EP2092838A1 - Tobacco/catalyst mixtures for reducing toxic compounds in tobacco smoke - Google Patents

Tobacco/catalyst mixtures for reducing toxic compounds in tobacco smoke Download PDF

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Publication number
EP2092838A1
EP2092838A1 EP07823034A EP07823034A EP2092838A1 EP 2092838 A1 EP2092838 A1 EP 2092838A1 EP 07823034 A EP07823034 A EP 07823034A EP 07823034 A EP07823034 A EP 07823034A EP 2092838 A1 EP2092838 A1 EP 2092838A1
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EP
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Prior art keywords
mcm
tobacco
additive
usy
zsm
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EP07823034A
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German (de)
English (en)
French (fr)
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EP2092838A4 (en
EP2092838B1 (en
Inventor
Antonio Marcilla Gomis
María Isabel BELTRAN RICO
Amparo Gomez Siurana
Rosa Navarro Martinez
Deseada BERENGUER MUÑOZ
Isabel Martinez Castellanos
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Universidad de Alicante
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Universidad de Alicante
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Publication of EP2092838A4 publication Critical patent/EP2092838A4/en
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Publication of EP2092838B1 publication Critical patent/EP2092838B1/en
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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
    • 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
    • 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
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D1/00—Cigars; Cigarettes
    • A24D1/002—Cigars; Cigarettes with additives, e.g. for flavouring

