MXPA96001643A - Article for smoking - Google Patents
Article for smokingInfo
- Publication number
- MXPA96001643A MXPA96001643A MXPA/A/1996/001643A MX9601643A MXPA96001643A MX PA96001643 A MXPA96001643 A MX PA96001643A MX 9601643 A MX9601643 A MX 9601643A MX PA96001643 A MXPA96001643 A MX PA96001643A
- Authority
- MX
- Mexico
- Prior art keywords
- zeolite
- further characterized
- article
- tobacco
- filter
- Prior art date
Links
- 230000000391 smoking Effects 0.000 title claims description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 109
- 241000208125 Nicotiana Species 0.000 claims abstract description 41
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- 150000001768 cations Chemical class 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 125000004429 atoms Chemical group 0.000 claims abstract description 12
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical group C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 claims abstract description 6
- 229940075554 Sorbate Drugs 0.000 claims abstract description 6
- 239000000779 smoke Substances 0.000 claims description 37
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052680 mordenite Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 5
- 230000002209 hydrophobic Effects 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive Effects 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- AIRCTMFFNKZQPN-UHFFFAOYSA-N AlO Inorganic materials [Al]=O AIRCTMFFNKZQPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940091292 Alo Drugs 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000002734 clay mineral Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 235000012438 extruded product Nutrition 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052763 palladium Inorganic materials 0.000 abstract 1
- 229910052904 quartz Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000004332 silver Substances 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 235000019506 cigar Nutrition 0.000 description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 230000001603 reducing Effects 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 12
- 239000011797 cavity material Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 235000019504 cigarettes Nutrition 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000004113 Sepiolite Substances 0.000 description 6
- TUKQLEWOUPCTOS-UHFFFAOYSA-N dimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane;hydrate Chemical compound O.[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O TUKQLEWOUPCTOS-UHFFFAOYSA-N 0.000 description 6
- 229910052624 sepiolite Inorganic materials 0.000 description 6
- 235000019355 sepiolite Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- SNICXCGAKADSCV-JTQLQIEISA-N Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 5
- 229960002715 Nicotine Drugs 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229930015196 nicotine Natural products 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 210000000416 Exudates and Transudates Anatomy 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000004005 nitrosamines Chemical class 0.000 description 3
- FLAQQSHRLBFIEZ-UHFFFAOYSA-N N-Methyl-N-nitroso-4-oxo-4-(3-pyridyl)butyl amine Chemical compound O=NN(C)CCCC(=O)C1=CC=CN=C1 FLAQQSHRLBFIEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N acrylaldehyde Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- UMFJAHHVKNCGLG-UHFFFAOYSA-N DMNA Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229960004873 LEVOMENTHOL Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L Magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229940041616 Menthol Drugs 0.000 description 1
- 235000004262 Pinguicula vulgaris Nutrition 0.000 description 1
- 240000000697 Pinguicula vulgaris Species 0.000 description 1
- 229910020169 SiOa Inorganic materials 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000001143 conditioned Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008202 granule composition Substances 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011776 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000004430 oxygen atoms Chemical group O* 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Abstract
The present invention relates to a smoker article comprising a filter, a tobacco cylinder and a wrapper, the tobacco cylinder containing a catalytically active zinc-free catalyst, platinum, palladium and silver and consisting of a hydrated zeolite or a molecular sieve similar to zeolite or combinations of different members, wherein said zeolite-like material has a thermally stable structure and defined by the following formula: Mm, M'o, M "p [a'AIO2.b ' SiO2.c'TO2] q'Q, where M is a monovalent cation, M'is a divalent cation, M "is a trivalent cation a ', b', c ', n', m ', p and q'son numbers that reflect the stequeometric proportions, m ', n', can also be zero, AI and Si are atoms of AI and Si tetrahedrally coordinated, T is a tetrahedrally coordinated atom that is able to replace AIóSi and Q is a sorbate capable of traversing the pore system of the zeoli
Description
ARTICLE FOR SMOKERS
FIELD OF THE INVENTION
This invention relates to articles for smoking, and very particularly to cigarettes containing zeolites or molecular sieves similar to the zeolite in the cigar and optionally in the filter.
