US20020195115A1 - Tobacco product carrying catalytically active material and its use in a smokers' article - Google Patents
Tobacco product carrying catalytically active material and its use in a smokers' article Download PDFInfo
- Publication number
- US20020195115A1 US20020195115A1 US10/078,492 US7849202A US2002195115A1 US 20020195115 A1 US20020195115 A1 US 20020195115A1 US 7849202 A US7849202 A US 7849202A US 2002195115 A1 US2002195115 A1 US 2002195115A1
- Authority
- US
- United States
- Prior art keywords
- catalytically active
- active material
- tobacco product
- tobacco
- product according
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- 239000011149 active material Substances 0.000 title claims abstract description 30
- 235000019505 tobacco product Nutrition 0.000 title claims abstract description 22
- 241000208125 Nicotiana Species 0.000 claims abstract description 43
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000000779 smoke Substances 0.000 claims abstract description 17
- 229910001679 gibbsite Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 239000004411 aluminium Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 230000001473 noxious effect Effects 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 229910001680 bayerite Inorganic materials 0.000 claims description 5
- 229910001648 diaspore Inorganic materials 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 229910001682 nordstrandite Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical group [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- -1 gibbsite Chemical compound 0.000 abstract description 2
- 239000010457 zeolite Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 14
- 235000019504 cigarettes Nutrition 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000000391 smoking effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910017089 AlO(OH) Inorganic materials 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004924 electrostatic deposition Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910006587 β-Al2O3 Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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
- A24B15/24—Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts
- A24B15/241—Extraction of specific substances
- A24B15/246—Polycyclic aromatic compounds
-
- 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
Definitions
- This invention relates to a tobacco product carrying catalytically active material, to articles for smoking containing such a tobacco product and more particularly to cigarettes which contain non-zeolitic catalysts in the tobacco rod.
- the catalytically active material is useful for reducing toxic components in tobacco smoke of smokers' articles, particularly of cigarettes.
- mainstream smoke is the smoke which enters the mouth of the smoker when he draws on the cigarette through the filter part
- sidestream smoke is the smoke which is released by the smouldering 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.
- zeolites were the first catalysts to be found to reduce significant amounts of undesirable compounds in sidestream as well as mainstream smoke (U.S. Pat. No. 5,727,537, EP-A-0 740 907).
- zeolites have an inherent disadvantage in that larger PAH molecules like benzo(a)pyrine, one of the worst carcinogenic smoke constituents, are not reduced in the mainstream.
- the overall PAH reduction values are less than a 25% in the mainstream compared to over 50% in the sidestream.
- the disappointing performance in the mainstream has been assigned to the sieving effect of the pore openings in the zeolite framework structure (W. M. Meier and K. Siegmann, Microporous and Mesoporous Materials, 33 (1999) 307-310).
- U.S. Pat. Nos. 3,572,348 and 3,703,901 suggest the use of zeolites for incorporating in tobacco material for reducing toxic compounds in the smoke.
- the proposed zeolite compounds contain substantial amounts of zinc besides palladium or platinum which are not suitable for several reasons for a product which cannot be recycled.
- These typical preparations known in petrochemistry of those days were heated in nitrogen (rather than burned in the presence of oxygen) and have little to do with a burning cigarette, and the process was pyrolysis rather than combustion. Mainstream and sidestream could not be distinguished in the set-up used.
- the use of zinc is not permissible in open systems by environmental laws.
- EP-A-0 740 907 Described in EP-A-0 740 907 are smokers' articles wherein the tobacco comprises a catalyst of a zeolite compound. It is proposed that the catalyst in the tobacco be bound to the tobacco with or without a binding agent, such as silica gel or attapulgite, a meerschaum-like clay mineral. Attempts to fix catalyst particles on the tobacco by electrostatic deposition failed. The catalyst particles were observed to discharge on the tobacco fibers within seconds and sputtered. It was found that the use of binding agents has serious drawbacks because the catalytic activity of the material which is bound by the agent is affected. Without binding agent, the binding strength of the catalytically active material to the tobacco is not sufficient, and therefore a separation of the catalyst from the material can occur easily during the manufacturing process of smokers' articles or during transportation.
- a binding agent such as silica gel or attapulgite, a meerschaum-like clay mineral.
