US20050274390A1 - Ultra-fine particle catalysts for carbonaceous fuel elements - Google Patents

Ultra-fine particle catalysts for carbonaceous fuel elements Download PDF

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US20050274390A1
US20050274390A1 US10/868,126 US86812604A US2005274390A1 US 20050274390 A1 US20050274390 A1 US 20050274390A1 US 86812604 A US86812604 A US 86812604A US 2005274390 A1 US2005274390 A1 US 2005274390A1
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fuel element
carbon monoxide
carbon
ultrafine particles
catalyst composition
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US10/868,126
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Chandra Banerjee
Stephen Sears
Sheila Cash
Henry Chung
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R J Reynolds Tobacco Co
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R J Reynolds Tobacco Co
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Priority to US10/868,126 priority Critical patent/US20050274390A1/en
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Assigned to R. J. REYNOLDS TOBACCO COMPANY reassignment R. J. REYNOLDS TOBACCO COMPANY MERGER (SEE DOCUMENT FOR DETAILS). Assignors: BROWN & WILLIAMSON U.S.A., INC., R. J. REYNOLDS TOBACCO COMPANY
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Publication of US20050274390A1 publication Critical patent/US20050274390A1/en
Assigned to JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT reassignment JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: R.J. REYNOLDS TOBACCO COMPANY
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    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SMOKERS' REQUISITES
    • A24FSMOKERS' REQUISITES; MATCH BOXES
    • A24F47/00Smokers' requisites not provided for elsewhere, e.g. devices to assist in stopping or limiting smoking
    • A24F47/002Simulated smoking devices, e.g. imitation cigarettes
    • A24F47/004Simulated smoking devices, e.g. imitation cigarettes with heating means, e.g. carbon fuel
    • A24F47/006Simulated smoking devices, e.g. imitation cigarettes with heating means, e.g. carbon fuel with chemical heating means
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes
    • A24B15/10Chemical features of tobacco products or tobacco substitutes
    • A24B15/16Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
    • A24B15/165Chemical features of tobacco products or tobacco substitutes of tobacco substitutes comprising as heat source a carbon fuel or an oxidized or thermally degraded carbonaceous fuel, e.g. carbohydrates, cellulosic material
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/28Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/285Treatment of tobacco products or tobacco substitutes by chemical substances characterised by structural features, e.g. particle shape or size
    • A24B15/286Nanoparticles
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/28Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/287Treatment of tobacco products or tobacco substitutes by chemical substances by inorganic substances only
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/28Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/287Treatment of tobacco products or tobacco substitutes by chemical substances by inorganic substances only
    • A24B15/288Catalysts or catalytic material, e.g. included in the wrapping material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063Titanium; Oxides or hydroxides thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48Silver or gold
    • B01J23/52Gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/745Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/0013Colloids
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/26Conditioning of the fluid carrier; Flow patterns
    • G01N30/38Flow patterns
    • G01N30/46Flow patterns using more than one column
    • G01N30/466Flow patterns using more than one column with separation columns in parallel
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/62Detectors specially adapted therefor
    • G01N30/72Mass spectrometers
    • G01N30/7206Mass spectrometers interfaced to gas chromatograph

Abstract

The present invention provides fuel elements comprising a carbonaceous material and a catalyst composition comprising ultrafine particles of a metal oxide and/or metal. The present invention additionally provides smoking articles demonstrating reduced amounts of carbon monoxide in the smoke-like aerosol produced by the smoking article. In a further aspect, the present invention provides methods and apparatus for the simultaneous resolution and quantification of a carbon monoxide content and a carbon dioxide content of a gaseous mixture.