BACKGROUND OF THE INVENTION
As is well known, there are two types of smoke when smoking a cigar: the main smoke and secondary smoke. The main smoke is the smoke that enters the mouth of the smoker when he smokes the cigarette through a filter, while the secondary smoke is the smoke that is released by the smoking combustion of the cigarette in intermediate stages. From technical literature it can be learned that approximately two times more tobacco is burned during the incandescence of a cigarette between puffs than during puffs. Although in the prior art many means (although insat isfactopas) have been proposed to remove harmful substances from the main smoke, there has been no solution so far that it can remove the harmful substances from secondary smoke.
Consequently, there is a demand for articles for smokers, especially cigars with filters, whose main smoke as well as secondary smoke is significantly lower in harmful substances. In the many attempts made to improve the cigar filter, activated carbon and also zeolite and the like have been used. In the Swiss patent CH-A-653 220, for example, a cigar filter containing 10 to 200 mg of zeolite granules treated with entol was described. Here the granules have the function of continuously releasing menthol when smoking. The types of zeolite used that supposedly were of type A and L, do not present characteristics with respect to the absorption of harmful substances. The use of zeolite, which has not been sufficiently well defined in part, has also been described in other documents of the most advanced art. The zeolites used to be incorporated into tobacco material according to the E. U. A. US-A-3, 703,901 contain heavy metals or also platinum. For various reasons, that type of composition is not suitable for a product that can not be recirculated. French patent FR-A-2 165 174 describes a filter material for cigars containing synthetic or natural molecular sieves as an absorber, the pores of which are at least 4 A and preferably greater than 6 A. Screening is mentioned Molecular types of A, X, Y and mordenite. They can be present in the form of Na, K, Li, Ag, Ca or La. According to the patent, the molecular sieves are integrated into the filter of the cigar in granular form or as a layer on the paper strip that has been previously treated with an adhesive, the strip being subsequently rolled to form the filter. In a special embodiment, the molecular sieve is at least partially charged with water so it can form an apparent equilibrium with moisture in the tobacco. By means of the filter arrangement described, it is assumed that nicotine and other components of the main smoke can be absorbed. In all these patents only the use in the filter of hydrophilic zeolites is described, whose absorption properties in practice have been shown to be ineffective. The zeolite materials, both natural and synthetic, have in the past shown to have absorption properties that make them useful tools in filters. In the proper form they can have catalytic capabilities of various types of organic reactions. Zeolites are crystalline, crystalline aluminosilicates having defined crystal structures having a large number of cavities connected to one another by channels. These cavities and channels are absolutely uniform in size, and their dimensions can be determined by means of probe molecules as well as crystal structure analysis. In most cases, these data are known and do not need to be determined. Since the dimensions of these pores are such that they absorb molecules of particular dimensions while rejecting those of larger dimensions, those materials have come to be known as "molecular sieves" and are used in a variety of ways to take advantage of these properties. These molecular sieves comprise a wide variety of structural types (almost 100; see W.M. Meier and D.H. Olson, Atlas of Zeolite Structure Types, 3 ». Edition, 1992, Butterwort, Heinemann ISBN 0-7506-9331-2) of crystalline alumina and isostructural materials with free pore diameters on the scale of 0.3 to 1.3 nm or 3 to 13 A. These aluminosi 1 icates can be describe as a rigid three-dimensional network of SiO ^ and AlO ^, where the tetrahedra are intertwined by sharing oxygen atoms, the ratio of the aluminum and silicon atoms being 1: 2. Said network containing aluminum is negatively charged and requires a monovalent cation (eg Ma) or half a divalent cation (eg Ca or Cu) for each Al in the network. These cations can be exchanged either completely or partially using ion exchange techniques. The exchange of cations is a possible means of fine-tuning the critical pore diameter in a particular application. The volume of a typical zeolite is occupied by water molecules before dehydration. Dehydrated or activated zeolites are excellent absorbers for molecules that are small enough to pass through the screen openings. Syntheses using organic cations (such as tetrapropylaman 10) have led to "zeolites with high siliceous content" containing only a few Al in the network, if any, and the composition approaches that of SiO ^. Zeolites with high silica content are not considered unanimously as zeolites; although they have the same type of structure, their exchange capacities are comparatively low, their very different selectivities and those materials are hydrophobic. Consequently they are known as molecular sieves in the form of zeolite in this specification, after widely distributed use. The sieving effect of the molecular sieve is based on the pore size. The absorption is also controlled by electrostatic interactions. Many of the physicochemical properties depend on the Al content of the zeolite. A lifting module means an increased temperature stability of up to 1000 ° C in the case of silicalite, which is a molecular sieve with a pure SiOa base structure. The selectivity of the internal surfaces changes from strongly polar and hydrophilic in the case of molecular sieves rich in aluminum to apolar and hydrophobic in the case of a zeolite with a modulus of > 400. Therefore, the object of this invention is to provide an article for smokers that contains means to reduce or eliminate harmful substances in both the main smoke and secondary smoke.
