurry containing about 50 to 60 wt.% catalyst loading or less of nanoparticle iron oxide catalytic particle on calcium carbonate, the slurry dries to a powdery substance; for a slurry containing a catalyst loading of greater than about 60 to 70 wt.% catalyst loading of the nanoparticle iron oxide catalytic particle on calcium carbonate, the slurry dries to a self-supporting solid mass.
  • the average particle size of the catalyst modified web-filler can be reduced to an average particle size of 0.1 to 10 microns, preferably about 1 micron or less.
  • the catalyst modified web-filler can be ball milled to form a powder by milling, for example, with 1 cm agate milling balls for 2 to 4 hours at 100 to 300 rpm. Ball milling may not be necessary where the slurry dries to a powdery substance.
  • the catalyst modified web-filler e.g., the nanoparticle carbon monoxide catalyst/web-filler material, can be incorporated into the paper through the papermaking processes.
  • the catalyst modified web-filler can be used as filler material in the papermaking processes.
  • particles of web-filler material such as CaCO 3
  • support the nanoparticle carbon monoxide catalyst such as nanoparticle iron oxide
  • the slurry is formed substantially as described above with respect to the first approach.
  • the catalyst modified web-filler After drying the slurry to form a self-supporting solid mass and ball milling to form a powder (if necessary to reduce the size of the filler), the catalyst modified web-filler is calcined by heating the catalyst modified web-filler to a suitable calcining temperature of no more than 500EC, preferably from 200EC to 400EC, for a suitable period of time such as from 1 to 3 hours, preferably 2 hours.
  • the catalyst modified web-filler e.g., the nanoparticle carbon monoxide catalyst/web-filler material, can be used as filler material in conventional papermaking processes.
  • the catalyst modified web-filler material can be used as web-filler in the papermaking processes.
  • An exemplary process of making catalyst modified web filler comprising a 50/50 NANOCAT ® iron oxide nanoparticle catalyst/CaCO 3 mixture utilizing milling can be carried out as follows:
  • An exemplary process of making catalyst modified web filler comprising a 50/50 NANOCAT ® iron oxide nanoparticle catalyst/CaCC> 3 mixture utilizing spray drying can be carried out as follows:
  • calcination can be performed in air for 2 hours at 300EC.
  • the catalytic paper is shredded and mixed with the tobacco cut filler to form a composition of tobacco for subsequent manufacture into a cigarette tobacco rod in a cigarette making machine.
  • Any suitable tobacco mixture may be used for the cut filler.
  • suitable types of tobacco materials include flue-cured, Burley, Maryland or Oriental tobaccos, the rare or specialty tobaccos, and blends thereof.
  • the tobacco material can be provided in the form of tobacco lamina, processed tobacco materials such as volume expanded or puffed tobacco, processed tobacco stems such as cut-rolled or cut-puffed stems, reconstituted tobacco materials, or blends thereof.
  • the tobacco can also include tobacco substitutes.
  • the tobacco is normally employed in the form of cut filler, i.e., in the form of shreds or strands cut into widths ranging from about 1/10 inch to about 1/20 inch or even 1/40 inch. The lengths of the strands range from between about 0.25 inches to about 3.0 inches.
  • the cigarettes may further comprise one or more flavorants or other additives (e.g., burn additives, combustion modifying agents, coloring agents, binders, etc.) known in the art.
  • the nanoparticle carbon monoxide catalyst can be fixed to the filler material to form a catalyst modified web-filler material by any suitable technique.
  • the nanoparticle carbon monoxide catalyst can be combined with the web-filler material by co-precipitating the nanoparticle iron oxide catalytic particle from a liquid phase onto the web-filler material or co-depositing the nanoparticle iron oxide catalytic particle from a vapor phase onto the web-filler material.
  • the catalyst modified web-filler e.g., the nanoparticle carbon monoxide catalyst/web-filler material
  • the catalyst modified web-filler is incorporated in the catalytic paper through conventional papermaking processes.
  • the catalyst modified web-filler can be used as all or part of the web-filler material in the papermaking processes or can be distributed directly onto the paper, such as by spraying or coating onto wet or dry base web to form the catalytic paper.
