WO1990010394A1 - Articles a fumer contenant un catalyseur pour reduire le monoxyde de carbone - Google Patents

Articles a fumer contenant un catalyseur pour reduire le monoxyde de carbone Download PDF

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Publication number
WO1990010394A1
WO1990010394A1 PCT/US1989/001080 US8901080W WO9010394A1 WO 1990010394 A1 WO1990010394 A1 WO 1990010394A1 US 8901080 W US8901080 W US 8901080W WO 9010394 A1 WO9010394 A1 WO 9010394A1
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WO
WIPO (PCT)
Prior art keywords
fuel element
alumina
smoking article
amount
group
Prior art date
Application number
PCT/US1989/001080
Other languages
English (en)
Inventor
Michael David Shannon
Richard Long Lehman
James Lee Resce
Olivia Pence Surin
Joseph Tinsley Meers
Dennis Michael Riggs
Ernest Gilbert Farrier
Original Assignee
R.J. Reynolds Tobacco Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by R.J. Reynolds Tobacco Company filed Critical R.J. Reynolds Tobacco Company
Priority to PCT/US1989/001080 priority Critical patent/WO1990010394A1/fr
Publication of WO1990010394A1 publication Critical patent/WO1990010394A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/10—Chemical features of tobacco products or tobacco substitutes
    • A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
    • A24B15/165—Chemical 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
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D1/00—Cigars; Cigarettes
    • A24D1/22—Cigarettes with integrated combustible heat sources, e.g. with carbonaceous heat sources

Definitions

  • the present invention relates to cigarettes and other smoking articles which contain a catalytic composition, preferably as part of the fuel element, that substantially decreases the amount of carbon monoxide contained in the mainstream smoke during smoking.
  • the present invention also relates to the catalyst-containing carbonaceous fuels themselves, as well as to methods of making such carbonaceous fuels.
  • Fuel elements which contain a catalytic composition in accordance with the present invention are especially useful in smoking articles having an aerosol generating means which is physically separate from the fuel element.
  • Preferred smoking articles of the present invention are capable of providing the user with the pleasures of smoking (e.g., smoke taste, feel, satisfaction, pleasure, and the like) , by heating but not burning tobacco, and with reduced levels of carbon monoxide.
  • smoking article includes cigarettes, cigars, pipes, and the like, which use tobacco in various forms.
  • Cigarettes, cigars and pipes are popular forms of tobacco smoking articles. Many smoking products and smoking articles have been proposed through the years as improvements upon, or as alternatives to, these popular forms of tobacco smoking articles, particularly cigarettes.
  • U.S. Patent No. 4,397,321 to Stuetz proposes tobacco and non-tobacco smoking compositions which contain a catalyst composition consisting of a fine ash and a transition metal compound, especially oxides of manganese or iron. This patent also describes several previous attempts at incorporating catalysts into cigarettes to decrease levels of selected smoke constituents.
  • U.S. Patent No. 4,182,348 to Seehofer et al. proposes a method for removing nitric oxide and carbon monoxide from the tobacco smoke of cigarettes by adding a ruthenium compound having a perovskite structure (M 2 M / Ru ⁇ 6 ) to the cigarette.
  • U.S. Patent No. 3,368,566 to Avedikian proposed a filter containing catalytic oxides, such as manganese dioxide, chromium trioxide and other oxides of chromium and copper to convert carbon monoxide to carbon dioxide.
  • U.S. Patent No. 4,317,460 to Dale et al. proposes the use of microporous supported, low temperature catalysts in cigarette filters for the oxidation of carbon monoxide to carbon dioxide. Dale also refers to prior unsatisfactory attempts of Eastman Chemical Products Inc. to incorporate various oxidants and catalysts into filters to convert carbon monoxide to carbon dioxide.
  • U.S. Patent No. 4,215,708 to Bron describes a novel cigarette holder with a catalytic afterburner which is intended to convert carbon monoxide and incompletely burned hydrocarbons into acceptable smoke compounds.
  • Non-catalytic methods for decreasing the levels of carbon monoxide in cigarette smoke have also been attempted. See inter alia.
  • U.S. Patent No. 4,142,534 to Branti use of tobaccoless region
  • U.S. Patent No. 4,258,730 to Tuskamoto use of magnetic field
  • the present invention relates to cigarettes and other smoking articles which contain a catalytic composition, preferably as part of a fuel element, which substantially decreases the amount of carbon monoxide in the mainstream smoke of the smoking article.
  • a substantial decrease in the amount of carbon monoxide means a decrease in the amount of carbon monoxide in the mainstream smoke of the smoking article of at least about 30%, preferably at least about 50%, and most preferably at least about 70%, as compared with a similar smoking article having no catalytic composition, as measured by the technique described in the above referenced RJR Monograph, the disclosure of which is hereby incorporated by reference herein.
  • the present ⁇ invention also relates to catalyst-containing fuel elements for use in smoking articles which substantially reduce the amount of carbon monoxide produced by burning such elements, as well as to methods of making such fuel elements.
  • the smoking articles utilizing such fuel elements include a pressure formed carbonaceous fuel element; a physically separate aerosol generating means including an aerosol forming material, attached to one end of said fuel element; a mass of tobacco; and a mouthend piece, attached to the aerosol generating means.
