AU2011232769A1 - Cigarette Wrapper with Catalytic Filler and Methods of Making Same - Google Patents

Abstract

A wrapper for a smoking article includes a web including cellulosic fibers and a 5 catalyst modified web-filler incorporated into the web. The catalyst modified web filler includes a web-filler supporting a nanoparticle carbon monoxide catalyst. The nanoparticle carbon monoxide catalyst can be a nanoparticle iron oxide catalyst. Also provided is a smoking article including a cigarette tobacco rod having a wrapper including a web, a web-filler, and a nanoparticle carbon monoxide catalyst, the web 10 filler supporting the nanoparticle catalyst. A method of making the wrapper and a method of making a smoking article utilizing the wrapper are also provided.

Description

AUSTRALIA Patents Act 1990 ORIGINAL COMPLETE SPECIFICATION INVENTION TITLE: CIGARETTE WRAPPER WITH CATALYTIC FILLER AND METHODS OF MAKING SAME The following statement is a full description of this invention, including the best method of performing it known to us:- 2 CIGARETTE WRAPPER WITH CATALYTIC FILLER AND METHODS OF MAKING SAME BACKGROUND 5 [00011 This application claims priority under 35 USC §119 to U.S. Provisional Application No. 60/477,922 entitled CIGARETTE WRAPPER WITH CATALYTIC FILLER AND METHODS OF MAKING SAME and filed on June 13, 2003, the entire content of which is hereby incorporated by reference. 100021 In the description that follows reference is made to certain structures and 10 methods, however, such references should not necessarily be construed as an admission that these structures and methods qualify as prior art under the applicable statutory provisions. Applicants reserve the right to demonstrate that any of the referenced subject matter does not constitute prior art. [00031 Smoking articles, such as cigarettes or cigars, produce both mainstream 15 smoke during a puff and sidestream smoke during static burning. One constituent of both mainstream smoke and sidestream smoke is carbon monoxide (CO). The reduction of carbon monoxide in smoke is desirable. 100041 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. 20 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. Patent No. 4,453,553 issued to Cohn, U.S. Patent No. 4,450,847 issued to Owens, U.S. Patent No. 25 4,182,348 issued to Seehofer et al., U.S. Patent No. 4,108,151 issued to Martin et al., U.S. Patent No. 3,807,416, and U.S. Patent No. 3,720,214. 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. 06/10/ jb19518 specification,2 3 [0005] 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 5 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). [0006] 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 article during smoking. 10 SUMMARY [00071 A preferred embodiment of a smoking article comprises a cigarette tobacco rod having a wrapper, the wrapper including a web, a web-filler material, and a nanoparticle carbon monoxide catalyst, the web-filler material supporting 15 the nanoparticle catalyst. Preferably, the nanoparticle carbon monoxide catalyst comprises a nanoparticle iron oxide catalyst supported by calcium carbonate. [00081 A preferred method of making a smoking article comprises (i) optionally incorporating a nanoparticle carbon monoxide catalyst with a web-filler material utilized in production of a wrapper to form a catalyst modified web-filler, (ii) 20 optionally making the wrapper, the wrapper including the catalyst modified web filler, (iii) providing a cut filler comprising tobacco to a cigarette making machine, and (iv) placing the wrapper including the web-filler material supporting a nanoparticle carbon monoxide catalyst around the cut filler to form a tobacco rod portion of the smoking article. The method optionally includes calcining the 25 catalyst modified web-filler prior to step (ii) and/or (v) placing a second wrapper around the tobacco rod portion. [00091 A preferred embodiment of a wrapper for a smoking article comprises a paper web and a catalyst modified web-filler supported on the paper web, the catalyst modified web-filler including a nanoparticle carbon monoxide catalyst 30 supported by a web-filler material. 0610/l 1 jbI9518 specification,3 4 [0010] Another preferred method of manufacturing cigarette paper comprises (i) supplying a catalyst modified web-filler and a cellulosic material to a head box in a forming section of a papermaking machine, the catalyst modified web-filler including a web-filler material supporting a nanoparticle carbon monoxide 5 catalyst, (ii) depositing an aqueous slurry including the catalyst modified web filler and the cellulosic material onto the forming section of the papermaking machine to form a base web with the catalyst modified web-filler distributed therein, and (iii) removing water from the base web so as to form an intermediate web. The method optionally includes calcining the catalyst modified web-filler 10 prior to step (iii). 100111 A further preferred method of manufacturing cigarette paper including a catalyst modified web-filler comprises (i) supplying a cellulosic material to a first head box of a forming section of a papermaking machine, (ii) depositing an aqueous slurry from the first head box onto the forming section of the 15 papermaking machine so as to form a base web of the cellulosic material, (iii) distributing a catalyst modified web-filler on the base web, the catalyst modified web-filler comprising a web-filler material supporting a nanoparticle carbon monoxide catalyst, and (iv) removing water from the base web so as to form an intermediate web. The method optionally includes calcining the catalyst modified 20 web-filler prior to step (iii) and/or distributing the catalyst modified web-filler within a fibrous network of the base web, wherein the layer forms a band, a stripe, or a lattice pattern on the intermediate web. [00121 A preferred method of manufacturing a bilayer cigarette paper comprises (i) depositing a first layer of the bilayer cigarette paper from a first head box onto 25 a wire of a papermaking machine, the first head box holding a first furnish composition (ii) depositing a second layer of the bilayer cigarette paper from a second head box onto a portion of the first layer, the second head box holding a second furnish composition, the second furnish composition including a catalyst modified web-filler comprising a web-filler material supporting a nanoparticle 30 carbon monoxide catalyst, and (iii) removing water from the first layer and the 06/10/1 IjbI9518 specification,4 5 second layer so as to form a single sheet of intermediate web. The method optionally includes calcining the catalyst modified web-filler. [00131 A preferred method of manufacturing cigarette paper comprises (i) supplying a furnish including a cellulosic material to a first head box of a forming 5 section of a papermaking machine, (ii) transporting a support web through the papermaking machine, (iii) depositing a catalyst modified web-filler onto the support web, the catalyst modified web-filler including a web-filler material supporting a nanoparticle carbon monoxide catalyst, (iv) depositing an aqueous slurry from the first head box onto the support web so as to form a base web of the 10 cellulosic material with the support web embedded therein, (v) removing water from the base web so as to form a sheet, and (vi) taking up the sheet. 100141 A preferred catalyst modified web-filler utilized in production of a wrapper for a smoking article comprises a web-filler material and a nanoparticle carbon monoxide catalyst supported on the web-filler material. 15 [00151 A preferred method of making a catalyst modified web-filler including a nanoparticle carbon monoxide catalyst supported on a web-filler material comprises (i) forming an aqueous slurry of the nanoparticle carbon monoxide catalyst and the web-filler material, (ii) optionally spreading the aqueous slurry on a support surface, and (iii) drying the aqueous slurry to evaporate water and to 20 form a catalyst modified web-filler. [00161 A further preferred method of making a catalyst modified web-filler including a nanoparticle carbon monoxide catalyst supported on a web-filler material comprises (i) precipitating the nanoparticle carbon monoxide catalyst from a liquid phase onto the web-filler material, (ii) removing at least a portion of 25 the liquid phase, and (iii) drying the web-filler to evaporate a remainder of the liquid phase and to form the catalyst modified web-filler. 100171 Another preferred method of making a catalyst modified web-filler including a nanoparticle carbon monoxide catalyst supported on a web-filler material comprises depositing the nanoparticle carbon monoxide catalyst from a 30 vapor phase onto the web-filler material, wherein the nanoparticle carbon 06/10/11 jb19518 specification,5 6 monoxide catalyst comprises FeOOH, a-Fe 2 0 3 , y-Fe 2 0 3 , or mixtures thereof and the web-filler material is selected from the group consisting of CaCO 3 , TiO 2 , SiO 2 , A1 2 0 3 , MgCO 3 , MgO and Mg(OH) 2 . [00181 A preferred embodiment of a cigarette comprises a tobacco rod having a 5 wrapper, the wrapper comprising a web of fibrous cellulosic material and a loading of web-filler material, at least some of the web-filler material comprising a mineral particle and a nanoparticle supported by the mineral particle. [00191 A preferred embodiment of a furnish for use in a papermaking process comprises an aqueous slurry including a catalyst modified web-filler and a 10 cellulosic material. [0020] A preferred embodiment of a cigarette wrapper comprises a web having a web-filler material, at least some of the web-filler material comprising FeOOH. BRIEF DESCRIPTION OF THE DRAWING FIGURES 15 [0021] FIG. 1(a) shows an exemplary smoking article with a nanoparticle carbon monoxide catalyst supported on the web-filler material of the wrapper. FIG. 1(b) shows a magnified view of the wrapper. [0022] FIG. 2(a) shows an exemplary smoking article with a nanoparticle carbon monoxide catalyst supported on the web-filler material of a first wrapper 20 with a second outermost wrapper. FIG. 2(b) shows a magnified view of the first wrapper with a second outermost wrapper. [00231 FIG. 3(a) shows an exemplary smoking article with a wrapper including a nanoparticle carbon monoxide catalyst. An inner web region of the wrapper contains catalyst-supporting web-filler material. FIG. 3(b) shows a magnified 25 view of the wrapper. [00241 FIG. 4 shows a schematic of a papermaking machine wherein the chalk box may contain a catalyst modified web-filler. [00251 FIG. 5 illustrates one type of construction of a cigarette, which can be used with an electrical smoking device. 