  • a catalytic paper can be any wrapper for smoking articles, including wrappers containing flax, hemp, kenaf, esparto grass, rice straw, cellulose and so forth.
  • Optional filler materials, flavor additives, and burning additives can be included.
  • the catalytic paper can have more than one layer in cross-section, such as in a bilayer paper as disclosed in commonly-owned U.S. Patent No. 5,143,098, issued to Rogers, the entire content of which is herein incorporated by reference.
  • the papermaking process can be carried out using conventional paper making equipment.
  • An exemplary method of manufacturing catalytic paper including catalyst modified web-filler comprising nanoparticle carbon monoxide catalyst supported by a web-filler material comprises supplying the catalyst modified web-filler and a cellulosic material to a papermaking machine.
  • an aqueous slurry including the catalyst modified web-filler and the cellulosic material can be supplied to a head box of a forming section of a Fourdrinier papermaking machine.
  • the catalyst modified web-filler includes a nanoparticle carbon monoxide catalyst, e.g., nanoparticle iron oxide catalyst, supported by a web-filler material, e.g., CaCO 3 .
  • the catalyst modified web-filler can include nanoparticle iron oxide catalyst/CaCO 3 particles or any other suitable nanoparticle carbon monoxide catalyst and web-filler material, such as an oxide, a carbonate, or a hydroxide of a Group II, Group III or Group IV metal, CaCO 3 , TiO 2 , silicates such as SiO 2 , Al 2 O 3 , MgCO 3 , MgO and Mg(OH) 2 .
  • the aqueous slurry can be supplied to the head box by a plurality of conduits which communicate with a source, such as a storage tank.
  • the exemplary method can optionally include calcining the catalyst modified web-filler in a step prior to supplying the furnish to the papermaking machine.
  • the catalyst modified web-f ⁇ ller can be supplied to the papermaking process in any suitable form, such as in the form of an aqueous slurry or in the form of a dry powder to be slurried during the papermaking process prior to addition to the head box.
  • the catalyst modified web-filler can be produced on site as a slurry.
  • the aqueous slurry containing the catalyst modified web-filler can be used immediately or stored for future use.
  • the head box is supplied with an aqueous slurry of furnish containing the catalyst modified web- filler and cellulosic material used to form a web.
  • an aqueous slurry of furnish containing catalyst modified web-filler and an aqueous slurry furnish of cellulosic material without catalyst modified web-filler or with a different concentration of catalyst modified web-filler can be supplied to separate head boxes or multiple head boxes.
  • An exemplary method deposits the aqueous slurry from the head box onto a forming section so as to form a base web of the cellulosic material and the catalyst modified web-filler.
  • the forming section is a Fourdrinier wire which is arranged as an endless forming wire immediately below the head box.
  • a slice defined in a lower portion of the head box adjacent to the endless wire permits the aqueous slurry of catalyst modified web- filler and cellulosic material from the head box to flow through the slice onto the top surface of the endless wire to form a wet base web.
  • the aqueous slurry can be deposited onto a support web that is retained within the paper.
  • a support web can be transported through the forming section of a papermaking machine and can be a foundation on which the aqueous slurry is deposited.
  • the aqueous slurry dries and the paper sheet (e.g., finished web) is formed with the support web embedded therein.
  • the support web can be a conventional web, such as a flax support web, or can include a web with an incorporated catalytic component, such as a nanoparticle carbon monoxide catalyst. If the support web includes a catalytic component, the incorporated catalytic component can be supported on a web-filler material or can be directly supported on the support web without a web-filler material.
  • catalytic paper After depositing the aqueous slurry onto the forming section, water is removed from the wet base web and, with additional processing such as further drying and pressing, if necessary, forms a sheet of catalytic paper (e.g., finished web). The catalytic paper is subsequently taken up for storage or use, e.g. the catalytic paper is coiled in a sheet or roll.
  • a cigarette papermaking machine 200 includes a head box 202 operatively located at one end of a Fourdrinier wire 204, and source of feed stock slurry such as a run tank 206 in communication with the head box 202.
  • the head box 202 can be one typically utilized in the papermaking industry for laying down cellulosic pulp upon the Fourdrinier wire 204.