- Zeolitic materials both natural and synthetic, in appropriate form, 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. D. H. Olson, W. M. Meier and Ch. Baerlocher, Atlas of Zeolite Framework Types, 5rd Edition, 2001, Elsevier, (formerly: Atlas of Zeolite Structure Types )) of crystalline aluminosilicates and isostructural materials with free pore diameters in the range of 0.3 to 1.3 nm or 3 to 13 ⁇ .
- 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.
- monovalent cation e.g. Na or K
- divalent cation e.g. Ca
- Cation exchange is a possible means of fine tuning the critical pore diameter in a particular application.
- zeolite-like molecular sieves 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 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 Si/Al ratio 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 a polar and hydrophobic in the case of a zeolite with a modulus >400.
- the object of the present invention can be achieved by incorporating certain catalytically active materials, which fulfill the necessary catalytic criteria, into tobacco by distributing the catalytically active material regularly on conditioned tobacco and by pressing the catalytically active material on the tobacco.
- the catalytic properties of the material which is pressed on the tobacco can develop its catalytic activity completely.
- the advantage is that the pores of the material remain open.
- the method assures an even distribution of catalyst particles on the tobacco which is all-important.
- a first object of the present invention is therefore to provide a tobacco product having a considerably lower content of noxious compounds such as PAHs and nitrosamines in its smoke than known products and which is free of the above-mentioned drawbacks.
- one subject matter of the present invention is thus a tobacco product carrying on its surface catalytically active material for improving the burning process, wherein the catalytically active material is selected from the group of crystalline and non-crystalline oxides and hydroxides of aluminium
- a further subject matter of the present invention is a smokers' article comprising a filter, a tobacco rod and a wrapper in which the tobacco rod contains a catalyst selected from the group of oxides or hydroxides of aluminium. They are preferably acid or slightly acidic.
- the catalyst may contain Fe or Si in minor amounts (e.g. 0 to 3%) or more Si for amorphous material.
- the catalyst can comprise particles consisting of single crystals or particles consisting of agglomerates of smaller crystals which are bound with a binder as kaolinite (“granulate”). Normally the catalyst is not highly crystalline.
- the catalyst is selected from the compounds of the group alumina (Al-oxide), diaspore, natural or synthetic boehmite, natural or synthetic gibbsite, natural or synthetic doylite, natural or synthetic nordstrandite, natural or synthetic bayerite and hydrargillite.
- the particle size of the catalyst is in the range of 1 to 100 ⁇ m (e.g. 3, 5 or 10 ⁇ m) and its specific surface is in the range of 75 to 250 m 2 /g (e.g. 100 or 150 m 2 /g).
- Non-crystalline or X-ray-amorphous alumina can contain over 3% of Si and is then mesoporous.
- Al is octahedrally coordinated by oxygen whereas in aluminosilicates (like felspars and zeolites) Al is in tetrahedral coordination.
- the catalytically active material is distributed evenly on the smoking tobacco.
- the tobacco can consist of leaves or reconstituted tobacco sheets, cut or uncut.
- the tobacco is made reasonably soft by conditioning it, i.e. it has a defined degree of moisture. If the tobacco is too dry it is brittle and not suitable for receiving the catalytic material.
- the catalyst is pressed on the tobacco by a single or double layer cylinder press.
- a single or double layer cylinder press can work in combination with a conveyor belt.
- the process can be carried out with two or more distributing and pressing steps, e.g. on the upper and lower side of the tobacco.
- the catalyst content in relation to the tobacco is about 4-8% (wt/wt).
- PAH polycyclic aromatic hydrocarbons
- W. M. Meier and K.Siegmann Microporous and Mesoporous Materials, 33 (1999) 307-310
- This method is based on a photoelectric PAH sensor in combination with a commercially available light scattering instrument which determines the total mass of particles smaller than 10 ⁇ m (PM-10).
- the signal of the photoelectric aerosol sensor is proportional to the amount of particle bound PAH.
- Light scattering reflects the number and size of particles, independently of chemical composition, and was found to agree with the results obtained with conventional methods in numerous tests. The method allows the simultaneous measurement of tar and PAH values.