06/10/1 Ijb19518 specification,6 7 100261 FIG. 6 is a perspective view of a cigarette having catalyst modified paper surrounding a fuel element. [00271 FIG. 7 shows a cross section of the cigarette shown in FIG. 6. [00281 FIG. 8 shows a cross section of a cigarette having catalyst modified 5 wrapper centrally located in the form of a tube. 100291 FIG. 9 shows conversion of CO to CO 2 for nanoparticle iron oxide catalyst and nanoparticle iron oxide catalyst/CaCO 3 mixture. 100301 FIG. 10 shows the effect of calcination conditions on 30% loading of nanoparticle iron oxide catalyst on web-filler material on the conversion of CO to 10 CO 2 as a function of temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [00311 Catalytic paper, compositions of catalyst modified web-filler, cigarettes, methods for making smoking articles which involve the use of nanoparticle 15 additives incorporated into the wrapper as web-filler material 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. 20 100321 The term "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. 25 [00331 Carbon monoxide (CO) oxidation catalysts, such as nanoparticle iron oxide catalysts of the preferred embodiments, can be incorporated into the web filler material of a wrapper of smoking articles, such as cigarettes. Such a wrapper is used to assemble the smoking article and is consumed during smoking. While not wishing to be bound by theory, it is believed that during smoking, the 30 incorporated nanoparticle catalyst catalyzes a constituent gas component in the 06/10/11,jb19518 specification.7 8 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 (02) in the gas stream of the smoking article to form carbon dioxide (C0 2 ) following equation 1: 5 2 CO + 0 2 = 2CO 2 Eq. 1 It is also believed that subsequent to the catalytic reaction, the catalyst may also act as an oxidant, e.g., can oxidize CO in the absence of oxygen in the gas stream to reduce the level of CO in the mainstream and/or sidestream smoke. [00341 Referring to FIG. 1(a), a preferred embodiment of a smoking article 100 10 has a tobacco rod portion 90 and filtering tip 92. Optionally, embodiments of the smoking article 100 can be practiced without a filtering tip 92. Preferably, the tobacco rod portion 90 comprises a column of tobacco 102 that is enwrapped with a cigarette (tobacco) wrapper 104. As shown in expanded view in FIG. 1(b), the wrapper 104 includes a web of fibrous cellulosic material 106 in which is 15 dispersed particles of web-filler material 108, such as calcium carbonate (CaCO 3 ). In practice, the web-filler material 108 serves as an agent for determining the permeability of the wrapper 104 (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 20 kilopascals) and also serves as a support for nanoparticles of carbon monoxide catalyst, preferably nanoparticles of iron oxide. If desired, the wrapper 104 can optionally include a catalyst-free web-filler material 110. The web-filler material is a filler material utilized in production for the wrapper 104. [00351 FIGS. 2(a) and 2(b) show an embodiment of a smoking article with a 25 nanoparticle carbon monoxide catalyst supported on the web-filler material of a first wrapper with a second outermost wrapper. In the FIG. 2(a) embodiment, the smoking article 100 includes a cigarette tobacco column 102 surrounded by a first inner wrapper 112. As shown in expanded view in FIG. 2(b), the first wrapper 112 includes a web 114 and a nanoparticle carbon monoxide catalyst supported on 30 a web-filler material 116. If desired, the first wrapper 112 can optionally include 06/10/1 Ijb[9518 specification.8 9 a catalyst-free web-filler material 118. The web-filler material is a filler material utilized in production of the first wrapper 112. A ratio, in weight percent, of a nanoparticle carbon monoxide catalyst to a web-filler material in the first inner wrapper is preferably from 0.1 to 3.0, more preferably the ratio is 0.1 to 1.0, and 5 most preferably the ratio is 0.33 to 1.0. The smoking article 100 has a second wrapper 120 surrounding the first wrapper 112. The total amount of nanoparticle carbon monoxide catalyst in the second outer wrapper 120 is preferably less than I mg for a given single cigarette 100, more preferably the second wrapper 120 does not include the nanoparticle carbon monoxide catalyst so as to provide an 10 appearance to the cigarette 100 that is not affected by any coloration from the nanoparticle catalyst. In exemplary embodiments, a total amount of nanoparticle carbon monoxide catalyst in the first wrapper is 10 to 100 mg and in the second wrapper is less than 1 mg, preferably 0 mg and/or a ratio, in weight percent, of a nanoparticle carbon monoxide catalyst in the second wrapper 120 to the 15 nanoparticle carbon monoxide catalyst in the first wrapper 112 is less than 0.25. [00361 FIG. 3(a) shows an embodiment of a smoking article with a wrapper including a nanoparticle carbon monoxide catalyst. In the FIG. 3(a) embodiment, the smoking article 100 includes a cigarette tobacco column 102 and a wrapper 122. As shown in expanded view in FIG. 3(b), the wrapper 122 includes a web 20 124 and a nanoparticle carbon monoxide catalyst supported on a web-filler material 126. If desired, the wrapper 122 can optionally include a catalyst-free web-filler material 128. The web-filler material is a filler material utilized in production of the wrapper 122. The wrapper 122 has a radially inner portion 130 and a radially outer portion 132, the radially inner portion 130 having a first 25 loading of the nanoparticle carbon monoxide catalyst and the radially outer portion 132 having a second loading of the nanoparticle carbon monoxide catalyst. In one embodiment, the first loading of the nanoparticle carbon monoxide catalyst is greater than the second loading of the nanoparticle carbon monoxide catalyst. For example, the first loading of the nanoparticle carbon 30 monoxide catalyst in the wrapper for a given single cigarette 100 can be up to 100 06/10/1 Ijb]9518 specification,9 10 mg and the second loading of the nanoparticle carbon monoxide catalyst can be less than I mg. Preferably the second loading of the nanoparticle carbon monoxide catalyst is zero. In another embodiment, the ratio, in weight percent, of the nanoparticle carbon monoxide catalyst to the web-filler material in the radially 5 inner portion 130 is preferably from 0.1 to 3.0, more preferably from 0.1 to 1.0., most preferably from 0.33 to 1.0. The total loading of the nanoparticle carbon monoxide catalyst in the radially outer portion 132 is preferably less than I mg, more preferably zero mg. [00371 By "nanoparticles" is meant that the particles have an average particle 10 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 I 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. 15 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 NANOCAT7 Superfine Iron Oxide, available from Mach I, Inc., 20 of King of Prussia, PA. The nanoparticle iron oxide catalyst can comprise FeOOH, a-Fe 2 0 3 , y-Fe 2 0 3 , or mixtures thereof. [00381 The nanoparticle carbon monoxide catalyst is incorporated into the wrapping paper by fixing the nanoparticle carbon monoxide catalyst to filler material utilized as web-filler material in the production of cigarette wrapping 25 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 , A1 2 0 3 , MgCO 3 , MgO and Mg(OH) 2 . In a preferred example, the web-filler material is CaCO 3 or other conventional filler material used in cigarette paper manufacture. 06/10/1 1jb19518 specification,10 11 If desired, the wrapper paper can include web-filler material which does not include the nanoparticle carbon monoxide catalyst. [0039] In a preferred embodiment of a smoking article, the nanoparticle iron oxide catalyst includes FeOOH, a-Fe 2 0 3 , y-Fe 2 0 3 , or mixtures thereof. The 5 catalyst modified web-filler preferably comprises nanoparticle iron oxide catalyst fixed to filler particles selected from the group consisting of CaCO 3 , TiO 2 , silicates such as SiO 2 , A120 3 , MgCO 3 , MgO and Mg(OH) 2 . An average particle size of the catalyst modified paper web-filler is 0.1 to 10 microns, preferably less than or equal to 1.5 microns. 