  • the head box 202 is communicated to the run tank 206 through a plurality of conduits.
  • the run tank 206 receives furnish from a furnish supply 218.
  • the feed stock from the run tank 206 is a refined cellulosic pulp such as a refined flax or wood pulp as is the common practice in the cigarette papermaking industry.
  • a chalk tank 228 (containing the catalyst modified filler described above) is communicated with the run tank 206 so as to establish a desired "chalk" level in the slurry supplied to the head box 202.
  • the Fourdrinier wire 204 carries the laid slurry pulp (e.g., base web) from the head box 202 along a path in the general direction of arrow A in FIG. 2, whereupon water is allowed to drain from the pulp through the wire 204 by the influence of gravity and at some locations with the assistance of vacuum boxes 210, 210', 210" at various locations along the Fourdrinier wire 204 as is the established practice in the art of cigarette papermaking.
  • laid slurry pulp e.g., base web
  • the intermediate web 212 separates from the Fourdrinier wire 204 at a couch roll 214. From there, the Fourdrinier wire 204 continues on the return loop of its endless path.
  • the intermediate web 212 continues on through the remainder of the papermaking system which further dries and presses the intermediate web 212 and surface conditions it to a desired final moisture content and texture to form a paper 220 (e.g., finished web).
  • drying apparatus are well known in the art of papermaking and may include drying section 216 including drying felts, vacuum devices, rolls, and/or presses, applied thermal energy, and the like.
  • the cigarette making machine 200 can optionally include more than one head box and/or more than one Fourdrinier wire with either separate or common furnish supply.
  • the optional second head box 202' suitably integrated with a runtank and furnish supply, can lay slurry pulp onto the slurry pulp laid from the first head box 202 and carried along Fourdrinier wire 204.
  • the second and/or additional head box can be supplied with catalyst modified web filler to a desired "chalk" level or can be free of catalyst modified web-filler, as desired based on the number of layers of slurry pulp to be deposited and/or the use of the wrapper formed from the papermaking process.
  • the optional second Fourdrinier wire 204' can form a second intermediate web 212'.
  • the second intermediate web 212' can be separated from the second Fourdrinier wire 204' at a second couch roll 214' and laid on the first intermediate web 212 from the Fourdrinier wire 204 to be processed into double layer paper.
  • Multiple optional Fourdrinier wires can be employed to form multiple layer paper having any desired number of layers, such as three, four and so forth, up to ten to twelve layers.
  • a catalytic paper e.g., a paper with a nanoparticle carbon monoxide catalyst.
  • a laminated, a bilayer or multilayer catalytic paper can be made. Examples of bilayer and multilayer paper is disclosed in commonly-owned U.S. Patent No. 5,143,098, issued to Rogers, the entire content of which is herein incorporated by reference.
  • a bilayer or multilayer catalytic paper including a nanoparticle carbon monoxide catalyst at least one of a first layer and a second layer can include the nanoparticle carbon monoxide catalyst as described in embodiments herein.
  • the bilayer catalytic paper can then be reduced in size, mixed with tobacco cut filler, and the composition formed into a tobacco rod in a cigarette making machine.
  • Additional examples of paper configurations and types of paper that can be formed as catalytic paper and used in a composition of tobacco include bilayer paper in which either the first paper layer or the second paper layer can be a banded paper, a paper having a plurality of regions of variable basis weight in the cross direction, and/or a catalytic paper formed with catalyst modified web-filler.
  • the bilayer or multilayer single sheet catalytic paper may be made using ordinary paper furnish such as pulped wood, flax fibers, or any standard cellulosic fiber. Preferably flax fibers are used.
  • a first head box can hold the materials for a catalytic paper that includes the nanoparticle carbon monoxide catalyst and a second head box can hold the materials for a conventional paper (wrapper).
  • the first head box can hold the materials for a catalytic paper that includes the nanoparticle carbon monoxide catalyst at a first concentration or loading level and a second head box can hold the materials for a catalytic paper that includes the nanoparticle carbon monoxide catalyst at a second concentration or loading level.
  • the first concentration or first loading level is different from the second concentration or second loading level.