- the tobacco blend (American blend type) was received from a tobacco lot and kept in a humidifier at 60% relative humidity. 5% by weight of synthetic gibbsite (obtained from Fluka, Switzerland) was evenly distributed over the tobacco, and then pressed on by a heavy cylinder on a rubber belt.
- a smoking panel noted a smoother taste without off-taste in the products of the above examples.
Abstract
The tobacco product carries on its surface catalytically active material for improving the burning process. The catalytically active material is selected from the group of crystalline and non-crystalline oxides and hydroxides of aluminium, e.g. gibbsite, having a particle size of 1 to 100 μm and a specific surface of 75 to 250 m2/g. With the use of the catalyst in the tobacco, the amount of noxious compounds in the mainstream and sidestream smoke can be considerably reduced in the combustion process of the smokers' article during its consumption.
The said tobacco product is useful for smoker's articles comprising a filter, a tobacco rod and a wrapper. In such articles the tobacco rod consists of the tobacco product.
Description
- This invention relates to a tobacco product carrying catalytically active material, to articles for smoking containing such a tobacco product and more particularly to cigarettes which contain non-zeolitic catalysts in the tobacco rod. The catalytically active material is useful for reducing toxic components in tobacco smoke of smokers' articles, particularly of cigarettes.
- 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 smouldering 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 in sufficient manner.
- Large pore zeolites were the first catalysts to be found to reduce significant amounts of undesirable compounds in sidestream as well as mainstream smoke (U.S. Pat. No. 5,727,537, EP-A-0 740 907). However, zeolites have an inherent disadvantage in that larger PAH molecules like benzo(a)pyrine, one of the worst carcinogenic smoke constituents, are not reduced in the mainstream. The overall PAH reduction values are less than a 25% in the mainstream compared to over 50% in the sidestream. The disappointing performance in the mainstream has been assigned to the sieving effect of the pore openings in the zeolite framework structure (W. M. Meier and K. Siegmann,Microporous and Mesoporous Materials, 33 (1999) 307-310).
- U.S. Pat. Nos. 3,572,348 and 3,703,901 suggest the use of zeolites for incorporating in tobacco material for reducing toxic compounds in the smoke. However, the proposed zeolite compounds contain substantial amounts of zinc besides palladium or platinum which are not suitable for several reasons for a product which cannot be recycled. These typical preparations known in petrochemistry of those days were heated in nitrogen (rather than burned in the presence of oxygen) and have little to do with a burning cigarette, and the process was pyrolysis rather than combustion. Mainstream and sidestream could not be distinguished in the set-up used. Moreover, the use of zinc is not permissible in open systems by environmental laws.
- Described in EP-A-0 740 907 are smokers' articles wherein the tobacco comprises a catalyst of a zeolite compound. It is proposed that the catalyst in the tobacco be bound to the tobacco with or without a binding agent, such as silica gel or attapulgite, a meerschaum-like clay mineral. Attempts to fix catalyst particles on the tobacco by electrostatic deposition failed. The catalyst particles were observed to discharge on the tobacco fibers within seconds and sputtered. It was found that the use of binding agents has serious drawbacks because the catalytic activity of the material which is bound by the agent is affected. Without binding agent, the binding strength of the catalytically active material to the tobacco is not sufficient, and therefore a separation of the catalyst from the material can occur easily during the manufacturing process of smokers' articles or during transportation.
- Zeolitic materials, both natural and synthetic, in appropriate form, 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. D. H. Olson, W. M. Meier and Ch. Baerlocher,Atlas of Zeolite Framework Types, 5rd Edition, 2001, Elsevier, (formerly: Atlas of Zeolite Structure Types)) of crystalline aluminosilicates and isostructural materials with free pore diameters in the range of 0.3 to 1.3 nm or 3 to 13 Å. These aluminosilicates can be described as a rigid three-dimensional network of SiO4 and AlO4, 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 SiO2. 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 Si/Al ratio means an increased temperature stability, up to 1000° C. in the case of silicalite, which is a molecular sieve with a pure SiO2 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 a polar and hydrophobic in the case of a zeolite with a modulus >400.
