WO2004041008A1 - Nanoparticules d'oxydant/catalyseur destinees a reduire des constituants de la fumee du tabac tels que le monoxyde de carbone - Google Patents

Nanoparticules d'oxydant/catalyseur destinees a reduire des constituants de la fumee du tabac tels que le monoxyde de carbone Download PDF

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Publication number
WO2004041008A1
WO2004041008A1 PCT/US2003/034879 US0334879W WO2004041008A1 WO 2004041008 A1 WO2004041008 A1 WO 2004041008A1 US 0334879 W US0334879 W US 0334879W WO 2004041008 A1 WO2004041008 A1 WO 2004041008A1
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WO
WIPO (PCT)
Prior art keywords
additive
cigarette
carbon monoxide
carbon dioxide
catechol
Prior art date
Application number
PCT/US2003/034879
Other languages
English (en)
Inventor
Ping Li
Mohammad Hajaligol
Eun-Jae Shin
Firooz Rasouli
Original Assignee
Philip Morris Products S.A.
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
Publication date
Priority claimed from US10/286,968 external-priority patent/US7017585B2/en
Application filed by Philip Morris Products S.A. filed Critical Philip Morris Products S.A.
Priority to AU2003286857A priority Critical patent/AU2003286857A1/en
Publication of WO2004041008A1 publication Critical patent/WO2004041008A1/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
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/287—Treatment of tobacco products or tobacco substitutes by chemical substances by inorganic substances only
    • A24B15/288—Catalysts or catalytic material, e.g. included in the wrapping 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
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/285—Treatment of tobacco products or tobacco substitutes by chemical substances characterised by structural features, e.g. particle shape or size
    • A24B15/286—Nanoparticles
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/287—Treatment of tobacco products or tobacco substitutes by chemical substances by inorganic substances only

Definitions

  • Oxidant/Catalyst Nanoparticles to Reduce Tobacco Smoke Constituents Such as Carbon Monoxide
  • British Patent No. 863,287 describes methods for treating tobacco prior to the manufacture of tobacco articles, such that incomplete combustion products are removed or modified during smoking of the tobacco article. This is said to be accomplished by adding a calcium oxide or a calcium oxide precursor to the tobacco. Iron oxide is also mentioned as an additive to the tobacco.
  • Cigarettes comprising absorbents, generally in a filter tip, have been suggested for physically absorbing some of the carbon monoxide, but such methods are usually not completely efficient.
  • a cigarette filter for removing unwanted byproducts formed during smoking is described in U.S. Reissue Patent No. RE 31,700, where the cigarette filter comprises dry and active green algae, optionally with an inorganic porous adsorbent such as iron oxide.
  • Other filtering materials and filters for removing unwanted gaseous byproducts, such as hydrogen cyanide and hydrogen sulfide are described in British Patent No. 973,854. These filtering materials and filters contain absorbent granules of a gas-adsorbent material, impregnated with finely divided oxides of both iron and zinc.
  • an additive for smoking tobacco products and their filter elements which comprises an intimate mixture of at least two highly dispersed metal oxides or metal oxyhydrates, is described in U.S. Patent No. 4,193,412.
  • Such an additive is said to have a synergistically increased absorption capacity for toxic substances in the tobacco smoke.
  • .British Patent No. 685,822 describes a filtering agent that is said to oxidize carbon monoxide in tobacco smoke to carbonic acid gas.
  • This filtering agent contains, for example, manganese dioxide and cupric oxide, and slaked lime. The addition of fe ⁇ ic oxide in small amounts is said to improve the efficiency of the product.
  • Another filter for smoking articles is described in Swiss patent 609,217, where the filter contains tetrapyrrole pigment containing a complexed iron (e.g. haemoglobin or chlorocruorin), and optionally a metal or a metal salt or oxide capable of fixing carbon monoxide or converting it to carbon dioxide.
  • a complexed iron e.g. haemoglobin or chlorocruorin
  • a metal or a metal salt or oxide capable of fixing carbon monoxide or converting it to carbon dioxide.
  • British Patent No. 1,104,993 relates to a tobacco smoke filter made from sorbent granules and thermoplastic resin. While activated carbon is the preferred material for the sorbent granules, it is said that metal oxides, such as iron oxide, may be used instead of, or in addition to the activated carbon.
  • catalysts suffer drawbacks because under normal conditions for smoking, catalysts are rapidly deactivated, for example, by various byproducts formed during smoking and/or by the heat. In addition, as a result of such localized catalytic activity, such filters often heat up during smoking to unacceptable temperatures.