10 100401 In another preferred embodiment, 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 . For cigarettes, a preferred amount of catalyst per cigarette is 1 to 100 mg, I to 50 mg or 50 to 100 mg, 2 to 25 mg or 25 to 50 mg, I to 15 mg or 15 to 40 mg, or 4 to 10 mg or 10 to 20 mg. 15 [00411 In one approach, the nanoparticle carbon monoxide catalyst, such as nanoparticle iron oxide catalyst, is supported by web-filler material, such as CaCO 3 , by forming an aqueous slurry of the nanoparticle carbon monoxide catalyst and the web-filler material. The CaCO 3 used in this process can be the same as the filler material used in the papermaking process, such as ALBACAR7 20 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 radiation lamp at 75EC, although other methods such as vacuum filtering 25 followed by drying can also be used. 100421 The catalyst and filler can be provided in any desired amounts, e.g., 10 to 90% catalyst and 90 to 10% web-filler material. The dried slurry forms 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 30 containing less than about 50 to 60 wt.% catalyst loading of nanoparticle iron 06/10/11jb19518 specificationll 12 oxide on calcium carbonate, the slurry dries to a powdery substance; for a slurry containing greater than about 60 to 70 wt.% catalyst loading of the nanoparticle iron oxide on calcium carbonate, the slurry dries to a self-supporting solid mass. Prior to incorporating the catalyst modified web-filler into the wrapper, e.g., the 5 web-filler material supporting nanoparticle carbon monoxide catalyst such as nanoparticle iron oxide catalyst/CaCO 3 particles, 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. For example, the catalyst modified web-filler can be ball milled to form a powder by milling, for example, with 1 cm 10 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. Subsequently, the catalyst modified web-filler, e.g., nanoparticle carbon monoxide catalyst/web filler material, can be incorporated into the wrapper through a papermaking process. For example, the catalyst modified web-filler can be used as filler 15 material in the papermaking processes. In a preferred embodiment, the level of web-filler material in the wrapper (both catalyst modified web-filler and/or web filler material without catalyst), can be from 3 to 50%. 100431 In another approach, particles of web-filler material, such as CaCO 3 , support the nanoparticle carbon monoxide catalyst, such as nanoparticle iron 20 oxide catalyst, by forming an aqueous slurry of the nanoparticle carbon monoxide catalyst and the web-filler material, drying the slurry to form the catalyst modified web-filler, and subsequently calcining the catalyst modified web-filler. The slurry is formed substantially as described above with respect to the first approach. After drying the slurry to form a self-supporting solid mass and ball milling to 25 form a powder (if necessary to reduce the size of the catalyst modified web-filler), the catalyst modified web-filler is calcined by heating the catalyst modified web filler to a suitable calcining temperature, e.g., up to 500EC, preferably from 200EC to 400EC, for a suitable period of time such as from 1 to 3 hours, preferably 2 hours. 06/10/11jb19518 specification,12 13 [00441 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: 1. Mix 150 lb distilled water and 25 lb CaCO 3 into 55 gallon stainless steel kettle. 5 2. Add slowly with continued mixing 25 lb NANOCAT* iron oxide nanoparticle catalyst. 3. Mix at maximum allowable rate for 2 hours after adding remaining 50 lb water. 4. Vacuum filter the slurry into filter cakes using Buchner funnel (25 cm) and 10 flask (2000 ml). 5. Cut the filter cake into small -1 inch pieces and place them in frying pans (pan: 14" - 10"-2"). 6. Freeze dry the filter cake. 15 7. Place pans in vacuum bell and vacuum dry at I1 OEC for 24 hours. 8. Mill the powders using (Rotary Mill), Ceramic Ball and cylinder for 6 hours. 9. Calcine in air for 2 hours. at 300EC. [00451 An exemplary process of making catalyst modified web filler comprising a 50/50 NANOCAT* iron oxide nanoparticle catalyst/CaCO 3 mixture utilizing 20 spray drying can be carried out as follows: 1. Prepare a catalyst mixture in water slurry by adding 1 part NANOCAT* iron oxide nanoparticle catalyst and I part of CaCO 3 with 12 parts of water by weight. Stir the mixture to get a homogenous slurry (at least 30 minutes). 25 2. Feed the slurry to a spray drying machine. 3. Adjust air temperature to obtain dry powder (e.g., 175EC air temperature). 4. Depending on the temperature used for drying calcination is optional. If carried out, calcination can be performed in air for 2 hours at 300EC. 06/10/11 jb19518 specification,13 14 [00461 The nanoparticle carbon monoxide catalyst can be fixed to the web-filler material by any suitable technique. For example, the nanoparticle carbon monoxide catalyst can be combined with the web-filler material by precipitating the nanoparticle iron oxide catalyst from a liquid phase onto the web-filler 5 material or depositing the nanoparticle iron oxide catalyst from a vapor phase onto the web-filler material. [00471 According to a preferred embodiment, the catalyst modified web-filler, e.g., the nanoparticle carbon monoxide catalyst/web-filler material, is incorporated in the wrapper through conventional papermaking processes. For 10 example, the catalyst modified web-filler can be used as all or part of the filler material in the papermaking processes or can be distributed directly onto the wrapper, such as by spraying or coating onto wet or dry base web. In production of a smoking article such as a cigarette, the wrapper is wrapped around cut filler to form a tobacco rod portion of the smoking article by a cigarette making 15 machine, which has previously been supplied or is continuously supplied with tobacco cut filler and one or more ribbons of wrapper. [00481 Any suitable tobacco mixture may be used for the cut filler. Examples of suitable types of tobacco materials include flue-cured, Burley, Maryland or Oriental tobaccos, the rare or specialty tobaccos, and blends thereof. The tobacco 20 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. 10049] In cigarette manufacture, the tobacco is normally employed in the form 25 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. 06/10/l l,jb19518 spccification,14 15 [0050] A wrapper can be any wrapping surrounding the cut filler, 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. When supplied to the cigarette making machine, the wrapper can be 5 supplied from a single bobbin in a continuous sheet (a monowrap) or from multiple bobbins (a multiwrap, such as a dual wrap from two bobbins). Further, the wrapper 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. 10 100511 The papermaking process can be carried out using conventional paper making equipment. An exemplary method of manufacturing paper wrapper, e.g., cigarette 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 15 machine. For example, an aqueous slurry (or "furnish") 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 . For example, 20 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 , A1 2 0 3 , MgCO 3 , MgO and Mg(OH) 2 . The aqueous slurry can be supplied to the 25 head box by a plurality of conduits which communicate with a source, such as a storage tank. [0052] The exemplary method can optionally include calcining the catalyst modified web-filler in a step prior to supplying the furnish to the papermaking machine. 06/10111 jb19518 specification, iS 16 [00531 The catalyst modified web-filler 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. For example, the catalyst modified web-filler can be 5 produced on site as a slurry. The aqueous slurry containing the catalyst modified web-filler can be used immediately or stored for future use. In a preferred embodiment, 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. Optionally, an aqueous slurry of furnish containing catalyst modified web 10 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. [00541 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 15 catalyst modified web-filler. For example, in a typical Fourdrinier machine, 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 20 slice onto the top surface of the endless wire to form a wet base web. Optionally, the aqueous slurry can be deposited onto a support web that is retained within the paper. For example, 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 on the Fourdrinier wire in the 25 forming section to an intermediate web, which may still retain an aqueous component, and is further processed to form a paper sheet (e.g., finished web) 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 30 support web includes a catalytic component, the incorporated catalytic component 06/10/ ljbl9518 specificalion.16 17 can be supported on a web-filler material or can be directly supported on the support web without a web-filler material. [0055] After depositing the aqueous slurry onto the forming section, water is removed from the wet base web to form an intermediate web and, with additional 5 processing such as further drying and pressing if necessary, forms a sheet of cigarette paper (e.g., finished web). The cigarette paper is subsequently taken up for storage or use, e.g. the cigarette paper is coiled in a sheet or roll. 100561 Referring to FIG. 4, a cigarette papermaking machine 200 includes a head box 202 operatively located at one end of a Fourdrinier wire 204, and source 10 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. In the usual context, the head box 202 is communicated to the run tank 206 through a plurality of 15 conduits. The run tank 206 receives furnish from a furnish supply 218. Preferably, 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. Preferably, a chalk tank 228 (containing the catalyst modified web-filler described above) is communicated with the run tank 206 so as 20 to establish a desired "chalk" level in the slurry supplied to the head box 202. 100571 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. 