  • a pressure formed carbonaceous fuel element e.g., a pressure formed carbonaceous fuel element
  • a physically separate aerosol generating means including an aerosol forming material, attached to one end of said fuel element
  • a mass of tobacco e.g., a mouthend piece, attached to the aerosol generating means.
  • Examples of such smoking articles are described in the above-referenced European Patent Publication Nos. 0174645 and 0212234, U.S. Patent No. 4,714,082 to Banerjee et al. and U.S. Patent No. 4,756,318 to Shannon et al. , the disclosures of which are incorporated herein by reference.
  • Preferred smoking articles which contain a catalytic composition, particularly as part of the fuel element contain no more than about 6 mg of carbon monoxide in the mainstream smoke, preferably no more than about 4 mg, most preferably no more than about 2 mg when smoked for at least 10 puffs under FTC conditions comprising 35 ml puff volumes of 2 seconds duration, separated by 58 seconds of smolder (hereinafter "FTC conditions").
  • FTC conditions a catalytic composition
  • the catalytic composition may be incorporated into the carbonaceous fuel in a number of ways.
  • formed fuel elements are prepared, e.g., by intimately mixing a carbonaceous material and a catalytic composition such as a platinum group.metal and/or a ceramic material (e.g. alumina, zirconia, titania, and the like,).
  • a catalytic composition such as a platinum group.metal and/or a ceramic material (e.g. alumina, zirconia, titania, and the like,).
  • the ceramic material can act both as a catalytic material and/or as a support for the platinum group metals when they are employed.
  • the carbonaceous fuel element is formed so as to concentrate the catalytic compositions in one or more longitudinal passageways extending at least partially through the fuel element.
  • 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 a ceramic material and/or platinum group metal, preferably having at least one longitudinal passageway extending at least partially therethrough.
  • the fuel element may also comprise a formed coherent mass of carbonaceous material which has applied thereto (e.g. by dipping, spraying, and the like) a solution such as a chloride solution of the platinum group metals.
  • it is preferred that the fuel have at least one passageway extending at least partially therethrough.
  • the catalyst may also be placed in other locations of the smoking article to effect the conversion of carbon monoxide to carbon dioxide.
  • alternate locations include a) between the fuel element and aerosol generating means and b) in the aerosol generating means itself.
  • Preferred catalytic compositions include a wide range of ceramic materials such as oxides, nitrides carbides and borides.
  • Non-oxide ceramic materials include silicon nitride, aluminum nitride, titanium boride, boron nitride, boron carbide, silicon carbide, tungsten carbide, and the like.
  • Preferred ceramic materials include oxides such as alumina, zirconia, titania, yttria, silica, phosphates, aluminosilicates, and amorphous oxide materials such as glasses and amorphous ceramic powders.
  • Especially preferred ceramic materials include alumina hydroxide and products of alumina hydroxide such as transition aluminas.
  • catalysts which may be used either alone, or supported on the above ceramic materials, include the platinum group metals such as platinum, palladium, rhodium, iridium, ruthenium, and the like or a base metal catalyst such as iron, manganese, vanadium, copper, nickel, cobalt, and the like.
  • the currently most preferred catalytic composition comprise one or more of the transition aluminas, particularly alpha and theta alumina, alone, or in conjunction with palladium or platinum.
  • the catalytic composition added to the smoking articles of the present invention is one of the platinum group metals, it may either be in a supported form, or in an unsupported form, but supported forms are preferred.
  • a supported catalytic composition is prepared by depositing by either chemical or mechanical means on some base material or "support.” This support is then incorporated into the smoking article, e.g. into the fuel element of the smoking article.
  • Typical supports for the platinum group metals include charcoal, carbon black, as well as the ceramic materials described above.
  • a preferred support in this invention is alumina, most preferably transition aluminas.
  • the amount of catalyst added to a carbonaceous fuel element by wt. % can be as low as 2% in the preferred small (10 mm x 4.5 mm) fuel elements.
  • the amount may be as low as about 5 micrograms of metal.
  • the catalytic composition in whatever location selected, must be present in an amount which decreases the levels of delivered carbon monoxide in the mainstream aerosol during the burning of the fuel element.
  • carbonaceous means that the material, exclusive of any catalytic compositions and non carbon-containing supports, primarily comprises carbon.
  • the term “substantially free of an active metal component” means having less than about 2 micrograms of such component.
  • pressure formed means formed under pressure, e.g., pressed, molded or extruded.
  • Figure 1 is a longitudinal view of one preferred smoking article which may employ the catalyst-carbon containing fuel element of the present invention.
  • Figures 1A - 1C are sectional views of preferred fuel element passageway configurations useful in the preferred smoking articles.
  • smoking articles which contain a catalytic composition in one or more locations of the smoking article.
  • the catalytic composition is advantageously employed as part of the carbonaceous fuel element of such smoking articles.
  • These fuels are especially useful in making smoking articles that produce an aerosol containing or resembling tobacco smoke, but which contain little or no incomplete combustion or pyrolysis products.
  • the preferred smoking articles which may employ such catalyst-carbon fuels are described in the above-referenced European Patent Publication Nos. 0174645 and 0212234, and in U.S. Patent Nos. 4,714,082-and 4,756,318.
  • the catalytic composition is employed as one component of a pressure formed carbonaceous fuel element such as those described in the above-referenced EPO Publication Nos. 0174645 and 0212234, and U.S. Patent Nos.4,714,082 and 4,756,318.
