Smoker's article

Abstract: The smoker's article comprises a filter, a tobacco rod and a wrapper. The filter comprises a sorbent consisting of a hydrophobic member of zeolites or zeolite-like molecular sieves, the zeolite or zeolite-like material being defined by the following formula: M m M' n [aAlO 2 · b SiO 2 ·cTO 2 ] q Q wherein M is a monovalent cation, M' is a divalent cation a, b, c, n, m, and q are numbers which reflect the stoichiometric proportions, c, m, n or q can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, T is a tetrahedrally coordinated metal atom being able to replace Al or Si and Q is a sorbate molecules corresponding to the pore geometry of zeolite, the modulus a/b of the zeolite or the zeolite-like material, enclosed in the filter, has a value >400 and the pore size of the sorbent lays wihin the range of 5 to 7 Å; and/or the smoker's article contains a tobacco rod containing a catalyst consisting of a hydrated zeolite or a zeolite-like molecular sieve, the said zeolite or zeolite-like material being defined by the following formula: M m' M' n' M'' p [a' AlO 2 · b' SiO 2 ·c' TO 2 ] q' Q wherein M is a monovalent cation M' is a divalent cation M'' is a trivalent cation a', b', c', n', m', p and q' are numbers which reflect the stoichiometric proportions, c', m', n', p' or q' can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, T is a tetrahedrally coordinated metal atom being able to replace Al or Si and Q is a sorbate capable of passing the pore system of the zeolite, or of mixtures thereof, which characterized in that the catalyst consisting of a zeolite or the zeolite-like material, enclosed in the tobacco rod is present at least in part in the H form, the Q is mainly water and that the catalyst comprises a thermally stable structure. The zeolite sorbent incorporated in the filter reduces harmful products in the main stream smoke and the zeolite catalyst which is incorporated in the tobacco rod reduces harmful products in the side stream smoke

Description: This invention relates to articles for smoking, and more particularly to cigarettes which contain zeolites or zeolite-like molecular sieves in the tobacco rod. As is well known, two kinds of smoke arise during the smoking of a cigarette, the mainstream smoke and the sidestream smoke. The mainstream smoke is the smoke which enters the mouth of the smoker when he draws on the cigarette through the filter part, while the sidestream smoke is the smoke which is released by the smoldering combustion of the cigarette in the interim phases. From technical literature it can be learned that approximately twice as much tobacco is burned during the glowing of a cigarette between the puffs than during the puffs. Although in the prior art many -- albeit unsatisfactory -- means of reducing the mainstream smoke of noxious substances have been proposed, there has been no solution so far which makes it possible to remove the noxious substances from the sidestream smoke. Consequently there is a demand for smokers' articles, especially filter cigarettes, whose mainstream as well as sidestream smoke is significantly lower in noxious substances. WO-A-8502848 describes i.a. the use of modified zeolites in pipe or cigarette filters to remove CO from the mainstream smoke, or in cigar or cigarette wrapping to remove CO from the sidestream smoke. The document does not suggest treating tobacco rods of smoker's articles with zeolite or zeolite-like molecular sieves. The zeolites (clinoptilolite, mordenite, and to a lesser extent ferrierite and erionite) are modified by acid leaching of Al, followed by calcination, and finally by silylation reactions. These derivated microporous silicates possess a substantially reduced pore diameter compared with the molecular sieves used in the present invention, and are thus not suitable for adsorbing carcinogenic components (e.g. aldehydes, aromatics to nitrosamines) of the main and side stream smoke. According to the U.S. patents US-A-3,703,901 and US-A-3,572,348 zeolites are used for incorporation in tobacco material. However, these zeolites contain heavy metals or also platinum. For various reasons this kind of composition is not suitable for a product which cannot be recycled. In addition the long-term impact of adsobents containing zinc ions and catalytic active metals such as platinum or silver on the organism