  • Catalysts for the conversion of carbon monoxide to carbon dioxide are described, for example, in U.S. Patent Nos. 4,956,330 and 5,258,330.
  • a catalyst composition for the oxidation reaction of carbon monoxide and oxygen to carbon dioxide is described, for example, in U.S. Patent No. 4,956,330.
  • U.S. Patent No. 5,050,621 describes a smoking article having a catalytic unit containing material for the oxidation of carbon monoxide to carbon dioxide.
  • the catalyst material may be copper oxide and/or manganese dioxide.
  • the method of making the catalyst is described in British Patent No. 1,315,374.
  • U.S. Patent No. 5,258,340 describes a mixed transition metal oxide catalyst for the oxidation of carbon monoxide to carbon dioxide. This catalyst is said to be useful for incorporation into smoking articles.
  • Metal oxides such as iron oxide have also been incorporated into cigarettes for various purposes.
  • WO 87/06104 the addition of small quantities of zinc oxide or ferric oxide to tobacco is described, for the purposes of reducing or eliminating the production of certain unwanted byproducts, such as nitrogen-carbon compounds, as well as removing the stale "after taste" associated with cigarettes.
  • the iron oxide is provided in particulate form, such that under combustion conditions, the ferric oxide or zinc oxide present in minute quantities in particulate form is reduced to iron.
  • the iron is claimed to dissociate water vapor into hydrogen and oxygen, and cause the preferential combustion of nitrogen with hydrogen, rather than with oxygen and carbon, thereby preferentially forming ammonia rather than the unwanted nitrogen- carbon compounds.
  • U.S. Patent No. 3,807,416 describes a smoking material comprising reconstituted tobacco and zinc oxide powder.
  • U.S. Patent No. 3,720,214 relates to a smoking article composition comprising tobacco and a catalytic agent consisting essentially of finely divided zinc oxide. This composition is described as causing a decrease in the amount of polycyclic aromatic compounds during smoking.
  • Another approach to reducing the concentration of carbon monoxide is described in WO 00/40104, which describes combining tobacco with loess and optionally iron oxide compounds as additives. The oxide compounds of the constituents in loess, as well as the iron oxide additives are said to reduce the concentration of carbon monoxide.
  • iron oxide has also been proposed for incorporation into tobacco articles, for a variety of other purposes.
  • iron oxide has been described as particulate inorganic filler (e.g. U.S. Patent Nos. 4,197,861; 4,195,645; and 3,931,824), as a coloring agent (e.g. U.S. Patent No. 4,119,104) and in powder form as a burn regulator (e.g. U.S. Patent No. 4,109,663).
  • several patents describe treating filler materials with powdered iron oxide to improve taste, color and/or appearance (e.g. U.S. Patent Nos. 6,095,152; 5,598,868; 5,129,408; 5,105,836 and 5,101,839).
  • metal oxides such as FeO or Fe 2 O 3 have not led to the effective reduction of carbon monoxide in mainstream smoke.
  • the additive is capable of reducing at least one constituent from mainstream and/or sidestream tobacco smoke, the at least one constituent being selected from the group consisting of aldehyde, carbon monoxide, 1,3- butadiene, isoprene, acrolein, acrylonitrile, hydrogen cyanide, o-toluidine, 2- naphtylamine, nitrogen oxide, benzene, N-nitrosonornicotine, phenol, catechol, benz(a)anthracene, benzo(a)pyrene, and mixtures thereof.
  • the additive is effective for the conversion of carbon monoxide to carbon dioxide and/or catalyst for the conversion of hydrocarbon such as isoprene and/or aldehydes such as acetaldehyde and acrolein and/or phenolic compounds such as catechol to carbon dioxide and water.
  • hydrocarbon such as isoprene and/or aldehydes such as acetaldehyde and acrolein
  • phenolic compounds such as catechol to carbon dioxide and water.
  • FIG. 1 depicts the temperature dependence of the Gibbs Free Energy and Enthalpy for the oxidation reaction of carbon monoxide to carbon dioxide.
  • FIG. 2 depicts the temperature dependence of the percentage conversion of carbon dioxide to carbon monoxide by carbon to form carbon monoxide.
  • FIG. 3 depicts a comparison between the catalytic activity of Fe 2 O 3 nanoparticles (NANOCAT® Superfine Iron Oxide (SFIO) from MACH I, Inc., King of Prussia, PA) having an average particle size of about 3 nm, versus Fe 2 O 3 powder (from Aldrich Chemical Company) having an average particle size of about 5 ⁇ m.