Description

    Field of the Invention
  • The present invention relates generally to fuel elements for smoking articles, and more particularly to fuel elements comprising a carbonaceous material and ultrafine particles. In an embodiment, the fuel elements may be utilized in smoking articles to reduce the amount of carbon monoxide in the mainstream smoke and improve the thermal efficiency of the fuel.
  • BACKGROUND OF THE INVENTION
  • Cigarettes are popular smoking articles that use tobacco in various forms. Descriptions of cigarettes and the various components thereof are set forth in Tobacco Production, Chemistry and Technology, Davis et al. (Eds.) (1999).
  • Cigarettes generally include a substantially cylindrical rod-shaped structure and include a charge, roll or column of smokeable material such as shredded tobacco (e.g., in cut filler form) surrounded by a paper wrapper thereby forming a so-called “tobacco rod.” Normally, a cigarette has a cylindrical filter element aligned in an end-to-end relationship with the tobacco rod. Typically, a filter element includes cellulose acetate tow circumscribed by plug wrap, and is attached to the tobacco rod using a circumscribing tipping material. It also has become desirable to perforate the tipping material and plug wrap, in order to provide dilution of drawn mainstream smoke with ambient air.
  • Carbonaceous materials can be employed as components of combustible material components in a smoking article that are designed to burn and provide heat to aerosolize physically separate aerosol-forming materials. Cigarettes having carbonaceous combustible material components have been marketed by the R. J. Reynolds Tobacco Company under the tradenames Premier and Eclipse. See, for example, U.S. Pat. No. 4,708,151 to Shelar et al.; U.S. Pat. No. 5,016,654 to Bernasek et al.; U.S. Pat. No. 4,991,596 to Lawrence et al.; U.S. Pat. No. 5,038,802 to White et al.; U.S. Pat. No. 4,793,365 to Sensabaugh et al.; U.S. Pat. No. 4,961,438 to Korte; U.S. Pat. No. 4,991,606 to Serrano et al.; U.S. Pat. No. 5,020,548 to Farrier et al.; U.S. Pat. No. 5,076,297 to Farrier et al.; U.S. Pat. No. 5,148,821 to Best et al.; U.S. Pat. No. 5,178,167 to Riggs et al.; U.S. Pat. No. 5,183,062 to Clearman et al.; U.S. Pat. No. 5,345,955 to Clearman et al.; U.S. Pat. No. 5,551,451 to Riggs et al.; and U.S. Pat. No. 5,595,577 to Bensalem et al. The disclosure of each of these patents is incorporated herein by reference. See, also, Chemical and Biological Studies on New Cigarette Prototypes that Heat Instead of Burn Tobacco, R. J. Reynolds Tobacco Company Monograph (1988).
  • It also has been suggested to incorporate non-combustible materials into the carbonaceous combustible material components of certain types of smoking articles. See, for example, U.S. Pat. No. 5,040,551 to Schlatter et al.; U.S. Pat. No. 5,211,684 to Shannon et al.; U.S. Pat. No. 5,240,014 to Deevi et al.; and U.S. Pat. No. 5,258,340 to Augustine et al. The disclosure of each of these patents is incorporated herein by reference.
  • It would be desirable to provide a fuel element for a smoking article that reduces the amount of carbon monoxide present in the aerosol of the smoking article. It would additionally be desirable to provide a fuel element that displays a more efficient combustion.
  • SUMMARY OF THE INVENTION
  • The present invention provides fuel elements comprising ultrafine particles. In an embodiment of the present invention, the ultrafine particles catalyze the conversion of carbon monoxide to carbon dioxide, thereby reducing the amount of carbon monoxide present in the combustion gases produced by burning of the fuel element. In a smoking article embodiment, a fuel element comprising ultrafine particles reduces the amount of carbon monoxide present in the aerosol and demonstrates a more efficient combustion by producing more energy per gram of fuel combusted.
  • The present invention also provides methods for altering the performance characteristics of smoking articles to reduce the amount of carbon monoxide present in aerosol produced by the smoking article.
  • In one aspect, the present invention provides a fuel element comprising a carbonaceous material and at least one catalyst composition, the catalyst composition comprising ultrafine particles.
  • In another aspect, the present invention provides a method for reducing the amount of carbon monoxide produced by an article comprising a fuel element, the method comprising incorporating ultrafine particles in the fuel element.
  • In a further aspect, the present invention provides a smoking article having reduced amounts of carbon monoxide in the aerosol produced by the smoking article. In an embodiment, the smoking article comprises: a fuel element comprising a carbonaceous material and ultrafine particles.
  • In a still further aspect, the present invention provides methods and apparatus for the simultaneous relative quantification of carbon monoxide and carbon dioxide in a gaseous mixture. In an embodiment, the method comprises injecting a gaseous mixture into a split single injector of a gas chromatograph for splitting the gaseous mixture onto two chromatographic columns; resolving the carbon monoxide content of the gaseous mixture on a first chromatographic column; simultaneously resolving the carbon dioxide content of the gaseous mixture on a second chromatographic column; and detecting and quantifying the resolved carbon monoxide and carbon dioxide contents with a mass spectrometer. Embodiments of the method may be utilized to simultaneously quantify the relative amounts of carbon monoxide and carbon dioxide in aerosol from a smoking article.
  • An advantage of the present invention is that that fuel elements of the present invention may be used in applications where it is desirable to reduce amounts of carbon monoxide.
  • Further features and advantages of the present invention are set forth in the following more detailed description.
  • BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 illustrates a smoking article according to an embodiment of the present invention.
  • FIG. 2 illustrates a method according to an embodiment of the present invention.
  • FIG. 3 illustrates an apparatus according to an embodiment of the present invention.
  • FIG. 4 illustrates an ion chromatogram of a standard gaseous mixture resolved on dual columns according to an embodiment of the present invention.
  • FIG. 5 illustrates an ion chromatogram of a standard gaseous mixture resolved on a Molsieve column according to an embodiment of the present invention.
  • FIG. 6 illustrates an ion chromatogram of a standard gaseous mixture resolved on a Carbon Plot column according to an embodiment of the present invention.
  • FIG. 7 illustrates an ion chromatogram of heated tobaccos resolved on dual columns according to an embodiment of the present invention.
  • FIG. 8 illustrates an ion chromatogram of cigarette smoke resolved on dual columns according to an embodiment of the present invention.
  • FIG. 9 illustrates the reduced production of carbon monoxide by carbon upon combustion in the presence of various ultrafine particles according to embodiments of the present invention.
  • FIG. 10 illustrates the reduced production of carbon monoxide by combustion of carbon and mixtures comprising carbon, Guar gum, graphite, and tobacco in the presence of iron oxide ultrafine particles of various sizes according to embodiments of the present invention.
  • FIG. 11 illustrates the reduced production of carbon monoxide by combustion of carbon in the presence of various metal oxide ultrafine particles according to embodiments of the present invention.
  • FIG. 12 illustrates the effect of catalyst compositions on a CO/CO2 ratio when tobacco is pyrolized in the presence of various ultrafine particles according to embodiments of the present invention.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention provides fuel elements comprising a carbonaceous material and at least one catalyst composition. The present invention additionally provides articles of manufacture including, but not limited to, smoking articles. The present invention further provides methods for altering the performance characteristics of smoking articles. Moreover, the present invention provides methods and apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture comprising these and various other chemical species.
  • Reference is made below to specific embodiments of the present invention. Each embodiment is provided by way of explanation of the invention, not as a limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment may be incorporated into another embodiment to yield a further embodiment. Thus, it is intended that the present invention cover such modifications and variations as come within the scope of the appended claims and their equivalents.
  • For the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification are approximations that can vary, depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
  • Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein, and every number between the end points. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more, e.g., 1 to 6.1, and ending with a maximum value of 10 or less, e.g., 5.5 to 10, as well as all ranges beginning and ending within the end points, e.g., 2 to 9, 3 to 8, 3.2 to 9.3, 4 to 7, and finally to each number 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 contained within the range. Additionally, any reference referred to as being “incorporated herein” is to be understood as being incorporated in its entirety.
  • It is further noted that, as used in this specification, the singular forms “a,” “an,” and “the” include plural referents unless expressly and unequivocally limited to one referent.
  • In one embodiment of the present invention, a fuel element comprises a carbonaceous material and at least one catalyst composition. The catalyst composition comprises ultrafine particles of a metal oxide, metal, or mixtures thereof. As used herein, the term ultrafine particle is generally used to indicate particles with dimensions less than 100 nanometers (one nanometer is one-billionth of a meter). The metal oxide and metal ultrafine particles can demonstrate activity for catalyzing chemical reactions, such as the oxidation of carbon monoxide to carbon dioxide.
  • Ultrafine particles suitable for use in catalytic compositions of the present invention comprise, but are not limited to, iron oxides (e.g. FeO, Fe2O3 and Fe3O4), gold, copper, silver, platinum, palladium, rhodium, nickel, zinc, zirconium, other transition metals, metal oxides, and mixtures thereof.
  • The catalyst compositions comprising ultrafine particles facilitate a more complete production of carbon dioxide by catalyzing the oxidation reaction of carbon to carbon dioxide. In an embodiment wherein combustion of a fuel element generates a gaseous stream comprising carbon monoxide, the catalyst composition acts upon carbon monoxide in the gaseous stream. Ultrafine particles of the catalyst compositions may also improve the performance characteristics of a fuel element for particular applications. For example, the ultrafine particles of the catalyst compositions can increase the caloric output of a particular fuel.
  • In an embodiment of the present invention, ultrafine particles of the catalyst compositions may have an average particle size of 10 nanometers, generally between 1 nanometer and 1 micron. In an embodiment of a smoking article of the present invention, the ultrafine particles may have an individual particle size of up to about five nanometers. In another embodiment of a smoking article of the present invention, the ultrafine particles may have an individual particle size between about two and four nanometers.
  • Ultrafine particles according to the present invention may be produced by a variety of methods including sol-gel synthesis, chemical deposition, deposition precipitation, inert gas condensation, mechanical alloying or high-energy ball milling, plasma synthesis, and electrodeposition. Using such methods, ultrafine particles can be produced in various symmetric shapes, such as spheres, cylinders, prisms, cubes, tetrapods and amorphous clusters. In embodiments of the present invention, the physical properties of the ultrafine particles, including for example, their electrical, optical, chemical, mechanical, and magnetic properties, may be selectively controlled for example by engineering the size, morphology, and/or composition of the ultrafine particles. The resulting materials may have enhanced or entirely different properties from their parent materials.
  • Representative types of ultrafine particles and materials for use in the present invention are of the type, and may be produced by methods, described in U.S. Pat. No. 6,503,475 to McCormick U.S. Pat. No. 6,472,459 to Morales et al., U.S. Pat. No. 6,467,897 to Wu et al., U.S. Pat. No. 6,479,146 to Caruso et al., and U.S. Pat. No. 6,479,156 to Schmidt et al. and U.S. Published Pat. Applications 2002/0194958 to Lee et al., 2002/014453 to Lilly Jr., et al., 2003/0000538 to Bereman et al., 2002/0167118, 2002/0172826 and 2002/0127351, the disclosure of each patent and published application being incorporated herein by reference.
  • Ultrafine particles for use in the catalyst composition can be obtained commercially. For example, Superfine Iron oxide (Fe2O3) can be obtained from MACH-1 Inc. of King of Prussia, Pa. Nanopowder Enterprise Inc. of Piscataway, N.J. is an additional commercial source of ultrafine particles for use in catalyst compositions of the present invention.
  • In embodiments of the present invention, the fuel element additionally comprises a carbonaceous material. The fuel element may additionally comprise binders like Guar gum, other metallic particles such as aluminum or the like, inert filler material like graphite, and/or burn modifiers such as sodium or potassium carbonate. In some embodiments, the carbonaceous materials for use in the fuel element include at least 50%, by weight carbon. In other embodiments the carbonaceous materials for use in the fuel element can include about 60-95% by weight carbon. In still further embodiments, the carbonaceous materials for use in the fuel element can include about 70-80% by weight carbon. The carbonaceous materials may be in powder form and may be partially activated. The carbonaceous materials may also be heat treated. The carbonaceous materials may comprise organic carbon containing materials, for example tobacco.
  • The carbonaceous materials of the present invention may be prepared from several starting materials. Suitable starting materials include, but are not limited to, cellulosic materials with a high (i.e., greater than about 80%) alpha-cellulose content, such as cotton, rayon, paper, and the like. The carbonaceous materials of fuel elements of the present invention may be generally prepared by pyrolysis of the starting material at a temperature between about 400° C. and 1300° C., preferably between about 500° C. and 950° C., in a non-oxidizing atmosphere, for a period of time sufficient to ensure that a large portion or substantially all of the starting material has reached the desired carbonization temperature. Although the pyrolysis may be conducted at a constant temperature, it has been found that a slow pyrolysis, employing a gradually increasing heating rate, e.g., from about 1° C. to 20° C. per hour, preferably from about 5° C. to 25° C. per hour, over many hours, produces a uniform and higher carbon yield.
  • After cooling, the carbonaceous material may be pulverized. In some embodiments, the carbonaceous material is pulverized to a fine powder. This powder may be subjected to a second pyrolysis or polishing step, wherein the carbonized particulate material, is again pyrolyzed in a non-oxidizing atmosphere, at a temperature between about 650° C. to about 1250° C., preferably from about 700° C. to 900° C. At this point, the carbonaceous material is ready for combination with the ultrafine particle catalyst composition along with the other components of the fuel to produce a fuel element composition.
  • In embodiments of the present invention, the ultrafine particles of the catalyst compositions can be combined with a carbonaceous material in a number of ways to produce the fuel element composition. One method of combination comprises intimately mixing the carbonaceous material with the ultrafine particles. Ultrafine particles in dry powder form (e.g. nanopowder) may be mixed directly in a carbon mix along with other dry ingredients for extrusion. Alternatively, the ultrafine particles may be suspended in a liquid and the suspension mixed with extrudate.
  • Another method of combining the ultrafine catalyst compositions with a carbonaceous material comprises forming the carbonaceous material so as to concentrate the catalytic compositions in one or more longitudinal passageways extending partially through the fuel element. For example, the fuel element may comprise an inner core/outer shell arrangement where the outer shell comprises a carbonaceous material surrounding the inner core, and the inner core comprises ultrafine particle catalyst compositions. In some embodiments, the fuel element may include at least one longitudinal passageway extending at least partially therethrough.
  • Other methods of combining ultrafine particle catalyst compositions with a carbonaceous material can include wash coating, dipping, painting, spraying, or other methods known to those ordinary skill in the art. In another embodiment, the ultrafine particle catalyst compositions can be placed on inert support located directly behind the fuel element in an end to end relationship. The support for the ultrafine particles can be an inert carbon material such as graphite or a porous material such as alumina or porous graphite.
  • Once combined with the carbonaceous material, the catalyst composition may comprise up to 10% by weight of the resulting mixture. In some embodiments, the catalyst compositions may comprise 1% by weight of the resulting mixture. In another embodiment, catalyst composition may comprise 0.5% to 2% by weight of the resulting mixture.