It has been found that this object can be achieved by means of zeolite or zeolite-like molecular sieves, which have not been used until now, as long as they satisfy certain criteria. When they are incorporated into the tobacco of a cigarette, its catalytic properties become advantageous, so for reasons of health, economy and ecology, zeolites should not contain any heavy metals or precious metals. The subject matter of this invention, therefore, is a smoking article comprising a filter, a tobacco cylinder and a wrapper, the tobacco cylinder containing a catalyst consisting of a zeolite or a molecular sieve similar to zeolite, the zeolite or the material similar to the zeolite being defined by the following formula: Mfn.M / r, -M "p [a / A10a-b'SjO¡B-c'TD5a3q'Q where M is a monovalent cation, usually H,
N > , or. M 'is a divalent cation, as Ca or Cu M "is a trivalent cation, as La a', b ', c', n ', m', p and q 'are numbers that reflect the stequeometic proportions,', n ', poc 'can also be zero, Al and Si are tetrahedrally coordinated atoms of Al and Si, T is a tetrahedrally coordinated atom that is capable of replacing Al or Si eg B or P, and Q represents ssrbato molecules capable of passing through the pores of the zeolite, or mixtures thereof, wherein the catalyst consisting of zeolite or material similar to the zeolite found in the tobacco cylinder is present in the form of an H, the Q it is mainly water and the catalyst comprises a stable structure. The tobacco cylinder preferably contains hydrophilic zeolite or a molecular sieve similar to zeolite, whose modulus is as a rule b '/ a' 10, which is loaded with water, and has a structure thermally stable The typical zeolites used in the cylinder and tobacco are based on a 12-member ring structure. The subject matter of the invention is also an article for smokers of the above type which is characterized in that the filter contains zeolite or a molecular sieve in the form of zeolite, wherein the modulus is b / a.4 0, and the tobacco cylinder contains sieve Hydrophilic zeolite molecular or hydrophilic zeolite form which is charged with water, is at least partly »H-shaped and has a thermally stable structure. A special embodiment of the above defined smoking article comprises a filter having an absorber consisting of a zeolite-shaped zeolite molecular sieve, the zeolite material or the zeolite form being defined by the following formula: MmM'n-- a A10a-b SiOa-cTGa-lq Q where M is a monovalent cation, usually Na or K, M 'is a divalent cation in the form of Ca a, b, c, n, myq are numbers that reflect the proportions stequeometric icas, c,, noq can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, T is a tetrahedrally coordinated atom, being able to replace Al or Si, v. gr. B or P, and Q represents sorbate molecules capable of passing through the pores of the zeolite, the b / a modulus of the zeolite or zeolite-like material, contained in the filter, has a value of
> 4-00 and the critical pore size of the absorber is within the range of 5 to 7 & or of mixtures thereof, said article for smokers being characterized in that the filter contains zeolite or a molecular sieve in the form of zeolite, M being mainly Na and the modulus being b / a > M-00 Typical zeolite absorbers used in the filter to treat the main smoke are based on a 10-member structure. In the filter they use exclusively hydrophobic zeolites with the trade name of silicalite or ZSM, whose modulus is b / a 400 as well as other zeolites with high silica content such as ZSM-11 (MEL), ZSM-22 (TON) ZSM ~ 23 (MTT), ZSM-50 (EUO), SIGMA-2 (SGT). Silicalite and ZSM-5 have the MFI structure code and can be identified based on the separations d listed in Table A. Consequently, this material, which contains little or nothing Al, is hudraphobic. Attapulgite, which is a clay mineral similar to magnesite, serves as a binding agent. The molecular sieve can be applied to the filter material as an exudate together with the binder. The acid and hydrophilic zeolites, saturated with water, including X, Y, L and mordenite zeolites and BETA, are used in the tobacco / are linked