Definitions

  • This invention fits within the smoking products preparation industry. Specifically, this invention refers to the use of tobacco-catalyst mixtures for reducing the toxic compounds present in tobacco smoke.
  • the process of smoking a cigarette generates two types of smoke, the one called "main stream", which consists of the smoke that is inhaled and exhaled by the smoker directly from the cigarette; and the secondary stream, which consists of the smoke that is eliminated through the lit cigarette, which is diluted through the surrounding air and is inhaled by passive smokers.
  • the main stream corresponds to the smoke that is generated from the combustion of tobacco and travels through the cigarette from the lit tip and exits at the filter end. Since this is the stream that is inhaled by smokers, it is of great interest to eliminate or reduce the toxic substances it contains.
  • Rosen can also be found [Rosen, W.E., "Method of treating tobacco", US 3,840,026, Oct 8, 1974 ], which proposes the use of an absorption material with a high degree of humidity and a proportion found between 1 and 50% in order to reduce non desirable products generated from the combustion of tobacco.
  • the material type belongs to the ground infusorian type, diatoms and calcium or magnesium silicates.
  • Li et al. Li, P., Hajaligol, M., "Oxidant/catalyst nanoparticles to reduce carbon monoxide in the mainstream smoke of a cigarette", US 20030075193, 24 April 2003 ] have described the use of nanoparticles of Fe 2 O 3 , CuO, TiO 2 , CeO 2 , Ce 2 O 3 , Al 2 O 3 , Y 2 O 3 doped with Zr, Mn 2 O 3 doped with Pb, as well as mixtures of these materials to increase the degree of conversion from CO to CO 2 .
  • This patent also describes the procedure for preparing the cigarettes, which includes a) addition of the additive composed of Nan particles to the tobacco mixture, b) addition of more additives to the tobacco mixture at the cigarette manufacturing machine that make a cigarette and c) placing of a paper wrap around the tobacco to give the cigarette its final shape.
  • Li et al. Li, P., Rasouli, F., Hajaligol, M., "Application of nanoparticle iron oxide in cigarette for simultaneous CO and NO removal in the mainstream smoke", Beitraege zur Tabkforschubg International 21 (1) (2004), 1 ] described the use of an additive formed by nanoparticles of iron oxide that is generated in place while the cigarette is burning and is capable of increasing the degree of conversion of CO and NO to CO 2 and N 2 respectively.
  • potassium organic salts can also be used as additives that allow reducing the CO, nicotine and nicotine free dry material particles (NFDMP) [ Li, C., Parry, A., "Potassium organic salts as burn additives in cigarettes", Beitraege Kunststoff Tabkforschubg International 20 (5) (2003), 341 ].
  • Example Jianhua et al. Jianhua, Z., Ying, W., Yilun, W, "Mesopore solid alkali, mesopore functional material, its preparation method and application", CN 1460641 , 2003-12-10] describe the use of a solid alkali catalyst and a functional material based on a silicon based mesoporous molecular screen (for example, MCM-41 or zeolytes NaA, NaY and ZSM-5), which contains a lanthannoid or actinoid transition metal for reducing nitrosamines by selective absorption.
  • a silicon based mesoporous molecular screen for example, MCM-41 or zeolytes NaA, NaY and ZSM-5
  • the additive is deposited into the tobacco stream during the cigarette manufacturing process by using a device that allows placing the material in dust or liquid form, in suspension or foam.
  • any of the mentioned additives can also be added directly to tobacco by using the cigarette rolling machines described by Pascual [Pascual U.A., "Máquinas de liar cigarillos y liar tobaco" (cigarette and tobacco rolling machines), U200202253 , 18 September 2002].
  • EP 740907 describes the use of natural and synthetic zeolitic materials used as additives to reduce the toxic compounds found in tobacco smoke.
  • This invention claims an article for smoking that is made of a filter, tobacco and the paper wrapper.
  • the additives which have different characteristics depending on the purpose of the additive, are added to the filter as well as the tobacco. Therefore, while the additive that is inserted in the filter is hydrophobic, for mixing in with tobacco hydrophilic materials are preferred.
  • These hydrophilic additives are used saturated in water and consist of X, Y, L, mordenites and BETA zeolites, and are added to tobacco by using or not using adhesive agents such as silica gel. At elevated temperatures, these materials act as catalysts and have positive effects regarding the reduction of toxic compounds generated during the combustion of tobacco without affecting its taste.
  • this invention provides the use of an additive that is mixed in with the tobacco to reduce the quantity of toxic and cancerous substances present in tobacco smoke, where such additive is selected among a group formed by:
  • this invention provides a composition that consists of any form of tobacco i.e. soft, black, leaf, fine cut, hand rolling (RYO), pipe tobacco (MYO) or any other item capable of being smoked with at least one additive from the following list:
  • this invention provides a method for reducing the quantity of toxic and cancerous substances present in tobacco smoke, which includes the use of these additives dry mixed with the tobacco.
  • this invention provides a method for preparing the composition according to the invention, which is comprised by placing the right amount of additive in contact with the tobacco and mixing both ingredients.
  • this invention provides a KIT that administers the right amount of catalyst for preparing the above mentioned tobacco-additive mixture "on the spot”.
  • This kit includes separate compartments for tobacco and additive in the right proportions as well as instructions for preparing the mixture.
  • an additive that belongs to the group formed by the following materials used to reduce the presence of toxic and cancerous compounds in tobacco smoke are described.
  • Acid, sodium or interchanged with iron forms of BETA zeolites H-BETA, Na-BETA, Na-Fe-BETA, Na-Ce-BETANa-Zr-BETA
  • acid, sodium or exchanged with iron forms of zeolite ZSM-5 H-ZSM-5, Na-ZSM-5, Na-Fe-ZSM-5, Na-Ce-ZSM-5, Na-Zr-ZSM-5
  • acid, sodium or interchanged with iron zeolite forms USY H-USY, Na-USY, Na-Fe-USY, Na-Ce-USY, Na-Zr-USY
  • acid, sodium or interchanged with mesoporous aluminosilicate iron forms MCM-41 Na-MCM-41, Na-Fe-MCM-41, Na-Ce-MCM-41, Na-Z
  • the additive used is selected among the group formed by H-ZSM-5, Na-ZSM-5, Na-Fe-ZSM-5, Na-Ce-ZSM-5, Na-Zr-ZSM-5, H-USY, Na-USY, Na-Fe-USY, Na-Ce-USY, Na-Zr-USY, Na-MCM-41, Na-Fe-MCM-41, Na-Ce-MCM-41, Na-Zr-MCM-41, Na-MCM-22, Na-Fe-MCM-22, Na-Ce-MCM-22, Na-Zr-MCM-22, mixture of these with Fe, Ce or Zr oxides and mixtures of these materials.