  • The density of a fuel element according to some embodiments of the present invention can be generally greater than about 0.5 g/cc, greater than about 0.7 g/cc and greater than about 1 g/cc.
  • The overall length of the fuel element, prior to burning, can be generally less than about 20 mm, often less than about 15 mm, and can be typically about 12 mm. However, shorter fuel elements may be used if desired, depending upon the configuration of the cigarette in which they are employed. In an embodiment, the overall outside diameter of the fuel element can be less than about 8 mm, less than about 6 mm, and can be about 4.2 mm.
  • The carbonaceous and binder portions of the fuel compositions useful herein may be any of those carbonaceous and binder materials described in the patents recited in the Background of the Invention, supra. Several carbonaceous and binder materials are described in U.S. application Ser. No. 07/722,993, filed 28 Jun. 1991, now U.S. Pat. No. 5,178,167 the disclosure of which is hereby incorporated herein by reference.
  • In a further aspect, the present invention provides smoking articles. In an embodiment, a smoking article comprises a fuel element comprising a carbonaceous material and at least one catalyst composition, the catalyst composition comprising ultrafine particles. With reference to a cigarette as a smoking article, the cigarette further includes an aerosol generating means, which includes a substrate and at least one aerosol-forming material. An aerosol-generating means includes an aerosol forming material (e.g. glycerin), tobacco in some form (e.g. tobacco powders, tobacco extract or tobacco dust) and other aerosol forming materials and/or tobacco flavoring agents such as cocoa, licorice, and sugar. The aerosol forming material generally is carried on a substrate material such as a reconstituted tobacco cut filler or on a substrate such as tobacco cut filler, gathered paper, gathered tobacco paper, or the like.
  • In an embodiment of the present invention, the substrate is reconstituted tobacco, which is formed into a continuous rod or substrate tube assembly on a conventional cigarette making machine. Typically, the overwrap material for the rod is a barrier material such as a paper foil laminate. The foil serves as a barrier, and is located on the inside of the overwrap. Alternatively, the substrate may be a gathered paper formed into a rod or plug. When the substrate is a paper-type material, it can be positioned in a spaced-apart relationship from the fuel element comprising a carbonaceous material and a catalyst composition. A spaced-apart relationship is desired to minimize contact between the fuel element and the substrate, thereby preventing migration of the aerosol forming materials to the fuel element, as well as limiting the scorching or burning of the paper substrate. The spacing is normally provided during manufacture of the cigarette in accordance with one method of making the present invention. Appropriately spaced substrate plugs are overwrapped with a barrier material to form a substrate tube assembly having spaced substrate plugs therein. The substrate tube assembly is cut between the substrate plugs to form substrate sections. The substrate sections include a tube with a substrate plug and void(s), which can be at each end.
  • The barrier material for making the tube aids in preventing migration of the aerosol former to other components of the cigarette. The barrier material forming the tube is a relatively stiff material so that when formed into a tube, it will maintain its shape and will not collapse during manufacture and use of the cigarette.
  • In embodiments of the present invention, fuel elements of a smoking article can be advantageously circumscribed by an insulating and/or retaining jacket material. The insulating and retaining material is adapted such that drawn air can pass therethrough, and is positioned and configured so as to hold the fuel element in place. The jacket is flush with the ends of the fuel element, however, it may extend from about 0.5 mm to about 3 mm beyond each end of the fuel element.
  • The components of the insulating and/or retaining material which surrounds the fuel element can vary. Examples of suitable materials include glass fibers and other materials as described in U.S. Pat. No. 5,105,838; European Patent Publication No. 339,690; and pages 48-52 of the RJR Monograph, supra. Examples of other suitable insulating and/or retaining materials are glass fiber and tobacco mixtures such as those described in U.S. Pat. Nos. 5,105,838, 5,065,776 and 4,756,318; and U.S. patent application Ser. No. 07/354,605, filed 22 May 1989 now U.S. Pat. No. 5,119,837.
  • Other suitable insulating and/or retaining materials are gathered paper-type materials which are spirally wrapped or otherwise wound around the fuel element, such as those described in U.S. patent application Ser. No. 07/567,520, filed 15 Aug. 1990, now U.S. Pat. No. 5,105,836. The paper-type materials can be gathered or crimped and gathered around the fuel element; gathered into a rod using a rod making unit available as CU-10 or CU2OS from DeCoufle s.a.r.b., together with a KDF-2 rod making apparatus from Hauni-Werke Korber & Co., KG, or the apparatus described in U.S. Pat. No. 4,807,809 to Pryor et al.; wound around the fuel element about its longitudinal axis; or provided as longitudinally extending strands of paper-type sheet using the types of apparatus described in U.S. Pat. No. 4,889,143 to Pryor et al. and U.S. Pat. No. 5,025,814 to Raker, the disclosures of which are incorporated herein by reference.
  • If desired, the fuel element may be extruded into the insulating jacket material as set forth in U.S. patent application Ser. No. 07/856,239, filed 25 Mar. 1992, the disclosure of which is incorporated herein by reference.
  • Examples of paper-type sheet materials are available as P-2540-136-E carbon paper and P-2674-157 tobacco paper from Kimberly-Clark Corp.; and the longitudinally extending strands of such materials (e.g., strands of about 1/32 inch width) extend along the longitude of the fuel element. The fuel element also can be circumscribed by tobacco cut filler (e.g., flue-cured tobacco cut filler treated with about 2 weight percent potassium carbonate). The number and positioning of the strands or the pattern of the gathered paper is sufficiently tight to maintain, retain or otherwise hold the composite fuel element structure within the cigarette.
  • In embodiments of the present invention, the fuel element-jacket assembly is combined with a substrate section or substrate tube assembly by a wrapper material, which has a propensity not to burn, to form a fuel element/substrate section. In some embodiments of the cigarettes, the wrapper typically extends from the mouthend of the substrate section, over a portion of the jacketed fuel element, whereby it is spaced from the lighting end of the fuel element. The wrapper material assists in limiting the amount of oxygen which will reach the burning portion of the fuel element during use, thereby causing the fuel element to extinguish after an appropriate number of puffs. In an embodiment of the cigarette, the wrapper is a paper/foil/paper laminate. The foil provides a path to assist in dissipating or transferring the heat generated by the fuel element during use. The jacketed fuel element and the substrate section are joined by the overwrap.
  • A tobacco section can be formed by a reconstituted tobacco cut filler rod, made on a typical cigarette making machine, and cut into appropriate lengths. A filter rod is formed and cut into appropriate lengths for joining to the tobacco section to form a mouthend section. The fuel element/substrate section and the mouthend section are joined by aligning the reconstituted ends of each section, and overwrapped to form a cigarette.
  • When a paper substrate is used, a tobacco paper rod and a reconstituted cut filler rod are formed and cut into appropriate lengths and joined to form a tobacco section. The tobacco section and the fuel element assembly/substrate section are joined by aligning the tobacco paper plug end of the tobacco section with the substrate end of the fuel element assembly/substrate section and joining the sections with a wrapper which extends from the rear end of the tobacco roll to an appropriate length past the junction of the two sections for forming the tobacco roll/fuel element assembly. The tobacco roll/fuel element assembly is then joined to a filter by a tipping material.
  • As described above, the substrate carries aerosol forming materials and other ingredients, e.g., flavorants and the like, which, upon exposure to heated gases passing through the aerosol generating means during puffing, are vaporized and delivered to the user as a smoke-like aerosol. Aerosol forming materials used herein include glycerin, propylene glycol, water, and the like, flavorants, and other optional ingredients. The patents referred to in the Background of the Invention (supra) teach additional useful aerosol forming materials that need not be repeated here.
  • Cast sheets of tobacco dust or powder, a binder, such as an alginate binder, and glycerin can also be used to form useful substrates herein. Suitable cast sheet materials for use as substrates are described in U.S. Pat. No. 5,101,839 and U.S. patent application Ser. No. 07/800,679, filed Nov. 27, 1991.
  • Suitable cast sheet materials typically contain between about 30 to 75 weight percent of an aerosol former such as glycerin; about 2 to 15 weight percent of a binder, such as ammonium alginate; 0 to about 2 weight percent of a sequestering agent such as potassium carbonate; about 15 to about 70 to 75 weight percent of organic, inorganic filler materials, or mixtures thereof, such as tobacco dust, aqueous extracted tobacco powder, starch powder, rice flower, ground puffed tobaccos, carbon powder, calcium carbonate powder, and the like, and from about 0 to about 20 weight percent of flavors such as tobacco extracts, and the like.
  • In one embodiment, a cast sheet material includes 60 weight percent glycerin, 5 weight percent ammonium alginate binder, 1 weight percent potassium carbonate, 2 weight percent flavors such as tobacco extracts and 32 weight percent aqueous extracted tobacco powder.
  • The cast sheets are formed by mixing aqueous extracted tobacco powder, water and the potassium carbonate in a high sheer mixer to produce a smooth, flowable paste. Glycerin and ammonium alginate are then added and the high shear mixing is continued until a homogenized mixture is produced. The homogenized mixture is cast on a heated belt (about 200.degree. F.) with a 0.0025 to 0.0035 inch casting clearance and is dried to yield a 0.0004 to 0.0008 inch thick sheet under high temperature air (about 200.degree. to 250.degree. F.). The sheet is doctored from the belt and either wound onto spools for slitting into webs or chopped into rectangular pieces about 2 inches by 1 inch which are formed into cut filler. If the cast sheet material is used in a web or cut filler form, normally the substrate will be from about 10 mm to 40 mm in length and extend from the rear end of the fuel element to the tobacco segment or the front end of an extra long filter segment (e.g., about 30 mm to 50 mm in length). In such instances the tobacco paper plug can be omitted.
  • In embodiments of the present invention, the combination of the fuel element and the substrate (also known as the front end assembly) is attached to a mouthend piece; although a disposable fuel element/substrate combination can be employed with a separate mouthend piece, such as a reusable cigarette holder. The mouthend piece provides a passageway which channels vaporized aerosol forming materials into the mouth of the smoker; and can also provide further flavor to the vaporized aerosol forming materials.
  • Flavor segments (i.e., segments of gathered tobacco paper, tobacco cut filler, or the like) can be incorporated in the mouthend piece or the substrate segment, e.g., either directly behind the substrate or spaced apart therefrom, to contribute flavors to the aerosol. Gathered carbon paper can be incorporated, particularly in order to introduce menthol flavor to the aerosol. Such papers are described in European Patent Publication No. 342,538. Other flavor segments useful herein are described in U.S. patent application Ser. No. 07/414,835, filed 29 Sep. 1989, now U.S. Pat. No. 5,076,295 Ser. No. 07/606,287, filed 6 Nov. 1990; now U.S. Pat. No. 5,105,834 and Ser. No. 07/621,499, filed 7 Dec. 1990, now abandoned.
  • FIG. 1 illustrates a smoking article according to an embodiment of the present invention. The smoking article depicted in FIG. 1 comprises a fuel element 10 of the present invention comprising a carbon source and at least one catalytic composition comprising ultrafine particles of a metal oxide and/or metal. The fuel element displays a plurality of passageways 11 therethrough, about thirteen passageways altogether. The fuel element 10 is surrounded by insulating sheet material 16 having a plurality of grooves which facilitate the formation of the sheet material into a jacket surrounding the fuel element. In embodiments of the smoking article, the jacket can be made of calcium sulfate (CaSO4).
  • A metallic capsule 12 overlaps a portion of the mouthend of the fuel element 10 and encloses the physically separate aerosol generating means which contains a substrate material 14. The substrate material carries one or more aerosol forming materials. The substrate may be in particulate form, in the form of a rod, and other geometric shapes advantageous for generating an aerosol.
  • Capsule 12 is circumscribed by a roll of tobacco 18. Alternatively, in other smoking articles, the capsule may be circumscribed with an additional or continuous jacket of an insulating sheet material. Insulating sheet materials suitable for use in smoking articles of the present invention are further described in U.S. Pat. No. 5,303,720 to Banerjee which is hereby incorporated by reference. Two slit-like passageways 20 are provided at the mouth of the capsule in the center of the crimped tube.
  • At the mouth end of the tobacco roll 18, is a mouthend piece 22, comprising a cylindrical segment of a flavored carbon filled sheet material 24 and a segment of non-woven thermoplastic fibers 26 through which the aerosol passes to the user. The smoking article, or portions thereof, is overwrapped with one or more layers of cigarette papers 30-36
  • In some embodiments, catalyst compositions comprising metal oxide and/or metal ultrafine particles are incorporated into the filter element of the smoking article as described in U.S. patent application Ser. No. 10/730,962 which is hereby incorporated by reference.
  • In certain embodiments of the cigarettes of the present invention, convective heating is the predominant mode of energy transfer from the burning fuel element comprising a carbonaceous material and at least one catalyst composition to the aerosol-generating means disposed longitudinally behind the fuel element. When a foil/paper laminate is used as an overwrap to join the fuel/substrate section some heat may be transferred to the substrate by the foil layer. As described above, the heat transferred to the substrate volatilizes the aerosol-forming material(s) and any flavorant materials carried by the substrate, and, upon cooling, these volatilized materials are condensed to form a smoke-like aerosol which is drawn through the cigarette during puffing, and which exits the filter piece. This smoke-like aerosol can contain reduced amounts of carbon monoxide resulting from the reduced carbon monoxide production of a fuel element of the present invention upon combustion.
  • In some embodiments, the catalyst compositions can be deposited on a porous support such as graphite or alumina wherein the porous support is placed behind the fuel in an end to end relationship.
  • In a further aspect, the present invention provides a method for facilitating the reduction in the amount of carbon monoxide produced by a smoking article, comprising incorporating at least one catalyst composition comprising ultrafine particles of a metal oxide and/or metal into the fuel element of a smoking article.
  • In another aspect, the present invention provides methods and apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture. In an embodiment, a method for quantifying the carbon monoxide content and carbon dioxide content of a gaseous mixture comprises injecting the gaseous mixture into a split injection tube of a gas chromatograph through a single injector, resolving a relative carbon monoxide content of the gaseous mixture on a first chromatographic column, simultaneously resolving a relative carbon dioxide content on a second chromatographic column, and detecting and quantifying the eluate carbon monoxide and carbon dioxide with a mass spectrometer. In further embodiments, the gaseous mixture containing carbon monoxide and carbon dioxide comprises mainstream smoke or a smoke-like aerosol produced from a smoking article.
  • Under some circumstances, carbon monoxide and carbon dioxide can be resolved on a single chromatographic column. Single columns that are capable of resolving both carbon monoxide and carbon dioxide, however, use carrier gas at flow rates that are too high for use with a mass spectrometer. As a result, their use precludes the numerous advantages gained by the two-dimensional analysis of GC/MS. Moreover, other single chromatographic columns that use a carrier gas at acceptable flow rates for use with a mass spectrometer cannot effectively resolve both carbon monoxide and carbon dioxide.
  • The utilization of dual chromatographic columns allows for the complete resolution of the carbon monoxide and carbon dioxide contents of the gaseous mixture at flow rates that are acceptable for use with a mass spectrometer. The two-dimensional analysis provided by gas chromatography/mass spectrometry (GC/MS) can provide precise relative quantifications of carbon monoxide and carbon dioxide amounts present in gaseous mixtures.