to the tobacco with a binding agent, such as silica. At higher temperatures, these molecular sieves function as catalysts and, with respect to the harmful components of smoke, have positive effects during the combustion of tobacco with no residue left in the ashes that is hazardous to the environment. When smoking articles are smoked which are equipped in the aforementioned manner, the harmful substances such as lower aldehydes, nitrosamines and the like are reduced considerably in the main smoke and in the secondary smoke, without affecting the taste. For a flavor evaluation of the cigars containing zeolites, a panel of six-member experts smoked cigars that had silicalite in the filter compared to a standard that had a charcoal / septa filter. In a unanimous way, the test cigars were preferred with respect to the standards, having smoother and less dry smoke. Cigars with Y and BETA zeolites were compared to a standard without additives. In no case was an unpleasant taste found and the test cigars compared favorably with respect to the normals. Typical zeolite materials that are considered are:
Zeolite Type of structure Free pore diameter according to IUPAC A (nm) Silicalite or Silicalite 1 MFI 5.6 (0.5)
Silicalite II MEL 5.6 (0.5)
ZSM-5 MFI 5.5-5.6 (0.55-0.56)
And FAU 7.4 (0.74)
Mordenita MOR 6.6-7.0 (0.66-0.70)
BETA BEA 6.4-7.6 (0.64-0.76)
The separations d characteristics used for the identification of these materials are listed in the following
TABLE A TABLE A: X-RAY POWDER DIFFERENCE FILE (PDF)
SEPARATIONS OF D ACCORDING TO THE RESEARCH MANUAL OF (1994) STC and Separations in d in A (3 refills plus PDF Strong material in bold letters) FAU Zeolite X 14.5 3-61 2.69 6.65 5.73 3.34 7.45 4.42 36-237 Zeolite Y 14.3 3.31 2. £ 3.76 5.66 4.36 6.75 7.46 36-236
LTL Zeolite L 16.0 3.19 3.92 2.91 3.46 4.61 3.07 7.56 22-773 MFI
ZSM-5 11.1 9.91 10.0 3.61 3.65 3.71 9.69 3.75 44-003 Silicalite 11.1 10.0 3.62 3.62 3.71 9.75 5.99 2.99 43-764 or Silica-lita 1 MEL
ZSM-11 3.66 3.73 11.2 10.1 2.01 3.00 4.37 1.66 36-246 Silicalite 2 11.1 10.0 3.65 3.72 5.99 2.99 6.71 5.57 42-022
MOR Mordenita 9.06 4.00 3.46 3.22 3.39 3.20 4.53 13.6 29-1257
MTW
ZSM-12 4.29 3.67 3.96 11.9 3.36 476 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 3.64 4.33 3.59 10.6 3.44 6.66 2.51 6.56 37-355 or Teta-1 BEA Beta 3-91- 3.95 and a very wide (peak) maximum value at 11.2
STC: three letter structure type code Official Remarks: The values of d and the relative intensities (which determine the order of the listed peaks) may change slightly with ion exchange and other changes in the compass i c ióp. The invention will now be explained in more detail, using examples describing special modalities. In those, examples, various zeolite materials contained in a cigarette filter cavity have been investigated with respect to their effect on certain gas phase smoke products. Of those that were tested, ZSM-5 type zeolites have produced up to 50% quantitative reduction of undesirable smoke components based on absorption. Zeolites, smoke products and the indication of the absorption procedure are mentioned. The composition of the main smoke of a cigar is divided into two phases: the particle phase and the gas phase. The gas phase analysis can be used to determine the filter efficiency, and the test materials can be used in the filter cavities. In order to determine the efficiency of different zeolite materials for absorbing undesirable compounds in the main smoke, experimental cigars were prepared and smoked for a gas phase smoke analysis according to the standard method used in the applicant's laboratories (K. Grob., Beitr, Tabakforsch, 1,265, (1962), K. Grob., Beitr. Tabakforsch, 1,315, (1962), K. Grob., Beitr. Tabakforsch, 3,243, (1965), K, Grob, 3. Gas. Chro., 3,52, (1965), K. Grob, Helv. Chim Acta 49, 1766, (1966)). For quantitative analysis, the gas chromatography technique was used. For comparison, reference cigars containing either a mixture of activated carbon and sepiolite in the filter cavity or simply sepiolite were used. The percentage reduction values were obtained with respect to the reference cigar.