- It has been discovered that the object of the present invention can be achieved by incorporating certain catalytically active materials, which fulfill the necessary catalytic criteria, into tobacco by distributing the catalytically active material regularly on conditioned tobacco and by pressing the catalytically active material on the tobacco. When incorporated into the tobacco rod of a cigarette, the catalytic properties of the material which is pressed on the tobacco can develop its catalytic activity completely. The advantage is that the pores of the material remain open. Moreover the method assures an even distribution of catalyst particles on the tobacco which is all-important.
- Consequently there is a demand for smokers' articles, especially filter cigarettes, whose mainstream as well as sidestream smoke is significantly lower in noxious substances than with smokers' articles of prior art.
- A first object of the present invention is therefore to provide a tobacco product having a considerably lower content of noxious compounds such as PAHs and nitrosamines in its smoke than known products and which is free of the above-mentioned drawbacks.
- To overcome the shortcomings of large pore zeolites like NaY in the mainstream other catalyst materials have been investigated. Good results were obtained with oxides and hydroxides of aluminium. These materials should have a particle size of around 1 μm (not smaller and be dusty) and a surface of some 100 m2/g or more.
- In a first aspect, one subject matter of the present invention is thus a tobacco product carrying on its surface catalytically active material for improving the burning process, wherein the catalytically active material is selected from the group of crystalline and non-crystalline oxides and hydroxides of aluminium
- In a second aspect, a further subject matter of the present invention is a smokers' article comprising a filter, a tobacco rod and a wrapper in which the tobacco rod contains a catalyst selected from the group of oxides or hydroxides of aluminium. They are preferably acid or slightly acidic. The catalyst may contain Fe or Si in minor amounts (e.g. 0 to 3%) or more Si for amorphous material. The catalyst can comprise particles consisting of single crystals or particles consisting of agglomerates of smaller crystals which are bound with a binder as kaolinite (“granulate”). Normally the catalyst is not highly crystalline. Typically the catalyst is selected from the compounds of the group alumina (Al-oxide), diaspore, natural or synthetic boehmite, natural or synthetic gibbsite, natural or synthetic doylite, natural or synthetic nordstrandite, natural or synthetic bayerite and hydrargillite. Typically the particle size of the catalyst is in the range of 1 to 100 μm (e.g. 3, 5 or 10 μm) and its specific surface is in the range of 75 to 250 m2/g (e.g. 100 or 150 m2/g).
- The following table lists a representative number of compounds which are suitable in the first aspect of the present invention.
TABLE A Crystalline aluminium oxides and hydroxides and characteristic lines according to Powder Diffraction File (PDF) d-values (in A) of the Material 3 strongest lines PDF # Alumina (Al-oxide) α-Al2O3 2.07 2.52 1.59 48-366 β-Al2O3 1.40 11.97 2.68 10-414 γ-Al2O3 1.98 1.40 2.39 10-425 1.40 2.41 2.12 13-373 1.40 1.98 2.39 29-63 δ-Al2O3 1.39 2.60 2.46 46-1215 Θ-Al2O3 1.39 2.84 2.73 23-1009 Diaspore α-AlO(OH) 3.99 232 2.13 5-355 Boehmite, syn. y-AlO(OH) 6.32 1.85 3.16 49-133 Gibbsite, syn. Al(OH)3 4.85 4.37 2.39 33-18 Doylite Al(OH)3 4.79 437 2.39 38-376 Nordstrandite, syn. Al(OH)3 4.79 2.27 4.32 24-6 Bayerite, syn. α-Al(OH)3 2.22 4.71 4.35 20-11 δ-Al(OH)3 3.62 2.27 1.80 37-1377 Hydrargillite (see gibbsite) - If not purely synthetic, these compounds frequently contain significant amounts of Si, Fe, Na and/or other elements. β-Alumina, widely listed as such, is not a true aluminium oxide, but at least in part a Na-aluminate. Many Al-compounds listed in Table A are alteration products, and are thus not highly crystalline. As indicated by the names, most of these compounds are also known minerals. They are environmentally safe, which is an important aspect in the present context.
- Non-crystalline or X-ray-amorphous alumina can contain over 3% of Si and is then mesoporous.
- In all these compounds Al is octahedrally coordinated by oxygen whereas in aluminosilicates (like felspars and zeolites) Al is in tetrahedral coordination.