  • FIG. 2 illustrates a flowchart for the quantification of carbon monoxide and carbon dioxide contents of a gaseous mixture according to an embodiment of the present invention. In particular embodiments, the gaseous mixture comprises mainstream smoke or smoke-like aerosol from a smoking article. The gaseous mixture is injected into the split injector of the gas chromatogram 201. The split injector 201 splits the gaseous mixture for simultaneous resolution on dual chromatographic columns. The carbon monoxide content of the mainstream smoke is resolved on a first chromatographic column 202, and the carbon dioxide content is simultaneously resolved on a second chromatographic column 203. The first chromatographic column can be selected for optimal resolution of carbon monoxide while the second chromatographic column can be selected for the optimal resolution of carbon dioxide. For example, a Molsieve column can be used to resolve carbon monoxide and a wide-bore GS-CarbonPLOT column can be used to resolve carbon dioxide.
  • Once resolved, the carbon monoxide content and carbon dioxide content of the mainstream smoke are quantified by a mass spectrometer 204. The use of a mass spectrometer adds a second dimension of analysis that is not present with traditional gas chromatographic detection devices. A mass spectrometer can further resolve the carbon monoxide content and carbon dioxide content of a gaseous mixture allowing for greater accuracy and precision when quantifying these chemical species.
  • In an embodiment, an apparatus for quantifying the carbon monoxide content and carbon dioxide content of a gaseous mixture comprises: a gas chromatograph comprising a single split injector, dual chromatographic columns; and a mass spectrometer.
  • FIG. 3 illustrates an apparatus for the simultaneous quantification of the carbon monoxide content and carbon dioxide content of a gaseous mixture comprising the two-dimensional analysis of gas chromatography and mass spectrometry in an embodiment according to the present invention. The gas chromatograph 301 comprises a single injector 302 which splits the sample onto two chromatographic columns 303, 304. The temperature of the split single injector 302 can be varied in accordance with desired analytical conditions. The temperature variance of the single split injector 302 can be controlled manually by a user or can be controlled electronically with any processor-equipped device such as a computer and/or dedicated controller. As previously discussed, one of the two columns 303 is suitable for resolving the carbon monoxide content of a gaseous mixture while the other column 304 is suitable for resolving the gaseous mixture's carbon dioxide content. Chromatographic columns for use in the gas chromatograph of the present apparatus are available commercially.
  • The two chromatographic columns feed into a mass spectrometer 305. Mass spectrometers suitable for use in further resolving and quantifying the carbon monoxide content and carbon dioxide content eluting from the two columns of the gas chromatograph can comprise mass analyzers comprising magnetic sector analyzers, double-focusing spectrometers, quadrupole mass filters, ion trap analyzers, and time-of-flight (TOF) analyzers.
  • The embodiments described above in addition to other embodiments can be further understood with reference to the following examples. Several of the fuel elements provided in the examples below comprise percentages of BKO carbon, Guar gum, graphite, and tobacco. Combustion of all the fuel elements in the examples below provides energy used to generate aerosol from tobacco and other aerosol formers like glycerin. Combustion of the fuel elements, however, also produces carbon monoxide and carbon dioxide. Moreover, complete combustion of the fuel elements produces a maximum amount of energy and a carbon dioxide by-product. Complete combustion is demonstrated by the chemical reaction:
    C (s)+O2 (g)→CO2 (g)
    Incomplete combustion, nevertheless, produces much less energy and a substantial carbon monoxide by-product. Incomplete combustion is demonstrated by the reaction sequence:
    C (s)+O (g)→CO (g)
    C (s)+O2 (g)→CO2 (g)
    As a result, complete combustion of the fuel element in desirable.
  • Graphite in the fuel elements comprising graphite, BKO carbon, Guar gum, and tobacco, is inactive up to the temperatures attained by combustion of the fuel element and remains substantially unchanged throughout the combustion of the fuel element. The remaining three carbonaceous components undergo oxidation during the combustion to provide energy and oxides of carbon. Among the carbonaceous components, BKO carbon is the major component and hence chosen for the study of the fuel elements in the examples below.
  • EXAMPLE 1
  • Several materials were prepared to evaluate the efficacy of a method and apparatus for simultaneously resolving the carbon monoxide content and carbon dioxide content of a gaseous mixture according to an embodiment of the present invention. The materials prepared for analysis by the method and apparatus were a standard gaseous mixture (CO:CO2:N2), tobaccos from 1R4F cigarettes, and 1R4F cigarette smoke. A small quantity of each sample was heated to 700° C. for 20 seconds in the presence of air. The standard gaseous mixture was analyzed in the absence of air to preserve the composition of the sample. A pyroprobe was used for sample heating. The temperatures of the pyroprobe interface and the gas chromatograph injector were set at ambient temperature. The gas chromatograph utilized was a Hewlett-Packard 5890 Series II. A single injection onto dual chromatographic columns was used for the carbon monoxide and carbon dioxide analysis. A Molsieve column (Chrompack, 25 M×0.32 mm I.D., 30 μm film) was used for carbon monoxide resolution, and a GS-CarbonPLOT column (J&W Scientific, 60 M×0.32 mm I.D., 1.5 μm film) was used for carbon dioxide resolution. The temperatures of the columns were held at 35° C. for 10 minutes, programmed to 150° C. at 25° C./min and held for 10 min. A single mass spectrometer was used to identify and quantify the resolved carbon monoxide and carbon dioxide peaks eluting from the chromatographic columns. The mass spectrometer utilized was a Hewlett-Packard 5972 mass selective detector. The mass spectrometer was operated at 70 eV in the EI mode with the temperature of the ion source being maintained at 180° C. The mass range scanned was 20-200 atomic mass units. The carbon monoxide and carbon dioxide quantified were only a fraction of the total carbon monoxide and carbon dioxide generated from the heated materials. Only the resolved carbon monoxide and carbon dioxide peak areas were used for quantification.
  • The results of the standard gaseous mixture resolved on the dual chromatographic columns are illustrated in FIG. 4. The ion chromatogram of FIG. 4 demonstrates a completely resolved carbon monoxide peak and a completely resolved carbon dioxide peak. For comparative purposes, the standard gaseous mixture (CO:CO2:N2) was injected and resolved on single column gas chromatographs under experimental conditions consistent with resolution on dual chromatographic columns. The standard gaseous mixture was resolved on a single column gas chromatograph comprising a Molsieve column. The results are illustrated in FIG. 5. As demonstrated in the ion chromatogram of FIG. 5, the Molsieve column completely resolved the carbon monoxide content but failed to completely resolve the carbon dioxide content of the standard gaseous mixture. Similarly, the standard gaseous mixture was additionally resolved on a single GS-CarbonPLOT chromatographic column. The results of this resolution are illustrated in FIG. 6. The ion chromatogram of FIG. 6 displays a complete resolution of carbon dioxide and an incomplete resolution of carbon monoxide. The carbon monoxide co-eluted with nitrogen and oxygen.
  • The results of the remaining sample materials comprising tobaccos from 1R4F cigarettes and 1R4F cigarette smoke resolved on dual chromatographic columns in accordance with the present invention are illustrated in FIGS. 7 and 8 respectively. The ion chromatograms of FIGS. 7 and 8 demonstrate completely and sharply resolved carbon monoxide and carbon dioxide peaks.
  • EXAMPLE 2
  • Seven samples were generated for analysis of carbon monoxide/carbon dioxide (CO/CO2) ratios. These samples were: (1) Control Carbon Black 950, (2) Carbon Black 950 with 5% Fe2O3 ultrafine particles, (3) Carbon Black 950 with 2% Fe2O3 ultrafine particles, (4) Carbon Black 950 with 5% TiO2—Au ultrafine particles and (5) Carbon Black 950 with 2% TiO2—Au ultrafine particles, (6) Carbon Black 950 with 5% CeO2 ultrafine particles, and (7) Carbon Black 950 with 2% CeO2 ultrafine particles.
  • To simulate combustion of the fuel element, a pyroprobe was used to heat a small quantity of each sample to 700° C. for 20 seconds in the presence of air. 700° C. is the average temperature of a fuel element during combustion. The gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in FIG. 2. The pyroprobe and gas chromatogram injector were set at ambient temperature. A Molsieve chromatographic column was used for carbon monoxide resolution and a GS-CarbonPLOT chromatographic column was used for carbon dioxide resolution. A mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples. It should be noted that the carbon monoxide and the carbon dioxide contents quantified were only a fraction of the carbon monoxide and carbon dioxide contents produced by the samples and that the resolved peak areas were used for quantification. Table 1 summarizes the results produced by the samples in this example. TABLE 1 MASS ABUNDANCE (COUNTS)A CO/CO2 SAMPLES CO CO2 Ratio (1) Control Carbon 383,013,104 1,284,639,516 0.298 (2) Carbon and 5% Fe2O3 53,357,015 1,202,285,067 0.0444 (3) Carbon and 2% Fe2O3 65,069,392 1,093,984,395 0.0595 (4) Carbon and 5% TiO2-Au 131,461,228 926,581,662 0.142 (5) Carbon and 2% TiO2-Au 264,095,113 956,314,408 0.276 (6) Carbon and 5% CeO2 268,205,948 965,498,063 0.278 (7) Carbon and 2% CeO2 279,547,847 977,688,888 0.286 Air Blank 655,583 7,602,213
    AMass abundance is the total abundance of ions in a mass spectrum for compound with unit of counts.
  • The results displayed in Table 1, which are additionally illustrated in FIG. 9, demonstrate that ferric oxide (Fe2O3) ultrafine particles effectuate a significant reduction in the amount of carbon monoxide produced by the fuel element. Fuel element sample (2) comprising 5% ferric oxide (Fe2O3) ultrafine particles by weight exhibited an 85% reduction in the amount of carbon monoxide produced when heated. Similarly, fuel element sample (3) comprising 2% ferric oxide (Fe2O3) ultrafine particles by weight displayed an 80% reduction in the amount of carbon monoxide produced upon sample heating. The titanium oxide-gold (TiO2—Au) ultrafine particles of sample (4) demonstrated a carbon monoxide reduction of 52% while the ceric oxide (CeO2) ultrafine particles of sample (6) resulted in approximately a 7% reduction.
  • EXAMPLE 3
  • Eight fuel element samples were generated for analysis of (CO/CO2) ratios. These samples were: (1) BKO Carbon 950, (2) BKO Carbon 950 with 5% gamma-Fe2O3-large particle, (3) BKO 950 Carbon with 5% Fe2O3-nanoparticle, (4) BKO 950 Carbon with 2% Fe2O3-nanoparticle, (5) Carbon Mix 1 (78.3% BKO 950 Carbon, 10.1% Guar gum, 6.55% graphite, and 5.05% tobacco), (6) Carbon Mix 1 with 5% Fe2O3-nanoparticle, (7) Carbon Mix 2 (82.4% BKO Carbon 950, 10.6% Guar gum, and 7.0% graphite) and (8) Carbon Mix 2 with 5% Fe2O3-nanopaticle.
  • To simulate combustion of the fuel element, a pyroprobe was used to heat a small quantity of each sample to 700° C. in the presence of air for 20 seconds. 700° C. is the average temperature of a fuel element during combustion. The gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in FIG. 2. The pyroprobe and gas chromatogram injector were set at ambient temperature. A Molsieve chromatographic column was used for carbon monoxide resolution and a GS-CarbonPLOT chromatographic column was used for carbon dioxide resolution. A mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples. It should be noted that the carbon monoxide and the carbon dioxide contents quantified were only a fraction of the carbon monoxide and carbon dioxide contents produced by the samples and that the resolved peak areas were used for quantification. Table 2 summarizes the results produced by the samples in this example. TABLE 2 MASS ABUNDANCE (COUNTS)A SAMPLES CO CO2 CO/CO2 Ratio (1) BKO Carbon 950 136,632,880 439,836,557 0.311 (2) BKO Carbon 950 and 34,403,969 511,214,899 0.0673 5% γ-Fe2O3-large particle (3) BKO 950 and 5% 16,068,614 489,909,229 0.0328 Fe2O3-nanoparticle (4) BKO 950 and 2% 26,802,880 508,261,449 0.0527 Fe2O3-nanoparticle (5) Carbon Mix 1 98,093,373 458,829,259 0.214 (6) Carbon Mix 1 and 5% 89,003,804 491,290,439 0.181 Fe2O3-nanoparticle (7) Carbon Mix 2 105,287,470 463,439,227 0.227 (8) Carbon Mix 2 and 5% 34,534,408 478,608,718 0.0722 Fe2O3-nanoparticle
    AMass abundance is the total abundance of ions in a mass spectrum for compound with unit of counts.
  • The results summarized in Table 2, which are further illustrated in FIG. 10, demonstrate that ferric oxide (Fe2O3) ultrafine particles can effectuate a reduction in the amount of carbon monoxide produced by a fuel element. Comparison of the CO/CO2 ratios of sample (2) comprising 5% gamma-Fe2O3-large particle and sample (3) comprising 5% Fe2O3 nanoparticle reveals the dependency of catalytic activity on particle size. The smaller Fe2O3 ultrafine particles exhibit a greater surface area than the γ—Fe2O3-large particles which leads to higher catalyst turnover rates and a greater reduction in the amount of carbon monoxide produced by the fuel element upon heating. The Fe2O3 ultrafine particles of sample (3) reduced the carbon monoxide content of the gaseous mixture analyzed by 89.5%, which is an 11% increase over the γ—Fe2O3-large particles.
  • The results of the sample testing further demonstrate the catalytic activity of ferric oxide ultrafine particles in fuel elements that comprise the additional components of Guar gum and graphite. Sample (7) is an example of a fuel element containing these additional components. Sample (8) comprises the components of sample (7) with the addition of 5% by weight of ferric oxide (Fe2O3) ultrafine particles. The ferric oxide (Fe2O3) ultrafine particles reduced the carbon monoxide production of the fuel element of sample (8) by 68% in comparison with sample (7) which did not contain ferric oxide (Fe2O3) ultrafine particles.
  • Fuel elements containing tobacco components were additionally analyzed in this example. Sample (5) is a fuel element containing a 5.05% tobacco content in addition to BKO Carbon 950, Guar gum, and graphite. Sample (6) comprises the components of sample (5) with the addition of 5% by weight of ferric oxide (Fe2O3) nanoparticle. The ferric oxide (Fe2O3) ultrafine particles reduced the carbon monoxide production of the fuel element of sample (6) by 15.4% in comparison with sample (5) which did not contain ferric oxide (Fe2O3) ultrafine particles. The catalytic activity of the ferric oxide (Fe2O3) ultrafine particles in sample (6) was diminished due to the tobacco content in the fuel element composition. The combustion of tobacco produces several chemical species that inhibit the catalytic behavior of the ultrafine particles. This catalytic inhibition is displayed in the 15.4% reduction of carbon monoxide production.
  • EXAMPLE 4
  • Seven carbon samples were generated for analysis of CO/CO2 ratios. The sample were: (1) Control Carbon (BKO 950), (2) Carbon with 5% Fe2O3 ultrafine particles obtained from MACH-1, Inc., (3) Carbon with 5% Al2O3 ultrafine particles obtained from NEI, Inc., (4) Carbon with 5% CeO2 ultrafine particles obtained from NEI, Inc., (5) Carbon with 5% TiO2 ultrafine particles obtained from NEI, Inc., (6) Carbon with 5% tobacco and 5% Fe2O3 ultrafine particles obtained from MACH-1, Inc., and (7) Carbon with 5% tobacco (heat treated) and 5% Fe2O3 ultrafine particles obtained from MACH-1, Inc.
  • To simulate combustion of the fuel element, a pyroprobe was used to heat a small quantity of each sample to 700° C. in the presence of air for 20 seconds. 700° C. is the average temperature of a fuel element during combustion. The gaseous mixture resulting from the combustion of each sample was analyzed in accordance with the method delineated in FIG. 2. The pyroprobe and gas chromatogram injector were set at ambient temperature. A Molsieve chromatographic column was used for carbon monoxide resolution and a GC-CarbonPLOT chromatographic column was used for carbon dioxide resolution. A mass spectrometer was used as a second dimension of analysis in the quantification of the carbon monoxide and carbon dioxide contents generated by the samples. It should be noted that the carbon monoxide and the carbon dioxide contents quantified were only a fraction of the carbon monoxide and carbon dioxide contents produced by the samples and that the resolved peak areas were used for quantification. Table 3 summarizes the results produced by the samples in this example. TABLE 3 CO/ MASS ABUNDANCE CO2 (COUNTS)B Ra- SAMPLESA CO CO2 tio (1) Control Carbon (BKO 349,722,771 1,097,283,105 0.319 950) (2) Carbon and 5% Fe2O3 73,461,112 1,171,782,023 0.0627 ultrafine particles (3) Carbon and 5% Al2O3 323,332,586 988,477,673 0.327 ultrafine particles (4) Carbon and 5% CeO2 285,376,477 1,032,058,820 0.277 ultrafine particles (5) Carbon and 5% TiO2 379,654,967 1,164,775,102 0.326 ultrafine particles (6) Carbon, 5% Tobacco, 184,501,337 1,042,248.352 0.177 and 5% Fe2O3 ultrafine particles (7) Carbon, 5% Tobaccoc, 199,972,837 1,165,685,787 0.172 and 5% Fe2O3 ultrafine particles Air Blank 2,501,751 12,070,258
    AAll carbon samples were baked at 950 C. prior to the analysis.