4, whereupon water is allowed to drain from the pulp through the wire 204 by the influence of gravity and (optionally) at some locations with the assistance of 25 vacuum boxes 210, 210', 210" at various locations along the Fourdrinier wire 204 as is the established practice in the art of cigarette papermaking. At some point along the Fourdrinier wire 204, sufficient water is removed from the base web to establish what is commonly referred to as a dry line where the texture of the slurry transforms from one of a glossy, watery appearance to a surface appearance more 30 approximating that of the finished base web (but in a wetted condition, e.g., an 06/10/1l jb19518 spccificafion,17 18 intermediate web). At and about the dry line, the moisture content of the pulp material is approximately 85 to 90%, which may vary depending upon operating conditions and the like. 100581 Downstream of the dry line, the intermediate web 212 is separated from 5 the Fourdrinier wire 204 at a couch roll 214. From there, the Fourdrinier wire 204 continues on the return loop of its endless path. Beyond the couch roll 214, 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 the intermediate web 212 to a desired final moisture content and 10 texture to form a paper 220 (e.g. finished web). Such 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. 100591 The cigarette making machine 200 can optionally include more than one 15 head box and/or more than one Fourdrinier wire with either separate or common furnish supply. Referring to FIG. 4, 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 20 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. Optionally and/or in the alternative, some or all of the catalyst modified web-filler may be introduced from the first, upstream head box 202. 25 [00601 Referring to FIG. 4, the optional second Fourdrinier wire 204', suitably integrated with a head box 202' laying slurry pulp on the Fourdrinier wire 204' and draining and drying equipment, 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 30 from the Fourdrinier wire 204 to be processed into double layer paper. Multiple 06/10/1 Ijb19518 specification,18 19 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. 100611 Other papermaking processes can be used to make a wrapper with a 5 nanoparticle carbon monoxide catalyst. For example, a laminated, bilayer or multilayer wrapper can be made. Examples of bilayer and multilayer wrappers are disclosed in commonly-owned U.S. Patent No. 5,143,098, issued to Rogers, the entire content of which is herein incorporated by reference. In an embodiment of a bilayer or multilayer wrapper including a nanoparticle carbon monoxide 10 catalyst, at least one of a radially inner layer and/or a radially outer layer can include the nanoparticle carbon monoxide catalyst as described in embodiments herein. Preferably, for cosmetic appearance due to darkening of paper containing catalyst modified web-filler with iron oxide as the nanoparticle catalyst, a radially innermost layer of the multilayer paper adjacent the cut filler in the smoking 15 article is the portion of the multilayer wrapper that includes the web-filler material that supports a nanoparticle carbon monoxide catalyst. [00621 The bilayer or multilayer single sheet wrapper may be made using ordinary paper furnish such as pulped wood, flax fibers, or any standard cellulosic fiber. Preferably flax fibers are used. Different fillers, including different 20 catalytic fillers such as the catalyst modified web-filler described herein, or different fibers may be used for each layer and may be contained in different head boxes, as disclosed in U.S. Patent No. 5,143,098, issued to Rogers, the entire content of which is herein incorporated by reference. For example, a first head box can hold the materials for a wrapper that includes the nanoparticle carbon 25 monoxide catalyst and a second head box can hold the materials for a conventional wrapper. [00631 In another example of making bilayer or multilayer single sheet wrapper, the first head box can hold the materials for a wrapper that includes the nanoparticle carbon monoxide catalyst at a first concentration or loading level and 30 a second head box can hold the materials for a wrapper that includes the 06/10/1 jb19518 specification,19 20 nanoparticle carbon monoxide catalyst at a second concentration or loading level. In preferred embodiments, the first concentration or first loading level is different from the second concentration or second loading level. For example, the wrapper can have a radially inner layer and a radially outer layer, the radially inner layer 5 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. In one embodiment, the first loading of the nanoparticle carbon monoxide catalyst is 10 up to 100 mg and the second loading of the nanoparticle carbon monoxide catalyst is less than 1 mg. Preferably, the second loading of the nanoparticle carbon monoxide catalyst is zero. In another embodiment 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 15 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 details on the manufacturing of bilayer and multilayer papers are disclosed in commonly-owned U.S. Patent No. 5,143,098, issued to Rogers, the 20 entire content of which is herein incorporated by reference. [00641 Additional examples of papermaking processes include the method for making banded smoking article wrappers disclosed in commonly-owned U.S. Patent No. 5,342,484, the entire content of which is herein incorporated by reference, and the method for producing paper having a plurality of regions of 25 variable basis weight in the cross direction disclosed in commonly-owned U.S. Patent Nos. 5,474,095 and 5,997,691, the entire contents of which are herein incorporated by reference. Further and in the alternative to incorporating nanoparticle catalyst into the web of the wrapper in a papermaking process, it is contemplated that the paper (wrapper) can be manufactured first and the 30 nanoparticle catalyst placed onto the surface. For example, the nanoparticle can 06/10/1 Ijb19518 specification,20 21 be distributed directly onto the wrapper, such as by spraying or coating onto wet base web, the intermediate web or the finished web. Further, the nanoparticle can be coated and/or printed (text or images) within the papermaking process or in a separate application of nanoparticle catalyst on-line during manufacture of the 5 cigarette. The amount of printing and/or the amount of catalyst can be varied to adjust the level of CO reduction. The use of retention aids is also contemplated. [0065] The catalyst-containing paper can be used as a wrapper 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; 10 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. [00661 FIG. 5 illustrates one type of construction of a cigarette 300, which can be used with an electrical smoking device. As shown, the cigarette 300 includes a 15 tobacco rod 360 and a filter portion 362 joined by tipping paper 364. The filter portion 362 preferably contains a tubular free-flow filter element 302 and a mouthpiece filter plug 304. The free-flow filter element 302 and mouthpiece filter plug 304 may be joined together as a combined plug 310 with plug wrap 312. The tobacco rod 360 can have various forms incorporating one or more of 20 the following items: an overwrap 371, another tubular free-flow filter element 374, a cylindrical tobacco plug 380 preferably wrapped in a plug wrap 384, a tobacco web 366 comprising a base web 368, and a void space 391. The catalyst modified web-filler is preferably incorporated into the overwrap 371, but in addition or in the alternative, could be incorporated into any one or more of the 25 plug wrap 384 or a component or components of the tobacco web 366, preferably the based web 368 thereof. 100671 FIG. 6 illustrates a cigarette 410 construction having a fuel element 411 as described in U.S. Patent No. 5,345,951, the disclosure of which is hereby incorporated by reference. The cigarette 410 includes the fuel element 411 and an 30 expansion tube 412 overwrapped by cigarette wrapping paper 414, and a filter 06/10/11 jbl9518specificafion,21 22 element 413 attached by tipping paper 405. With reference to FIG. 7, the fuel element 411 includes a heat source 420 and a flavor bed 421 which releases flavored vapors and gases when contacted by hot gases flowing through one or more longitudinal passages in the heat source. The vapors pass into the expansion 5 chamber 412 and then to mouthpiece element 413. The heat source may contain pure substantially carbon and optionally catalysts or burn additives. One or more layers of catalyst modified paper 418 surrounding the heat source 420 can be used to reduce CO produced by the heat source 420. Alternatively, or in addition thereto, catalyst modified paper can be provided downstream of the heat source 10 420, e.g., catalyst modified paper can be dispersed between the heat source and the flavor bed 421 or in the flavor bed 421. Flavor bed 421 can include any material that releases desirable flavors, e.g., tobacco filler or inert substrate on which flavor forming compounds have been deposited. 