  • the catalytic paper can have a radially inner layer and a radially outer layer, the radially inner layer having a first loading of the nanoparticle carbon monoxide catalyst and the radially outer layer having a second loading of the nanoparticle carbon monoxide catalyst.
  • the first loading of the nanoparticle carbon monoxide catalyst can be greater than the second loading of the nanoparticle carbon monoxide catalyst.
  • the first loading of the nanoparticle carbon monoxide catalyst is up to 100 mg and the second loading of the nanoparticle carbon monoxide catalyst is less than 1 mg.
  • the second loading of the nanoparticle carbon monoxide catalyst is zero.
  • a ratio, in weight percent, of the nanoparticle carbon monoxide catalyst to the web-filler material in the radially inner layer is from 0.1 to 3.0, more preferably from 0.1 to 1.0, most preferably from 0.33 to 1.0, and a total loading of the nanoparticle carbon monoxide catalyst in the radially outer layer is less than 1 mg, more preferably the total loading of the nanoparticle carbon monoxide catalyst in the radially outer layer is zero.
  • Additional examples of papermaking processes include the method for making banded paper for banded smoking article wrappers disclosed in U.S. Patent No. 5,342,484, the entire content of which is herein incorporated by reference, the method for producing paper having a plurality of regions of variable basis weight in the cross direction disclosed in U.S. Patent No. 5,474,095, the entire content of which is herein incorporated by reference, and the method of making a catalytic wrapper disclosed in commonly-owned U.S. Provisional Patent Application No. 60/477,922 (Attorney Docket No.
  • Reducing the size of the catalytic paper can be by any suitable technique such as tearing, shearing, shredding and so forth.
  • the catalytic paper is reduced in size to approximate the shape, size and form of tobacco cut filler.
  • the reduced catalytic paper can have an average thickness from 0.10 mm to 0.13 mm (with a range of the thickness of 0.03 mm to 0.15 mm), an average width of less than 1.0 mm (with a maximum width of 5 mm), and an average length of less than 3.0 mm (with a maximum length of 25 mm).
  • the nanoparticle carbon monoxide catalyst can also be directly incorporated into the catalytic paper either during or after the papermaking process. This can occur instead of, or in addition to, incorporating the nanoparticle carbon monoxide catalyst into the web-filler material.
  • the nanoparticle carbon monoxide catalyst can be distributed, e.g., sprinkled, cast, spread, sprayed, drip coated, curtain coated, or otherwise placed in contact with the spread wet base web prior to drying.
  • the wet base web is subsequently dried to form a catalytic paper and the nanoparticle carbon monoxide catalyst is retained within the catalytic paper.
  • the nanoparticle carbon monoxide catalyst, with or without being incorporated into a web-filler material can be distributed, e.g., sprinkled, cast, spread, sprayed, drip coated, curtain coated, or otherwise placed in contact with the finished web.
  • a retention aid can be incorporated into the papermaking process to improve the distribution of the nanoparticle carbon monoxide catalyst in the paper component, e.g., the aqueous slurry used in the paper making process can include a retention aid.
  • a preferred catalytic paper for inclusion in a composition of tobacco comprises a web including cellulosic fibers and a catalyst modified web-filler incorporated into the web.
  • the catalyst modified web-filler includes a web-filler material supporting a nanoparticle carbon monoxide catalyst.
  • the nanoparticle carbon monoxide catalyst is a nanoparticle iron oxide catalytic particle.
  • the nanoparticle iron oxide catalytic particle can include FeOOH, Ot-Fe 2 O 3 , ⁇ -Fe 2 O 3 , or mixtures thereof.
  • a suitable nanoparticle iron oxide catalytic particle is NANOCATD Superfine Iron Oxide.
  • the nanoparticle carbon monoxide catalyst e.g., the nanoparticle iron oxide catalytic particle
  • the nanoparticle carbon monoxide catalyst is present in the catalyst modified web-filler up to about 60 wt.% catalyst loading, more preferably from about 10 wt.% to about 50 wt.% catalyst loading, and most preferably is at about 20 to 30 wt.% catalyst loading, relative to the total web-filler material.