  • the additive is selected from the group formed by the sodium and exchanged with iron zeolites or aluminosilicate forms, Fe, Ce or Zr oxides mixed with any of the above mentioned materials, and their mixtures.
  • the additive is selected between Na-MCM-41, Na-Fe-MCM-41, Na-Ce-MCM-41, Na-Zr-MCM-41, its mixtures with Fe, Ce or Zr oxides and mixtures of these materials.
  • the invention compositions are characterized by containing the above mentioned materials as additives. Therefore, according to the embodiment of this invention, the additive is selected from a group formed by:
  • the additive is selected between H-ZSM-5, Na-ZSM-5, Na-Fe-ZSM-5, Na-Ce-ZSM-5, Na-Zr-ZSM-5, H-USY, Na-USY, Na-Fe-USY, Na-Ce-USY, Na-Zr-USY, Na-MCM-41, Na-Fe-MCM-41, Na-Ce-MCM-41, Na-Zr-MCM-41, Na-MCM-22, Na-Fe-MCM-22, Na-Ce-MCM-22, Na-Zr-MCM-22, mixture of these with Fe, Ce or Zr oxides and mixtures of these materials.
  • the additive is selected from the group formed by the sodium and exchanged with iron zeolites or aluminosilicate forms, Fe, Ce or Zr oxides mixed with any of the above mentioned materials, and their mixtures.
  • the additive is selected between the group formed by Na-MCM-41, Na-Fe-MCM-41, Na-Ce-MCM-41, Na-Zr-MCM-41, its mixtures with Fe, Ce or Zr oxides and mixtures of these materials.
  • the composition is characterized by the additive being found in concentrations between 0.5 and 15% of the tobacco weight. Preferably found in concentrations amounts between 2 and 7% of tobacco weight.
  • the considered additives in dust form are added and mixed directly with the tobacco fine cut without needing to use any type of adhesive agent or any other specific type of technology for preparing the mixtures.
  • the additives of this invention no toxic or fibrous materials are included.
  • additives belonging to the above mentioned group of materials allows obtaining important reductions in the generation of a considerably high amount of toxic and cancerous compounds generated when smoking tobacco (CO, nicotine, tars, aldehydes, etc.) apart from what is claimed in the state of the art documents, which refer only to the reduction of a few compounds (NO and NOx, in the case of Cvetkovic et al., nitrosamines in the case of Jianhua et al. or NFDMP and polynuclear aromatic hydrocarbons (PAH) in the case of Radojicic et al.).
  • NO and NOx in the case of Cvetkovic et al.
  • nitrosamines in the case of Jianhua et al. or NFDMP
  • PAH polynuclear aromatic hydrocarbons
  • the Meier et al. Patent explicitly recognizes that in the smoking product, the catalyst is added to the tobacco using an adhesive. This is a very important fact since the presence of adhesive or the mixing of active element with other components can cause the undesired effects of interparticle diffusion or even partially or totally block the catalyst pores with the resulting loss of effectiveness.
  • kits can be used with separate containers for tobacco and additive. This kit or dispenser provides the proper amount of catalyst for the preparation of soft, black, leaf, fine cut, hand rolling, pipe tobacco and any other item capable of being smoked.
  • This kit can consist of a blister, where each cavity contains the selected amount (between 5 and 70 mg, in order to obtain a dose between 0.5 and 15 % of additive with respect to tobacco, preferably between 2 and 7% weight, which will usually be consumed in portions of around 1 g of tobacco), individual capsules that contain these quantities, a container that includes a calibrated or graduated spoon or any other type of calibrated dispenser.
  • This invention describes the use of catalysts with the required characteristics from this point of view since they possess a non fibrous morphology, are approximately spherical and of such a particle or aggregate size that in the proportions described in the examples, none are observed in the secondary filters used and therefore guarantees they are not going to travel through the conventional filter. For other types of applications, it may be necessary to adjust the particle size in order to guarantee this behavior.
  • This patent describes the use of certain zeolites and other aluminosilicates and mesoporous solids in their neutral, acid or exchanged with metallic ion forms as well as modifications and/or mixtures of these materials with non-toxic metallic ions or with oxides from these metals as additives of tobacco to drastically reduce the amount of toxic and/or cancerous compounds that are generated when smoking and which appear in the primary and secondary tobacco smoke.
  • These additives also reduce the fraction of condensable and non-condensable products which are generated during the combustion of tobacco without substantially altering their organoleptic characteristics while the amount of solid residue (coke) in the ashes increases.
  • additives in dust form can be added and mixed directly with the tobacco without needing to use any type of adhesive or special technology. These are useful and can be used for this purpose with any direct smoking tobacco type (conventional cigarette packs, leaf and fine cut cigars, etc.) as well as with those forms that require prior handling in order to obtain the product that can be smoked (MYO, RYO, pipe tobacco, etc.).
  • an objective of this invention refers to the use of additives for the direct elimination of a large part of these undesirable gas and condensable product compounds that are found in the tobacco smoke of direct consumable products (cigarette packs, leaf and fine cut cigars, etc.) as well as a kit that incorporates separate containers for tobacco and additive.
  • This kit or dispenser can be used preferably for those forms that require prior handling in order to obtain the product that can be smoked (rolling tobacco-RYO-, pipe filling tobacco-MYO-, pipe tobacco, etc.)
  • the USY zeolite has a smaller Si/Al relation and a larger pore size than the ZSM-5 zeolite and a structure that is characterized for having large internal cavities that are essentially spherical ("supercages"), joined tetrahedrically by the pore apertures, defined by 12 oxygen atom rings (12 member or 12MR rings) [ Boxiong S., Chunfei W., Rui W., Binbin G. and Cai L., "Pyrolysis of scrap tyres with zeolite USY", Journal of hazardous materials, in Press (2006 )].
  • the ZSM-5 zeolite has a 10 member (10MR) ring system with a three dimensional network of interconnected sinusoidal and circular canals with a pore size of 5.3x5.6 A and 5.1x5.5 A and intersections between canals measuring 0.9nm [ N. Kumar, "Synthesis, modification and application of high silica catalysts in the transformation of light hydrocarbons to aromatic hydrocarbons", N. Kumar, Ph.D. thesis, Abo Akademi University, Abo/Tuku, Finland, 1996 ].
  • the BETA zeolite has a structure with 12MR type orifices [ J.M. Newsam, M.M.J. Tracy, W.T. Koetsier, Proc. R. Soc. Lond.