    BMass abundance is the total abundance of ions in a mass spectrum for compound with unit of counts.

    cTobacco was heat-treated at 100° C. for 4 hours.
  • The results summarized in Table 3 and further illustrated in FIG. 11 reiterate the efficacy of ferric oxide (Fe2O3) ultrafine particles in reducing the carbon monoxide production of fuel elements according to the present invention. When compared to titanium oxide (TiO2), aluminum oxide (Al2O3), and ceric oxide (CeO2) ultrafine particles, ferric oxide (Fe2O3) ultrafine particles demonstrate a greater reduction in the carbon monoxide production of heated fuel elements. In this example, samples (3) and (5) containing aluminum oxide (Al2O3) and titanium oxide (TiO2) ultrafine particles respectively exhibited a slight increase in carbon monoxide content. Moreover, sample (4) comprising ceric oxide (CeO2) ultrafine particles displayed a carbon monoxide reduction of 13%. Sample (2) comprising ferric oxide (Fe2O3) ultrafine particles, however, exhibited a carbon monoxide reduction of 80%.
  • In samples (6) and (7), ferric oxide (Fe2O3) ultrafine particles were additionally incorporated into fuel elements that contained tobacco as well. The reduction of carbon monoxide produced from these fuel elements when heated was diminished due to the catalyst poisoning chemical species generated upon tobacco combustion.
  • EXAMPLE 5
  • Seven tobacco samples were generates for analysis of CO/CO2 ratios. The samples were: (1) Control Camel LT® Tobacco, (2) Camel LT® Tobacco with 5% Fe2O3 ultrafine particles, (3) Camel LT® Tobacco with 2% Fe2O3 ultrafine particles (4) Camel LT® Tobacco with 5% TiO2—Au ultrafine particles, (5) Camel LT® Tobacco with 2% TiO2—Au ultrafine particles, (6) Camel LT® Tobacco with 5% CeO2 ultrafine particles, and (7) Camel LT® Tobacco with 2% CeO2 ultrafine particles.
  • A Chemical Data System (CDS) Model 2000 pyroprobe was used for sample heating. A small quantity of each sample (approximately 7 mg) was heated at 700° C. in the presence of air for 20 seconds. The gaseous mixture resulting from the heating of each sample was analyzed in accordance with the method delineated in FIG. 2. The temperatures of the pyroprobe interface and the injector on the gas chromatogram were set at ambient temperature. The GC used was a Hewlett-Packard 5890 Series II gas chromatograph. A single injection onto dual columns was used for CO and CO2 analysis. A Molsieve column (Chrompack, 25 M×0.32 mm I.D., 30 μm film) was used for CO analysis. A GS-CarbonPLOT column (J&W Scientific, 60 M×0.32 mm I.D., 1.5 μm film) was used for CO2 analysis. The temperature of the CG columns was held at 35° C. for 10 minutes, programmed to 150° C. at 25° C./min and held for 10 min. A mass spectrometer (MS) was used to identify and quantify the resolved CO and CO2 peaks eluting from the gas chromatograph. The MS used was a Hewlett-Packard 5972 mass selective detector. The mass spectrometer was operated at 70 eV in the El mode. The temperature of the ion source was maintained at 180° C. and the mass range scanned was 20-200 atomic mass units. It should be noted that the CO and CO2 quantities determined were only a fraction of the total CO and CO2 content generates from the samples. Only the resolved CO and CO2 peak areas were used for quantification. Table 4 summarizes the results produced by the samples in this example. TABLE 4 MASS ABUNDANCE (COUNTS)A CO/CO2 SAMPLES CO CO2 Ratio (1) Camel LT Tobacco 544,728,554 1,383,849,048 0.394 (2) Camel LT ® Tobacco 526,196,075 1,343,828,130 0.392 with 5% Fe2O3 (3) Camel LT ® Tobacco 532,589,297 1,354,841,196 0.393 with 2% Fe2O3 (4) Camel LT ® Tobacco 540,678,974 1,370,604,676 0.395 with 5% TiO2-Au (5) Camel LT ® Tobacco 536,124,377 1,392,004,504 0.385 with 2% TiO2-Au (6) Camel LT ® Tobacco 529,191,513 1,361,128,568 0.389 with 5% CeO2 (7) Camel LT ® Tobacco 523,482,876 1,365,668,545 0.383 with 2% CeO2 Air Blank 655,583 7,602,213
    AMass abundance is the total abundance of ions in a mass spectrum for each compound with unit of counts.
  • The results summarized in Table 4 and further illustrated in FIG. 12 display that the catalytic activities of the metal and metal-oxide ultrafine particles comprising the catalyst compositions of the present invention are inhibited when combined with only tobacco to compose a fuel element. These results are consistent with fuel element samples of previous examples that contained specific amounts of tobacco. When heated or combusted, the tobacco content of the fuel element produces several chemical species that poison the catalytic ultrafine particles and thereby significantly reduce, if not eliminate, the catalytic oxidation of carbon monoxide to carbon dioxide. Consequently, tobacco components of fuel elements according to the present invention are disfavored. As displayed in the previous examples, however, a small component of tobacco within the fuel element does not destroy the catalytic activity of the metal oxide and metal ultrafine particles an appreciable amount and is, therefore, tolerable. The inclusion of a tobacco component in the fuel element of a smoking article can provide more flavor to the aerosol comprising the mainstream smoke of a smoking article.