  • the carbonaceous starting material which is used to prepare the preferred fuel elements should contain primarily carbon, hydrogen and oxygen.
  • Preferred carbon containing materials are cellulosic materials, preferably those with a high (i.e.. greater than about 80%) alpha-cellulose content, such as cotton, rayon, paper and the like.
  • One especially preferred high alpha-cellulose starting material is hardwood paper stock such as non-talc containing grades of Grande Prairie Canadian Kraft paper, obtained from Buckeye Cellulose Corp., Memphis, TN.
  • the carbon component of the fuels of the present invention is generally prepared by the pyrolysis of the starting material, at a temperature between about 400°C to about 1300°C, preferably between about 500°C to about 950°C, in a non-oxidizing atmosphere, for a period of time sufficient to ensure that all of the cellulose material has reached the desired carbonization temperature.
  • 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.. at from about 1°C to 20°C per hour, preferably from about 5°C to 15°C per hour, over many hours, produces a more uniform material and a higher carbon yield.
  • the carbon is pulverized, preferably 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° to 900°C.
  • the catalytic composition component of the preferred fuel elements include materials which substantially decrease the amount of carbon monoxide in the mainstream of a smoking article employing such fuel elements when such smoking articles are smoked under FTC conditions for at least 10 puffs.
  • Ceramic materials includes oxides, nitrides, carbides and borides.
  • Non-oxide ceramic materials include silicon nitride, aluminum nitride, titanium boride, boron nitride, boron carbide, silicon carbide, tungsten carbide, and the like.
  • Preferred ceramic materials include oxides such as alumina, zirconia, titania, yttria, silica, phosphates, aluminosilicates, and amorphous oxide materials such as glasses and amorphous ceramic powders.
  • One especially preferred ceramic material comprise aluminas such as alumina hydroxide and products of alumina hydroxide such as transition aluminas.
  • Transition alumina hydroxides which may be advantageously used as the catalytic composition include i) the low transition aluminas such as chi, gamma, and eta forms of alumina, ii) the high transition aluminas such as the kappa, delta and theta forms of alumina, iii) alpha alumina, iv) beta alumina such as sodium, potassium, magnesium and calcium aluminates, v) zeta aluminates such as lithium aluminates, or vi) mixtures thereof.
  • these aluminas While many of these aluminas are available commercially, e.g., from W.R. Grace, these aluminas may also be prepared by calcining Gibbsite, Bayerite or Boehmite as described in Chapter 4 of Oxides and Hydroxides of Alumina. Alcoa Technical Paper No. 19, Revised (1987) .
  • aluminas useful in practicing the present invention will have a surface area (as measured by the nitrogen BET method) greater than about 0.1 m 2 /g, preferably greater than about 1.0 m 2 /g, and most preferably greater than about 5.0 m 2 /g.
  • the pore volume of the alumina should, in general, be greater than about 0.01 cc/g, preferably greater than about 0.05 cc/g, and most preferably greater than about 0.1 cc/g, measured by, e.g., the nitrogen BET method.
  • the particle size of the alumina is in general less than about 500 microns preferably less than about 100 microns, and most preferably less than about 30 microns.
  • the amount of alumina by weight percent of the fuel element is between about 1 and 60%, preferably between about 2 and 25%, and most preferably between about 4 and 15%.
  • the most preferred alumina is a theta alumina containing from 1 to 95% alpha alumina.
  • One particularly preferred alumina is produced by W.R. Grace and is described in more detail in Example I.
  • the catalytic composition may comprise the ceramic material, and in particular alumina, either alone (e.g., substantially free of an active metal component) , or it may contain a second active metal component such as one of the platinum group metals or base metal catalysts discussed below.
  • a second active metal component such as one of the platinum group metals or base metal catalysts discussed below.
  • the ceramic material When used in conjunction with such second component, it may act as a both catalytic composition, as well as a support for the metal component of the catalytic composition.
  • the amount of the platinum group metal or base metal catalyst may vary depending on the type of metal, the degree of dispersion of the metal on the ceramic material, the manner in which the metal is added, the crystalline size of the metal, porosity of the support and the particle size of the support. In general, when used with the preferred amount of transition aluminas, the amount of such second component by weight percent of the ceramic material or other support will be less than about 5%, preferably less than about 3%, and most preferably less than about
  • the catalytic composition comprises a metal component selected from the group of a platinum group metal or a base metal catalyst.
  • the preferred platinum group metals are selected from the group of platinum, palladium, rhodium, iridium, ruthenium, or mixtures thereof.
  • the preferred base metal catalysts are selected from the group of iron, manganese, vanadium, copper, nickel, cobalt, or mixtures thereof.
  • the most preferred catalytic composition of the platinum group metals or base metal catalysts are platinum and palladium.
  • these components be supported on a ceramic material such as one of the transition alumina hydroxides.
  • the preferred platinum group metal may, however, be incorporated into the fuel in an unsupported state.
  • the amount of platinum group metal by weight percent of the fuel element should be less than about 1.0%, preferably less than about 0.5%, most preferably less than about 0.2%.
  • the overall amount of platinum group metal in such smoking articles is preferably less than about 400 micrograms, most preferably less than 280 micrograms per cigarette.
  • the two major fuel components, the carbonaceous material and the catalytic composition may be combined or formed into a fuel in a number of ways.