  • This zeolite presents a structure that is highly unorganized consisting in the aleatory growing of A and B polymorphs with tetragonal and monoclinic symmetries respectively, usually in an approximate ratio of 60:40 [ Q, Li, A. Navrotsky, F. Rey, A. Corma, Micropor. Mater., 59 (2003), 177 ]. It presents two types of straight canals in the /a/ and /b/ directions with diameters of 7.3 x 6.8 A for the tetragonal system and 7.3 x 6.0 A for the monoclinic system and a sinusoidal canal in the /c/ direction measuring 5.5 x 5.5 A.
  • the material MCM-22 [ M.K. Rubin, P. Chu, US patent 4954325 , 1990 ] is a relatively recent aluminosilicate preparation that was obtained for the first time by Rubin et al. in 1990.
  • the MCM-22 structure consists of two independent pore systems, one of them made up of two-dimensional canals with 10 member apertures (10MR) and the other one consisting of a supercage system with 12 member apertures (12MR). Due to this porous structure, the MCM-22 combines the behavior of both systems, the 10MR and 12 MR, which grant it some unique catalytic properties.
  • the MCM-41 material is also a mesoporous aluminosilicate that was synthesized for the first time by Beck et al.
  • the MCM-41 presents a hexagonal mesoporous composition with a highly regular pore system of a variable size between 1.5 and 10 nm, which grants it a considerably large surface area. This property is of great importance regarding the reduction of the harmful effects of tobacco.
  • the non acid forms when used as additives for tobacco in the way described in this procedure, provide excellent results from the point of view of reducing the toxic and dangerous products present in tobacco smoke since they avoid the negative effects associated to the possible hydrolysis of lignocellulosic materials present in tobacco that can be produced when acid forms are used in environments with a high degree of humidity.
  • Table 1 shows the chemical and structural characteristics of the additives that are studied in this application, as representative examples of these type of materials. For all of them, the Si/Al ratio, the external surface and other characteristics can be modified within relatively wide intervals with different aims without substantially modifying the behavior and the general properties of the material.
  • Another important aspect is the size and shape of the catalyst particles. Particles of small size improve contact with the solid and the released gases but can travel easier through filters or the tobacco bed and enter the lungs. Therefore, it is important to consider this aspect and reduce or eliminate the possibility of this occurring. In any case, it is very important that these types of additives not contain toxic compounds or elements or have a fibrous morphology that could be hazardous to health.
  • the materials used have particle sizes of around 0.1-2 ⁇ m, which in many cases are found forming aggregates measuring 20-30 ⁇ m. Under the experimental conditions used in the examples described in this invention, the described materials with these particle sizes allow to achieve highly satisfactory results from a toxic compound reduction in tobacco smoke point of view without observing a significant presence of particles capable of traveling through the cigarette filters. However, for other types of smoking tobacco it will be necessary to optimize the particle size of additives so that these are present in a small enough size to produce good results but not so small that they travel through the cigarette filters or the tobacco bed.
  • Example 1 Comparative study of smoking cigarettes with and without additive.
  • cigarettes are made by manually mixing the tobacco fiber with the catalyst by using a few drops of ethanol. This task was performed over a sieve to separate the catalyst that would not adhere to the tobacco and in this way achieving a nominal catalyst percentage in the mixtures that corresponded to the amount of catalyst that was initially weighed and an actual percentage, which was the one finally retained by the sample.
  • Other agents alternative to ethanol that can help the tobacco-catalyst mixing process are water, glycerin and other similar solvents that do not affect the properties of tobacco and evaporate with relative ease. Nevertheless, the mixtures can also be performed in a satisfactory manner without needing to use any of these substances.
  • the additive used in all cases is Na-Fe-MCM-41.
  • the catalyst weight percentages are listed.
  • the cigarettes are made using the procedure described in " conditions for making the cigarettes " using the following nominal concentrations (weight percentage): Mixtures % additive Na-Fe-MCM-41 1% 1 Na-Fe-MCM-41 4% 4 Na-Fe-MCM-41 7% 7 Na-Fe-MCM-41 10% 10
  • Tables 2, 3 and 4 list the results obtained when smoking the cigarettes using the cigarette preparation conditions, the smoking conditions, the conditions of generated product analysis and the examples from group a), which correspond to the different tobacco-additive mixtures. The values obtained for the following are listed:
  • table 4 lists the results obtained for the production of some of the toxic and cancerous compounds that appear in tobacco smoke.
  • the use of proposed additives provides a reduction of more than 50% in most of the compounds. For example, when Na-MCM-41 is used as an additive, the following reductions with respect to the reference cigarette are observed.
  • All the described mixtures can also be prepared using quick mixers, fluidized and entrained beds or any other type of equipment that helps to mix the tobacco fiber with the additive. Sieves can also be used for separating and recirculating the additive that has not stuck to the tobacco fibers.
  • a dispenser can be used that provides the right amount of catalyst for preparing the soft, black, leaf, fine cut, hand rolling, pipe tobacco and for any other item capable of being smoked.
  • This dispenser can consist of a blister, where each cavity contains the selected amount (between 5 and 70 mg, in order to obtain between 0.5 and 7 % with respect to tobacco, which will usually be consumed in portions of around 1 g of tobacco), individual capsules that contain these quantities, a container that includes a calibrated or graduated spoon or any other type of calibrated dispenser.
  • the ready to smoke product MYO, RYO, pipe or other forms
  • the content of the calibrated dispenser is poured over the tobacco fiber and is carefully mixed by hand. This procedure guarantees excellent results as good as the ones listed in tables 2 through 4.
EP07823034A 2006-11-07 2007-11-05 Tobacco/catalyst mixtures for reducing toxic compounds in tobacco smoke Not-in-force EP2092838B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200602816A ES2301392B1 (es) 2006-11-07 2006-11-07 Mezclas tabaco-catalizador para la reduccion de los compuestos toxicos presentes en el humo del tabaco.
PCT/ES2007/000628 WO2008056011A1 (es) 2006-11-07 2007-11-05 Mezclas tabaco-catalizador para la reducción de los compuestos tóxicos presentes en el humo del tabaco