  • a preferred catalytic paper can have a basis weight of from about 18 g/m to about 60 g/m and a permeability of from about 5 CORESTA units to about 80 CORESTA units. More preferably, the catalytic paper has a basis weight from about 30 g/m 2 to about 45 g/m 2 and the permeability is about 30 to 35 CORESTA units.
  • any suitable basis weight for the catalytic paper can be selected. For example, a higher basis weight, e.g., 35 to 45 g/m 2 , can support a higher loading of catalyst. If a lower catalyst loading is selected, then a lower basis weight wrapper can be used.
  • the ratio of nanoparticle carbon monoxide catalyst to web-filler material can be varied by subjecting a slurry of nanoparticle carbon monoxide catalyst/web- filler material, e.g., the slurry of nanoparticle iron oxide catalyst/CaCO 3 or other catalyst modified web-filler, to calcining at different temperatures for different time periods. Also, the mixing conditions of the slurry can be selected to achieve a desired distribution of the web-filler material with the nanoparticle carbon monoxide catalyst. For example, the speed, time, blade type, and temperature can all be adjusted to achieve a desired uniformity of the nanoparticle carbon monoxide catalyst to web-filler material ratio.
  • the nanoparticle carbon monoxide catalyst/web-filler material can be co-precipitated to form a particle or a powder, e.g., chemical precipitation methods can be used, such as precipitating CaCO 3 from CaCl 3 by adding a carbonate, such as Na 2 CO 3 .
  • Gas phase precipitation methods to deposit nanoparticle carbon monoxide catalyst in-situ onto a web-filler material can also be employed. For example, vapor deposition or spray techniques can be used.
  • CO catalyst in the form of nanoparticle iron oxide catalyst starts to convert CO to CO 2 at a temperature above 150EC, preferably at a temperature above 400EC.
  • the conversion rate of CO to CO 2 by nanoparticle iron oxide catalyst is enhanced by the rapid and efficient transport of CO to the region of the nanoparticle carbon monoxide catalyst and CO 2 away from the region of the catalyst, e.g., air flow within the smoking article.
  • the operating temperature and the air flow within the smoking article can affect the operation of the nanoparticle carbon monoxide catalyst.
  • CO in mainstream smoke flows toward the filter end of a smoking article.
  • oxygen diffuses into and carbon monoxide diffuses out of the smoking article through the paper wrapper.
  • CO is concentrated in the periphery of the cigarette, e.g., near the cigarette paper wrapper, in front of the burn zone.
  • the oxygen concentration is high in the same region as high CO concentration due to diffusion of O 2 from outside the cigarette.
  • Airflow into the tobacco and during the puffing process is largest near the burn zone on the periphery of the smoking article and is approximately commensurate with the gradient of temperature, e.g, larger airflow is associated with higher temperature gradients.
  • the highest airflow is also the region of highest temperature gradient.
  • the highest temperature gradient is from >850- 900EC at the periphery of the smoking article at the burn zone to approximately 300EC toward the center of the smoking article.
  • the temperature further drops to near ambient near the filter end.
  • the temperature drop at the lit end is very fast and within a couple of mm behind the burn zone in the axial direction the temperature drops from 900EC to 200EC.
  • composition of tobacco with catalytic filler can be used as cut filler for conventional cigarettes or non-conventional cigarettes such as cigarettes for electrical smoking systems described in commonly-assigned U.S. Patent Nos. 6,026,820; 5,988,176; 5,915,387; 5,692,526; 5,692,525; 5,666,976; 5,499,636 and 5,388,594 or non-traditional types of cigarettes having a fuel rod such as are described in commonly-assigned U.S. Patent No. 5,345,951.
  • the position and quantity of paper with catalyst modified web-filler, e.g., catalytic filler, in the tobacco composition, e.g., the position and quantity of the shredded paper with catalyst modified web-filler, can be selected as a function of the temperature and airflow characteristics exhibited in a burning cigarette in order to adjust, e.g., increase, decrease, minimize or maximize, the conversion rate of CO to CO 2 .
  • solid coal in a smoking article reaches the peak temperature of greater than 850-900EC at about the burn zone, e.g., within about 2 mm of the burn zone, and is at 300EC to 400EC within 2 to 3 mm of the burn zone.