  • these components are admixed with a binder, water, and any desired minor components, and shaped or formed into fuel elements using extrusion or pressure forming techniques.
  • binders which may be used in preparing such fuel elements are well known in the art.
  • a preferred binder is sodium carboxymethylcellulose (SCMC) , which may be used alone, which is preferred, or in conjunction with materials such as sodium chloride, vermiculite, bentonite, calcium carbonate, and the like.
  • SCMC sodium carboxymethylcellulose
  • Other useful binders include gums, such as guar gum, other cellulose derivatives, such as ethylcellulose and carboxymethylcellulose (CMC) , hydroxypropyl cellulose, starches, alginates, and polyvinyl alcohols.
  • Other materials which may be added to the fuel element include those described in the above-referenced EPO publications and U.S. Patent Nos. 4,714,082 and 4,756,318.
  • lampblack e.g., about 10 percent
  • fuel elements containing carbon and binder may be further pyrolyzed in a non-oxidizing atmosphere after formation, for example, at from about 450°C to 1100°C, preferably at from about 850°C to 1000°C, for about two hours, to convert the binder to carbon.
  • This post-formation "baking" step reduces any taste contributions which the binder may contribute to the mainstream aerosol.
  • the fuel element comprises a pressure formed mass of carbonaceous material having at least one longitudinal passageway extending at least partially therethrough, and a catalytic composition contained at least partially within the longitudinal passageway of the carbonaceous mass.
  • the catalytic composition is also provided with at least one longitudinal passageway extending at least partially therethrough.
  • This concentrated catalytic bed of material is particularly effective at decreasing the amount of carbon monoxide in the mainstream smoke as it provides a concentrated fixed controllable catalytic bed through which a majority of the combustion products must pass in order to enter into the mainstream aerosol of the smoking article.
  • This type of fuel having a concentrated bed of the catalytic composition may be prepared in a number of ways.
  • a fuel element comprising a pressure formed mass of carbonaceous, material may be prepared as described above.
  • This fuel may be provided with one or more longitudinal passageways into which the catalytic composition is deposited in the form of a solid rod or a paste.
  • the catalytic composition is preferably one of the platinum group metals supported on one of the preferred alumina supports, or it may be one of the alumina materials itself.
  • the catalytic composition contained within the longitudinal passageway of the pressure formed mass of carbonaceous material is also provided with at least one longitudinal passageway extending at least partially therethrough.
  • This inner core/outer shell - type fuel element with its preferred longitudinal passageway may be formed by co-extruding the carbonaceous material along with the catalytic composition using an appropriate die.
  • the catalytic composition may be impregnated or otherwise applied to a fuel element comprising a pressure formed carbonaceous mass of material.
  • a fuel element comprising a pressure formed carbonaceous mass of material.
  • the term "impregnate” means absorbed, adsorbed, permeated, having deposited thereon.
  • the fuel element may be coated with the catalytic composition.
  • the fuel element preferably comprises a pressure formed mass of carbonaceous material, preferably having one or more longitudinal passageways extending at least partially therethrough.
  • the formed fuel element may also have incorporated therein one of the ceramic materials described above.
  • fuel elements are thereafter preferably contacted with a solution of the catalytic composition.
  • a fuel element having a plurality of longitudinal passageways may be contacted with a solution of palladium chloride which is allowed to impregnate the surface of the fuel element, including the surface of the longitudinal passageways.
  • the platinum group metal may thereafter be reduced by any suitable means such as by heating in a flowing stream of nitrogen or hydrogen or contacted with a reducing agent, such as hydrazine or sodium borohydride.
  • Preferred fuel elements of the present invention are from about 5 to 15 mm, more preferably, from about 8 to 12 mm in length, and from about 2 to 8, preferably about 4 to 6 mm in diameter.
  • the apparent bulk density is greater than 0.85 cc/g as measured by mercury intrusion.
  • the fuel element of the present invention is preferably provided with one or more longitudinally extending passageways. These passageways help to control transfer of heat from the fuel element to the aerosol generating means, which is important both in terms of transferring enough heat to produce sufficient aerosol and in terms of avoiding the transfer of so much heat that the aerosol former is degraded. Such passageways also help provide ease of lighting.
  • FIG. 1 One preferred cigarette employing the catalyst-carbon fuel element of the present invention is illustrated in Figure 1 accompanying this specification.
  • This fuel element is shown surrounded by a resilient jacket of insulating fibers 16, such as glass fibers.
  • Another preferred fuel element configuration shown in Figure IB employs a fuel element having seven holes.
  • the fuel element 10 may be formed from an extruded mixture of (i) the catalytic composition and (ii) carbon (preferably from carbonized paper) , lampblack, sodium carboxymethyl cellulose (SCMC) binder, K 2 C0 3 , and water, as described in greater detail below as well as in the above referenced patents and EPO publications.
  • Capsule 12 containing aerosol forming material 14 is circumscribed by a roll of tobacco 18.
  • the roll of tobacco can be employed as cut filler, although other forms of tobacco can be employed.
  • the tobacco can be employed as strands or shreds of tobacco laminae, reconstituted tobacco, volume expanded tobacco, processed tobacco stems, or blends thereof.
  • Extruded tobacco materials and other forms of tobacco, such as tobacco extracts, tobacco dust, or the like, can also be employed.