Claims (20)

1. A fuel element comprising:
a carbonaceous material; and
at least one catalyst composition comprising ultrafine particles of a metal oxide, metal, or mixtures thereof.
2. The fuel element of claim 1, wherein the metal oxide comprises ferric oxide.
3. The fuel element of claim 1, wherein the metal comprises gold, copper, silver, platinum, palladium, rhodium, nickel, and mixtures thereof.
4. The fuel element of claim 1, wherein the catalyst composition comprises up to 5% by weight of the fuel element.
5. The fuel element of claim 1 wherein the ultrafine particles have an individual particle size up to about 1 micrometer.
6. The fuel element of claim 1, wherein the ultrafine particles have an individual particle size of up to about 5 nanometers.
7. The fuel element of claim 1, wherein the ultrafine particles have an individual particle size between about 2 and about 4 nanometers.
8. A smoking article comprising:
a fuel element comprising a carbonaceous material and at least one catalyst composition comprising ultrafine particles of a metal oxide, metal, or mixtures thereof; and
a physically separate aerosol generating means comprising at least one aerosol forming material.
9. The smoking article of claim 8 wherein the metal oxide comprises ferric oxide.
10. The smoking article of claim 8, wherein the catalyst composition is operable to convert carbon monoxide to carbon dioxide at temperatures between about 700° C. and about 950° C.
11. A method for reducing carbon monoxide production of a fuel element comprising:
incorporating a catalyst composition into the fuel element, the catalyst composition comprising:
ultrafine particles of a metal oxide, metal, or mixtures thereof.
12. The method of claim 11, wherein incorporating a catalyst composition into the fuel element comprises wash coating, dipping, painting, or spraying the fuel element with the catalyst composition.
13. The method of claim 11, wherein incorporating a catalyst composition into the fuel element comprises placing the catalyst composition in an inner core of the fuel element wherein the inner core is surrounded by an outer shell comprising carbonaceous material.
14. The method of claim 11, wherein incorporating a catalyst composition into a fuel element comprises placing the catalyst composition on a substrate located behind the fuel element.
15. The method of claim 14, wherein the substrate comprises an inert carbon material or a porous material.
16. A method for simultaneously quantifying a carbon monoxide content and a carbon dioxide content of a gaseous mixture comprising:
injecting the gaseous mixture into a split single injector of a gas chromatogram;
resolving the carbon monoxide content of the gaseous mixture on a first chromatographic column and simultaneously resolving the carbon dioxide content of the gaseous mixture on a second chromatographic column; and
detecting and quantifying the resolved carbon monoxide content and carbon dioxide content with a mass spectrometer.
17. The method of claim 16, wherein the gaseous mixture comprises smoke from a smoking article, mainstream smoke from a smoking article, smoke-like aerosol from a smoking article, or mixtures thereof.
18. An apparatus for simultaneously quantifying a carbon monoxide content and a carbon dioxide content of a gaseous mixture comprising:
a gas chromatograph comprising a split single injector and two chromatographic columns; and
a mass spectrometer.
19. The apparatus of claim 18, wherein one of the chromatographic columns possesses the ability to resolve carbon monoxide from a gaseous mixture, and the remaining chromatographic column possesses the ability to resolve carbon dioxide from a gaseous mixture.
20. The apparatus of claim 18, wherein the temperature of the split single injector of the gas chromatograph is variable.
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Cited By (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070207079A1 (en) * 2005-01-04 2007-09-06 Brady John T Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold
WO2007108877A2 (en) 2006-03-16 2007-09-27 R.J. Reynolds Tobacco Company Smoking article
US20100065075A1 (en) * 2008-09-18 2010-03-18 R.J. Reynoldds Tobacco Company Method for Preparing Fuel Element For Smoking Article
US20100125039A1 (en) * 2008-11-20 2010-05-20 R. J. Reynolds Tobacco Company Carbonaceous Material Having Modified Pore Structure
US20100122708A1 (en) * 2008-11-20 2010-05-20 R. J. Reynolds Tobacco Company Adsorbent Material Impregnated with Metal Oxide Component
EP2241203A2 (en) 2006-03-16 2010-10-20 R. J. Reynolds Tobacco Company Smoking Article
WO2011028372A1 (en) 2009-08-24 2011-03-10 R.J. Reynolds Tobacco Company Segmented smoking article with insulation mat
US20110108044A1 (en) * 2009-11-11 2011-05-12 R.J. Reynolds Tobacco Company Filter element comprising smoke-altering material
US20110180082A1 (en) * 2008-09-18 2011-07-28 R.J. Reynolds Tobacco Company Method for preparing fuel element for smoking article
WO2011139730A1 (en) 2010-05-06 2011-11-10 R.J. Reynolds Tobacco Company Segmented smoking article
WO2011140430A1 (en) 2010-05-07 2011-11-10 R. J. Reynolds Tobacco Company Filtered cigarette with modifiable sensory characteristics
WO2012016051A2 (en) 2010-07-30 2012-02-02 R. J. Reynolds Tobacco Company Filter element comprising multifunctional fibrous smoke-altering material
WO2012138630A1 (en) 2011-04-08 2012-10-11 R. J. Reynolds Tobacco Company Filtered cigarette comprising a tubular element in filter
WO2013043299A2 (en) 2011-09-20 2013-03-28 R.J. Reynolds Tobacco Company Segmented smoking article with substrate cavity
WO2013043806A2 (en) 2011-09-23 2013-03-28 R. J. Reynolds Tobacco Company Mixed fiber product for use in the manufacture of cigarette filter elements and related methods, systems, and apparatuses
US8424538B2 (en) 2010-05-06 2013-04-23 R.J. Reynolds Tobacco Company Segmented smoking article with shaped insulator
WO2013098380A1 (en) * 2011-12-29 2013-07-04 Philip Morris Products S.A. Composite heat source for a smoking article
WO2013148810A1 (en) 2012-03-28 2013-10-03 R. J. Reynolds Tobacco Company Smoking article incorporating a conductive substrate
WO2013158323A1 (en) 2012-04-17 2013-10-24 R.J. Reynolds Tobacco Company Method for preparing smoking articles
WO2014004648A1 (en) 2012-06-28 2014-01-03 R. J. Reynolds Tobacco Company Reservoir and heater system for controllable delivery of multiple aerosolizable materials in an electronic smoking article
WO2014018645A1 (en) 2012-07-25 2014-01-30 R. J. Reynolds Tobacco Company Mixed fiber sliver for use in the manufacture of cigarette filter elements
WO2014037794A2 (en) 2012-09-04 2014-03-13 R. J. Reynolds Tobacco Company Electronic smoking article comprising one or more microheaters
WO2014058678A1 (en) 2012-10-08 2014-04-17 R. J. Reynolds Tobacco Company An electronic smoking article and associated method
WO2014120479A1 (en) 2013-01-30 2014-08-07 R. J. Reynolds Tobacco Company Wick suitable for use in an electronic smoking article
US8839799B2 (en) 2010-05-06 2014-09-23 R.J. Reynolds Tobacco Company Segmented smoking article with stitch-bonded substrate
US8910639B2 (en) 2012-09-05 2014-12-16 R. J. Reynolds Tobacco Company Single-use connector and cartridge for a smoking article and related method
US9078473B2 (en) 2011-08-09 2015-07-14 R.J. Reynolds Tobacco Company Smoking articles and use thereof for yielding inhalation materials
US20150237913A1 (en) * 2012-10-18 2015-08-27 Japan Tobacco Inc. Non-burning type flavor inhaler
US9149072B2 (en) 2010-05-06 2015-10-06 R.J. Reynolds Tobacco Company Segmented smoking article with substrate cavity
WO2015180167A1 (en) * 2014-05-30 2015-12-03 深圳麦克韦尔股份有限公司 Electronic cigarette and atomizer thereof
US9220302B2 (en) 2013-03-15 2015-12-29 R.J. Reynolds Tobacco Company Cartridge for an aerosol delivery device and method for assembling a cartridge for a smoking article
US9277770B2 (en) 2013-03-14 2016-03-08 R. J. Reynolds Tobacco Company Atomizer for an aerosol delivery device formed from a continuously extending wire and related input, cartridge, and method
US9301546B2 (en) 2010-08-19 2016-04-05 R.J. Reynolds Tobacco Company Segmented smoking article with shaped insulator
WO2016119273A1 (en) * 2015-01-26 2016-08-04 梅小建 Packaging structure of electronic cigarette oil
US9423152B2 (en) 2013-03-15 2016-08-23 R. J. Reynolds Tobacco Company Heating control arrangement for an electronic smoking article and associated system and method
US9451791B2 (en) 2014-02-05 2016-09-27 Rai Strategic Holdings, Inc. Aerosol delivery device with an illuminated outer surface and related method
US9491974B2 (en) 2013-03-15 2016-11-15 Rai Strategic Holdings, Inc. Heating elements formed from a sheet of a material and inputs and methods for the production of atomizers
WO2017004185A2 (en) 2015-06-30 2017-01-05 R. J. Reynolds Tobacco Company Heat generation segment for an aerosol-generation system of a smoking article
WO2017040608A2 (en) 2015-08-31 2017-03-09 R. J. Reynolds Tobacco Company Smoking article
US9597466B2 (en) 2014-03-12 2017-03-21 R. J. Reynolds Tobacco Company Aerosol delivery system and related method, apparatus, and computer program product for providing control information to an aerosol delivery device via a cartridge
US9609893B2 (en) 2013-03-15 2017-04-04 Rai Strategic Holdings, Inc. Cartridge and control body of an aerosol delivery device including anti-rotation mechanism and related method
WO2017098464A1 (en) 2015-12-10 2017-06-15 R. J. Reynolds Tobacco Company Smoking article
WO2017145095A1 (en) 2016-02-24 2017-08-31 R. J. Reynolds Tobacco Company Smoking article comprising aerogel
US9788571B2 (en) 2013-09-25 2017-10-17 R.J. Reynolds Tobacco Company Heat generation apparatus for an aerosol-generation system of a smoking article, and associated smoking article
US9833019B2 (en) 2014-02-13 2017-12-05 Rai Strategic Holdings, Inc. Method for assembling a cartridge for a smoking article
US9839238B2 (en) 2014-02-28 2017-12-12 Rai Strategic Holdings, Inc. Control body for an electronic smoking article
US9839237B2 (en) 2013-11-22 2017-12-12 Rai Strategic Holdings, Inc. Reservoir housing for an electronic smoking article
US9877510B2 (en) 2014-04-04 2018-01-30 Rai Strategic Holdings, Inc. Sensor for an aerosol delivery device
US9918495B2 (en) 2014-02-28 2018-03-20 Rai Strategic Holdings, Inc. Atomizer for an aerosol delivery device and related input, aerosol production assembly, cartridge, and method
US9924741B2 (en) 2014-05-05 2018-03-27 Rai Strategic Holdings, Inc. Method of preparing an aerosol delivery device
US9974334B2 (en) 2014-01-17 2018-05-22 Rai Strategic Holdings, Inc. Electronic smoking article with improved storage of aerosol precursor compositions
US10031183B2 (en) 2013-03-07 2018-07-24 Rai Strategic Holdings, Inc. Spent cartridge detection method and system for an electronic smoking article
US10117460B2 (en) 2012-10-08 2018-11-06 Rai Strategic Holdings, Inc. Electronic smoking article and associated method
US10172387B2 (en) 2013-08-28 2019-01-08 Rai Strategic Holdings, Inc. Carbon conductive substrate for electronic smoking article
US10188140B2 (en) 2005-08-01 2019-01-29 R.J. Reynolds Tobacco Company Smoking article
US10238145B2 (en) 2015-05-19 2019-03-26 Rai Strategic Holdings, Inc. Assembly substation for assembling a cartridge for a smoking article
US10405579B2 (en) 2016-04-29 2019-09-10 Rai Strategic Holdings, Inc. Methods for assembling a cartridge for an aerosol delivery device, and associated systems and apparatuses

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* Cited by examiner, † Cited by third party
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RS58890B1 (en) 2011-06-02 2019-08-30 Philip Morris Products Sa Combustible heat source for a smoking article
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CN107348561A (en) * 2016-05-10 2017-11-17 韩力 Micro-explosion micro-capsule for smoke product and smoke product including same

Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4708151A (en) * 1986-03-14 1987-11-24 R. J. Reynolds Tobacco Company Pipe with replaceable cartridge
US4756318A (en) * 1985-10-28 1988-07-12 R. J. Reynolds Tobacco Company Smoking article with tobacco jacket
US4793365A (en) * 1984-09-14 1988-12-27 R. J. Reynolds Tobacco Company Smoking article
US4807809A (en) * 1988-02-12 1989-02-28 R. J. Reynolds Tobacco Company Rod making apparatus for smoking article manufacture
US4889143A (en) * 1986-05-14 1989-12-26 R. J. Reynolds Tobacco Company Cigarette rods and filters containing strands provided from sheet-like materials
US4961438A (en) * 1989-04-03 1990-10-09 Brown & Williamson Tobacco Corporation Smoking device
US4991596A (en) * 1989-07-11 1991-02-12 R. J. Reynolds Tobacco Company Smoking article
US4991606A (en) * 1988-07-22 1991-02-12 Philip Morris Incorporated Smoking article
US5016654A (en) * 1988-12-21 1991-05-21 R. J. Reynolds Tobacco Company Flavor substances for smoking articles
US5020548A (en) * 1985-08-26 1991-06-04 R. J. Reynolds Tobacco Company Smoking article with improved fuel element
US5025814A (en) * 1987-05-12 1991-06-25 R. J. Reynolds Tobacco Company Cigarette filters containing strands of tobacco-containing materials
US5038802A (en) * 1988-12-21 1991-08-13 R. J. Reynolds Tobacco Company Flavor substances for smoking articles
US5040551A (en) * 1988-11-01 1991-08-20 Catalytica, Inc. Optimizing the oxidation of carbon monoxide
US5065776A (en) * 1990-08-29 1991-11-19 R. J. Reynolds Tobacco Company Cigarette with tobacco/glass fuel wrapper
US5076295A (en) * 1989-09-29 1991-12-31 R. J. Reynolds Tobacco Company Cigarette filter
US5076297A (en) * 1986-03-14 1991-12-31 R. J. Reynolds Tobacco Company Method for preparing carbon fuel for smoking articles and product produced thereby
US5101839A (en) * 1990-08-15 1992-04-07 R. J. Reynolds Tobacco Company Cigarette and smokable filler material therefor
US5105834A (en) * 1989-12-18 1992-04-21 R.J. Reynolds Tobacco Company Cigarette and cigarette filter element therefor
US5105838A (en) * 1990-10-23 1992-04-21 R.J. Reynolds Tobacco Company Cigarette
US5105836A (en) * 1989-09-29 1992-04-21 R. J. Reynolds Tobacco Company Cigarette and smokable filler material therefor
US5148821A (en) * 1990-08-17 1992-09-22 R. J. Reynolds Tobacco Company Processes for producing a smokable and/or combustible tobacco material
US5178167A (en) * 1991-06-28 1993-01-12 R. J. Reynolds Tobacco Company Carbonaceous composition for fuel elements of smoking articles and method of modifying the burning characteristics thereof
US5183062A (en) * 1990-02-27 1993-02-02 R. J. Reynolds Tobacco Company Cigarette
US5211684A (en) * 1989-01-10 1993-05-18 R. J. Reynolds Tobacco Company Catalyst containing smoking articles for reducing carbon monoxide
US5240014A (en) * 1990-07-20 1993-08-31 Philip Morris Incorporated Catalytic conversion of carbon monoxide from carbonaceous heat sources
US5246018A (en) * 1991-07-19 1993-09-21 Philip Morris Incorporated Manufacturing of composite heat sources containing carbon and metal species
US5258340A (en) * 1991-02-15 1993-11-02 Philip Morris Incorporated Mixed transition metal oxide catalysts for conversion of carbon monoxide and method for producing the catalysts
US5303720A (en) * 1989-05-22 1994-04-19 R. J. Reynolds Tobacco Company Smoking article with improved insulating material
US5345955A (en) * 1992-09-17 1994-09-13 R. J. Reynolds Tobacco Company Composite fuel element for smoking articles
US5396911A (en) * 1990-08-15 1995-03-14 R. J. Reynolds Tobacco Company Substrate material for smoking articles
US5551451A (en) * 1993-04-07 1996-09-03 R. J. Reynolds Tobacco Company Fuel element composition
US5595577A (en) * 1993-06-02 1997-01-21 Bensalem; Azzedine Method for making a carbonaceous heat source containing metal oxide
US20020014453A1 (en) * 2000-02-07 2002-02-07 Lilly A. Clifton Filtering unsaturated hydrocarbons using intermetallic nano-clusters
US20020127351A1 (en) * 2001-03-12 2002-09-12 Futaba Corporation Method for preparing nano-carbon and nano-carbon prepared by such method and composite material or mixed material containing nano-carbon and metal fine particle, apparatus for preparing nano-carbon, method for patterning nano-carbon and nano carbon base material patterned by the use of such method, as well as electron emission source using such patterned nano-carbon base material
US6467897B1 (en) * 2001-01-08 2002-10-22 3M Innovative Properties Company Energy curable inks and other compositions incorporating surface modified, nanometer-sized particles
US6472459B2 (en) * 1999-06-02 2002-10-29 Sandia Corporation Fabrication of metallic microstructures by micromolding nanoparticles
US6479146B1 (en) * 1998-03-19 2002-11-12 Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften, E.V. Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates
US6479156B1 (en) * 1997-05-14 2002-11-12 Institut für Neue Materialien Gemeinnützige GmbH Nanocomposite for thermal insulation
US20020167118A1 (en) * 2001-03-23 2002-11-14 Romain Billiet Porous nanostructures and method of fabrication thereof
US20020172826A1 (en) * 1998-11-06 2002-11-21 Tapesh Yadav Nanoscale catalyst compositions from complex and non-stoichiometric compositions
US20020194958A1 (en) * 2001-06-08 2002-12-26 Chien-Liang Lee Process for preparing noble metal nanoparticles
US20030000538A1 (en) * 2000-11-10 2003-01-02 Bereman Robert D. Method and product for removing carcinogens from tobacco smoke
US6503475B1 (en) * 1998-05-15 2003-01-07 Advanced Nano Technologies Pty Ltd. Process for the production of ultrafine powders of metal oxides
US20030131859A1 (en) * 2001-08-31 2003-07-17 Ping Li Oxidant/catalyst nanoparticles to reduce tobacco smoke constituents such as carbon monoxide
US20040173229A1 (en) * 2003-03-05 2004-09-09 Crooks Evon Llewellyn Smoking article comprising ultrafine particles

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990010394A1 (en) * 1989-03-16 1990-09-20 R.J. Reynolds Tobacco Company Catalyst containing smoking articles for reducing carbon monoxide
JPH03296659A (en) * 1990-04-17 1991-12-27 Osaka Oxygen Ind Ltd Analysis of carbon monoxide in gas
CA2079495A1 (en) * 1991-10-03 1993-04-04 John H. Kolts Smoking article with co oxidation catalyst
US6769437B2 (en) * 2002-04-08 2004-08-03 Philip Morris Incorporated Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette
PL204274B1 (en) * 2002-04-12 2009-12-31 Philip Morris Products, S.A. PARTIALLY REDUCED NANOPARTICLE ADDITIVES for using to reduce the amount of carbon monoxide and/or nitric oxide present in mainstream smoke

Patent Citations (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4793365A (en) * 1984-09-14 1988-12-27 R. J. Reynolds Tobacco Company Smoking article
US5020548A (en) * 1985-08-26 1991-06-04 R. J. Reynolds Tobacco Company Smoking article with improved fuel element
US4756318A (en) * 1985-10-28 1988-07-12 R. J. Reynolds Tobacco Company Smoking article with tobacco jacket
US4708151A (en) * 1986-03-14 1987-11-24 R. J. Reynolds Tobacco Company Pipe with replaceable cartridge
US5076297A (en) * 1986-03-14 1991-12-31 R. J. Reynolds Tobacco Company Method for preparing carbon fuel for smoking articles and product produced thereby
US4889143A (en) * 1986-05-14 1989-12-26 R. J. Reynolds Tobacco Company Cigarette rods and filters containing strands provided from sheet-like materials
US5025814A (en) * 1987-05-12 1991-06-25 R. J. Reynolds Tobacco Company Cigarette filters containing strands of tobacco-containing materials
US4807809A (en) * 1988-02-12 1989-02-28 R. J. Reynolds Tobacco Company Rod making apparatus for smoking article manufacture
US4991606A (en) * 1988-07-22 1991-02-12 Philip Morris Incorporated Smoking article
US5040551A (en) * 1988-11-01 1991-08-20 Catalytica, Inc. Optimizing the oxidation of carbon monoxide
US5016654A (en) * 1988-12-21 1991-05-21 R. J. Reynolds Tobacco Company Flavor substances for smoking articles
US5038802A (en) * 1988-12-21 1991-08-13 R. J. Reynolds Tobacco Company Flavor substances for smoking articles
US5211684A (en) * 1989-01-10 1993-05-18 R. J. Reynolds Tobacco Company Catalyst containing smoking articles for reducing carbon monoxide
US4961438A (en) * 1989-04-03 1990-10-09 Brown & Williamson Tobacco Corporation Smoking device
US5303720A (en) * 1989-05-22 1994-04-19 R. J. Reynolds Tobacco Company Smoking article with improved insulating material
US4991596A (en) * 1989-07-11 1991-02-12 R. J. Reynolds Tobacco Company Smoking article
US5076295A (en) * 1989-09-29 1991-12-31 R. J. Reynolds Tobacco Company Cigarette filter
US5105836A (en) * 1989-09-29 1992-04-21 R. J. Reynolds Tobacco Company Cigarette and smokable filler material therefor
US5105834A (en) * 1989-12-18 1992-04-21 R.J. Reynolds Tobacco Company Cigarette and cigarette filter element therefor
US5183062A (en) * 1990-02-27 1993-02-02 R. J. Reynolds Tobacco Company Cigarette
US5240014A (en) * 1990-07-20 1993-08-31 Philip Morris Incorporated Catalytic conversion of carbon monoxide from carbonaceous heat sources
US5396911A (en) * 1990-08-15 1995-03-14 R. J. Reynolds Tobacco Company Substrate material for smoking articles
US5101839A (en) * 1990-08-15 1992-04-07 R. J. Reynolds Tobacco Company Cigarette and smokable filler material therefor
US5148821A (en) * 1990-08-17 1992-09-22 R. J. Reynolds Tobacco Company Processes for producing a smokable and/or combustible tobacco material
US5065776A (en) * 1990-08-29 1991-11-19 R. J. Reynolds Tobacco Company Cigarette with tobacco/glass fuel wrapper
US5105838A (en) * 1990-10-23 1992-04-21 R.J. Reynolds Tobacco Company Cigarette
US5258340A (en) * 1991-02-15 1993-11-02 Philip Morris Incorporated Mixed transition metal oxide catalysts for conversion of carbon monoxide and method for producing the catalysts
US5178167A (en) * 1991-06-28 1993-01-12 R. J. Reynolds Tobacco Company Carbonaceous composition for fuel elements of smoking articles and method of modifying the burning characteristics thereof
US5246018A (en) * 1991-07-19 1993-09-21 Philip Morris Incorporated Manufacturing of composite heat sources containing carbon and metal species
US5345955A (en) * 1992-09-17 1994-09-13 R. J. Reynolds Tobacco Company Composite fuel element for smoking articles
US5551451A (en) * 1993-04-07 1996-09-03 R. J. Reynolds Tobacco Company Fuel element composition
US5595577A (en) * 1993-06-02 1997-01-21 Bensalem; Azzedine Method for making a carbonaceous heat source containing metal oxide
US6479156B1 (en) * 1997-05-14 2002-11-12 Institut für Neue Materialien Gemeinnützige GmbH Nanocomposite for thermal insulation
US6479146B1 (en) * 1998-03-19 2002-11-12 Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften, E.V. Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates
US6503475B1 (en) * 1998-05-15 2003-01-07 Advanced Nano Technologies Pty Ltd. Process for the production of ultrafine powders of metal oxides
US20020172826A1 (en) * 1998-11-06 2002-11-21 Tapesh Yadav Nanoscale catalyst compositions from complex and non-stoichiometric compositions
US6472459B2 (en) * 1999-06-02 2002-10-29 Sandia Corporation Fabrication of metallic microstructures by micromolding nanoparticles
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US20030000538A1 (en) * 2000-11-10 2003-01-02 Bereman Robert D. Method and product for removing carcinogens from tobacco smoke
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US20020127351A1 (en) * 2001-03-12 2002-09-12 Futaba Corporation Method for preparing nano-carbon and nano-carbon prepared by such method and composite material or mixed material containing nano-carbon and metal fine particle, apparatus for preparing nano-carbon, method for patterning nano-carbon and nano carbon base material patterned by the use of such method, as well as electron emission source using such patterned nano-carbon base material
US20020167118A1 (en) * 2001-03-23 2002-11-14 Romain Billiet Porous nanostructures and method of fabrication thereof
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US20030131859A1 (en) * 2001-08-31 2003-07-17 Ping Li Oxidant/catalyst nanoparticles to reduce tobacco smoke constituents such as carbon monoxide
US20040173229A1 (en) * 2003-03-05 2004-09-09 Crooks Evon Llewellyn Smoking article comprising ultrafine particles