of the smoker is not sufficiently known. In the many attempts made to improve the cigarette filters, activated carbon and also zeolite and the like have already been used. In Swiss patent CH-A-653 220, for example, a cigarette filter is described which contains 10 to 200 mg of zeolite granules treated with menthol. Here the granules have the function of continuously releasing menthol during smoking. The types of zeolite used which were presumably of type A and L display no optimized characteristics with respect to sorption of noxious substances. The use of zeolite, which in part has not been sufficiently well defined, has been described in other state-of-the-art documents too. Described in French patent FR-A-2 165 174 is a filter material for cigarettes which contains synthetic or natural molecular sieves as a sorbent, the pores of which are at least 4 Å and preferably larger than 6 Å. Molecular sieves of the A, X, Y, L and mordenite types are mentioned. They can be present in the Na, K, Li, Ag, Ca or La form. According to the patent, the molecular sieves are integrated in the cigarette filter in granular form or as a layer on the paper strip which has been pretreated with an adhesive, the strip being subsequently rolled to form the filter. In a special embodiment, the molecular sieve is at least partly loaded with water so that it can form an apparent equilibrium with the moisture in the tobacco. By means of the filter arrangement described, nicotine and other components of the mainstream smoke are supposed to be sorbed. Described in all these patents is the use in the filter of hydrophilic zeolites only, the sorption properties of which have been shown in practice to be ineffective. Zeolitic materials, both natural and synthetic, have been shown in the past to have sorption properties which make them useful tools in filtering. In the appropriate form they can have catalytic capabilities for various kinds of organic reactions. Zeolites are microporous crystalline aluminosilicates which have definite crystal structures having a large number of cavities connected to each other by channels. These cavities and channels are absolutely uniform in size, and their dimensions can be determined by probe molecules as well as by crystal structure analysis. In most cases these data are known and do not have to be determined further. Since the dimensions of these pores are such that they sorb molecules of particular dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties. Such molecular sieves comprise a large variety of structural types (nearly 100; cf W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types, 3rd Edition, 1992, Butterworth, Heinemann ISBN 0-7506-9331-2) of crystalline aluminosilicates and isostructural materials with free pore diameters in the range of 0.3 to 1.3 nm or 3 to 13 A. These aluminosilicates can be described as a rigid three-dimensional network of SiO 4 and AlO 4 , wherein the tetrahedra are cross-linked by sharing of oxygen atoms, the ratio of all aluminium and silicon atoms to oxygen being 1:2. Such a network containing aluminium is negatively charged and requires for charge balance one monovalent cation (e.g. Na or K) or half a divalent cation (e.g. Ca) for each Al in the network. These cations can be exchanged either completely or partially using standard ion exchange techniques. Cation exchange is a possible means of fine tuning the critical pore diameter in a particular application. The pore volume of a typical zeolite is occupied by water molecules before dehydration. Dehydrated or activated zeolites are excellent sorbents for molecules which are small enough to pass through the apertures of the sieve. Syntheses using organic cations (such as tetrapropylammonium) have led to "high silica zeolites", which contain only few Al in the network, if any at all, and the composition approaches that of SiO 2 . High silica zeolites are not unanimously considered to be zeolites; although they have the same kind of structure, their exchange capacities are comparatively low, their selectivities very different, and these materials are hydrophobic. Consequently they are referred to as zeolite-like molecular sieves in this specification, following widespread usage. The sieving effect of the molecular sieve is based on the pore size. Sorption is also controlled by electrostatic interactions. Many