  • Two slit-like passageways 20 are provided at the mouth end of the capsule in the center of the crimped tube.
  • a mouthend piece 22 preferably comprising a cylindrical segment of a tobacco paper sheet material 24 and a segment of non-woven thermoplastic fibers 26 through which the aerosol passes to the user.
  • the article, or portions thereof, is overwrapped with one or more layers of cigarette papers 30 - 36.
  • the mouthend may also be air diluted, if desired.
  • the fuel element 10 Upon lighting of the aforesaid smoking article, the fuel element 10 burns, generating the heat used to volatilize the aerosol generating means 12.
  • the preferred carbon fuel typically produces three main combustion products, water, carbon dioxide and carbon monoxide. With a catalytic composition present in the fuel, much of the carbon monoxide produced by the incomplete combustion of the carbon interacts with oxygen from the incoming air in the presence of catalyst and the catalyst, and is converted to carbon dioxide.
  • a smoke-like aerosol passes out of capsule 12 through slit-like passageways 20, where it mixes with tobacco flavor components of the tobacco roll. These materials then pass through the mouthend piece 22 and to the user.
  • the catalytic composition may be placed in other locations in the smoking article to effect the conversion of carbon monoxide to carbon dioxide.
  • the catalytic composition may be advantageously located between the fuel element 10 and the aerosol forming materials 14, and/or mixed with aerosol forming materials 14, where the catalytic composition is exposed to elevated temperatures during smoking, e.g., in excess of about 100°C.
  • the catalytic compositions can also be placed both in the fuel element and in other locations.
  • a smoking article of the type illustrated in Figure 1 was made in the following manner:
  • Two fuel elements (10 mm long, 4.5 mm o.d.) having an apparent density of about 0.9 cc/g were prepared from hardwood pulp carbon (79 wt. %) , SCMC binder (10 wt. %) , K 2 C0 3 (1 wt. %) and catalytic composition (io wt. %)
  • the catalytic composition in the first fuel element is a theta alumina powder prepared by calcining Gibbsite to about 1120°C.
  • This material is available from Davison Chemical Division of W.R. Grace and Company, Columbia, Maryland under designation No. SMR-37-35. It has a surface area of 79 m /g and a pore volume of about 0.3 cc/g, as measured by N 2 BET. Powder X-Ray diffraction analysis revealed that the material was comprised of 94% of the theta form of alumina and 6% of the alpha form of alumina. The average particle size was 5.5 micron by volume.
  • the catalytic composition in the second.fuel element was comprised of the same theta alumina powder described above onto which was loaded palladium (0.5 wt. %) . This loaded material was also provided by W.R. Grace and Company under designation No. SMR-37-35.
  • the hardwood pulp carbon was prepared by carbonizing a non-talc containing grade of Grand Prairie Canadian Kraft hardwood paper under a nitrogen blanket, at a step-wise increasing temperature rate of about 10°C per hour to a final carbonizing temperature of 750°C.
  • the paper carbon was ground to a mesh size of minus 200 (U.S.) .
  • the paper carbon was ground to a fine powder, i.e., a powder having an average particle size of from about 0.1 to 50 microns.
  • This fine paper carbon powder was admixed with the catalytic composition, Hercules 7HF SCMC binder and K 2 C0 3 in the weight ratios set forth above, together with sufficient water to make a stiff, dough-like paste.
  • Fuel elements were extruded from this paste having seven axial holes each about 0.6 mm in diameter. Six holes were equally spaced about the center of the fuel element on a 1.6 mm bolt radius. The seventh hole was directly in the center.
  • a blend of flue cured tobaccos were ground to a medium dust and extracted with water in a stainless steel tank at a concentration of from about 1 to 1.5 pounds tobacco per gallon water.
  • the extraction was conducted at ambient temperature using mechanical agitation for from about 1 hour to about 3 hours.
  • the admixture was centrifuged to remove suspended solids and the aqueous extract was spray dried by continuously pumping the aqueous solution to a conventional spray dryer, an Anhydro Size No. 1, at an inlet, temperature of from about 215° - 230°C and collecting the dried powder material at the outlet of the drier.
  • the outlet powder material at the outlet of the drier The outlet temperature varied from about 82° - 90°C.
  • the spray dried tobacco extract was mixed with sufficient water to form a slurry.
  • This slurry was then applied to the alumina carrier described above by mixing until the slurry was uniformly absorbed by the alumina.
  • the treated alumina was then dried to reduce the moisture content to about 1 wt. %.
  • this treated alumina was mixed with a combination of the other listed ingredients until the liquid was substantially absorbed within the alumina carrier.
  • the capsule used to construct the Figure 1 cigarette was prepared from deep drawn aluminum.
  • the capsule had an average wall thickness of about 0.004 in. (0.1 mm), and was about 30 mm in length, having an outer diameter of about 4.5 mm.
  • the rear of the container was sealed with the exception of two slot-like openings (each about 0.65 x 3.45 mm, spaced about 1.14 mm apart) to allow passage of the aerosol former to the user.
  • the fuel element - capsule combination was overwrapped at the fuel element with a 10 mm long, glass fiber jacket of Owens-Corning 6437 glass with 3 weight percent pectin binder, to a diameter of about 7.5 mm.
  • the glass jacket was then wrapped with an innerwrap material from Kimberly-Clark designate P78-63-5.