10068] The fuel element 411 is housed in a composite sleeve having a radiant 15 energy reflector sleeve 422 (e.g., perforated metallized paper) and optional inner sleeve 423 (e.g., perforated metallized paper). The inner sleeve 422 can be folded in to form a lip 424 at the upstream end thereof to hold the heat source suspended away from the interior wall of the reflector sleeve 422 with an annular space therebetween. Flavor bed 421 is held within inner sleeve 423. The wrapper 414 20 which holds the fuel element and expansion chamber 412 together preferably has sufficient porosity to allow air to be admitted through the paper 414 and support combustion of the heat source. The fuel element 411 also includes a reflective end cap 415 with one or more openings 416 to allow air into the fuel element 411. Methods to make smoking articles can include dual paper wrappers, e.g., an inner 25 wrapper and an outer wrapper. If desired, the catalyst modified paper can be used at other locations and/or for any of the paper layers of the cigarette shown in FIGS. 6 and 7. Further, while one embodiment of a fuel element cigarette is shown in FIGS. 6 and 7, the catalyst modified paper disclosed herein can be used to surround the fuel element and/or in place of paper layers in other fuel element 30 cigarette arrangements than shown in FIGS. 6 and 7. 06/10/l 1jb]9518 specificafion,22 23 [00691 FIG. 8 illustrates a cigarette 500 having a concentric tobacco rod 510 that includes an inner tube or sheath of cigarette wrapper 515 whose web-filler material supports a nanoparticle carbon monoxide catalyst, such as an iron oxide and/or any other oxidation catalyst described herein. As shown, the cigarette 500 5 comprises a filter 505 and a tobacco rod 510 which are attached to one another with tipping paper 511 in a conventional fashion. The tobacco rod 510 is a "concentric core" or "coaxial" layout that can be produced on a Hauni Baby rod making machine available from Hauni Machinenbau AG of Hamburg, Gemany. An inner core region 512 is defined by the inner wrapper 515, which is 10 surrounded by tobacco cut filler material 520. An outer cigarette wrapper 525 extends along the outside of the tobacco rod 510. The filter 505 can comprise one or more plugs of cellulose tow and optionally could include an adsorbent such as carbon. In this embodiment, any coloration in the inner wrapper 515 is hidden from view. 15 100701 The central core region 512 can be hollow and/or can be partially or wholly filled with tobacco cut filler and is preferably approximately 2-5 mm in diameter, more preferably 2-3 mm in diameter. In one alternative, the inner wrapper 515 can be constructed in a layered arrangement with at least one of the layers formed of catalytic paper wherein a nanoparticle catalyst, such as 20 nanoparticle iron oxide, is supported on a web-filler material, such a CaCO 3 . Optionally, the outer wrapper 525 may be constructed similarly to include a nanocatalyst. [0071] Optionally, the central tube can be constructed such that heat applied to an end of the tube will cause the end portion of the tube to collapse upon itself and 25 seal off (or close) the end of the tube. The collapsing feature can be achieved by a number of different embodiments of the central tube. In an alternative where the central tube collapses when heat is applied, the central tube 515 can be constructed in a layer arrangement such that an outer or top layer is made from a material having a higher thermal expansion coefficient than an inner or bottom 30 layer. As a result, when the end of the tube is heated, the difference in thermal 06/10/1 1jb19518 specification,23 24 expansion coefficient between the two layers will result in the end portion of the tube collapsing upon itself and, optionally, sealing off the end. The layers of the central tube 515 can be constructed from different types of paper having the different thermal expansion coefficients. The difference in thermal expansion 5 coefficients of the layers can be a result of the types of paper having different proportions of cellulose and/or different binders. One or more of the different types of paper can be a catalytic paper wherein a nanoparticle catalyst, such as nanoparticle iron oxide, is supported on a web-filler material, such as CaCO 3 . Alternatively, other polymeric, starch or cellulosic based films can be used for the 10 central tube 515, anyone of which can include the catalyst modified web-filler. [0072] If desired, the catalytic paper can be used at other locations and/or for any of the paper layers of the cigarette shown in FIG. 8. Further, while one embodiment of a cigarette with a porous heat transfer tube is shown in FIG. 8, the catalytic paper disclosed herein can be used to surround the tobacco rod portion, 15 or can be used as the wrapper, be incorporated into a cellulosic component of the filter portion, and/or in place of paper layers in other porous heat transfer tube cigarette arrangements than shown in FIG. 8. [0073] Referring now to the embodiment of FIGS. 2(a) and 2(b), the inner wrapper and the outer wrapper are individual wrappers formed in separate 20 papermaking processes and later wrapped around tobacco cut filler to from a cigarette tobacco rod. The inner wrapper, the outer wrapper or both wrappers can include the catalyst modified web-filler, e.g., the nanoparticle carbon monoxide catalyst supported by a web-filler material. In examples where both wrappers include a catalyst modified web-filler, the specific nanoparticle carbon monoxide 25 catalyst and the catalyst loading in each wrapper can be the same or different. In some embodiments, the addition of a catalyst modified web-filler can discolor the wrapper, e.g., the wrapper becomes non-white or brown. For aesthetic reasons, an outer wrapper that is a conventional color, e.g., white, can be placed around the inner wrapper. Both the inner wrapper and the outer wrapper can be selected to 30 give a desired smoking article performance with respect to smoking article 06/10/1 1jb19518 specification,24 25 properties, such as puff count, tar, bum rate, and ash appearance. Accordingly and as shown and described, for example, with reference to FIGS. 2(a) and 2(b), preferred embodiments of smoking articles and methods of making smoking articles can include a tobacco rod portion of a cigarette with a nanoparticle carbon 5 monoxide catalyst supported on the web-filler material of a first wrapper with a second outermost wrapper, which does not contain the catalyst modified web filler. Also with reference to FIG. 8, the central tube formed with catalytic paper can satisfy aesthetics by placing the catalytic paper in the interior of the smoking article. 10 [0074] An exemplary wrapper for a smoking article comprises a paper web including cellulosic fibers and a catalyst modified web-filler incorporated into the paper web. The catalyst modified web-filler includes a web-filler material supporting a nanoparticle carbon monoxide catalyst. [0075] The wrapper can be any suitable conventional wrapper. For example, a 15 preferred wrapper can have a basis weight of from about 18 g/m2 to about 60 g/m 2 and a permeability of from about 5 CORESTA units to about 80 CORESTA units. More preferably, the wrapper 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. However, any suitable basis weight for the wrapper can be selected. For example, a higher basis 20 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. [00761 Other permeabilities of the wrapper (as measured by CORESTA units) can be selected based on the application and location of the wrapper. For example, in multilayer wrappers the permeability of a first layer can be up to 25 30,000 CORESTA units, although a permeability that is lower or higher can be utilized. Thickness of single-layer wrapper can preferably be from 15 to 100 microns, more preferably from 20 to 50 microns. Additional layers in a multilayer wrapper can be from 0.1 to 10 times the permeability of the first layer and can have a thickness of from 0.1 to 2 times the thickness of the first layer. 30 Both the permeability and the thickness of the first layer and the second layer can 06/10/l1 jb195 18 specification,25 26 be selected to achieve a desired total air permeability and total thickness for the smoking article. [00771 Nanoparticle carbon monoxide catalyst loaded wrappers were produced and compared to wrappers without the nanoparticle carbon monoxide catalyst. 5 Table 1 summarizes selected properties of a control paper (designated X) and a wrapper paper with a catalyst modified web-filler, e.g., nanoparticle carbon monoxide catalyst/support material (designated Y) as a filler material. The nanoparticle carbon monoxide catalyst was nanoparticle iron oxide catalyst in the form of iron oxide and was supported on the CaCO 3 web-filler material at 25 10 wt.