  • NANOCAT® Superfine Iron Oxide (SFIO) from MACH I, Inc., King of Prussia, PA
  • FIGs. 4A and 4B depict the pyrolysis region (where the Fe 2 O 3 nanoparticles act as a catalyst) and the combustion zone (where the Fe 2 O 3 nanoparticles act as an oxidant) in a cigarette.
  • FIG. 5 depicts a schematic of a quartz flow tube reactor.
  • FIG. 6 illustrates the temperature dependence on the production of carbon monoxide, carbon dioxide and oxygen, when using Fe 2 O 3 nanoparticles as the catalyst for the oxidation of carbon monoxide with oxygen to produce carbon dioxide.
  • FIG. 7 illustrates the relative production of carbon monoxide, carbon dioxide and oxygen, when using Fe 2 O 3 nanoparticles as an oxidant for the reaction of Fe 2 O 3 with carbon monoxide to produce carbon dioxide and FeO.
  • FIGs. 8 A and 8B illustrate the reaction orders of carbon monoxide and carbon dioxide with Fe 2 O 3 as a catalyst.
  • FIG. 9 depicts the measurement of the activation energy and the pre-exponential factor for the reaction of carbon monoxide with oxygen to produce carbon dioxide, using Fe 2 O 3 nanoparticles as a catalyst for the reaction.
  • FIG. 10 depicts the temperature dependence for the conversion rate of carbon monoxide, for flow rates of 300 mL/min and 900 mL/min respectively.
  • FIG. 11 depicts contamination and deactivation studies for water wherein curve 1 represents the condition for 3% H 2 O and curve 2 represents the condition for no H 2 O.
  • FIG. 12 depicts the temperature dependence for the conversion rates of CuO and Fe 2 O 3 nanoparticles as catalysts for the oxidation of carbon monoxide with oxygen to produce carbon dioxide.
  • FIG. 13 depicts a flow tube reactor to simulate a cigarette in evaluating different nanoparticle catalysts.
  • FIG. 14 depicts the relative amounts of carbon monoxide and carbon dioxide production without a catalyst present.
  • FIG. 15 depicts the relative amounts of carbon monoxide and carbon dioxide production with a catalyst present.
  • FIG. 16 shows the effect of oxidation of carbon monoxide without isoprene in the gas stream.
  • FIG. 17 shows the oxidation of isoprene without the presence of carbon monoxide in the gas stream.
  • FIG. 18 shows the effect of simultaneous oxidation of carbon monoxide and isoprene.
  • FIG. 19 is a proposed model of a cyclopentadienyl-like structure on the iron oxide surface of the catalyst material.
  • FIG. 20 shows the product distribution for conversion of catechol at 350°C with a 1 : 1 weight % ratio of substrate to catalyst using 2 mg catechol and 2.5 mg NANOCAT® catalyst.
  • FIG. 21 shows the product distribution for conversion of catechol at 600 °C in the absence of a catalyst using 2 mg catechol.
  • FIG. 22 shows the product distribution for conversion of catechol at 350°C with a 10:1 weight % ratio of substrate to catalyst using 20 mg catechol and 2.5 mg NANOCAT® catalyst.
  • FIG. 23 shows the product distribution for conversion of catechol at 650 °C with a 10:1 weight % ratio of substrate to catalyst using 20 mg catechol and 2.5 mg NANOCAT® catalyst.
  • Cut filler compositions, cigarettes, methods for making cigarettes and methods for smoking cigarettes which involve the use of nanoparticle additives capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide are described herein.
  • the . amount of carbon monoxide in mainstream smoke can be reduced, thereby also reducing the amount of carbon monoxide reaching the smoker and/or given off as second-hand or sidestream smoke.
  • mainstream smoke refers to the mixture of gases passing down the tobacco rod and issuing through the filter end, i.e. the amount of smoke issuing or drawn from the mouth end of a cigarette during smoking of the cigarette.
  • the mainstream smoke contains smoke that is drawn in through both the lighted region, as well as through the cigarette paper wrapper.
  • the total amount of carbon monoxide formed during smoking comes from a combination of three main sources: thermal decomposition (about 30%), combustion (about 36%) and reduction of carbon dioxide with carbonized tobacco (at least 23%).
  • thermal decomposition about 30%
  • combustion about 36%
  • reduction of carbon dioxide with carbonized tobacco at least 23%).