  • a 7.5 mm diameter tobacco roll (28 mm long) with an overwrap of Kimberly-Clark's P1487-125 paper was modified by insertion of a probe to have a longitudinal passageway of about 4.5 mm diameter therein.
  • the jacketed fuel element - capsule combination was inserted into the tobacco roll passageway until the jacket of insulating material abutted the tobacco.
  • the jacket of insulating material and the tobacco roll sections were joined together by an outerwrap material which circumscribed both the fuel element/insulating jacket/innerwrap combination and the wrapped tobacco roll.
  • the outerwrap was a Kimberly-Clark paper designated P1768-182.
  • a mouthend piece of the type illustrated in Figure 1 was constructed by combining two sections: (1) a 10 mm long, 7.5 mm diameter segment of folded tobacco sheet material (Kimberly-Clark Designation No.
  • P144-185-GAPF adjacent the capsule, overwrapped with Kimberly-Clark's P850-184-2 paper and (2) a 30 mm long, 7.5 mm diameter cylindrical segment of a folded non-woven meltblown thermoplastic polypropylene web obtained from Kimberly-Clark Corporation, designated P-100-F, overwrapped with Kimberly-Clark's P1487-184-2 paper.
  • the combined mouthend piece section was joined to the jacketed fuel element - capsule section by a final overwrap of Ecusta's 30637-801-12001 tipping paper.
  • the resulting models were smoked by under FTC conditions for 10 puffs. This consisted of 2 second 35 ml puffs separated by a 58 second smolder periods.
  • the results of the mainstream CO and C0 2 delivery were compared to a control model.
  • the control was prepared in an identical fashion except that the fuel composition contained no catalytic material, i.e., 89% carbon, 10% SCMC and 1% K 2 C0 3 .
  • the mainstream smoke of the smoking article with the fuel element containing 10 wt. % theta alumina contained 2.3 mg CO and 36 mg C0 2 .
  • the fuel with 10% wt. % theta alumina onto which was loaded 0.5% palladium generated a mainstream smoke which contained l.o mg CO and 36 mg C0 2 .
  • the control contained 9.6 mg CO and 43 mg C0 2 .
  • Fuels were prepared in the same manner as described in Example I except that they contained 5% wt. % Type 207 alumina from Degussa Corporation, South Plainfield, NJ. This alumina had a surface area of 344 m 2 /g and a pore volume of 0.31 CC/g as measured by N BET. The particle size was 2-15 microns.
  • Palladium was added to the formed and baked fuels by dipping them into an acidic salt solution of palladium.
  • the dry weight percent of palladium metal on these fuels was 0.05, 0.16 and 0.50.
  • the fuel elements were then dried and the palladium was reduced to the metallic state.
  • the fuels were used in smoking articles as described in Example I and analyzed for CO and C0 2
  • a smoking article similar to that shown in Figure 1 was made in the following manner except that a fuel having an outer shell of carbonaceous material and an inner core of a catalytic composition was prepared as follows:
  • the hardwood pulp carbon was prepared by carbonizing a non-talc containing grade of Grand Prairie Canadian Kraft hardwood paper under a nitrogen blanket, at a step-wise increasing temperature rate of about 10°C per hour to a final carbonizing temperature of 750°C.
  • the paper carbon was ground to a fine powder, i.e., a powder having an average particle size of from about 0.1 to 50 microns.
  • This fine paper carbon powder was admixed with the Hercules 7HF SCMC binder and K 2 C0 3 in the weight ratios set forth above, together with fuel elements were extruded either with: 1) no peripheral holes - a central single hole was drilled by hand with a diameter of about 2.29 mm (.090") (after baking); 2) a single central hole with a diameter of about 2.29 mm (.090”); or 3) a single central hole with a diameter of about 2.29 mm (.090") plus 6 peripheral holes each with a diameter of about 0.25 mm (.010").
  • These fuel elements were then baked-out under a nitrogen atmosphere at 950°C for 3 hours after formation.
  • the inner core material was prepared in the following manner: A) The below ingredients were mixed either by hand or in a high shear mixer with sufficient water to make a flowable paste (e.g., about 40-50% moisture) - 10% alpha alumina with .5% Pd
  • the paste was extruded into a rod having a diameter of about 2.24 mm (.088") having a single central passageway of about l mm diameter.
  • the cores that were extruded were allowed to dry at room temperature for 24 hours. They were then cut to 10 mm lengths and placed inside an unbaked carbon fuel through a single central hole. The fuels were then baked under nitrogen for 3 hours at 950°C.
  • Mainstream CO for fuels similar to preparation B in models similar to those descried in Example I was about 1.3 mg under FTC conditions.
  • Example I except that they were prepared from hardwood pulp carbon (79 wt. %) , SCMC (10 wt. %) , K 2 C0 3 (1 wt. %) and catalytic composition (10 wt. %) .
  • the catalytic composition of one fuel was silica designated MP-680 obtained from Kali-Chemie Corporation,
  • the catalytic composition in the other fuel was silicon nitride approximately 0.1 microns in diameter obtained from UBE Industries of Japan, designated UBE-SN-E10, Lot A710-492. These two fuel elements were made into models and tested as described in Example I. Models with fuel elements containing the silica contained 5.6 mg CO and 33 mg C0 2 while models containing the silicon nitride contained 3.1 mg CO and 35 mg C0 2 . The control contained 9.6 mg CO and 43 mg C0 2 .
