US20030005940A1 - Smoking article including a selective carbon monoxide pump - Google Patents

Smoking article including a selective carbon monoxide pump Download PDF

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Publication number
US20030005940A1
US20030005940A1 US10/233,876 US23387602A US2003005940A1 US 20030005940 A1 US20030005940 A1 US 20030005940A1 US 23387602 A US23387602 A US 23387602A US 2003005940 A1 US2003005940 A1 US 2003005940A1
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Prior art keywords
carbon monoxide
pump
pump according
adsorbent
catalyst
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US10/233,876
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Alexander Dyakonov
David Grider
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Lorillard Licensing Co LLC
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Individual
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Priority to US10/233,876 priority Critical patent/US20030005940A1/en
Assigned to LORILLARD LICENSING COMPANY, LLC reassignment LORILLARD LICENSING COMPANY, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DYAKONOV, ALEXANDER J., GRIDER, DAVID A.
Publication of US20030005940A1 publication Critical patent/US20030005940A1/en
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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials

Definitions

  • the present invention relates generally to a smoking article and, more particularly, to a carbon monoxide pump for removing carbon monoxide from main stream smoke during the combustion of a smoking article.
  • An alternative approach to adsorbing carbon monoxide is to oxidize it, for example, by the catalytic oxidation to carbon dioxide.
  • a difficulty with this approach is that the temperature of the main stream smoke is substantially that of the environment. These low temperatures make it difficult to oxidize carbon monoxide to carbon dioxide even when using a catalyst.
  • the present invention fulfills this need by providing a smoking article including a tobacco column; a wrapper surrounding the tobacco column; and a carbon monoxide pump.
  • the pump includes a separator, an adsorbent for carbon monoxide downstream from said separator and may include a catalyst for oxidizing carbon monoxide to carbon dioxide.
  • the carbon monoxide pump selectively diverts carbon monoxide from main stream combustion products
  • the separator impedes the entry of large molecules into the carbon monoxide pump
  • the catalyst at least partially oxidizes the carbon monoxide to carbon dioxide
  • the venting holes provide an alternative path for the diverted carbon monoxide and the oxidized carbon monoxide to reduce inhalation by a smoker.
  • venting holes adjacent to the adsorbent to facilitate the further diversion of carbon monoxide from main stream smoke.
  • the catalyst may be at least one of a transition metal, an oxide of a transition metal, and a transition metal and an oxide of a transition metal, such as any one of a rare earth metal, a platinum group metal, their alloys, their mixtures and combinations thereof.
  • Some transition metals that may work well include at least one of copper, cobalt, iron, silver, nickel, palladium.
  • Applicants have found that at least silver, its alloys, mixtures including silver and combinations thereof and, preferably, with silver in the form of an oxide work satisfactorily. Also, applicants have found that at least one of silver and palladium, their alloys, their mixtures and combinations thereof and, preferably, with silver in the form of an oxide of silver work satisfactorily. Further, applicants have found that at least nickel, its alloys, mixtures including nickel and combinations thereof and, preferably, with nickel in the form of an oxide of nickel work satisfactorily. Moreover, applicants have found that at least one of copper and palladium, their alloys, their mixtures and combinations thereof and, preferably, in the form of a Wacker type catalyst and, more preferably, in the form of a modified Wacker type catalyst work well.
  • the CO pump includes at least one additional filter element, preferably cellulose acetate.
  • a catalyst may be distributed through the at least one additional filter element.
  • the concentration of carbon monoxide is increased, thereby increasing the flux of carbon monoxide from the adsorbent.
  • the adsorbing is momentary, preferably for between about 0.1 and about 10 seconds.
  • the separator is a molecular sieve.
  • the effective aperture size is selected to be large enough to permit carbon monoxide to pass while at the same time preventing larger molecules from entering. Applicants believe that an effective aperture size from about 3 angstroms ( ⁇ ) and greater will permit carbon monoxide to enter while a the same time an effective aperture size is up to about 9 angstroms ( ⁇ ) will prevent certain larger molecules from entering. Alternatively if there is any hydrolyzation anticipated, a good starting point may be an effective aperture size from about 5 angstroms ( ⁇ ) and greater may permit carbon monoxide to enter while at the same time an effective aperture size is up to about 9 angstroms ( ⁇ ) will prevent certain larger molecules from entering.
  • the molecular sieve may exhibit properties of an adsorbent.
  • the molecular sieve may be any one of a zeolite, whether occurring in nature, or synthetic or combination thereof, and an oxide.