% catalyst loading. The nanoparticle carbon monoxide catalyst/web-filler material was formed as described herein from a slurry without calcining. Table 1 - Selected Properties of Wrapper with Catalyst Modified Web-filler as Compared to Paper Wrapper Without Catalyst Modified Web-filler Catalyst Catalyst Loading in Modified Total Catalyst fie Catalyst Web-Filler Modified Web-filler Loading Sample Material Web-filler Loading in ng Weight (CORESTA Matere Wrapper S e (g/m 2) Units) catalyst (% paper filler Sample loading) loading) X CaCO 3 ----- 30 ---- 45V1 33V5 (ALBACAR7 5970) Y nanoparticle 25 30 7.5 45VI 33V5 iron oxide catalyst/CaCO 3 particles 15 [00781 The nanoparticle carbon monoxide catalyst to web-filler material ratio can be varied by subjecting a slurry of nanoparticle carbon monoxide catalyst/web-filler material, e.g., the slurry of nanoparticle iron oxide 06/10/1 1jbl9518 specification.26 27 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, 5 and temperature can all be adjusted to achieve a desired uniformity of the nanoparticle carbon monoxide catalyst to web-filler material ratio. Alternatively, 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 10 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. [00791 While not wishing to be bound by theory, it appears that CO catalyst in the form of nanoparticle iron oxide catalyst, such as NANOCAT7 Superfine Iron 15 Oxide, starts to convert CO to CO 2 at a temperature above 150EC, preferably at a temperature above 400EC. Additionally, 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. Together, 20 the operating temperature and the air flow within the smoking article can affect the operation of the nanoparticle carbon monoxide catalyst. [00801 During the puffing process, CO in mainstream smoke flows toward the filter end of a smoking article. As carbon monoxide travels within the smoking article, oxygen diffuses into and carbon monoxide diffuses out of the smoking 25 article through the paper wrapper. After a typical 2-second puff of a cigarette, CO is concentrated in the periphery of the cigarette, e.g., near the cigarette wrapper, in front of the burn zone. The oxygen concentration is high in the same region as high CO concentration due to diffusion of 02 from outside the cigarette. Airflow into the tobacco rod is largest near the burn zone on the periphery of the smoking 30 article and is approximately commensurate with the gradient of temperature, e.g, 06/10/1 1Jb19518 specification.27 28 larger airflow is associated with higher temperature gradients. Thus, the highest airflow is also the region of highest temperature gradient. For example in a typical smoking article, the highest temperature gradient is from >850-900EC at the periphery of the smoking article at the burn zone to approximately 300EC 5 toward the center of the smoking article. The temperature further drops to near ambient near the filter end. Furthermore, 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. Further information on airflow patterns, the formation of constituents in cigarettes during smoking and smoke 10 formation and delivery can be found in Richard R. Baker, "Mechanism of Smoke Formation and Delivery", Recent Advances in Tobacco Science, vol. 6, pp. 184 224, (1980) and Richard R. Baker, "Variation of the Gas Formation Regions within a Cigarette Combustion Coal during the Smoking Cycle", Beitrage zur Tabakforschung International, vol. 11, no. 1, pp. 1-17, (1981), the contents of both 15 are incorporated herein by reference. 100811 The position and quantity of nanoparticle carbon monoxide catalyst in the wrapper 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 C0 2 , by depositing 20 aqueous slurry with catalyst modified web-filler selectively during the papermaking process. For example, the 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. Thus, a nanoparticle carbon monoxide catalyst can be selected that 25 operates in a given temperature range, and a wrapper can be manufactured in which the catalyst modified web-filler, e.g., nanoparticle iron oxide catalyst/CaCO 3 , can be incorporated in those portions of the wrapper that are predicted to coincide with the appropriate temperature for operation of the catalyst. The selective incorporation of catalyst modified web-filler can be 30 realized, for example, by using different head boxes containing the selected 06/10/1 Ijb19518 specification.28 29 concentration of catalyst modified web-filler and/or locating head boxes with different concentrations of catalyst modified web-filler at selected positions in the papermaking process corresponding to selected locations of the catalytic paper to be produced. 5 [00821 For example, a preferred nanoparticle carbon monoxide catalyst for use in a wrapper for a smoking article is catalytically active at temperatures as low as ambient temperature and preferably does not deactivate even at temperatures as high as 900E C. The preferred nanoparticle carbon monoxide catalyst can be positioned along the entire axial length of the anticipated burn zone, e.g., not only 10 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 nanoparticle carbon monoxide catalyst provides sufficient contact time between the mainstream smoke and the nanoparticle carbon monoxide catalyst for the CO to be converted to CO 2 . An example of a preferred nanoparticle carbon monoxide catalyst includes 15 NANOCAT7 Superfine Iron Oxide, which starts to convert CO to CO 2 at a temperature above 150EC. [0083] In a further example, 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 20 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. For example, 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 wrapper at which 25 conversion occurs. [00841 Although 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 affected. 06/10/I1 jb19518 specification,29 30 [0085] Samples of wrapper with CaCO 3 web-filler and wrapper with catalyst modified web-filler, e.g., nanoparticle iron oxide catalyst/CaCO3 web-filler material, were produced and tested in smoking article configurations under standard FTC testing conditions. The nanoparticle iron oxide catalyst was 5 NANOCAT7 Superfine Iron Oxide. CaCO 3 supported the nanoparticle iron oxide catalyst and was produced by a slurry method without calcining. Nanoparticle iron oxide catalyst loadings in the catalyst modified web-filler of from 15 wt.% to 50 wt.% were tested and compared to a control sample without nanoparticle iron oxide catalyst. Characteristics of sheets containing 30% web-filler loading (either 10 CaCO 3 web-filler material or catalyst modified web-filler) at two different basis weights of paper (35 g/m 2 and 45 g/m 2 ) were investigated. The smoking article configuration included a rod length of 63 mm having a diameter of about 8 mm and a full flavor filter having a length of 21 mm. Each sample had the same conventional tobacco blend. In each category 20 cigarettes were smoked. The 15 average results for mainstream smoke are summarized in Table 2. Table 2 - Average Results for Mainstream Smoke Catalyst % reduction 45 g/m 2 Loading in Tar Puff Ct. CO CO:Tar in CO:Tar Samples Web-Filler (mg/Cig.) (puff/Cig.) (mg/Cig.) Ratio compared to (wt.%) Control 1 0 17.7 8.1 18.3 1.03 control II 15 15.6 8.1 12.3 0.79 24 III 25 15.9 8.2 11.6 0.73 29 06/10/1 lJbl9518 specification,.30 31 IV 50 14.4 8.7 9.9 0.69 34 Catalyst % reduction 35 g/m 2 Loading in Tar Puff Ct. CO CO:Tar in CO:Tar Samples Web-Filler (mg/Cig.) (puff/Cig.) (mg/Cig.) Ratio compared to (wt.%) Control i 0 18.1 8.2 16.6 0.92 Control iii 25 17.0 8.2 11.6 0.68 26 iv 50 14.5 8.7 9.5 0.66 29 [0086] The results in Table 2 indicate that there is an increasing reduction in CO:Tar ratio in the test cigarettes made with wrapper having catalyst modified web-filler as compared to the control cigarette. The percent reduction in CO:Tar 5 ratio increases from 24% to 34% as the catalyst increases from 15 wt.% to 50 wt.% catalyst loading in the catalyst modified web-filler. Coincident to the reduction in CO:Tar, there is little variation (e.g., <1 or <10%) in the puff count. Further, the CO:Tar ratio decreased indicating correlation between the CO catalyst and the reduction in CO. When used in paper, the nanoparticle catalyst was more 10 selective to CO and CO was reduced by a greater proportion than Tar. Advantageously, the impact of the CO catalysis upon tar level is reduced. The amount of catalyst used in the wrapper for each cigarette is about 4 to 8 mg/cigarette, depending on the loading levels. 100871 Table 3 illustrates comparative test results of conventional cigarette 15 designs hand made without a filter. Sample A was wrapped in a handmade 45 g/m2 wrapper without catalyst modified web-filler and Sample I was wrapped in a 06/10/11 ljb19518 specification,31 32 handmade 45g/m 2 wrapper having embedded catalyst modified web-filler, e.g., nanoparticle iron oxide catalyst fixed to CaCO 3 support material. In the Sample I shown, the embedded nanoparticle iron oxide catalyst loading in the catalyst modified web-filler was 30 wt.% catalyst loading of NANOCAT7 Superfine Iron 5 Oxide with respect to the catalyst modified web-filler (about 9 wt.% catalyst loading with respect to the wrapper). The smoking article configuration included a rod length of 63 mm having a diameter of about 8 mm and a full flavor filter having a length of 21 mm. Each sample had the same conventional tobacco blend. The two sample cigarettes were then tested under the standard FTC conditions. Table 3 10 shows the change in properties of the two cigarettes. Table 3 - Comparative Test Results of Select Properties of Designated Cigarettes Sample Puff Total TPM/puff CO CO/puff CO/TPM Particulate (mg) Matter (TPM) (mg) Sample A 7.5 50.5 6.7 21.3 2.8 0.42 Sample I 8.3 48.7 5.9 13.5 1.6 0.28 change (%) +10.3 -3.6 -11.9 -36.6 -42.9 -33.3 [00881 FIG. 9 shows the conversation of CO to CO 2 for a 50 mg sample (A) of 15 NANOCAT7 Superfine Iron Oxide (Trace i) and a sample (B) of 100 mg mixture of 25 wt.% catalyst loading of NANOCAT7 Superfine Iron Oxide and CaCO 3 (Trace ii). In FIG. 9, the conversion of CO to CO 2 was investigated as a function of temperature in a flow tube reactor containing the samples (A) and (B) and an atmosphere with 3.7% 02 and 22% CO. The flow rate was 1000 ml/minute and the 20 heating rate was 12EC/minute. For both the sample of NANOCAT7 Superfine Iron Oxide and the mixture of NANOCAT7 Superfine Iron Oxide and CaCO 3 the onset of conversion occurs at about 100-125EC, indicating that the activation temperature of NANOCAT7 Superfine Iron Oxide is not substantially affected by the CaCO 3 . [00891 A calcination process was also investigated for heat treating the 25 NANOCAT* Superfine Iron Oxide on CaCO 3 . Calcination is achieved by taking 06/10/l 1 jb19518 specification,32 33 catalysts from the slurry method and heating them in the presence of air for an extended duration. For example, calcining at a temperature of no more than 500EC, preferably from 200EC to 400EC, for a period of time of from I to 3 hours, e.g., 2 hours. Without being held to any one theory, it is believed that a calcination step can 5 improve the bonding between the catalyst and the web-filler material and that during the calcination step the catalyst surface is improved due to evaporation of bound water molecules. [00901 FIG. 10 shows the effect of calcination of NANOCAT7 Superfine Iron Oxide and CaCO 3 at a 30 wt.