  • Fuels were prepared as described in Example I except that the level of alumina was varied from 5 to 25 weight percent of the fuel.
  • the alumina was type A-16 SG supplied by Alcoa Chemicals Division of Aluminum Company of America, Pittsburgh, PA. This alumina had a particle size of 0.3 microns to 0.5 microns and a surface area of 10 m 2 /g. X-Ray diffraction revealed that the material was alpha alumina.
  • the fuel elements were comprised of 10 wt. % SCMC, 1 wt. % K 2 C0 3 and the remaining 80% made up by hardwood pulp carbon and alumina. Alumina levels of 5, 10, 15, 25 weight percent were prepared which had the corresponding carbon concentrations of 84, 79, 74 and 64 weight percent, respectively. These fuel elements were prepared and evaluated as described in Example I.
  • a fuel element was made as described in Example I except that it was contained 10% alumina obtained from Degussa Corporation and designated type A-l. The surface area of this alumina was 130 m 2 /g and the pore volume was 0.17 cc/g. The material appeared to be amorphous when analyzed by powder X-ray diffraction.
  • the formed and baked fuel elements were soaked in 0.05% aqueous solution of tetra ine palladium (II) nitrate, PD (NH 3 ) 4 (N0 3 ) 2 . The solution also contained 1.0% Na C0 3 and 0.5% K 2 C0 3 .
  • the fuels were soaked for 3 hours, removed and heated at 300°C to decompose the palladium complex to the metallic state.
  • the resulting fuels were made into models and analyzed for CO and C0 2 as described in Example 1.
  • the CO contained in the mainstream smoke of such smoking articles was 2.4 mg and C0 2 was 45 mg.
  • Similar fuels not treated with palladium contained 5.3 mg CO.
  • Smoking articles employing a fuel element-capsule arrangement similar to those described in Example I were prepared except that the catalytic composition was impregnated onto alumina beads and placed immediately behind the fuel element.
  • the alumina-impregnated beads were prepared as follows:
  • High surface area alumina beads similar to those described in Example I for carrying the aerosol forming material, were sintered at 1000°C for one hour, washed with water and dried, and sieved through a 0.063" (1.6 mm) diameter perforated stainless steel grid. These beads were impregnated with 0.6 wt. % palladium as follows: PdCl 2 was dissolved in 50/50 isoprpyl alcohol/water; the beads were exchanged in this solution for one hour, dried, and reduced in a NaBH 4 solution. The impregnated beads were placed immediately behind the fuel element.
  • the mainstream smoke of smoking articles employing alumina beads behind the fuel element containing 0.2 mg of paaldium contained less than 2.5 mg of CO as measured by a Beck an Infrared Analyzer.

Abstract

Cigarettes et autres articles à fumer contenant un composé catalytique, intégré de préférence à l'élément combustible et qui réduit considérablement le taux de monoxyde de carbone contenu dans le flot principal de fumée lorsque l'on fume. Cette invention porte en outre sur les combustibles carbonés contenant le catalyseur, ainsi que sur des procédés pour produire ces combustibles carbonés. Les éléments combustibles contenant un composé catalytique selon la présente invention sont utiles en particulier dans les articles à fumer dotés d'un moyen de production d'aérosol physiquement séparé de l'élément combustible.
PCT/US1989/001080 1989-03-16 1989-03-16 Articles a fumer contenant un catalyseur pour reduire le monoxyde de carbone WO1990010394A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0467658A2 (fr) * 1990-07-20 1992-01-22 Philip Morris Products Inc. Conversion catalytique du monoxyde de carbone à partir de sources de chaleur carbonées
EP0494784A2 (fr) * 1991-01-09 1992-07-15 Philip Morris Products Inc. Procédé de fabrication de sources de chaleur à base de carbure métallique
US5146934A (en) * 1991-05-13 1992-09-15 Philip Morris Incorporated Composite heat source comprising metal carbide, metal nitride and metal
EP0535695A2 (fr) * 1991-10-03 1993-04-07 Phillips Petroleum Company Article à fumer avec catalyseur d'oxydation du monoxyde de carbone
US5246018A (en) * 1991-07-19 1993-09-21 Philip Morris Incorporated Manufacturing of composite heat sources containing carbon and metal species
WO1994027452A1 (fr) * 1993-05-28 1994-12-08 Brown & Williamson Tobacco Corporation Article pour fumeurs
US5944025A (en) * 1996-12-30 1999-08-31 Brown & Williamson Tobacco Company Smokeless method and article utilizing catalytic heat source for controlling products of combustion
WO2006002001A2 (fr) * 2004-06-15 2006-01-05 R.J. Reynolds Tobacco Company Catalyseurs a particules ultra-fines, destines aux elements combustibles carbones
EP2351495A4 (fr) * 2008-11-06 2016-10-05 Japan Tobacco Inc Article a fumer, procede a fabrication associe et procede de fabrication d'agent reducteur de monoxyde de carbone