  • the oxide may be an oxide of at least one of silicon, aluminum, magnesium, their mixtures and their compounds.
  • the oxide may be a dehydrated oxide, such as an oxide of aluminum.
  • the oxide may be amorphous.
  • the adsorbent is a zeolite such as an oxide, more preferably, at least one of silicon, aluminum, magnesium, their mixtures and their compounds.
  • a dehydrated oxide, particularly of aluminum has been found to be effective.
  • An amorphous oxide may also work.
  • the adsorbent is a support for the catalyst.
  • anyone of the one of the separator, the adsorbent, and the separator and the adsorbent may be a support for the catalyst.
  • one aspect of the present invention is to provide a smoking article including a tobacco column, a wrapper surrounding the tobacco column; and a carbon monoxide pump.
  • the carbon monoxide pump may include a separator and an adsorbent for carbon monoxide downstream from said separator.
  • the separator may impede the entry of large molecules into the carbon monoxide pump while permitting the adsorbent to accumulate the carbon monoxide from main stream combustion products.
  • Another aspect of the present invention is to provide a carbon monoxide pump for use in a smoking article including a tobacco column and a wrapper surrounding the tobacco column.
  • the carbon monoxide pump includes a separator, an adsorbent for carbon monoxide downstream from said separator; and a catalyst.
  • the carbon monoxide pump selectively diverts carbon monoxide from main stream combustion products by having the separator to impede the entry of large molecules into the carbon monoxide pump while permitting the adsorbent to accumulate the carbon monoxide from main stream combustion products and the catalyst at least partially oxidizes the carbon monoxide to carbon dioxide prior to being inhaled by a smoker.
  • Still another aspect of the present invention is to provide a smoking article including a tobacco column; a wrapper surrounding the tobacco column; and a carbon monoxide pump.
  • the pump includes a separator, an adsorbent for carbon monoxide downstream from said separator; a catalyst for oxidizing carbon monoxide to carbon dioxide, and venting holes adjacent to the adsorbent.
  • the carbon monoxide pump selectively diverts carbon monoxide from main stream combustion products by having the separator to impede the entry of large molecules into the carbon monoxide pump while permitting the adsorbent to accumulate the carbon monoxide from main stream combustion products, the catalyst at least partially oxidizes the carbon monoxide to carbon dioxide and the venting holes providing an alternative path for the diverted carbon monoxide and the oxidized carbon monoxide to check inhalation by a smoker.
  • the invention also provides a mouthpiece for a smoking article including a fitting to receive a smoking article, and a carbon monoxide pump including an adsorbent for adsorbing carbon monoxide, wherein the carbon monoxide pump is positioned with respect to the smoking article so as to selectively divert carbon monoxide from main stream combustion products prior to inhaling by a smoker.
  • FIG. 1A is a smoking article according to the present invention.
  • FIG. 1B is an exploded view of the smoking article of FIG. 1A;
  • FIG. 2 is a schematic of a tobacco column adjacent to a selective carbon monoxide pump according to the present invention
  • FIG. 3 is a block flow diagram for a carbon monoxide pump according to the present invention.
  • FIG. 4 is a partial perspective view of a mouthpiece according to the invention.