  • Formation of carbon monoxide from thermal decomposition starts at a temperature of about 180°C, and finishes at around 1050°C, and is largely controlled by chemical kinetics.
  • Formation of carbon monoxide and carbon dioxide during combustion is controlled largely by the diffusion of oxygen to the surface (k a ) and the surface reaction (k b ).
  • k a and k b are about the same.
  • the reaction becomes diffusion controlled.
  • the reduction of carbon dioxide with carbonized tobacco or charcoal occurs at temperatures around 390°C and above.
  • the temperature and the oxygen concentration are the two most significant factors affecting the formation and reaction of carbon monoxide and carbon dioxide.
  • the nanoparticle additives can target the various reactions that occur in different regions of the cigarette during smoking.
  • the combustion zone is the burning zone of the cigarette produced during smoking of the cigarette, usually at the lighted end of a cigarette.
  • the temperature in the combustion zone ranges from about 700°C to about 950°C, and the heating rate can go as high as 500°C/second.
  • the concentration of oxygen is low in this region, since it is being consumed in the combustion of tobacco to produce carbon monoxide, carbon dioxide, water vapor, and various organics.
  • the nanoparticle additive acts as an oxidant to convert carbon monoxide to carbon dioxide.
  • the nanoparticle additive oxidizes carbon monoxide in the absence of oxygen.
  • the oxidation reaction begins at around 150°C, and reaches maximum activity at temperatures higher than about 460°C.
  • the "pyrolysis region” is the region behind the combustion region, where the temperatures range from about 200°C to about 600°C. This is where most of the carbon monoxide is produced.
  • the major reaction in this region is the pyrolysis (i.e. the thermal degradation) of the tobacco that produces carbon monoxide, carbon dioxide, smoke components, and charcoal using the heat generated in the combustion zone.
  • the nanoparticle additive may act as a catalyst for the oxidation of carbon monoxide to carbon dioxide.
  • the nanoparticle additive catalyzes the oxidation of carbon monoxide by oxygen to produce carbon dioxide.
  • the catalytic reaction begins at 150°C and reaches maximum activity around 300°C.
  • the nanoparticle additive preferably retains its oxidant capability after it has been used as a catalyst, so that it can also function as an oxidant in the combustion region as well.
  • condensation/filtration zone where the temperature ranges from ambient to about 150°C.
  • the major process is the condensation/filtration of the smoke components. Some amount of carbon monoxide and carbon dioxide diffuse out of the cigarette and some oxygen diffuses into the cigarette. However, in general, the oxygen level does not recover to the atmospheric level.
  • the nanoparticle additives may function as an oxidant and/or as a catalyst, depending upon the reaction conditions.
  • the additive is capable of acting as both an oxidant for the conversion of carbon monoxide to carbon dioxide and as a catalyst for the conversion of carbon monoxide to carbon dioxide.
  • the catalyst will provide the greatest effect. It is also possible to use combinations of additives to obtain this effect.
  • nanoparticles that the particles have an average particle size of less than a micron.
  • the additive preferably has an average particle size less than about 500 nm, more preferably less than about 100 nm, even more preferably less than about 50 nm, and most preferably less than about 5 nm.
  • the additive has a surface area from about 20 m 2 /g to about 400 m /g, or more preferably from about 200 m 2 /g to about 300 m 2 /g.
  • the nanoparticles may be made using any suitable technique, or the nanoparticles can be purchased from a commercial supplier.
  • MACH I, Inc. King of Prussia, PA sells Fe 2 O 3 nanoparticles under the trade names NANOCAT® Superfine Iron Oxide (SFIO) and NANOCAT® Magnetic Iron Oxide.
  • the NANOCAT® Superfine Iron Oxide (SFIO) is amorphous ferric oxide in the form of a free flowing powder, with a particle size of about 3 nm, a specific surface area of about 250 m 2 /g, and a bulk density of about 0.05 g/mL.
  • the NANOCAT® Superfine Iron Oxide (SFIO) is synthesized by a vapor-phase process, which renders it free of impurities that may be present in conventional catalysts, and is suitable for use in food, drugs, and cosmetics.
  • the NANOCAT® Magnetic Iron Oxide is a free flowing powder with a particle size of about 25 nm and a surface area of about 40 m 2 /g.
  • the selection of an appropriate nanoparticle catalyst and/or oxidant will take into account such factors as stability and preservation of activity during storage conditions, low cost and abundance of supply.