EXAMPLES
EXAMPLE 1
Application of zeolites in the tobacco cylinder
Zeolite powder was applied directly onto cut tobacco prior to the manufacture of cigars. These unfiltered cigars showed high reductions in nicotine and tar levels in secondary smoke while reductions in main smoke were lower. The following zeolites were used in examples 9 and 10. All these were obtained from CU Uetikon (Switzerland): HY Zeolite type Y, H form, calcined Z6-06-02 exudates, of .159cm, milled to a size of 0.06mm particle
Na-Zeolite of type Y, form of a, powder of Z6-06-01, dried in oven, module 5.5-6, used as received. Na, H-X Zeolite of type X, Na partially exchanged for H-shaped ions. The powder sample was used as received. H-Beta Zeolite of type BEA, in the form of M. The powder sample was used as received. a-Beta Zeolite type BEA, in the Na form, the powder sample was used as received. H-Mordenite MOR-type, synthetic, H-form, powder, module 25. The sample was used as it was. ZSM-5 Zeolite type MFI, H-shaped, PZ-2/50 exudate, ground to a particle size of 0.06 mm. The MA type tobacco blend (from the applicant) was received from a batch of tobacco ready for the manufacture of. Cigars
Application of zeolites:
All the aforementioned zeolite types were applied in exactly the same way. The zeolite load of the tobacco was 5% (w / w). 100g of the zeolite powder and 20g of C-Gel were added to 250g of LC-674. The mixture was stirred uniformly until the application to keep the powders in suspension. For each sample of zeolite. a reference cigar without zeolite was prepared using the same tobacco but with the binder to minimize the influence of the processed tobacco. The reference suspension consists of 20g of C-Ge in 250g of LC-674. 2kg of tobacco was put in a concrete mixer and the suspension was sprayed on tobacco using compressed air while mixing. For reference, a pressure of 1.5 bar showed to be sufficient while the suspension containing zeolite had to be sprayed at 6.5 bar. The tobacco was dried at a suitable humidity before the manufacture of the cigars. The sample of tobacco containing zeolite is remarkably whiter, and under close observation, white powder particles homogeneously dispersed with tobacco can be recognized. The cigars are conditioned at 22 ° C and at a humidity of 603- for 46 hours before being distributed so that they have an average weight of 1000 mg (± 30mg).
Results and discussion:
The particle size of the applied zeolite powder is important for the manufacture of the cigars.
While processing H-Y tobacco, a cloud of zeolite powder could be observed above the machine and not all the cigars were evenly filled with tobacco. Meanwhile, Na, H-X and references passed smoothly and gave cigarettes well laden with tobacco. The results are given later. All reductions are given with respect to the reference cigars that contained only C-Gel. The numbers of puffs are comparable.
Gas Phase:
Small reductions of gas phase molecules could be detected. However, the results have to be carefully validated since the standard deviation is of the same magnitude.
Main Smoke:
Nicotine and tar were only slightly reduced by 12 and 9.1% respectively.
Secondary Smoke:
The reduction of tar is 17%, the reduction of nicotine is 21. Both reductions are significant.
Eiemolo 2: Na. H-X
The detailed results are given in Table B below. All reductions are given with respect to reference cigars that contain only C-Gel. The numbers of puffs are comparable.
Gas Phase:
Small reductions of gas phase molecules could be detected. The concentration of acrolein, however, is ignitically higher in the zeolite smoke.
Main Smoke:
Nicotine and tar were not significantly reduced. However, the figures for nitrosamines in the main smoke were reduced by as much as 50%.
Secondary Smoke:
The results obtained for nitrosamines in secondary smoke are truly remarkable. In Na-Y, v. gr. the reductions were 60% for NNK, 65% for NNN and 76% for NAB.
TABLE B
Abbreviations: MS Main smoke SS Secondary smoke NDMA Nitrosodimet ilamipa NNN Nitrosononicot ina NAT Nitrosoanata ipa NAB Nitrosoanabasin NNK 4-nitrosomethyl ilamipo-l- (3-pyridyl) -l-butanone TABLE C RESULTS OF ANALYSIS OF COMPOUNDS PQLICIC ICOS HETERQAROMATICOS
0 5? 0
HAP Polyaromatic heteroaromatic compound Application of zeolites in the cigar filter
(The following examples refer to cigar filters that are used in special embodiments of the cigars in accordance with the invention)
Example 3-10
Materials: The following granulated extruded zeolites were used: H-Morden i ta PZ-2/270 (type MFI) PZ 2/1600 (type MFI) Zeocat PZ-2 / 50H (ZSM-5) As reference materials the following were used: Activated carbon. PicActif (PICA Co., France) Sepiolite (Tolsa Co., Spain) The zeolites were milled gently and sieved to a size between 1.2 and 0.S rn. Before use they were treated in the following manner: -H-Mordenite was heated for 6 hours at 250 ° C -PZ-2/270 was washed in HCl solution at 0.1N for 20 minutes, and then rinsed in demineralized water, then it was dried for 3 hours at 250 ° C.