  • FIG. 5 shows retention time of an about 1 ml about 2%CO in He pulse in an about 10 ml zeolite bed at about ambient temperature against about 3, 4, 5 and 9 ⁇ pore size zeolites equilibrated with about 60% humidity room air (o) and annealed at about 300° C. for about 10 hrs (*) prior to injection;
  • FIG. 6 shows retention time of CO (o) and N 2 ( ⁇ ) pulses in an about 5 ⁇ zeolite vs. time elapsed from purging of dry zeolite with an about 60% humid air for about 1 hour, the other experiment conditions are in FIG. 5;
  • FIG. 7 a shows concentration profiles of CO and CO 2 during CO oxidation on air-dry (PdCl 2 +CuCl 2 )/C catalyst at about ambient temperature with about 50 ml/min (about 3% CO+12% O 2 +He) gas mixture passing through about 1 g of catalyst;
  • FIG. 7 b shows the concentration profiles of water and O 2 during CO oxidation on air-dry (PdCl 2 +CuCl 2 )/C catalyst at about ambient temperature with about 50 ml/min (about 3% CO+12% O 2 +He) gas mixture passing through about 1 g of catalyst;
  • FIG. 8 a shows concentration profile of the outlet gas after the 1 st pulse of about 1 ml CO through (PdCl 2 +CuCl 2 +Cu(NO 3 ) 2 )/C catalyst at about ambient temperature in an about 100 ml/min flow of about 10%O 2 in He;
  • FIG. 8 b shows concentration profile of the outlet gas after the 7 th pulse of about 1 ml CO through (PdCl 2 +CuCl 2 +Cu(NO 3 ) 2 )/C catalyst at about ambient temperature in an about 100 ml/min flow of about 10%O 2 in He;
  • FIG. 8 c shows concentration profile of the outlet gas after the 42 nd pulse of about 1 ml CO through (PdCl 2 +CuCl 2 +Cu(NO 3 ) 2 )/C catalyst at about ambient temperature in an about 100 ml/min flow of about 10%O 2 in He;
  • FIG. 9 a shows profiles of the catalyst temperature during CO oxidation in a series of pulses of about 1 ml CO pulses through (PdCl 2 +CuCl 2 +Cu(NO 3 ) 2 )/C catalyst at ambient temperature in a about 100 ml/min flow of 10%O 2 in He;
  • FIG. 9 b shows the integral value of the heats of CO during CO oxidation in a series of pulses of about 1 ml CO pulses through (PdCl 2 +CuCl 2 +Cu(NO 3 ) 2 )/C catalyst at ambient temperature in a about 100 ml/min flow of 10%O 2 in He;
  • FIG. 10 a shows concentration profiles of the outlet gas after the 1 st pulse of about 1 ml CO through the dehydrated (PdCl 2 +CuCl 2 +Cu(NO3)2)/C catalyst under the experimental catalysis conditions described in FIG. 9;
  • FIG. 10 b shows concentration profiles of the outlet gas after the 15 th pulse of about 1 ml CO through the dehydrated (PdCl 2 +CuCl 2 +Cu(NO 3 ) 2 )/C catalyst under the experimental catalysis conditions described in FIG. 9;
  • FIG. 11 a shows the removal of CO from mainstream smoke by a freshly prepared partially reduced and dehydrated Pd/Cu/C catalyst
  • FIG. 11 b shows the removal of CO from mainstream smoke by the Pd/Cu/C catalyst of FIG. 11 a after aging
  • FIG. 12 shows the temperature dependence of CO oxidation on Pd/9 ⁇ zeolite.
  • a smoking article includes a wrapper 12 surrounding a tobacco column 14 adjacent to carbon monoxide pump 16 .
  • the pump 16 selects carbon monoxide for diversion from main stream smoke.
  • a further feature of the embodiment shown in FIG. 1 is the presence of venting holes 18 .
  • FIG. 1B which is an exploded view of the smoking article in FIG. 1A, the wrapper 12 surrounds tobacco column 14 .
  • FIGS. 1A and 1B are an exploded view of the smoking article in FIG. 1A.
  • the selective carbon monoxide pump 16 may be placed adjacent to, but not necessary abutting the tobacco column 14 . Typically it is aligned with the tobacco rod so that smoke from the tobacco combustion passes through the pump 16 . Other paths that expose the smoke to the pump may be used.
  • At least one additional filter element 24 may be included in the smoking article 10 .
  • FIG. 2 depicts the selective carbon monoxide pump 16 between two additional filter elements 24 , there may be a single additional filter element 24 .
  • the at least one filter element 24 may be at either between the tobacco column 14 and the selected carbon monoxide pump 16 .
  • the carbon monoxide pump 16 may be between the tobacco column 14 and the at least one additional filter element 24 .
  • the filter element 24 is typically of a conventional filter material such as cellulose acetate.
  • the selected carbon monoxide pump 16 diverts carbon monoxide from main stream smoke to, for example, side stream smoke.
  • a block diagram of the pump's operation is seen in FIG. 3. Starting at the top of FIG. 3, after a smoking article 10 including the carbon monoxide pump 16 is lit, a smoker draws on the article from the filtered end. As the smoker draws on the smoking article 10 , the combustion products are drawn through the carbon monoxide pump 16 for diverting carbon monoxide from the main stream smoke.
  • the carbon monoxide diverted from the combustion products interacts with the catalyst and is oxidized to carbon dioxide.
  • venting holes 18 are placed proximate to the carbon monoxide pump, the carbon dioxide is expressed through the venting holes 18 and inherent pores in the wrapping paper around the carbon monoxide pump 16 .
  • the inclusion of venting holes 18 proximate to the carbon monoxide pump 16 and the inherent porosity provide a passage for the oxidized carbon monoxide, which is carbon dioxide, to be expressed from smoking article.