  • a nanoparticle carbon monoxide catalyst can be selected that operates in a given temperature range, and a composition of tobacco can be manufactured in which the catalytic filler can be incorporated in those portions of the tobacco column that are predicted to coincide with the appropriate temperature for operation of the catalyst.
  • the selective incorporation of catalytic filler can be realized, for example, by using different supply lines to the cigarette making machine, each supply line having a different catalytic filler.
  • the different catalytic filler can differ either in concentration of catalyst modified web-filler, or type of catalyst modified web-filler, or operating temperature of catalyst modified web-filler.
  • the different supply line can be at selected positions in the cigarette making process corresponding to selected locations of the cigarette, e.g., radially or axially positioned.
  • a preferred nanoparticle carbon monoxide catalyst for use in a catalytic filler for a tobacco composition of a smoking article is catalytically active at temperature as low as ambient temperature and does not deactivate even at temperatures as high as 900EC.
  • the preferred catalytic filler can be positioned along the entire axial length of the anticipated burn zone, e.g., not only at the filter end of the smoking article, and can be catalytically active from the lit end to the filter end during use.
  • the axial distribution of the catalytic filler provides sufficient contact time between the mainstream smoke and the nanoparticle carbon monoxide catalyst for the CO to be converted to CO 2 .
  • Further exemplary distributions of the catalytic filler include a radial distribution within the tobacco column.
  • the radial distribution of catalytic filler can produce a higher concentration of nanoparticle carbon monoxide catalyst along a radially outer portion of the tobacco column, e.g., toward the surface of the cylindrical tobacco column that is encased by the wrapper in the smoking article.
  • Other distributions include a distribution along a length of the tobacco column.
  • a lengthwise distribution can produce a higher distribution of nanoparticle carbon monoxide catalyst toward a butt end of the tobacco rod, e.g., toward the end with a filter in a filtered smoking article.
  • An example of a preferred nanoparticle carbon monoxide catalyst includes NANOCATO Superfine Iron Oxide, which starts to convert CO to CO 2 at a temperature above 150EC.
  • a mixed catalyst e.g., a catalyst that is a combination of individual catalyst compositions that each operate at a different temperature range or overlapping temperature ranges, can be used to broaden the temperature range at which conversion of CO to CO 2 can occur and to increase the operating period of the catalyst as the smoking article burns.
  • a mixed catalyst may operate at both above about 500EC and at 300EC to 400EC and thus converts CO to CO 2 both at the burn zone and behind the burn zone, effectively increasing the conversion time and the area of the smoking article at which conversion occurs.
  • the catalyst is described herein as having an operating temperature, the term operating temperature refers to the preferred temperature for conversion of CO to CO 2 .
  • the catalyst may still operate to convert CO to CO 2 outside the described temperature range, but the conversion rate may be affected.
  • the nanoparticle carbon monoxide catalyst can be distributed continuously or discretely and can be distributed radially or linearly within the tobacco column. Also, the nanoparticle carbon monoxide catalyst can be distributed uniformly within the smoking article.
  • the nanoparticle carbon monoxide catalyst is present in the tobacco composition as catalytic filler in an amount effective to convert at least 40% of carbon monoxide to carbon dioxide at a temperature of at least 400EC to about 900EC.
  • the nanoparticle carbon monoxide catalyst converts at least 50% of carbon monoxide to carbon dioxide at a temperature of at least 500EC.
  • the nanoparticle carbon monoxide catalyst converts at least 80% of carbon monoxide to carbon dioxide at a temperature of at least 700EC.
  • Calcination is achieved by taking catalysts from the slurry method and heating them in the presence of air for an extended duration.
  • a calcination step can improve the bonding between the catalyst and the paper filler and that during the calcination step the catalyst surface is improved due to evaporation of bound water molecules.
  • the surface area of the supported catalyst was investigated using BET surface area measurements.
  • a low temperature nanoparticle carbon monoxide catalyst can be substituted for the high temperature nanoparticle carbon monoxide catalyst in the catalytic paper.
