EP1234512A2 - Tabakprodukt mit katalytisch aktivem Material, seine Verwendung in einem Raucherartikel und Verfahren zur Herstellung - Google Patents

Tabakprodukt mit katalytisch aktivem Material, seine Verwendung in einem Raucherartikel und Verfahren zur Herstellung Download PDF

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Publication number
EP1234512A2
EP1234512A2 EP01810928A EP01810928A EP1234512A2 EP 1234512 A2 EP1234512 A2 EP 1234512A2 EP 01810928 A EP01810928 A EP 01810928A EP 01810928 A EP01810928 A EP 01810928A EP 1234512 A2 EP1234512 A2 EP 1234512A2
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EP
European Patent Office
Prior art keywords
tobacco
catalytically active
active material
natural
synthetic
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.)
Withdrawn
Application number
EP01810928A
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English (en)
French (fr)
Other versions
EP1234512A3 (de
Inventor
Walter M. Meier Dr. Prof. Eth
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Individual
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Individual
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Filing date
Publication date
Priority claimed from EP01810198A external-priority patent/EP1234511A1/de
Application filed by Individual filed Critical Individual
Priority to EP01810928A priority Critical patent/EP1234512A3/de
Priority to US10/078,492 priority patent/US20020195115A1/en
Publication of EP1234512A2 publication Critical patent/EP1234512A2/de
Publication of EP1234512A3 publication Critical patent/EP1234512A3/de
Withdrawn legal-status Critical Current