  • inherent pores within the paper provide a path for the expression of oxidized carbon monoxide. Carbon dioxide, generated from carbon monoxide, may also remain in the main stream smoke, providing no harm to the smoker.
  • the carbon monoxide pump 16 includes an adsorbent material.
  • carbon monoxide is adsorbed from the main stream smoke onto the adsorbent material.
  • the concentration of carbon monoxide increases in gas phase within the adsorbent material due to its desorption.
  • the higher concentration of the carbon monoxide in the vicinity of the adsorbent material creates a driving force that increases the flux of carbon monoxide from the adsorbent material so that it exits holes 18 proximate to the carbon monoxide pump 16 .
  • the gas mixture was passed through the an about 2 milliliter (ml) GC gas loop, manufactured by Hewlett Packard, at about atmospheric pressure.
  • the adsorbent to be studied was loaded into a stainless steel tube reactor. Adsorption was then studied by injecting the content of the gas loop into a pure helium flow of about 200 ml/min rate; the CO mixture with the carrier gas was then passed through the adsorbent in the reactor. The resultant gas was then passed to the GC for analysis.
  • the reactor was maintained at about room temperature during these experiments.
  • the reactor was also used to pre-treat solid adsorbent samples at elevated temperatures.
  • Aluminum oxide was tested for CO adsorption application because of its Lewis acidity; this property is known to promote CO chemisorption.
  • the experimental results showed that fresh alumina is inactive in adsorption of CO at about room temperature. It is believed that the equilibration of the ambient atmosphere with the alumina surface blocks any CO active adsorption sites. For example, water molecules from the ambient atmosphere may occupy the CO active adsorption sites.
  • Heating of alumina (Al 2 O 3 ) to about 300-350° C. in air provided an improvement in CO. If water molecules occupy the CO active adsorption sites, a dehydration (e.g., desorption of water molecules) of the CO adsorption sites may explain the increased activity after heat treating. Applicants believe that the CO adsorption property of alumina may be enhanced by altering the surface structure of alumina by for example making it more irregular, as for example, in zeolites.
  • An Ag 2 O/ about 5 ⁇ zeolite and an Ag 2 O/about 9 ⁇ 13 ⁇ zeolite catalyst/adsorbents were prepared. About 5 grams (g) of silver nitrate were dissolved in about 15 ml of an about 10M NH 4 OH solution that was then combined with water for dilution to about 50 ml. About 20 g of about 0.4 to about 0.8 millimeter (mm) beads of a zeolite were added and allowed to remain overnight for a silver exchange. Each zeolite mixture was shaken frequently for about the first hour to remove evolved air. The catalyst was thoroughly washed with about 2L of water, dried for about 2 hours in air at about 60° C. and overnight at about 150° C. to decompose [Ag(NH 3 ) 2 ]NO 3 . After this treatment the resulting light-yellow catalyst was stored in a jar.
  • Catalyst/adsorbent samples comprising Ag 2 O-on-about 13 ⁇ zeolite (about 9 ⁇ ) from Lancaster, and CP861E (about 7 ⁇ ) and CBV5524G (about 5 ⁇ ) from Zeolyst International were prepared substantially as described in Example 3.
  • Sample 16 in Table 6 was made starting with a milled and sieved CP861 zeolite. Removal of CO by this material exceeded about 70%; its activity remained significant, although reduced, even after about 10 days at about room temperature in a vented CO pump. This result suggests that it may be preferred to a shape and sieve a zeolite prior to silver incorporation.
  • Nickel oxide particles modified with the rare-earth element dysprosium, were embedded into large-pore molecular sieves. These materials readily adsorb substantially all of the GC-detected, gas-phase organic molecules except light hydrocarbons. The filtering properties of the adsorbent appeared to be similar to that of activated carbon. The Ni/Dy/zeolite system also demonstrated significant carbon monoxide adsorption activity.
  • DyCl 3 (grade REO), from Strem Chemicals, were dissolved in about 50 ml water and mixed with the solid material. The mixture was retained at about room temperature for about 5 additional days to exchange Dy 3+ ions into the matrix. The solution was decanted. The solid material was washed with plenty of water, dried at about 50° C. for about 2 days and annealed at about 350° C. for about 2 days in air. The catalyst was stored in air as about 1 ⁇ 4 mm granules. Before conducting experiments, the sample was milled and about 40-60 mesh size particles were sieved off to be used in a CO pump.
  • Copper- and palladium-containing zeolite of about 5 ⁇ showed minor CO activity at about room temperature. Applicants believe that the high temperature activity and sensitivity to poisons (both known characteristics of copper and palladium compounds) explain the results.