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GB781539A (en) * 1954-10-27 1957-08-21 Jan Durandeaux Improvements in or relating to cigarette paper or the like and to tobacco smoking products comprising the same
US3338246A (en) * 1964-05-04 1967-08-29 Union Carbide Corp Smoking tobacco preparation
GB1435504A (en) * 1972-02-17 1976-05-12 Wald N Cigarette filter
GB2003720A (en) * 1977-09-06 1979-03-21 Bat Cigarettenfab Gmbh Method for the removal by elimination of nitric oxide and carbon monoxide from tobacco smoke and also from tobacco material smoke filters and cigarette papers
EP0135265A2 (fr) * 1983-08-22 1985-03-27 R.J. Reynolds Tobacco Company Produit à fumer
EP0174645A2 (fr) * 1984-09-14 1986-03-19 R.J. Reynolds Tobacco Company Article pour fumer
EP0212234A2 (fr) * 1985-08-26 1987-03-04 R.J. Reynolds Tobacco Company Article à fumer
EP0254848A2 (fr) * 1986-07-28 1988-02-03 R.J. Reynolds Tobacco Company Procédé pour modifier un substrat à utiliser dans des articles à fumer et produit ainsi obtenu
US4756318A (en) * 1985-10-28 1988-07-12 R. J. Reynolds Tobacco Company Smoking article with tobacco jacket

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Publication number Priority date Publication date Assignee Title
GB781539A (en) * 1954-10-27 1957-08-21 Jan Durandeaux Improvements in or relating to cigarette paper or the like and to tobacco smoking products comprising the same
US3338246A (en) * 1964-05-04 1967-08-29 Union Carbide Corp Smoking tobacco preparation
GB1435504A (en) * 1972-02-17 1976-05-12 Wald N Cigarette filter
GB2003720A (en) * 1977-09-06 1979-03-21 Bat Cigarettenfab Gmbh Method for the removal by elimination of nitric oxide and carbon monoxide from tobacco smoke and also from tobacco material smoke filters and cigarette papers
EP0135265A2 (fr) * 1983-08-22 1985-03-27 R.J. Reynolds Tobacco Company Produit à fumer
EP0174645A2 (fr) * 1984-09-14 1986-03-19 R.J. Reynolds Tobacco Company Article pour fumer
EP0212234A2 (fr) * 1985-08-26 1987-03-04 R.J. Reynolds Tobacco Company Article à fumer
US4756318A (en) * 1985-10-28 1988-07-12 R. J. Reynolds Tobacco Company Smoking article with tobacco jacket
EP0254848A2 (fr) * 1986-07-28 1988-02-03 R.J. Reynolds Tobacco Company Procédé pour modifier un substrat à utiliser dans des articles à fumer et produit ainsi obtenu

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0467658A2 (fr) * 1990-07-20 1992-01-22 Philip Morris Products Inc. Conversion catalytique du monoxyde de carbone à partir de sources de chaleur carbonées
EP0467658A3 (en) * 1990-07-20 1992-03-11 Philip Morris Products Inc. Catalytic conversion of carbon monoxide from carbonaceous heat sources
EP0494784A2 (fr) * 1991-01-09 1992-07-15 Philip Morris Products Inc. Procédé de fabrication de sources de chaleur à base de carbure métallique
EP0494784A3 (fr) * 1991-01-09 1992-08-05 Philip Morris Products Inc. Procédé de fabrication de sources de chaleur à base de carbure métallique
US5247949A (en) * 1991-01-09 1993-09-28 Philip Morris Incorporated Method for producing metal carbide heat sources
US5146934A (en) * 1991-05-13 1992-09-15 Philip Morris Incorporated Composite heat source comprising metal carbide, metal nitride and metal
EP0514151A2 (fr) * 1991-05-13 1992-11-19 Philip Morris Products Inc. Source de chaleur composite
EP0514151A3 (en) * 1991-05-13 1993-01-13 Philip Morris Products Inc. A composite heat source
US5246018A (en) * 1991-07-19 1993-09-21 Philip Morris Incorporated Manufacturing of composite heat sources containing carbon and metal species
EP0535695A2 (fr) * 1991-10-03 1993-04-07 Phillips Petroleum Company Article à fumer avec catalyseur d'oxydation du monoxyde de carbone
EP0535695A3 (fr) * 1991-10-03 1994-04-13 Phillips Petroleum Co
WO1994027452A1 (fr) * 1993-05-28 1994-12-08 Brown & Williamson Tobacco Corporation Article pour fumeurs
US5944025A (en) * 1996-12-30 1999-08-31 Brown & Williamson Tobacco Company Smokeless method and article utilizing catalytic heat source for controlling products of combustion
EP0949873A1 (fr) * 1996-12-30 1999-10-20 BROWN & WILLIAMSON TOBACCO CORPORATION Article sans fumee utilisant une source de chaleur catalytique pour reguler la formation des produits de combustion, et procede de fabrication correspondant
EP0949873A4 (fr) * 1996-12-30 2005-03-23 Brown & Williamson Tobacco Article sans fumee utilisant une source de chaleur catalytique pour reguler la formation des produits de combustion, et procede de fabrication correspondant
WO2006002001A2 (fr) * 2004-06-15 2006-01-05 R.J. Reynolds Tobacco Company Catalyseurs a particules ultra-fines, destines aux elements combustibles carbones
WO2006002001A3 (fr) * 2004-06-15 2006-08-10 Reynolds Tobacco Co R Catalyseurs a particules ultra-fines, destines aux elements combustibles carbones
EP2351495A4 (fr) * 2008-11-06 2016-10-05 Japan Tobacco Inc Article a fumer, procede a fabrication associe et procede de fabrication d'agent reducteur de monoxyde de carbone

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