  • the nanoparticle additive will be a benign material. Further, it is preferred that the nanoparticles do not react or form unwanted byproducts during smoking.
  • FIG. 1 shows a thermodynamic analysis of the Gibbs Free Energy and Enthalpy temperature dependence for the oxidation of carbon monoxide to carbon dioxide.
  • FIG. 2 shows the temperature dependence of the percentage of carbon dioxide conversion with carbon to form carbon monoxide.
  • metal oxide nanoparticles are used. Any suitable metal oxide in the form of nanoparticles may be used.
  • one or more metal oxides may also be used as mixtures or in combination, where the metal oxides may be different chemical entities or different forms of the same metal oxide.
  • Preferred nanoparticle additives include metal oxides, such as Fe 2 O 3 , CuO, CeO 2 , Ce 2 O 3 , or doped metal oxides such as Y 2 O 3 doped with zirconium, Mn 2 O 3 doped with palladium. Mixtures of additives may also be used.
  • Fe 2 O 3 is preferred because it is not known to produce any unwanted byproducts, and will simply be reduced to FeO or Fe after the reaction. Further, when Fe 2 O is used as the additive, it will not be converted to an environmentally hazardous material. Moreover, use of a precious metal can be avoided, as the Fe 2 O 3 nanoparticles are economical and readily available.
  • NANOCAT® Superfine Iron Oxide (SFIO) and NANOCAT® Magnetic Iron Oxide, described above are preferred additives.
  • FIG. 3 shows a comparison between the catalytic activity of Fe 2 O 3 nanoparticles
  • the test conditions include flow rate of 1000 ml/min of He containing 20.6% O 2 and 3.4% Co, 50 mg catalyst and 12K/min heating rate.
  • the Fe 2 O 3 nanoparticles show a much higher percentage of conversion of carbon monoxide to carbon dioxide than the Fe 2 O 3 having an average particle size of about 5 ⁇ m.
  • Fe 2 O 3 nanoparticles are capable of acting as both an oxidant for the conversion of carbon monoxide to carbon dioxide and as a catalyst for the conversion of carbon monoxide to carbon dioxide.
  • the Fe 2 O 3 nanoparticles act as a catalyst in the pyrolysis zone A wherein 2CO+O 2 ⁇ 2CO 2 , and act as an oxidant in the combustion region B wherein Fe 2 O 3 +CO-CO 2 +2FeO
  • FIG. 4B shows various temperature zones in a lit cigarette wherein zone A represents approximately 700 to 900 °C, zone B represents approximately 200 to 600 °C and zone C represents approximately 30 to 200°C.
  • the oxidant/catalyst dual function and the reaction temperature range make Fe 2 O 3 nanoparticles a useful additive in cigarettes and tobacco mixtures for the reduction of carbon monoxide during smoking. Also, during the smoking of the cigarette, the Fe 2 O 3 nanoparticles may be used initially as a catalyst (i.e. in the pyrolysis zone), and then as an oxidant (i.e. in the combustion region).
  • a catalyst i.e. in the pyrolysis zone
  • an oxidant i.e. in the combustion region.
  • x the percentage of carbon monoxide converted to carbon dioxide
  • a 0 the pre-exponential factor, 5xl0 "6 s "1
  • R the gas constant, 1.987 x 10 "3 kcal/(mol » K)
  • FIG. 5 A schematic of a quartz flow tube reactor, suitable for carrying out such studies, is shown in FIG. 5.
  • Helium, oxygen/helium and/or carbon monoxide/helium mixtures may be introduced at one end of the reactor.
  • a quartz wool 10 dusted with Fe 2 O 3 nanoparticles is placed within the reactor between sections of quartz wool 12.
  • the products exit the reactor at a second end, which comprises an exhaust 14 and a capillary line 16 to a Quadrupole Mass Spectrometer ("QMS”) 18.
  • QMS Quadrupole Mass Spectrometer
  • FIG. 6 is a graph of temperature versus QMS intensity for a test wherein Fe 2 O 3 nanoparticles are used as a catalyst for the reaction of carbon monoxide with oxygen to produce carbon dioxide.
  • about 82 mg of Fe 2 O 3 nanoparticles are loaded in the quartz flow tube reactor.
  • Carbon monoxide is provided at 4% concentration in helium at a flow rate of about 270 mL/min, and oxygen is provided at 21% concentration in helium at a flow rate of about 270 mL/min.
  • the heating rate is about 12.1 K/min.