- For initial testing, the cigarettes were hand-rolled and the tobacco was loaded with 5% of the catalyst. This was done by using a procedure wherein the tobacco is treated with catalytically active materials, consisting of the steps of
- a) distributing catalytically active material on tobacco,
- b) pressing the catalytically active material on the tobacco.
- Advantageously the catalytically active material is distributed evenly on the smoking tobacco. The tobacco can consist of leaves or reconstituted tobacco sheets, cut or uncut.
- Advantageously the tobacco is made reasonably soft by conditioning it, i.e. it has a defined degree of moisture. If the tobacco is too dry it is brittle and not suitable for receiving the catalytic material.
- Preferably the catalyst is pressed on the tobacco by a single or double layer cylinder press. For a continuous working process such a press can work in combination with a conveyor belt. The process can be carried out with two or more distributing and pressing steps, e.g. on the upper and lower side of the tobacco. E.g. the catalyst content in relation to the tobacco is about 4-8% (wt/wt).
- For PAH (polycyclic aromatic hydrocarbons) analyses, the method described by W. M. Meier and K.Siegmann [Microporous and Mesoporous Materials, 33 (1999) 307-310] was applied using a smoking machine. This method is based on a photoelectric PAH sensor in combination with a commercially available light scattering instrument which determines the total mass of particles smaller than 10 μm (PM-10). The signal of the photoelectric aerosol sensor is proportional to the amount of particle bound PAH. Light scattering reflects the number and size of particles, independently of chemical composition, and was found to agree with the results obtained with conventional methods in numerous tests. The method allows the simultaneous measurement of tar and PAH values.
- The tobacco blend (American blend type) was received from a tobacco lot and kept in a humidifier at 60% relative humidity. 5% by weight of synthetic gibbsite (obtained from Fluka, Switzerland) was evenly distributed over the tobacco, and then pressed on by a heavy cylinder on a rubber belt.
- Hand-rolled cigarettes of 1 g tobacco each were then prepared without filter tips, i.e. using tobacco with catalyst and without catalyst (reference). The measurements gave reductions of
- 48-53% PAH in the mainstream
- 44-46% PAH in the sidestream
- Following the same procedure as described in example 1, but using α-alumina (supplied by Dr. Markus Meier, Sierre, Switzerland) and tested by X-ray diffraction. These gave the following results
- in mainstream 49% reduction in PAH
- in sidestream 45% reduction in PAH
- Following the same procedure as described in example 1, but using X-ray amorphous Siral 1.5 (supplied by CONDEA GmbH, Hamburg, Germany) containing 1.5% silica and having a BET surface of 330 m2/g. The following results were obtained:
- in mainstream 50-55% reduction in PAH
- in sidestream 55-60% reduction in PAH
- Note that the PAH reduction values in the mainstream are very much higher than those recorded for zeolite type catalysts (less than 20% overall measured by the same method).
- A smoking panel noted a smoother taste without off-taste in the products of the above examples.
Claims (17)
1. Tobacco product carrying on its surface catalytically active material for improving the burning process, wherein the catalytically active material is selected from the group of crystalline and non-crystalline oxides and hydroxides of aluminium.
2. Tobacco product according to claim 1 wherein the catalytically active material is bound to the surface, wherein the catalytically active material is preferably pressed into the tobacco surface so as to be bound without an adhesive in order to prevent the catalytically active material from being partially or completely inactivated by closed pores.
3. Tobacco product according to claim 1 or 2, wherein the oxides and hydroxides of aluminium are acid or slightly acidic.
4. Tobacco product according to claim 1 , wherein the oxides and hydroxides of aluminium contain Fe in an amount of less than 3%.
5. Tobacco product according to claim 1 , wherein the catalytically active material comprises crystalline hydroxides of aluminium which contain silicon in an amount of less than 3%.
6. Tobacco product according to claim 1 , wherein the catalytically active material comprises amorphous hydroxides of aluminium which contain silicon in an amount of more than 3%.
7. Tobacco product according to claim 1 , wherein the catalytically active material is not highly crystalline.
8. Tobacco product according to claim 1 , wherein the catalytically active material comprises particles consisting of single crystals.