of the chemical and physical properties are dependent upon the Al content of the zeolite. A rising modulus means an increased temperature stability, up to 1000 °C in the case of silicalite, which is a molecular sieve with a pure SiO 2 framework structure. The selectivity of the inner surfaces changes from strongly polar and hydrophilic in the case of the molecular sieves rich in aluminium to apolar and hydrophobic in the case of a zeolite with a modulus > 400. Thus it is the object of this invention to provide a smokers' article which contains means of reducing or eliminating the noxious substances both in the mainstream smoke and in the sidestream smoke. It has been discovered that this object can be achieved by means of certain zeolites or zeolite-like molecular sieves, which have not been used until now, in as far as they fulfil certain criteria. When incorporated into the tobacco rod of a cigarette, their catalytic properties become advantageous, whereby for reasons of health, economics and ecology, the zeolites must not contain any heavy metals or precious metals. The subject matter of this invention is a smokers' article comprising a filter, a tobacco rod and a wrapper, the tobacco rod containing a catalyst consisting of a zeolite or a zeolite-like molecular sieve, the zeolite or zeolite-like material being defined by the following formula: M m' M' n' M" p [a' AlO 2 · b' SiO 2 · c' TO 2 ] q' Q wherein M is a monovalent cation usually H, Na, or K, M' is a divalent cation, like Ca M" is a trivalent cation like La a', b', c', n', m', p and q' are numbers which reflect the stoichiometric proportions, c', m', n', p or q' can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, T is a tetrahedrally coordinated metal atom being able to replace Al or Si, e.g. B or P and Q represents sorbate molecules capable of passing the pores of the zeolite, or of mixtures thereof, wherein the catalyst consisting of zeolite or the zeolite-like material comprising in the tobacco rod is present partly or wholly in the H form, the Q is mainly water and that the catalyst comprises a stable structure, provided that it comprises no zinc, palladium, platinum, or silver. The tobacco rod contains preferably hydrophilic zeolite or a zeolite-like molecular sieve, the modulus of which is as a rule b'/a' < 10, which is loaded with water. Typical zeolites used in the tobacco rod are based on 12-membered ring frameworks. Acidic and hydrophilic zeolites, saturated with water, including zeolites X, Y, L, mordenite and BETA, are used in the tobacco which are bound to the tobacco with or without a binding agent, such as silica gel. At higher temperatures these molecular sieves function as catalysts and, with respect to the noxious components of the smoke, have positive effects during combustion of the tobacco without a residue being left in the ashes which is harmful to the environment. During the smoking of smokers' articles which are equipped in the aforementioned way, the noxious substances such as lower aldehydes, nitrosamines and the like are considerably reduced in the mainstream smoke and in the sidestream smoke, without affecting the taste. For a taste evaluation of cigarettes containing zeolites, an expert panel of 6 members has smoked cigarettes having silicalite in the filter against a standard, having a charcoal/sepiolite filter. Unanimously the trial was preferred over the standard, having a smoother and less dry smoke. Cigarettes with zeolites Y and BETA were compared to a standard without additives. In no case an off-taste was found and the trial cigarettes compared favorably to the standard. Typical zeolite materials which come into consideration are: Zeolite Structure Type according to IUPAC Free Pore Diameter Å (nm) Silicalite or Silicalite I MFI 5.6 (0.56) Silicalite II MEL 5.6 (0.56) ZSM-5 MFI 5.5-5.6 (0.55-0.56) Y FAU 7.4 (0.74) Mordenite MOR 6.6-7.0 (0.66-0.70) BETA BEA 6.4-7.6 (0.64-0.76) The characteristic d-spacings used for the identification of these materials are listed in table A below: X-RAY POWDER DEFRACTION FILE (PDF) d-SPACINGS ACCORDING TO HANAWALT SEARCH MANUAL (1994) STC & Material d-spacings in A (3 strongest reflections in bold face) PDF FAU Zeolite X 14.5 3-81 2.89 8.85 5.73 3.34 7.45 4.42 38-237 Zeolite Y 14.3 3.31 2.86 3.78 5.68 4.38 8.75 7.46 38-238 LTL Zeolite L 16.0 3.19 3.92 2.91 3.48 4.61 3.07 7.56 