Cited By (107)

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Publication number Priority date Publication date Assignee Title
US8058202B2 (en) 2005-01-04 2011-11-15 3M Innovative Properties Company Heterogeneous, composite, carbonaceous catalyst system and methods that use catalytically active gold
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US8678013B2 (en) 2005-08-01 2014-03-25 R.J. Reynolds Tobacco Company Smoking article
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US8617263B2 (en) 2008-09-18 2013-12-31 R. J. Reynolds Tobacco Company Method for preparing fuel element for smoking article
US20110180082A1 (en) * 2008-09-18 2011-07-28 R.J. Reynolds Tobacco Company Method for preparing fuel element for smoking article
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US9332784B2 (en) 2008-09-18 2016-05-10 R.J. Reynolds Tobacco Company Method for preparing fuel element for smoking article
US20100065075A1 (en) * 2008-09-18 2010-03-18 R.J. Reynoldds Tobacco Company Method for Preparing Fuel Element For Smoking Article
US20130255703A1 (en) * 2008-09-18 2013-10-03 R. J. Reynolds Tobacco Company Method for preparing fuel element for smoking article
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US8119555B2 (en) 2008-11-20 2012-02-21 R. J. Reynolds Tobacco Company Carbonaceous material having modified pore structure
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US9119420B2 (en) 2010-07-30 2015-09-01 R.J. Reynolds Tobacco Company Filter element comprising multifunctional fibrous smoke-altering material
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US10362809B2 (en) 2011-08-09 2019-07-30 Rai Strategic Holdings, Inc. Smoking articles and use thereof for yielding inhalation materials
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US9078473B2 (en) 2011-08-09 2015-07-14 R.J. Reynolds Tobacco Company Smoking articles and use thereof for yielding inhalation materials
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RU2608274C2 (en) * 2011-12-29 2017-01-17 Филип Моррис Продактс С.А. Composite heat source for smoking article
WO2013098380A1 (en) * 2011-12-29 2013-07-04 Philip Morris Products S.A. Composite heat source for a smoking article
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WO2013148810A1 (en) 2012-03-28 2013-10-03 R. J. Reynolds Tobacco Company Smoking article incorporating a conductive substrate
WO2013158323A1 (en) 2012-04-17 2013-10-24 R.J. Reynolds Tobacco Company Method for preparing smoking articles
US9345268B2 (en) 2012-04-17 2016-05-24 R.J. Reynolds Tobacco Company Method for preparing smoking articles
WO2014004648A1 (en) 2012-06-28 2014-01-03 R. J. Reynolds Tobacco Company Reservoir and heater system for controllable delivery of multiple aerosolizable materials in an electronic smoking article
US10004259B2 (en) 2012-06-28 2018-06-26 Rai Strategic Holdings, Inc. Reservoir and heater system for controllable delivery of multiple aerosolizable materials in an electronic smoking article
WO2014018645A1 (en) 2012-07-25 2014-01-30 R. J. Reynolds Tobacco Company Mixed fiber sliver for use in the manufacture of cigarette filter elements
US8881737B2 (en) 2012-09-04 2014-11-11 R.J. Reynolds Tobacco Company Electronic smoking article comprising one or more microheaters
US9980512B2 (en) 2012-09-04 2018-05-29 Rai Strategic Holdings, Inc. Electronic smoking article comprising one or more microheaters
WO2014037794A2 (en) 2012-09-04 2014-03-13 R. J. Reynolds Tobacco Company Electronic smoking article comprising one or more microheaters
US8910639B2 (en) 2012-09-05 2014-12-16 R. J. Reynolds Tobacco Company Single-use connector and cartridge for a smoking article and related method
US9949508B2 (en) 2012-09-05 2018-04-24 Rai Strategic Holdings, Inc. Single-use connector and cartridge for a smoking article and related method
WO2014058678A1 (en) 2012-10-08 2014-04-17 R. J. Reynolds Tobacco Company An electronic smoking article and associated method
US10117460B2 (en) 2012-10-08 2018-11-06 Rai Strategic Holdings, Inc. Electronic smoking article and associated method
US9854841B2 (en) 2012-10-08 2018-01-02 Rai Strategic Holdings, Inc. Electronic smoking article and associated method
US10420372B2 (en) * 2012-10-18 2019-09-24 Japan Tobacco Inc. Non-burning type flavor inhaler
US20150237913A1 (en) * 2012-10-18 2015-08-27 Japan Tobacco Inc. Non-burning type flavor inhaler
US9854847B2 (en) 2013-01-30 2018-01-02 Rai Strategic Holdings, Inc. Wick suitable for use in an electronic smoking article
WO2014120479A1 (en) 2013-01-30 2014-08-07 R. J. Reynolds Tobacco Company Wick suitable for use in an electronic smoking article
US8910640B2 (en) 2013-01-30 2014-12-16 R.J. Reynolds Tobacco Company Wick suitable for use in an electronic smoking article
US10258089B2 (en) 2013-01-30 2019-04-16 Rai Strategic Holdings, Inc. Wick suitable for use in an electronic smoking article
US10031183B2 (en) 2013-03-07 2018-07-24 Rai Strategic Holdings, Inc. Spent cartridge detection method and system for an electronic smoking article
US10274539B2 (en) 2013-03-07 2019-04-30 Rai Strategic Holdings, Inc. Aerosol delivery device
US9277770B2 (en) 2013-03-14 2016-03-08 R. J. Reynolds Tobacco Company Atomizer for an aerosol delivery device formed from a continuously extending wire and related input, cartridge, and method
US10306924B2 (en) 2013-03-14 2019-06-04 Rai Strategic Holdings, Inc. Atomizer for an aerosol delivery device formed from a continuously extending wire and related input, cartridge, and method
US9609893B2 (en) 2013-03-15 2017-04-04 Rai Strategic Holdings, Inc. Cartridge and control body of an aerosol delivery device including anti-rotation mechanism and related method
US9220302B2 (en) 2013-03-15 2015-12-29 R.J. Reynolds Tobacco Company Cartridge for an aerosol delivery device and method for assembling a cartridge for a smoking article
US9491974B2 (en) 2013-03-15 2016-11-15 Rai Strategic Holdings, Inc. Heating elements formed from a sheet of a material and inputs and methods for the production of atomizers
US9423152B2 (en) 2013-03-15 2016-08-23 R. J. Reynolds Tobacco Company Heating control arrangement for an electronic smoking article and associated system and method
US10143236B2 (en) 2013-03-15 2018-12-04 Rai Strategic Holdings, Inc. Cartridge for an aerosol delivery device and method for assembling a cartridge for a smoking article
US10172387B2 (en) 2013-08-28 2019-01-08 Rai Strategic Holdings, Inc. Carbon conductive substrate for electronic smoking article
US10314330B2 (en) 2013-09-25 2019-06-11 R.J. Reynolds Tobacco Company Heat generation apparatus for an aerosol-generation system of a smoking article, and associated smoking article
US9788571B2 (en) 2013-09-25 2017-10-17 R.J. Reynolds Tobacco Company Heat generation apparatus for an aerosol-generation system of a smoking article, and associated smoking article
US9839237B2 (en) 2013-11-22 2017-12-12 Rai Strategic Holdings, Inc. Reservoir housing for an electronic smoking article
US9974334B2 (en) 2014-01-17 2018-05-22 Rai Strategic Holdings, Inc. Electronic smoking article with improved storage of aerosol precursor compositions
US9451791B2 (en) 2014-02-05 2016-09-27 Rai Strategic Holdings, Inc. Aerosol delivery device with an illuminated outer surface and related method
US9833019B2 (en) 2014-02-13 2017-12-05 Rai Strategic Holdings, Inc. Method for assembling a cartridge for a smoking article
US9918495B2 (en) 2014-02-28 2018-03-20 Rai Strategic Holdings, Inc. Atomizer for an aerosol delivery device and related input, aerosol production assembly, cartridge, and method
US9839238B2 (en) 2014-02-28 2017-12-12 Rai Strategic Holdings, Inc. Control body for an electronic smoking article
US9597466B2 (en) 2014-03-12 2017-03-21 R. J. Reynolds Tobacco Company Aerosol delivery system and related method, apparatus, and computer program product for providing control information to an aerosol delivery device via a cartridge
US9877510B2 (en) 2014-04-04 2018-01-30 Rai Strategic Holdings, Inc. Sensor for an aerosol delivery device
US9924741B2 (en) 2014-05-05 2018-03-27 Rai Strategic Holdings, Inc. Method of preparing an aerosol delivery device
WO2015180167A1 (en) * 2014-05-30 2015-12-03 深圳麦克韦尔股份有限公司 Electronic cigarette and atomizer thereof
WO2016119273A1 (en) * 2015-01-26 2016-08-04 梅小建 Packaging structure of electronic cigarette oil
US10238145B2 (en) 2015-05-19 2019-03-26 Rai Strategic Holdings, Inc. Assembly substation for assembling a cartridge for a smoking article
US20170000188A1 (en) * 2015-06-30 2017-01-05 R.J. Reynolds Tobacco Company Heat generation segment for an aerosol-generation system of a smoking article
WO2017004185A2 (en) 2015-06-30 2017-01-05 R. J. Reynolds Tobacco Company Heat generation segment for an aerosol-generation system of a smoking article
US10154689B2 (en) * 2015-06-30 2018-12-18 R.J. Reynolds Tobacco Company Heat generation segment for an aerosol-generation system of a smoking article
WO2017040608A2 (en) 2015-08-31 2017-03-09 R. J. Reynolds Tobacco Company Smoking article
US10314334B2 (en) 2015-12-10 2019-06-11 R.J. Reynolds Tobacco Company Smoking article
WO2017098464A1 (en) 2015-12-10 2017-06-15 R. J. Reynolds Tobacco Company Smoking article
WO2017145095A1 (en) 2016-02-24 2017-08-31 R. J. Reynolds Tobacco Company Smoking article comprising aerogel
US10405579B2 (en) 2016-04-29 2019-09-10 Rai Strategic Holdings, Inc. Methods for assembling a cartridge for an aerosol delivery device, and associated systems and apparatuses

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