  • curve A represents CO
  • curve B represents O 2
  • curve C represents CO 2
  • Fe 2 O 3 nanoparticles are effective at converting carbon monoxide to carbon dioxide at temperatures above around 225°C.
  • FIG. 7 is a graph of time versus QMS intensity for a test wherein Fe 2 O 3 nanoparticles are studied as an oxidant for the reaction of Fe 2 O 3 with carbon monoxide to produce carbon dioxide and FeO.
  • curve A represents CO
  • curve B represents O 2
  • curve C represents CO 2 .
  • about 82 mg of Fe 2 O 3 nanoparticles are loaded in the quartz flow tube reactor.
  • Carbon monoxide is provided at 4% concentration in helium at a flow rate of about 270 mL/min, and the heating rate is about 137 K/min to a maximum temperature of 460 °C.
  • Fe 2 O 3 nanoparticles are effective in conversion of carbon monoxide to carbon dioxide under conditions similar to those during smoking of a cigarette.
  • FIG. 9 depicts the measurement of the activation energy and the pre- exponential factor for the reaction of carbon monoxide with oxygen to produce carbon dioxide, using Fe 2 O 3 nanoparticles as a catalyst for the reaction with 4% CO in He at 100 ml/min and 2% O 2 in He at 200 ml/min.
  • a summary of activation energies is provided in Table 1.
  • FIG. 10 depicts the temperature dependence for the conversion rate of carbon monoxide using 50 mg Fe 2 O 3 nanoparticles as catalyst in the quartz tube reactor with He containing 1.32% CO and 1.34% O 2 flowing through the reactor, for flow rates of 300 mL/min (curve A) and 900 mL/min (curve B) respectively.
  • FIG. 11 depicts contamination and deactivation studies for water using 50 mg Fe 2 O 3 nanoparticles as catalyst in the quartz tube reactor with flow rate of 1000 ml/min He containing 3.4% CO and 21% O 2 and heating rate of 12.4 K min.
  • curve 2 the presence of up to 3% water (curve 2) has little effect on the ability of Fe 2 O 3 nanoparticles to convert carbon monoxide to carbon dioxide.
  • FIG. 12 illustrates a comparison between the temperature dependence of conversion rate for CuO (Curve A) and Fe 2 O 3 (Curve B) nanoparticles using 50 mg Fe 2 O 3 and 50 mg CuO nanoparticles as catalyst in the quartz tube reactor with flow rate of 1000 ml/min He containing 3.4% CO and 21% O 2 and heating rate of 12.4 K/min. Although the CuO nanoparticles have higher conversion rates at lower temperatures, at higher temperatures the CuO and Fe 2 O 3 have the same conversion rates.
  • FIG. 13 shows a flow tube reactor to simulate a cigarette in evaluating different nanoparticle catalysts wherein the reactor 20 includes an inlet 22 for 21% O 2 in He, 1/8 inch stainless steel tubing 24, tobacco filler 26, Fe 2 O 3 or other oxides dusted on quartz wool 28, vent 30 and QMS analyzer 32.
  • Table 2 shows a comparison between the ratio of carbon monoxide to carbon dioxide, and the percentage of oxygen depletion when using CuO and Fe 2 O 3 nanoparticles.
  • FIG. 14 is a graph of temperature versus QMS intensity in a test which shows the amounts of carbon monoxide (curve A) and carbon dioxide (curve B) production without a catalyst present using 1000 ml/min He containing 21% O 2 , 350 mg tobacco and heating rate of 120 K/min.
  • curve A carbon monoxide
  • curve B carbon dioxide
  • FIG. 15 is a graph of temperature versus QMS intensity in a test which shows the amounts of carbon monoxide and carbon dioxide production when using 50 mg Fe 2 O 3 nanoparticles as a catalyst with 1000 ml/min He containing 21% O 2 , 350 mg tobacco and heating rate of 120 K/min.
  • the presence of Fe 2 O 3 nanoparticles increases the ratio of carbon dioxide to carbon monoxide present, and decreases the amount of carbon monoxide present.
  • Experiments were carried out in a quartz flow tube to study the effect of the iron oxide nanoparticles on reduction of carbon monoxide and isoprene in separate and combined gas flows.
  • the concentration of carbon monoxide, carbon dioxide and oxygen was measured by an NGA MLT 2000 multi-gas analyzer.
  • concentration range of isoprene (not shown) was measured by a Balzer Quadropole Mass Spectrometer (QMS).
  • QMS Quadropole Mass Spectrometer
  • 50 mg of iron oxide nanoparticles were used and the total inlet gas flow rate was 1000 ml/min. During the experiments, the heating rate was 12°C/minute.