22-773 MFI ZSM-5 11.1 9.91 10.0 3.81 3.85 3.71 9.69 3.75 44-003 Silicalite or 11.1 10.0 3.82 3.82 3.71 9.75 5.99 2.99 43-784 Silicalite 1 MEL ZSM-11 3.86 3.73 11.2 10.1 2.01 3.00 4.37 1.88 38-246 Silicalite 2 11.1 10.0 3.85 3.72 5.99 2.99 6.71 5.57 42-022 MOR Mordenite 9.06 4.00 3.48 3.22 3.39 3.20 4.53 13.6 29-1257 MTW ZSM-12 4.29 3.87 3.96 11.9 3.38 476 10.1 3.49 43-439 MTT ZSM-23 3.90 3.73 4.27 3.63 4.54 4.07 11.2 3.45 44-102 TON ZSM-22 or Theta-1 3.64 4.33 3.59 10.6 3.44 6.86 2.51 8.58 37-355 BEA Beta 3-91 - 3.95 and very broad peak at 11.2 STC: official three-letter structure type code Remark: The d-values and relative intensities (which determine the order of the peaks listed) can change slightly with ion exchange and other compositional changes. The invention will now be explained in more detail, using examples which describe special embodiments. In order to determine the efficiency of different zeolite materials for sorbing undesirable compounds in the mainstream smoke, experimental cigarettes were prepared and smoked for gas phase smoke analysis according to the standard method used in the laboratories of the applicant (K. Grob., Beitr. Tabakforsch. 1, 285, (1962); K. Grob., Beitr. Tabakforsch. 1, 315, (1962); K. Grob., Beitr. Tabakforsch. 3, 243, (1965); K. Grob, J. Gas Chrom., 3, 52, (1965); K. Grob, Helv. Chim. Acta 49, 1768, (1966)). For quantitative analysis the technique of gas chromatography is used. Examples of Application of the Zeolites onto the Tobacco Rod Zeolite powder was applied directly on cut tobacco before cigarette manufacturing. These filterless cigarettes showed high reductions of nicotine and tar levels in sidestream smoke whereas reductions in mainstream smoke were smaller. The following zeolites were used. All of these were obtained from CU Uetikon (Switzerland): H-Y Zeolite type FAU, H-form, calcinated Z6-06-02 extrudates 1/16", ground to a particle size of 0.08 mm. Na-X Zeolite type FAU, Na-form, oven dried Z6-06-01, powder, modul 5.5-6, used as received. Na, H-X Zeolite type FAU, Na partially ion exchanged to H-form, Powder sample used as received. H-Beta Zeollte type BEA, H-Form. Powder sample used as received. Na-Beta Zeolite type BEA, Na-form, Powder sample used as received. H-Mordenite Zeolite type MOR, synthetic, H-torm, powder, modul 25. Sample used as received. The tobacco blend type MA (Amercan blend type) was received from a tobacco lot ready for cigarette fabrication. Application of the Zeolites: All of the above mentioned zeolite types were applied exactly in the same way. The zeolite loading of the tobacco was about 4 % (wt/wt). 100 g of the zeolite powder and 20 g of C-Gel were added to 250 g of LC-674. The mixture was stirred thoroughly until application in order to keep the powders in suspension. For each zeolite sample a reference cigarette without zeolite using the same tobacco but with the binder was prepared to minimize the influence of the processing of the tobacco. The reference suspension consists of 20 g of C-Gel in 250 g of LC-674. 2 kg of tobacco were placed in a rotary mixer and the suspension was sprayed onto the tobacco using compressed air while mixing. For the reference a pressure of 1.5 bar proved to be sufficient whereas the suspension containing zeolite had to be sprayed on at 6.5 bar. The tobacco was dried to a suitable humidity before cigarette manufacturing. The zeolite-containing tobacco sample is of lighter color, and under closer observation, white powder particles can be recognized homogenously dispersed with the tobacco. The cigarettes are conditioned at 22°C and 60 % humidity for 48 h before being sorted to have an average weight of 1000 mg (± 30 mg). Results and discussion The particle size of the applied zeolite powder is important for the manufacturing of the cigarettes. Whereas Na,H-X and the references passed smoothly and gave nicely filled cigarette rods. The results are given in the table below. All the reductions are given with respect to the reference cigarettes containing C-Gel only. The puff numbers are comparable. Mainstream smoke: Nicotine and tar were only slightly reduced by 12 and 9.1 % respectively. Sidestream smoke: The reduction of tar is 17 %, the reduction of nicotine is 21 %. Both reductions are significant. The detailed results are given in table I and II below. All the reductions are given with respect to the