-PZ-2/1600 and Zeacat PZ-2 / 50H (type ZSM) did not require previous treatment.
Cigar test samples
The reference cigar for this work was a King Size cigar with a triple filter and no filter ventilation (SEK). The reference and experimental cigars were distributed by weight within a tolerance scale of ± 5? Ng. The experimental cigars were prepared manually by replacing the SEK 'filter cavity material with zeolite under test. This was done by simply removing the visible acetate filter cylinder from the outside, allowing the contents to be emptied. The filter was then filled with the test material, the filter cylinder was replaced. The length of the filter cavity was 4 mm. On average, the filter cavities used contained 55 mg of carbon / sepiolite granule mixture. Two types of experimental cigars were prepared containing: - 100% zeolite - 50% zeolite + 50% activated carbon Comparison Examples 1-2
Reference cigars were prepared as indicated; They contained the following absorbent material: 100% sepiolite (Tolsa): 75.1 - 76.1 mg (Table I) 50% activated carbon: 35.4 - 36.4 + 50% Sepiolite (Tolsa): 37,336.3 mg (Table II)
Examples 3-6
Test cigars were prepared in the same manner as indicated and the absorbent materials in the cavities were the following:
Cigars containing 100% zeolite:
H-Mordenite: 76.1 - 77.1 mg (Table III) PZ-2/270 (ZSM-5): 93.2 - 94.2 g (Table VID PZ-2/1600 (ZSM-5): 90.7 - 91.7 mg ( Table V) Zeocat PZ-2 / 50H (type ZSM-5): 69.5 - 90.5 mg (Table IX)
Examples 7- 10:
Cigars containing 50% Zeolite + 50% activated carbon (weight: 35.4 - 36.4 mg)
H-Mordenite: 37.6 - 36.6 mg (Table IV) PZ-2/270 (ZSM-5): 46.3 - 47.3 mg (Table VIII) PZ-2/1600 (ZSM-5): 45.1 - 46.1 mg (Table VI) Zeocat PZ-2 / 50H (ZSM-5): 44.5 - 45.5 mg (Table X)
Results and Discussion
The results are presented in the following I-X tables.
ZEOLITE TESTS ON SEK (non-porous cigars)
TABLE I TABLE II
TABLE III TABLE IV TABLE V l? L? TABLE VI
2 ¿> (O r irr a > oo ifi MI G
Generally, a result is considered an average value based on the individual results of 5 or 10 r ígarra. Ten operations of analysis were done for cigars with 1005 of zeolite and ten for cigars with 50 / 503- of zeolite PZ-2/270 and PZ-2 / 1Ó00, except that for H-Mordemta only five operations were carried out due to its defc lens performance. It is shown that zeolites of type ZSM-5 have a higher retention than the reference cigar. For some molecules it is shown that 1005 of zeolite has a better performance than the mixed material. In other cases, the yield of 5 carbon seems to be limited and apparently does not relate to the amount present. For some molecules, the presence of carbon has the normally expected absorption effect. In all three cases, reduction is observed for certain molecules analyzed, if not all. Different reduction values are probably obtained due to parameters that affect the absorption process, such as molecular size and polarity of the molecule. The reduction values are particularly important for the aromatics toluene, benzene and the aliphatic acetaldehyde, acrolein, isoprene and diacetyl.
Claims (7)
1. A smoker article comprising a filter, a tobacco cylinder and a wrapper, the tobacco cylinder containing a catalyst consisting of a zeolite or similar zeolite-like molecular sieve or mixtures of different members, wherein said zeolite material or similar to the zeolite has a thermally stable structure and is defined by the following formula: Mm. M '". M "p The 'AlO' - b 'SiOj, - c' T0a 3q ', where 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 that reflect the stequeometric proportions, m', n ', poc' can also be zero, Al and Si are tetrahedrally coordinated atoms of Al and Si, T is a tetrahedrally coordinated atom which is able to replace Al or Si and Q is a sorbate capable of traversing the pore system of the zeolite.