  • the resulting solids were filtered and washed with about 1L water on a filter and suspended in about 300 ml of an about 1M NH 4 OH solution under mixing for about another 20 hrs.
  • the supported polymers were washed with about 1L of water on a filter.
  • the solid materials were suspended in about 300 ml of an about 1M HCl solution under mixing for about another 20 hrs.
  • the final products, the HCl-doped supported polymers were thoroughly washed in about 2L of water, filtered, dried in air at about room temperature for about 24 hrs and stored.
  • a Pd-Cu supported catalyst was formed as a result of the degradation of a heterogenized homogeneous Wacker-type catalyst in a reaction gas.
  • Supported Gold Catalysts Prepared From A Gold Phosphine Precursor And As-Precipitated Metal-Hydroxide Precursors Effect Of Preparation Conditions On The Catalytic Performance, Journal of Catalysis 196 (2000) 56-65; Y. Yuan, K. Asakura, A. P. Kozlova, H. Wan, K. Tsai, Y. Iwasawa. Supported Gold Catalysts Derived From The Interaction Of A Au-Phosphine Complex With As-Precipitated Titanium Hydroxide And Titanium Oxide, Catalysis Today 44 (1998) 333-342; and Y. Yuan, A. P. Kozlova, K. Asakura, H.
  • the pre-treatments performed in the same adsorption reactor, comprised either dehydration by a dry gas or hydration by humid air.
  • the residence time of a CO pulse passed through about 10 ml of about 0.4 mm wide pore silica gel beads did not differ from that of a CO pulse passed through about 0.4 mm glass beads; this therefore provided a reference for adsorption measurements.
  • FIG. 5 is plots of the retention time (as well as the reference time) of a CO pulse within a zeolite bed as a function of the pore size of the zeolite.
  • the data represented by the upper curve were obtained for zeolites annealed at about 300° C. for about ten hours prior to carbon monoxide injection. This curve indicates that zeolite apertures up to about 4 ⁇ do not show significant carbon monoxide adsorption activity.
  • Adsorptive delay increased dramatically at about 5 ⁇ aperture; which is reasonable since the effective diameter of a CO molecule given in D. M. Young, A. D. Crowell. Physical Adsorption Of Gases. 426 pages. Butterworth , London, 1962, p. 226., for example, is approximately 4.5 ⁇ . Retention times may have decreased as zeolite aperture increased beyond about 5 ⁇ since CO molecules may have been more easily released.
  • the maximum measured carbon monoxide retention time was about 7.5 min. and was evident in dehydrated zeolites. Hydrated zeolites are represented by the lower curve in FIG. 5, which shows that hydration decreases delay times nearly sevenfold. Hydration may become an important factor in almost any practical application due to equilibration with ambient moisture over time. The dynamics of this change in adsorptive properties with hydration may be used to estimate the lifetime of an active site within the adsorptive material.
  • FIG. 6 shows a rapid decrease of zeolite adsorptive activity, as indicated by a reduction in retention time to about 1.5 min. This result is quite close to the result shown in FIG. 5 for hydrated zeolites.
  • This example describes a study of a Wacker catalyst for carbon monoxide oxidation in a model gas mixture and in smoke.
  • This catalyst type seemed to be promising for carbon monoxide removal from smoke at ambient temperature because of its high activity at low temperatures and its use of water, chloride and possibly other ligands as co-catalysts or promoters.
  • water, chloride and possibly other ligands as co-catalysts or promoters.
  • these constituents of the reaction mixture would slow the catalysis or even poison the active metal.
  • These compounds are always present in smoke, however, which imposes tough requirements on a catalyst design.
  • a Series of substantially about 100% CO about 1 ml gas pulses in the number of about 50 were passed through about 1 g of the air-dry catalyst. Carbon monoxide gas was saturated with water at about 70° C. prior to injection.
  • the profiles of the product concentrations, measured by a mass-spectrometer, are shown in FIGS. 8 a, 8 b and 8 c for the 1 st , 7 th and 42 nd pulses, respectively.
  • the concentration profiles of carbon oxides undergo broadening, whereas the width of oxygen peak remains the same. This may suggest that the Pd 2+ . . . Pd 0 -based active sites, responsible for CO x chemisorption change their composition, whereas Cu 0 . . . Cu 2+ -based oxygen chemisorption sites appear more stable.