reference cigarettes containing C-Gel only. The puff numbers are comparable. Mainstream smoke: Nicotine and tar were not reduced significantly. However the figures for nitrosamines and some of the polycyclic aromatic hydrocarbons in the mainstream smoke were reduced by as much as 50 %. Sidestream smoke: The results obtained for the nitrosamines in the sidestream smoke are truly remarkable. In Na-Y e.g. the reductions were 60 % for NNK, 65 % for NNN and 76 % for NAB (Table I). Similar reactions were obtained for PAH (Table II) Results of the analysis nitrosamines Cigarette Smoke Tar mg/cig Nicotine mg/cig NDMA ng/cig NNN ng/cig NAT ng/cig NAB ng/cig NNK ng/cig Ref. For MS 18 1.1 1 119 224 55 130 1 st series SS 33 4.0 204 705 463 330 6745 Na, H-X MS 18 1.1 1 114 197 35 62 SS 27 3.1 336 359 208 129 3784 H-Beta MS 19 1.1 2 91 168 27 38 SS 29 3.3 69 336 201 132 2686 Na-Beta MS 17 1.1 2 93 164 27 55 SS 29 3.2 489 324 224 138 3035 Na-Y MS 18 1.1 3 82 102 28 42 SS 32 3.6 55 251 166 79 2694 H-Mordenite MS 19 1.1 12 86 180 36 50 SS 30 3.5 376 302 199 115 3517 Ref. for MS 20 1.2 4 113 233 42 73 2nd series SS 41 4.4 323 455 308 199 5273 H-Y MS 18 1 5 111 118 34 86 SS 34 3.4 422 440 264 179 3984 Abbreviations: MS main stream SS side stream NDMA Nitrosodimethylamine NNN Nitrosonornicotine NAT Nitrosoanatabine NAB Nitrosoanabasine NNK 4-nitrosomethylamino-1-(3-pyridyl)-1-butanone Results of the analysis of heteroaromatic polycyclic arpmatic hydrocarbons main stream smoke side stream smoke reference Na, H-Y reference Na, H-Y Tar mg/cig. 18.3 18.1 32.6 26.8 Nicotine mg/cig. 1.13 1.11 4 3.09 PAH [ng/cig.] Naphthalene 1115 634 2769 1364 Acenaphthylene 5061 2715 7475 3620 Acenaphthene 1666 1625 32338 14167 Fluorene 999 846 4964 2777 Phenanthrene 319 322 5834 3494 Anthracene 369 161 3286 949 Fluoranthene 2205 2015 45878 25159 Pyrene trace trace 4900 2833 Benzo(a)anthracene 248 245 2267 1325 Chrysene 525 520 4790 2963 Benzo(b)fluoranthene 107 106 898 552 Benzo(k)fluoranthene 8 8 76 49 Benzo(a)pyrene 35 37 298 198 Benzo(g,h,i)perilene 77 83 492 328 HAP = polycyclic aromatic hydrocarbons

Claims: A smoker's article comprising a filter, a tobacco rod and a wrapper, the tobacco rod containing a catalyst consisting of a hydrated zeolite or a zeolite-like molecular sieve, the said zeolite or zeolite-like material being defined by the following formula: M m' M' n' M" p [a' AlO 2 · b' SiO 2 ·c' TO 2 ] q' Q wherein M is a monovalent cation M' is a divalent cation M" is a trivalent cation a', b', c', n', m', p and q' are numbers which reflect the stoichiometric proportions, c', m', n' p, or q' can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, T is a tetrahedrally coordinated metal atom being able to replace Al or Si and Q is a sorbate capable of passing the pore system of the zeolite, or of mixtures thereof, characterized in that the catalyst consisting of a zeolite or the zeolite-like material, enclosed in the tobacco rod is present at least in part in the H form, the Q is mainly water and that the catalyst comprises a thermally stable structure, provided that it comprises no zinc, palladium platinum, or silver. A smoker's article according to claim 1 characterized in that M" has the meaning La. A smoker's article according to claim 1 or 2 characterized in that the catalyst is bound to the tobacco rod by an adhesive. A smoker's article according to one of the claims 1 to 3 characterized in that the tobacco rod comprises reconstituted tobacco. A smoker's article according to one of the claims 1 to 4 characterized in that the catalyst used in the tobacco is at least one thermally stable member selected from the group consisting of X, Y, L, mordenite and BETA. A smoker's article according to one of the claims 1 to 5 characterized in that T is B or P. A smoker's article according to one of the claims 1 to 6 characterized in that the catalyst used in the tobacco is thermally stabilized by an appropriate ion exchange process. A smoker's article according to one of the claims 1 to 6 characterized in that the zeolite or the zeolite-like material has a modulus b'/a' < 10.

Inventors: MEIER WALTER M, SCANLAN FRANCIS, WILD JOST, MEIER, WALTER M., SCANLAN, FRANCIS, WILD, JOST
Applicants: BRITISH AMERICAN TOBACCO CO, BRITISH AMERICAN TOBACCO (INVESTMENTS) LIMITED
Application year: 1995
Main classification: A24B15
IPC codes: A24D1, A24B15, A24D3