2. A smoker article according to claim 1, further characterized in that Q consists mainly of water.
3. A smoking article according to claim 1 or 2, further characterized in that the catalyst consists of a zeolite material or the like to the zeolite and is present in part as H. < +. An article for smokers according to one of claims 3, further characterized in that li "has the meaning La. 5. An article for smoker according to one of claims 1 M-, further characterized in that the catalyst is attached to the cylinder of tobacco by means of an adhesive 6. An article for a smoker according to one of claims 5, further characterized in that the tobacco cylinder comprises reconstituted tobacco 7. An article for smoker according to one of the claims ia 6, further 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 ñ A smoking article according to one of the claims 7, further characterized in that the catalyst used in the tobacco is thermally stabilized by an appropriate ion exchange process. ticle for smoking according to one of claims l ß, further characterized in that the zeolite material or the like to the zeolite used as catalyst has a modulus b '/ a' < 10. A smoker article according to one of claims 1 to 9, further characterized in that the filter contains an absorber consisting of a member of the zeolites or molecular sieves similar to the zeolite with hydrophobic properties, the zeolite or the zeolite-like material being defined by the following formula: mMI "liCaA10a" bSi0a-cT0a-lq, where li is a monovalent cation, ti 'is a divalent cation, a, b, c, n, m, and q are numbers that reflect the proportions estequeamétricas,, c, m, n, oq can also be zero, Al and Si are atoms of Al and Si tetrahedrally coordinated, T is a tetrahedrally coordinated atom that is able to replace Al or Si and Q is a sorbate capable of traversing the pore system of the zeolite, or of mixtures thereof, wherein the b / a modulus of the zeolite material or similar to the zeolite, enclosed in the filter is > W00 and because The pore size is from 5 to 7 A. 11. An article p A smoker according to claim 10, further characterized in that ti is Na, K or H, and M 'is Ca or Mg. 12. A smoker article according to one of claims 10 to 11, further characterized in that the absorber is bonded to the filter material by means of an adhesive. 13. A smoking article according to one of claims 10 to 13 further characterized in that the absorber in the filter is at least one member selected from the group consisting of silicate, ZSM-5, ZSIi-ii, ZSM-22. , ZSM-23 and ZSM-50. 1
4. A smoking article according to one of claims 10 to 13 further characterized in that the absorber in the filter is applied as an extruded product comprising a clay mineral v. gr., attapulgite, as a binder. 1
5. An article for smokers according to one of the rei indications 10 to 14, further characterized because T is B o. 1
6. A smoking article according to one of claims 10 to 15, further characterized in that it contains a dealuminated zeolitic absorber having hydrophobic properties. 1
7. An article for smoker in accordance with one of the claims &; to 16, further characterized in that it contains a sililated, alkylated or lower alkoxylated zeolitic absorber having hydrophilic properties. ARTICLE FOR SMOKERS SUMMARY OF THE INVENTION A smoker article comprising a filter, a tobacco cylinder and a wrapper; the tobacco cylinder contains a catalyst consisting of a molecular sieve of zeolite or similar to zeolite, said zeolite material or similar to zeolite being defined by the following formula: Mm.M'p.M "p [a / A1 .0a-b'Si.üa-c'T0s,: iq'Q where li is a monovalent cation li 'is a divalent cation li "is a trivalent cation a', b ', c', n ', m' , p and q 'are numbers that reflect the stequometric proportions, m', n ', poc' can also be zero, Al and Si are tetrahedrally coordinated Al and Si atoms, T is a tetrahedrally coordinated atom that is capable of replace Al or Si and is a sorbate capable of traversing the pore system of the zeolite. or of mixtures thereof; said catalyst consisting of a zeolite or zeolite-like material, enclosed in the tobacco cylinder, is optionally present in H form and has a thermally stable structure; the sorbate Q is mainly water; the zeolite catalyst that is incorporated in the tobacco cylinder, especially in combination with the zeolite absorber incorporated in the filter, reduces the harmful products in the main or secondary smoke. JJ / ieoh
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95810294 | 1995-05-03 | ||
EP95810294A EP0740907B1 (en) | 1995-05-03 | 1995-05-03 | Smoker's article |
Publications (2)
Publication Number | Publication Date |
---|---|
MX9601643A MX9601643A (en) | 1997-07-31 |
MXPA96001643A true MXPA96001643A (en) | 1997-12-01 |
Family
ID=
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