  • FIG. 16 shows the concentration of CO (curve A), CO 2 (curve B) and O 2 (curve C) and establishes that in the absence of isoprene in the gas flow, the conversion of carbon monoxide to carbon dioxide reached 100% at about 350°C.
  • Nanoparticle iron oxide with the higher population of the coordinate-unsaturated iron site due to its small particle size, might be able to facilitate this surface complex and keep both carbon monoxide and isoprene close to the surface. It is expected that other types of conjugated double bond containing compounds such as acrolein would undergo the same reaction.
  • the nanoparticle catalyst can effect reduction of various constituents in mainstream and sidestream tobacco.
  • constituents in mainstream include, but are not limited to, aldehydes, carbon monoxide, 1,3-butadiene, isoprene, acrolein, acrylonitrile, hydrogen cyanide, o-toluidine, 2-naphtylamine, nitrogen oxide, benzene, N-nitrosonornicotine, phenol, catechol, benz(a)anthracene, and/or benzo(a)pyrene.
  • the cracking study was carried out under atmospheric pressure in the temperature range from 350 to 650°C with about 10 milli seconds contact time.
  • the ratio in weight % of substrate to catalyst was varied from 1:1 to 10:1.
  • the nanoparticle additives may be provided along the length of a tobacco rod by distributing the additive nanoparticles on the tobacco or incorporating them into the cut filler tobacco using any suitable method.
  • the nanoparticles may be provided in the form of a powder or in a solution in the form of a dispersion.
  • nanoparticle additives in the form of a dry powder are dusted on the cut filler tobacco.
  • the nanoparticle additives may also be present in the form of a solution and sprayed on the cut filler tobacco.
  • the tobacco may be coated with a solution containing the nanoparticle additives.
  • the nanoparticle additive may also be added to the cut filler tobacco stock supplied to the cigarette making machine or added to a tobacco rod prior to wrapping cigarette paper around the cigarette rod.
  • the nanoparticle additives will preferably be distributed throughout the tobacco rod portion of a cigarette and optionally the cigarette filter. By providing the nanoparticle additives throughout the entire tobacco rod, it is possible to reduce the amount of carbon monoxide throughout the cigarette, and particularly at both the combustion region and in the pyrolysis zone. Further, the nanoparticle additive can reduce other constituents of mainstream and/or sidestream tobacco smoke, such constituents including aldehydes such as acetaldehyde or acrolein, hydrocarbons such as isoprene and phenolic compounds such as catechol.
  • aldehydes such as acetaldehyde or acrolein
  • hydrocarbons such as isoprene
  • phenolic compounds such as catechol.
  • the amount of the nanoparticle additive should be selected such that the amount of carbon monoxide in mainstream smoke is reduced during smoking of a cigarette.
  • the amount of the nanoparticle additive will be from about a few milligrams, for example, 5 mg/cigarette, to about 100 mg/cigarette. More preferably, the amount of nanoparticle additive will be from about 40 mg/cigarette to about 50 mg/cigarette.
  • One embodiment of the invention relates to a cut filler composition
  • a cut filler composition comprising tobacco and at least one additive, as described above, which is capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide, where the additive is in the form of nanoparticles.
  • the nanoparticle additive can reduce other constituents of mainstream and/or sidestream tobacco smoke, such constituents including aldehydes such as acetaldehyde or acrolein, hydrocarbons such as isoprene and phenolic compounds such as catechol. Any suitable tobacco mixture may be used for the cut filler.
  • suitable types of tobacco materials include flue-cured, Burley, Maryland or Oriental tobaccos, the rare or specialty tobaccos, and blends thereof.
  • the tobacco material can be provided in the form of tobacco lamina; processed tobacco materials such as volume expanded or puffed tobacco, processed tobacco stems such as cut-rolled or cut-puffed stems, reconstituted tobacco materials; or blends thereof.
  • the tobacco may also include tobacco substitutes.
  • the tobacco is normally employed in the form of cut filler, i.e. in the form of shreds or strands cut into widths ranging from about 1/10 inch to about 1/20 inch or even 1/40 inch. The lengths of the strands range from between about 0.25 inches to about 3.0 inches.
  • the cigarettes may further comprise one or more flavorants or other additives (e.g. burn additives, combustion modifying agents, coloring agents, binders, etc.) known in the art.