% catalyst loading in the catalyst modified web-filler. 10 The conversion of CO to CO 2 was determined as a function of temperature in a flow tube reactor containing catalyst modified web-filler. The atmosphere included 20.6 % 02 and 3.4 % CO and the atmosphere flow rate was 1000 ml/minute. The heating rate was 12EC/minute. Five traces are presented in FIG 10. Trace A represents results of the catalyst modified web-filler without calcination, Trace B represents a 15 sample of catalyst modified web-filler calcined at 200EC for 2 hours, Trace C represents a sample of catalyst modified web-filler calcined at 300EC for 2 hours, Trace D represents a sample of catalyst modified web-filler calcined 400EC for 2 hours, and Trace E represents a sample of catalyst modified web-filler calcined at 500EC for 1 hour. As indicated by an increase in conversion to C0 2 , the onset 20 temperature and the conversion percentage is substantially unchanged between the four samples. At temperatures above about 400EC, all calcined samples had higher conversion percentages than the noncalcined sample (Trace A). [00911 Based on the CO to CO 2 conversion percent, in the exemplary embodiment the nanoparticle carbon monoxide catalyst is present in an amount effective to 25 convert at least 10% of carbon monoxide to carbon dioxide at a temperature of at least 400EC to about 900EC. Preferably, the nanoparticle carbon monoxide catalyst converts at least 25% of carbon monoxide to carbon dioxide at a temperature of at least 500EC. More preferably, the nanoparticle carbon monoxide catalyst converts at least 50% of carbon monoxide to carbon dioxide at a temperature of at least 700EC. 30 100921 Following the investigation into the effect of calcination, the surface area of the supported catalyst was investigated using BET surface area measurements. Three samples were tested: Sample I was as-prepared 30 wt.% catalyst loaded 06/10/1 ljbI9518 specification.33 34 NANOCAT7 Superfine Iron Oxide and CaCO 3 , Sample 2 was 30 wt.% catalyst loaded NANOCAT7 Superfine Iron Oxide and CaCO 3 calcined at 400EC for 2 hours, and sample 3 was CaCO 3 formed by chemical precipitation (so called precipitated calcium carbonate (PCC), as opposed to natural ground CaCO 3 , so called 5 ground calcium carbonate (GCC)) and was used as a control sample. All samples were outgassed at 150EC for 1 hour prior to the BET measurement. 100931 It was observed that the BET surface areas for the samples with NANOCAT7 Superfine Iron Oxide, e.g., Samples 1 and 2, had approximately the same BET surface areas before and after calcination, e.g., within 10%, and that the 10 BET surface area of these samples were approximately an order of magnitude greater than the BET surface area of samples without the nanoparticle carbon monoxide catalyst, e.g., Sample 3. Thus, Samples 1 and 2 indicate that calcining does not have an adverse effect on the catalyst surface area available for conversion of CO to CO 2 . [00941 In another exemplary embodiment, a low temperature nanoparticle carbon 15 monoxide catalyst can be used, either alone or in combination with another catalyst, as a nanoparticle carbon monoxide catalyst. 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 wrapper. 20 [00951 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 commonly owned U.S. Patent Application No. 10/314,449 entitled "CERIA-BASED CATALYSTS FOR CO OXIDATION AT NEAR-AMBIENT TEMPERATURES" 25 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 0 3 , CuO, CeO 2 , or Ce 2 0 3 , a doped metal oxide, such as Y 2 0 3 doped with 30 zirconium or Mn 2

O

3 doped with palladium, or mixtures thereof as disclosed in commonly-owned U.S. Patent Application No. 10/286,968 entitled "OXIDANT/CATALYST NANOPARTICLES TO REDUCE TOBACCO SMOKE 06/l0/1 1jb19518 spccification,34 35 CONSTITUENTS SUCH AS CARBON MONOXIDE" and filed on November 4, 2002, the entire contents of which are herein incorporated by reference. [0096] In addition, any of the wrappers, smoking articles or methods described herein can include additional additives conventionally used in wrappers for smoking 5 articles. These additives can include, for example, additives to control the appearance, e.g., color, of the wrapper, additives to control the burn rate of the wrapper, and/or additives to result in a desired ash appearance and/or web-fillers used in cigarette paper. [0097] The method can be implemented in an easy to use and economical manner 10 as explained herein. The catalyst modified web-filler can be used to: (1) remove carbon monoxide in the mainstream cigarette smoke or sidestream smoke of smoking articles; (2) reduce or eliminate particle entrainment since the catalyst is embedded in the wrapper; (3) remove a target constituent, such as carbon monoxide, highly selectively since the catalyst in the wrapper only catalyzes those gases that are near 15 the wrapper and/or for which the catalyst has an affinity; and/or (4) easily implement in large scale production through the papermaking process. 100981 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. In the 20 preferred embodiment, 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. Optionally, an expanded tobacco component might be included in the blend to adjust rod density, and flavors may be added. Optionally, a single variety of the aforementioned tobaccos may be used 25 instead of a blend. 100991 Although the present invention has been described in connection with exemplary embodiments thereof, it will be appreciated by those skilled in the art that additions, deletions, modifications, and substitutions not specifically described may be made without departing from the spirit and scope of the invention as defined in 30 the appended claims. 06/10/1 1jbl9518 specification,35 36 101001 This Application is a divisional of the present Applicant's Australian Patent Application No. 2004246883, and the whole contents thereof are incorporated herein by reference. 101011 Throughout this specification and the claims which follow, unless the 5 context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. 101021 The reference to any prior art in this specification is not and should not be 10 taken as an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge in Australia. 06/10/1 Ijb19518 specification.36

Claims (41)

1. 2. A catalyst modified web-filler according to claim 1, wherein the nanoparticle carbon monoxide catalyst includes nanoparticle iron oxide catalyst. 10
2. 3. A wrapper for a smoking article, the wrapper including: a web; and a catalyst modified web-filler according to claim 1. 15 4. A wrapper according to claim 3, wherein the web includes cellulosic fibers.
3. 5. A wrapper according to claim 3 or 4, wherein the nanoparticle carbon monoxide catalyst includes a nanoparticle iron oxide catalyst. 20 6. A wrapper according to claim 5, wherein the nanoparticle carbon monoxide catalyst further includes a nanoparticle catalyst other than iron oxide.
4. 7. A wrapper according to claim 5 or 6, wherein the nanoparticle iron oxide catalyst includes FeOOH, a-Fe2O3, y-Fe2O3, or mixtures thereof. 25
5. 8. A wrapper according to any one of claims 3 to 7, wherein the web-filler material includes an oxide, a carbonate, or a hydroxide of a Group II, Group III, or Group IV metal. 30 9. A smoking article including a tobacco rod having a wrapper according to any one of claims 3 to 8. 06/0/11 IjbI9518 specification.37 38
6. 10. A smoking article according to claim 9, wherein a ratio, in weight percent, of the nanoparticle carbon monoxide catalyst to the web-filler is from 0.1 to 3.0, preferably from 0.1 to 1.0, more preferably from 0.33 to 1.0. 5 11. A smoking article according to claim 9 or 10, wherein a total amount of nanoparticle carbon monoxide catalyst in the wrapper is up to 100 mg.
7. 12. A smoking article according to claim 9, 10 or 11, wherein the wrapper is a plug wrap, an overwrap or a tobacco web of the smoking article. 10
8. 13. A smoking article according to any one of claims 9 to 12, wherein the wrapper overwraps a fuel element and/or an expansion tube of the smoking article.
9. 14. A smoking article according to any one of claims 9 to 13, wherein the 15 wrapper surrounds a heat source of the smoking article.
10. 15. A smoking article according to any one of claims 9 to 14, wherein the wrapper is between a heat source and a flavor bed. 20 16. A smoking article according to claim 9, 10 or 11, wherein the wrapper is an inner tube surrounded by tobacco cut filler.
11. 17. A smoking article according to claim 16, wherein the inner tube is hollow. 25 18. A smoking article according to claim 16, wherein the inner tube is at least partially filled with tobacco cut filler.
12. 19. A smoking article according to any one of claims 9 to 18, wherein the nanoparticle catalyst includes a nanoparticle iron oxide catalyst and the web-filler 30 material includes calcium carbonate. 06/10/1 jb19518 specification.38 39
13. 20. A smoking article according to claim 19, wherein the nanoparticle iron oxide catalyst has an average particle size of 0.1 to 10 nm and the calcium carbonate includes 10 to 60 % by weight of the wrapper. 5 21. A smoking article according to claim 9, wherein the smoking article is a cigarette, the wrapper includes a web of fibrous cellulosic material and at least some of the web-filler material includes a mineral particle.