Publications (3)

Publication Number Publication Date
EP2092838A1 true EP2092838A1 (en) 2009-08-26
EP2092838A4 EP2092838A4 (en) 2010-08-11
EP2092838B1 EP2092838B1 (en) 2012-02-29

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EP07823034A Not-in-force EP2092838B1 (en) 2006-11-07 2007-11-05 Tobacco/catalyst mixtures for reducing toxic compounds in tobacco smoke

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EP (1) EP2092838B1 (es)
AT (1) ATE547015T1 (es)
DK (1) DK2092838T3 (es)
ES (2) ES2301392B1 (es)
WO (1) WO2008056011A1 (es)

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WO2014096486A1 (es) 2012-12-21 2014-06-26 Universidad De Alicante Aluminosilicato sab-15 como aditivo para la reducción de los compuestos tóxicos y cancerígenos presentes en el humo del tabaco
WO2015097327A1 (es) 2013-12-23 2015-07-02 Universidad De Alicante Inclusión de catalizadores en formulaciones de tabaco reconstituido para la reducción de la emisión de productos tóxicos
US10070664B2 (en) 2014-07-17 2018-09-11 Nicoventures Holdings Limited Electronic vapor provision system

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Publication number Priority date Publication date Assignee Title
WO2014096486A1 (es) 2012-12-21 2014-06-26 Universidad De Alicante Aluminosilicato sab-15 como aditivo para la reducción de los compuestos tóxicos y cancerígenos presentes en el humo del tabaco
WO2015097327A1 (es) 2013-12-23 2015-07-02 Universidad De Alicante Inclusión de catalizadores en formulaciones de tabaco reconstituido para la reducción de la emisión de productos tóxicos
US10070664B2 (en) 2014-07-17 2018-09-11 Nicoventures Holdings Limited Electronic vapor provision system

Also Published As

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DK2092838T3 (da) 2012-06-04
ES2383359T3 (es) 2012-06-20
ES2301392B1 (es) 2009-06-09
ATE547015T1 (de) 2012-03-15
EP2092838A4 (en) 2010-08-11
WO2008056011A1 (es) 2008-05-15
EP2092838B1 (en) 2012-02-29
ES2301392A1 (es) 2008-06-16

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