  • This catalyst deactivation process may involve an accumulation of carbon dioxide in a water film on the catalyst, thus providing more diffusion limitations for all molecules.
  • a verification of this model was attempted in the experiment with the catalyst, which was exposed to about 50 pulses of CO+O 2 + He as described above.
  • This catalyst was purged with about 50 ml/min of about 10% O 2 in He at ambient temperature for about 2 days. This was done to remove the possibly accumulated water solution of carbon dioxide and thus the diffusion limitations, associated with it. After this treatment the pulse catalysis experiment was resumed under the same conditions.
  • FIG. 10 a shows the concentration profiles of CO and CO 2 even in the first pulse remained as broad as before the described treatment. This suggests that the possible diffusion control by the water-dissolved or even by just chemisorbed products must not be a significant factor in the catalyst deactivation. However, a further deactivation of the catalyst has progressed even faster after removal of most of water from the catalyst surface.
  • FIG. 10 b shows the concentration profile of pulse 15 in the scale of FIG. 10 a. This result indicates a large widening of both CO x peaks.
  • Zeolites of particularly about 5 ⁇ aperture retain carbon monoxide at room temperature with a typical time of seconds, whereas amorphous silica does not have such activity.
  • Silver clusters, embedded into a zeolite cavity, increase this time by a factor of ten. This provides much longer time for carbon monoxide to react with oxygen.
  • Pd and Au catalysts were found to be capable of oxidizing CO at an ambient temperature.
  • FIG. 12 shows an Arrhenius plot of carbon monoxide conversion up to about 20% for Pd/zeolite.
  • the invention can also be carried out by providing a mouthpiece for a smoking article (such as a cigarette or cigar) to which the smoking article is attached when smoked. If the pumping capacity of the mouthpiece is great enough, it may be reused with multiple smoking articles.
  • the mouthpiece can be configured in numerous shapes and sizes as desired, but an example is seen in FIG. 4.
  • the mouthpiece M includes a fitting 22 to receive a smoking article C, and a carbon monoxide pump 24 including an adsorbent 116 for adsorbing carbon monoxide, wherein the carbon monoxide pump is positioned with respect to the smoking article C so as to selectively divert carbon monoxide from main stream combustion products prior to inhaling by a smoker. Vents 20 & 118 can be provided like the vents 18 mentioned above.
  • portions of the mouthpiece M may include a conventional filter material 120 , such as cellulose acetate or other filter material.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
  • Catalysts (AREA)
US10/233,876 2000-11-28 2002-09-03 Smoking article including a selective carbon monoxide pump Abandoned US20030005940A1 (en)

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US20030188758A1 (en) * 2002-04-08 2003-10-09 Mohammad Hajaligol Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette
US20050133053A1 (en) * 2003-12-22 2005-06-23 Philip Morris Usa Inc. Smoking articles comprising copper-exchanged molecular sieves
US20050155616A1 (en) * 2003-10-27 2005-07-21 Philip Morris Usa Inc. Use of oxyhydroxide compounds in cigarette paper for reducing carbon monoxide in the mainstream smoke of a cigarette
US20050279372A1 (en) * 2004-06-16 2005-12-22 Sundar Rangaraj S Silver and silver oxide catalysts for the oxidation of carbon monoxide in cigarette smoke
US20060037621A1 (en) * 2000-11-10 2006-02-23 Bereman Robert D Method of making a smoking composition
WO2005118133A3 (fr) * 2004-05-28 2006-04-27 British American Tobacco Co Articles et materiaux lies a l'usage du tabac
US20060196517A1 (en) * 2005-02-04 2006-09-07 Philip Morris Usa Inc. Tobacco powder supported catalyst particles
US20070119467A1 (en) * 2005-11-29 2007-05-31 Akhmetshin Marsil R Filter-tipped cigarette

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US7281540B2 (en) 2002-12-20 2007-10-16 R.J. Reynolds Tobacco Company Equipment and methods for manufacturing cigarettes
EP1729603A1 (fr) * 2004-04-02 2006-12-13 Reemtsma Cigarettenfabriken GmbH Filtre a fumee de tabac
US10034988B2 (en) 2012-11-28 2018-07-31 Fontem Holdings I B.V. Methods and devices for compound delivery
WO2015042412A1 (fr) 2013-09-20 2015-03-26 E-Nicotine Technology. Inc. Dispositifs et procédés de modification de dispositifs de distribution
US11397175B2 (en) 2020-01-27 2022-07-26 RJ. Reynolds Tobacco Company Method and apparatus for the inspection of a paper web wound on a bobbin

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