14. 22. A smoking article according to claim 21, wherein the mineral particle 10 includes at least one of calcium carbonate, titanium dioxide, silicon dioxide, alumina, magnesium carbonate, magnesium oxide, and magnesium hydroxide and the nanoparticle catalyst includes iron oxide.
15. 23. A smoking article according to claim 22, wherein the nanoparticle catalyst 15 further includes a nanoparticle other than iron oxide.
16. 24. A smoking article according to claim 22 or 23, wherein the nanoparticle catalyst includes FeOOH, a-Fe2O3, y-Fe2O3, or mixtures thereof. 20 25. A smoking article according to claim 9, wherein the wrapper has a radially inner portion and a radially outer portion, the radially inner portion having a first loading of the nanoparticle carbon monoxide catalyst and the radially outer portion having a second loading of the nanoparticle carbon monoxide catalyst. 25 26. A smoking article according to claim 25, wherein the first loading of the nanoparticle carbon monoxide catalyst is greater than the second loading of the nanoparticle carbon monoxide catalyst.
17. 27. A smoking article according to claim 26, wherein the first loading of the 30 nanoparticle carbon monoxide catalyst is up to 100 mg. 06/10/1l jb19518 specification.3) 40
18. 28. A smoking article according to claim 25, wherein a ratio, in weight percent, of the nanoparticle carbon monoxide catalyst to the web-filler material in the radially inner portion is from 0.1 to 3.0, preferably from 0.1 to 1.0, more preferably from 0.33 to 1.0. 5
19. 29. A smoking article according to any of claims 25 to 28, wherein the second loading of the nanoparticle carbon monoxide catalyst is less than I mg, preferably zero. 10 30. A smoking article according to claim 9 or 25, wherein the nanoparticle carbon monoxide catalyst includes nanoparticle iron oxide catalyst.
20. 31. A smoking article according to claim 9, wherein the wrapper is a first wrapper and the smoking article further includes a second wrapper. 15
21. 32. A method of making a catalyst modified web-filler according to claim 1, the method including the steps of: (i) forming an aqueous slurry of the nanoparticle carbon monoxide catalyst and the web-filler material; 20 (ii) optionally spreading the aqueous slurry on a support surface; and (iii) drying the aqueous slurry to evaporate water and to form the catalyst modified web-filler.
22. 33. A method according to claim 32, wherein the nanoparticle carbon monoxide 25 catalyst includes nanoparticle iron oxide catalyst.
23. 34. A method according to claim 32 or 33, wherein the nanoparticle carbon monoxide catalyst is a nanoparticle iron oxide catalyst and the web-filler material is calcium carbonate. 30
24. 35. A method of making a catalyst modified web-filler according to claim 1, the method including the steps of: 06/10/11 jb19518 specification.40 41 (i) precipitating the nanoparticle carbon monoxide catalyst from a liquid phase onto the web-filler material; (ii) removing at least a portion of the liquid phase; and (iii) drying the web-filler material with the precipitated nanoparticle carbon 5 monoxide to evaporate a remainder of the liquid phase and to form the catalyst modified web-filler.
25. 36. A method of making a catalyst modified web-filler according to claim 1, the method including the steps of: 10 depositing the nanoparticle carbon monoxide catalyst from a vapor phase onto the web-filler material, wherein the nanoparticle carbon monoxide catalyst includes FeOOH, a-Fe2O3, y-Fe2O3, or mixtures thereof and the web-filler material is selected from the group consisting of CaCO3, TiO2, SiO2, A1203, MgCO3, MgO and Mg(OH)2. 15
26. 37. A method of manufacturing a wrapper according to claim 3, the method includes the steps of: (i) supplying the catalyst modified web-filler and a cellulosic material to a head box of a forming section of a papermaking machine; 20 (ii) depositing an aqueous slurry including the catalyst modified web-filler and the cellulosic material onto the forming section of the papermaking machine to form a base web with the catalyst modified web-filler distributed therein; and (iii) removing water from the base web so as to form a sheet of intermediate web. 25
27. 38. A method according to claim 37, wherein the nanoparticle carbon monoxide catalyst includes a nanoparticle iron oxide catalyst, the web-filler material includes CaCO3, and the method includes calcining the catalyst modified web-filler prior to supplying the catalyst modified web-filler to the papermaking machine. 30
28. 39. A method of manufacturing a wrapper according to claim 3, the method including the steps of: 06/10/11 jb19518 specification,41 42 (i) supplying a cellulosic material to a head box of a forming section of a papermaking machine; (ii) depositing an aqueous slurry from the head box onto the forming section of the papermaking machine so as to form a base web of the cellulosic material; 5 (iii) distributing the catalyst modified web-filler on the base web; and (iv) removing water from the base web so as to form a sheet of intermediate web.
29. 40. A method according to claim 39, wherein step (iii) includes distributing the 10 catalyst modified web-filler on a portion of the base web.
30. 41. A method according to claim 40, wherein the catalyst modified web-filler forms a band, a stripe, or a lattice pattern. 15 42. A method of manufacturing a wrapper according to claim 3, the method including the steps of: (i) supplying a furnish including a cellulosic material to a head box of a forming section of a papermaking machine, (ii) transporting a support web through the papermaking machine; 20 (iii) depositing the catalyst modified web-filler onto the support web; (iv) depositing an aqueous slurry from the head box onto the support web so as to form a pulp web of the cellulosic material with the support web embedded therein; (v) removing water from the pulp web so as to form a sheet; and 25 (vi) taking up the sheet.
31. 43. A method of manufacturing a wrapper according to claim 3, wherein the wrapper is a bilayer wrapper, the method including the steps of: (i) depositing a first layer of the bilayer wrapper from a first head box onto a 30 wire of a papermaking machine, the first head box holding a first furnish composition; 06/10/1 IjbI9518 specification.42 43 (ii) depositing a second layer of the bilayer wrapper from a second head box onto a portion of the first layer, the second head box holding a second furnish composition, the second furnish composition, including the catalyst modified web filler; 5 (iii) removing water from the first layer and the second layer so as to form a single sheet; and (iv) taking up the sheet.
32. 44. A method according to claim 43, wherein the portion of the second layer 10 deposited in step (ii) forms a band, a stripe, or a lattice pattern.
33. 45. A method according to claim 44, wherein the portion is in the finished web.
34. 46. A method according to claim 43, 44 or 45, wherein the second furnish 15 composition includes a retention aid.
35. 47. A method according to any one of claims 43 to 46, including calcining the catalyst modified web-filler. 20 48. A method according to any one of claims 43 to 47, wherein the first furnish composition is free of catalyst modified web-filler.
36. 49. A method of making a smoking article according to claim 9, said method including the steps of: 25 (i) incorporating the nanoparticle carbon monoxide catalyst with the web filler material to form the catalyst modified web-filler utilized in production of the wrapper; (ii) making the wrapper; (iii) providing a cut filler comprising tobacco to a cigarette making machine; 30 and (iv) placing the wrapper around the cut filler to form a tobacco rod portion of the smoking article. 06/10/1 .jbI 9518 specification.43 44
37. 50. A method according to claim 49, wherein the wrapper is a first wrapper and the method further includes: (v) placing a second wrapper around the tobacco rod portion. 5
38. 51. A method according to claim 50, wherein the second wrapper is radially outward from the first wrapper.
39. 52. A method according to claim 49, 50 or 51, wherein the nanoparticle carbon 10 monoxide catalyst is incorporated with the web-filler material by precipitating a nanoparticle iron oxide catalyst from a liquid phase onto the web-filler material or depositing a nanoparticle iron oxide catalyst from a vapor phase onto the web-filler material. 15 53. A method according to claim 52, wherein the nanoparticle carbon monoxide catalyst is incorporated with the web-filler material by precipitating the nanoparticle iron oxide catalyst and the web-filler material is also precipitated to form the catalyst modified web-filler. 20 54. A method according to any one of claims 49 to 53, wherein the nanoparticle carbon monoxide catalyst includes a nanoparticle iron oxide catalyst and the web filler material includes calcium carbonate.
40. 55. A method according to claim 54, wherein the nanoparticle carbon monoxide 25 catalyst further includes a nanoparticle catalyst other than iron oxide.
41. 56. A method according to claim 49, wherein the nanoparticle carbon monoxide catalyst is incorporated with the web-filler material by forming an aqueous slurry of the nanoparticle carbon monoxide catalyst and the web-filler material, drying the 30 slurry to form agglomerates of the nanoparticle catalyst modified web-filler, reducing an average particle size of the agglomerates, and subsequently calcining the catalyst modified web-filler prior to step (ii). 06/10/11 .jh19518 spcCification,44