  • a cigarette comprising a tobacco rod, wherein the tobacco rod comprises cut filler having at least one additive, as described above, which is capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide, wherein the additive is in the form of nanoparticles.
  • a further embodiment of the invention relates to a method of making a cigarette, comprising (i) adding an additive to a cut filler, wherein the additive, as described above, which is capable of acting as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide, wherein the additive is in the form of nanoparticles; (ii) providing the cut filler comprising the additive to a cigarette making machine to form a tobacco rod; and (iii) placing a paper wrapper around the tobacco rod to form the cigarette.
  • the nanoparticle additive can reduce other constituents of mainstream and/or sidestream tobacco smoke, such constituents including aldehydes such as acetaldehyde or acrolein, hydrocarbons such as isoprene and phenolic compounds such as catechol.
  • aldehydes such as acetaldehyde or acrolein
  • hydrocarbons such as isoprene
  • phenolic compounds such as catechol.
  • the cigarettes may range from about 50 mm to about 120 mm in length.
  • a regular cigarette is about 70 mm long
  • a "King Size” is about 85 mm long
  • a "Super King Size” is about 100 mm long
  • a "Long” is usually about 120 mm in length.
  • the circumference is from about 15 mm to about 30 mm in circumference, and preferably around 25 mm.
  • the packing density is typically between the range of about 100 mg/cm 3 to about 300 mg/cm 3 , and preferably 150 mg/cm 3 to about 275 mg/cm 3 .
  • Yet another embodiment of the invention relates to a method of smoking the cigarette described above, which involves lighting the cigarette to form smoke and drawing the smoke through the cigarette, wherein during the smoking of the cigarette, the additive acts as an oxidant for the conversion of carbon monoxide to carbon dioxide and/or as a catalyst for the conversion of carbon monoxide to carbon dioxide.
  • the nanoparticle additive can reduce other constituents of mainstream and/or sidestream tobacco smoke, such constituents including aldehydes such as acetaldehyde or acrolein, hydrocarbons such as isoprene and phenolic compounds such as catechol.
  • "Smoking" of a cigarette means the heating or combustion of the cigarette to form smoke, which can be inhaled.
  • smoking of a cigarette involves lighting one end of the cigarette and drawing the cigarette smoke through the mouth end of the cigarette, while the tobacco contained therein undergoes a combustion reaction.
  • the cigarette may also be smoked by other means.
  • the cigarette may be smoked by heating the cigarette and/or heating using electrical heater means, as described in commonly-assigned U.S. Patent Nos. 6,053,176; 5,934,289; 5,591,368 or 5,322,075, for example.

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

Abstract

L'invention concerne de compositions de tabac haché, des cigarettes, des procédés de fabrication de cigarettes et des procédés de fumer la cigarette, impliquant l'utilisation de nanoparticules additives capables de réduire des quantités d'au moins un constituant de courant principal et/ou de courant secondaire de la fumée du tabac, ce constituant étant choisi parmi le groupe constitué d'aldéhyde, de MONOXYDE de carbone, de 1,3-butadiène, d'isoprène, d'acroléine, d'acrylonitrile, de cyanure d'hydrogène, d'o- toluidine, de 2-naphtylamine, d'oxyde d'azote, benzène, de N-nitrosonornicotine, de phénol, de catéchol, de benz(a)anthracène, de benzo(a)pyrène, et des mélanges de ces produits. Les nanoparticules additives sont efficaces en tant qu'oxydant pour la conversion de monoxyde de carbone en dioxyde carbone et/ou en tant que catalyseur pour la conversion de monoxyde de carbone en dioxyde de carbone et/ou entant que catalyseur de conversion d'aldéhydes telles que l'acétaldéhyde et l'acroléine, d'hydrocarbones tels que l'isoprène et/ou des composés phénoliques comme le catéchol en dioxyde de carbone et en vapeur d'eau.
PCT/US2003/034879 2002-11-04 2003-11-04 Nanoparticules d'oxydant/catalyseur destinees a reduire des constituants de la fumee du tabac tels que le monoxyde de carbone WO2004041008A1 (fr)

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US10/286,968 2002-11-04
US10/286,968 US7017585B2 (en) 2001-08-31 2002-11-04 Oxidant/catalyst nanoparticles to reduce tobacco smoke constituents such as carbon monoxide
US10/460,302 US20040025895A1 (en) 2001-08-31 2003-06-13 Oxidant/catalyst nanoparticles to reduce tobacco smoke constituents such as carbon monoxide
US10/460,302 2003-06-13

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