9. Tobacco product according to claim 1 , wherein the catalytically active material comprises a granulate consisting of agglomerates of crystals which are bound to each other with a binder.
10. Tobacco product according to claim 9 , wherein the binder is kaolinite.
11. Tobacco product according to claim 1 , wherein the catalytically active material comprises X-ray amorphous hydroxides of aluminium having a particle size in the range of 1-100 μm and a specific surface of up to 550 m2/g.
12. Tobacco product according to claim 1 , wherein the catalytically active material is selected from the compounds of the group alumina (Al-oxide), diaspore, natural or synthetic boehmite, natural or synthetic gibbsite, natural or synthetic doylite, natural or synthetic nordstrandite, natural or synthetic bayerite and hydrargillite.
13. Tobacco product according to claim 1 , wherein the particle size of the catalyst is in the range of 1-100 μm, and its specific surface is in the range of 75 to 250 m2/g.
14. A smokers' article comprising a filter, a tobacco rod and a wrapper, wherein the tobacco rod consists of a tobacco product according to claim 1 or 2.
15. Use of a catalytically active material comprising an oxide or hydroxide of aluminium for adding to the tobacco of a tobacco rod of a smokers' article for reducing the amount of noxious compounds in the mainstream and sidestream smoke in the combustion process of the smokers' article during its consumption.
16. Use according to claim 15 , wherein the catalytically active material is selected from the group consisting of alumina, diaspore, natural or synthetic boehmite, natural or synthetic gibbsite, natural or synthetic doylite, natural or synthetic nordstrandite, natural or synthetic bayerite and hydrargillite.
17. Use according to claim 16 , wherein the catalytically active materials comprise finely ground natural counterparts of oxides and hydroxides of aluminium and granulated using a binder such as kaolinite.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01810198A EP1234511A1 (en) | 2001-02-26 | 2001-02-26 | Process for treating tobacco with catalytically active material for reducing toxic components in tobacco smoke |
EP01810198.0 | 2001-02-26 | ||
EP01810928A EP1234512A3 (en) | 2001-02-26 | 2001-09-24 | Tobacco product carrying catalytically active material, its use in a smokers' article and a process for preparing it |
EP01810928.0 | 2001-09-24 |
Publications (1)
Publication Number | Publication Date |
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US20020195115A1 true US20020195115A1 (en) | 2002-12-26 |
Family
ID=26077349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/078,492 Abandoned US20020195115A1 (en) | 2001-02-26 | 2002-02-21 | Tobacco product carrying catalytically active material and its use in a smokers' article |
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US (1) | US20020195115A1 (en) |
EP (1) | EP1234512A3 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2003086112A1 (en) * | 2002-04-08 | 2003-10-23 | Philip Morris Products S.A. | Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette |
US20050155616A1 (en) * | 2003-10-27 | 2005-07-21 | Philip Morris Usa Inc. | Use of oxyhydroxide compounds in cigarette paper for reducing carbon monoxide in the mainstream smoke of a cigarette |
US20070131038A1 (en) * | 2005-12-09 | 2007-06-14 | Qiang Wei | Real-time particulate matter measuring system |
WO2012047347A1 (en) * | 2010-10-06 | 2012-04-12 | Celanese Acetate Llc | Smoke filters for smoking devices with porous masses of active and binder particles having disclosed void volumes |
WO2014164492A1 (en) * | 2013-03-13 | 2014-10-09 | Celanese Acetate Llc | Smoke filters for reducing components in a smoke stream |
CN105249534A (en) * | 2014-07-20 | 2016-01-20 | 刘先忠 | Open fire-free smoking device |
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US11351315B2 (en) * | 2016-08-10 | 2022-06-07 | Gary Stephen Shuster | Vaporizer improvements |
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GB201412752D0 (en) | 2014-07-17 | 2014-09-03 | Nicoventures Holdings Ltd | Electronic vapour provision system |