  • Low temperature and even room temperature catalysts can extend the effective region of the reaction zone for CO to CO 2 conversion to the whole cigarette, provided the temperature rise due to the exothermic reaction remains below the ignition temperature of the tobacco rod and/or its components.
  • An example of a suitable low temperature nanoparticle carbon monoxide catalyst includes ceria-based catalysts. Ceria-based catalysts can oxidize CO at near-ambient temperatures. A suitable ceria-based catalyst is disclosed in U.S. Patent Application No. 10/314,449 entitled “CERIA-BASED CATALYSTS FOR CO OXIDATION AT NEAR-AMBIENT TEMPERATURES" and filed on December 9, 2002, the entire contents of which are herein incorporated by reference. Another example of a low temperature nanoparticle carbon monoxide catalyst includes nanoparticle additives capable of acting as an oxidant for the conversion of CO.
  • a suitable nanoparticle additive includes a metal oxide, such as Fe 2 O 3 , CuO, CeO 2 , or Ce 2 O 3 , a doped metal oxide, such as Y 2 O 3 doped with zirconium or Mn 2 O 3 doped with palladium, or mixtures thereof as disclosed in U.S. Patent Application No. 10/286,968 entitled “OXID ANT/CATALYST NANOP ARTICLES TO REDUCE TOBACCO SMOKE CONSTITUENTS SUCH AS CARBON MONOXIDE” and filed on November 4, 2002, the entire contents of which are herein incorporated by reference.
  • supported nanoscale particles exhibit a reduced tendency to agglomerate with each other as well as a reduced tendency to leech out of the catalytic paper during cigarette paper manufacture.
  • the web-filler material for support of the nanoscale particles can comprise calcium carbonate (CaCO 3 ), which is used conventionally as a filler material in cigarette paper manufacturing.
  • the catalytic effect of nanoscale catalyst particles (e.g., for the reduction of CO and/or NO x from mainstream smoke) can be controlled by varying the loading of catalytic particles in the catalytic paper and/or the loading of catalytic paper in the tobacco composition.
  • the catalytic paper can be reduced in size, e.g., shredded in different shapes and sizes, and can be distributed continuously or discontinuously through the tobacco rod along different dimensions of a smoking article. By controlling the shape, size and distribution of the catalytic paper within the tobacco rod, adequate gas flow through the smoking article can be achieved.
  • the tobacco column preferably comprises cut filler of a blend of tobaccos typical of the industry, including blends comprising Bright, Burley and Oriental tobaccos and other blend components, including traditional cigarette flavors.
  • the shredded tobacco (cut filler) of the tobacco column comprises a blend of Bright, Burley and Oriental tobaccos with or without inclusion of reconstituted tobaccos or any after cut flavorings.
  • an expanded tobacco component might be included in the blend to adjust rod density, and flavors may be added.
  • a single variety of the aforementioned tobaccos may be used instead of a blend.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Paper (AREA)

Abstract

Compositions de remplissage pour le boudin de tabac d'un article pour fumeurs, comprenant un tabac de remplissage et un papier catalytique renfermant un catalyseur nanoparticulaire à monoxyde de carbone. Ce catalyseur nanoparticulaire à monoxyde de carbone est incorporé à une matière de remplissage de bande utilisée dans la fabrication du papier catalytique. Ledit catalyseur nanoparticulaire à monoxyde de carbone comprend des particules catalytiques nanoparticulaires d'oxyde de fer. On a également prévu un article pour fumeurs comprenant le boudin de tabac constitué d'une enveloppe en papier entourant un boudin de tabac renfermant un papier catalytique.
PCT/IB2004/002217 2003-06-13 2004-06-14 Papier effiloche a matiere de remplissage catalytique pour tabac de remplissage, et procedes de fabrication correspondants Ceased WO2004110188A2 (fr)

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US47792403P 2003-06-13 2003-06-13
US60/477,924 2003-06-13

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AR (1) AR045430A1 (fr)
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WO (1) WO2004110188A2 (fr)

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UY28364A1 (es) 2005-01-31
US20050022833A1 (en) 2005-02-03
TW200507771A (en) 2005-03-01
AR045430A1 (es) 2005-10-26

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