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US2007407A (en) * | 1932-03-22 | 1935-07-09 | Samuel S Sadtler | Prepared smoking tobacco |
US2967118A (en) * | 1957-09-16 | 1961-01-03 | Minerals & Chem Philipp Corp | Tobacco composition and smokable unit containing material for removing deleterious matter |
US3106210A (en) * | 1957-11-18 | 1963-10-08 | Reynolds Metals Co | Smoking tobacco |
US2938818A (en) * | 1957-11-19 | 1960-05-31 | Minerals & Chemicals Corp Of A | Tobacco composition and smoking unit containing material for eliminating deleterious matter |
US3011921A (en) * | 1957-12-19 | 1961-12-05 | Minerals & Chem Philipp Corp | Tobacco composition and smoking unit containing material for eliminating deleterious matter |
US3005732A (en) * | 1957-12-19 | 1961-10-24 | Minerals & Chem Philipp Corp | Tobacco composition and smoking unit containing material for eliminating deleterious matter |
US3076728A (en) * | 1960-02-12 | 1963-02-05 | Minerals & Chem Philipp Corp | Smoking composition containing alumina and smoking unit containing same |
US3057757A (en) * | 1960-02-12 | 1962-10-09 | Mincrals & Chemicals Philip Co | Smoking compositions and smoking unit containing same |
US3050421A (en) * | 1960-02-25 | 1962-08-21 | Minerals & Chem Philipp Corp | Smoking preparation containing laminar alumina and smoking unit containing same |
US3002863A (en) * | 1960-06-20 | 1961-10-03 | Richard J Shaw | Smoking tobacco mixture and method of making |
US3703901A (en) * | 1971-03-11 | 1972-11-28 | Liggett & Myers Inc | Tobacco composition |
US3840026A (en) * | 1972-08-23 | 1974-10-08 | Rosen Enterprises Inc | Method of treating tobacco |
DE2658479C3 (en) * | 1976-12-23 | 1981-10-01 | Rhodia Ag, 7800 Freiburg | Additives for smoking tobacco products and their filter elements |
US5671758A (en) * | 1994-12-13 | 1997-09-30 | Rongved; Paul I. | Catalytic cigarette smoke cleaning devise and process |
ATE209006T1 (en) * | 1995-05-03 | 2001-12-15 | British American Tobacco Co | SMOKING ITEMS |
-
2001
- 2001-09-24 EP EP01810928A patent/EP1234512A3/en not_active Withdrawn
-
2002
- 2002-02-21 US US10/078,492 patent/US20020195115A1/en not_active Abandoned
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US6769437B2 (en) * | 2002-04-08 | 2004-08-03 | Philip Morris Incorporated | Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette |
US20040159328A1 (en) * | 2002-04-08 | 2004-08-19 | Mohammad Hajaligol | Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette |
US7228862B2 (en) | 2002-04-08 | 2007-06-12 | Philip Morris Usa Inc. | Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette |
WO2003086112A1 (en) * | 2002-04-08 | 2003-10-23 | Philip Morris Products S.A. | Use of oxyhydroxide compounds for reducing carbon monoxide in the mainstream smoke of a cigarette |
US8701681B2 (en) | 2003-10-27 | 2014-04-22 | Philip Morris Usa Inc. | Use of oxyhydroxide compounds in cigarette paper for reducing carbon monoxide in the mainstream smoke of a cigarette |
US20050155616A1 (en) * | 2003-10-27 | 2005-07-21 | Philip Morris Usa Inc. | Use of oxyhydroxide compounds in cigarette paper for reducing carbon monoxide in the mainstream smoke of a cigarette |
US20070131038A1 (en) * | 2005-12-09 | 2007-06-14 | Qiang Wei | Real-time particulate matter measuring system |
WO2012047347A1 (en) * | 2010-10-06 | 2012-04-12 | Celanese Acetate Llc | Smoke filters for smoking devices with porous masses of active and binder particles having disclosed void volumes |
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US9149071B2 (en) | 2013-03-13 | 2015-10-06 | Celanese Acetate Llc | Smoke filters for reducing components in a smoke stream |
JP2016510993A (en) * | 2013-03-13 | 2016-04-14 | セラニーズ アセテート,エルエルシー | Smoke filter to reduce components in the smoke stream |
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US11351315B2 (en) * | 2016-08-10 | 2022-06-07 | Gary Stephen Shuster | Vaporizer improvements |
Also Published As
Publication number | Publication date |
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EP1234512A2 (en) | 2002-08-28 |
EP1234512A3 (en) | 2003-08-06 |
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