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    • 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, and to a process for treating tobacco with catalytically active material 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 (US-A-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).
  • US-A-3,572,348 and US-A-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 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. W.M. Meier, D.H. Olson and Ch. Baerlocher, Atlas of Zeolite Structure Types, 4rd Edition, 1996, Elsevier) of crystalline aluminosilicates and isostructural materials with free pore diameters in the range of 0.3 to 1.3 nm or 3 to 13 ⁇ .
  • 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.
  • 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 zeolites or zeolite-like molecular sieves or other catalytically active material, which fulfil 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.
  • a second object of the present invention is therefore to propose a method for binding catalytically active material to tobacco without the above mentioned drawbacks.
  • the aim is therefore to provide a method for binding catalytically active material to tobacco without adhesive or other additives affecting the catalytically activity at least partially.
  • 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 (0 to 3 %).
  • 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).
  • a further subject matter of this invention is a process for treating of tobacco with catalytically active materials, e.g. zeolites as well as non-zeolites, like oxides of aluminium and silicon having a surface area of around 100 m 2 /g or more, consisting of the steps of
  • 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 method can be used with all types of suitable catalytically active material (including zeolitic catalysts or catalyst based on alumina) is suitable for reducing noxious compound in tobacco smoke.
  • suitable catalytically active material including zeolitic catalysts or catalyst based on alumina
  • 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).
  • Aluminium oxides and hydroxides and characteristic lines according to Powder Diffraction File (PDF) Material d-values (in A) of the 3 strongest lines PDF# Alumina (Al-oxide) ⁇ -Al 2 O 3 2.07 2.52 1.59 48-366 ⁇ -Al 2 O 3 1.40 11.97 2.68 10-414 ⁇ -Al 2 O 3 1.98 1.40 2.39 10-425 1.40 2.41 2.12 13-373 1.40 1.98 2.39 29-63 ⁇ -Al 2 O 3 1.39 2.60 2.46 46-1215 ⁇ -Al 2 O 3 1.39 2.84 2.73 23-1009 Diaspore ⁇ -AlO(OH) 3.99 232 2.13 5-355 Boehmite, syn.
  • PDF Powder Diffraction File
  • Al is octahedrally coordinated by oxygen whereas in aluminosilicates (like felspars and zeolites) Al is in tetrahedral coordination.
  • 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
  • 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.
  • FIG. 1 shows a double layer cylinder press 1 equipped with conveyor belts 11,12 and devices 7, 8, 9, 10 which are adapted to the present method.
  • a first conveyor belt 11 is carried by the cylinders 2 and 6. Tobacco is distributed on the belt 11 by the tobacco dispenser 7.
  • a flattener 8 is responsible for regularizing the distributed tobacco T.
  • a suitable amount of catalytically active compound C1 is layered on the tobacco layer T by a catalyst supply device 9. After this step the belt 11 moves into a first cylinder press formed by the cylinders 5 and 6. These cylinders exercise an adjustable pressure on the tobacco/catalyst layer T, C1 for binding the catalyst on the soft tobacco particles.
  • a second conveyor belt joins to the tobacco/catalyst layer at the catalyst side.
  • the two conveyor belts carry the tobacco layer around the cylinder 6: the layer is now turned, i.e. the catalyst layer C1 is on the lower side of the layer and directly on the second conveyor belt 12, and is supported by this belt, whereas the first belt 11 is moving away from the tobacco layer.
  • a scraper 13 cleans the first belt of tobacco particles, which fall back on the tobacco layer T.
  • this layer moves on the second belt 12, passing a second catalyst supply 10, where a further layer C2 of catalytically active material is put on the tobacco layer T.
  • the layers C1, T, C2 are introduced into a second cylinder press, formed by the cylinders 3 and 4, which exercise again a suitable pressure on the tobacco layer, carrying on both sides a catalyst layer.
  • the loose catalyst is also bound on the tobacco particles of the layer on the belt 12.
  • the dust of catalyst not bound is removed, and the tobacco carrying a catalytically active compound exits, and is ready for direct use or storage. Simpler devices based on the same principle may also be applied.
  • acidic and hydrophilic zeolites saturated with water, including zeolites X, Y, L, mordenite and BETA, are used in the tobacco and are bound to the tobacco, without a binding agent, according to the present invention.
  • 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.
  • 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.
  • the tobacco blend type (Amercan blend Type) was received from a tobacco lot ready for cigarette manufacture and kept in a humidifier. 5% by weight of synthetic faujasite in powder form (obtained from CU Uetikon, Switzerland) were pressed on the tobacco in using a cylinder press rolled on a rubber belt. Hand rolled cigarettes of 1 g each were then prepared. In the sidestream a reduction of 50 % of PAH was observed using the method described by Meier and Siegmann, Microporous an Mesoporous Materials, 33 (1999) 307.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Manufacturing Of Cigar And Cigarette Tobacco (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
EP01810928A 2001-02-26 2001-09-24 Tabakprodukt mit katalytisch aktivem Material, seine Verwendung in einem Raucherartikel und Verfahren zur Herstellung Withdrawn EP1234512A3 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP01810928A EP1234512A3 (de) 2001-02-26 2001-09-24 Tabakprodukt mit katalytisch aktivem Material, seine Verwendung in einem Raucherartikel und Verfahren zur Herstellung
US10/078,492 US20020195115A1 (en) 2001-02-26 2002-02-21 Tobacco product carrying catalytically active material and its use in a smokers' article

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP01810198 2001-02-26
EP01810198A EP1234511A1 (de) 2001-02-26 2001-02-26 Verfahren zur Behandlung von Tabak mittels katalytisch aktiven Material zum Reduzieren schädlicher Bestandteile von Tabakrauch
EP01810928A EP1234512A3 (de) 2001-02-26 2001-09-24 Tabakprodukt mit katalytisch aktivem Material, seine Verwendung in einem Raucherartikel und Verfahren zur Herstellung

Publications (2)

Publication Number Publication Date
EP1234512A2 true EP1234512A2 (de) 2002-08-28
EP1234512A3 EP1234512A3 (de) 2003-08-06

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EP01810928A Withdrawn EP1234512A3 (de) 2001-02-26 2001-09-24 Tabakprodukt mit katalytisch aktivem Material, seine Verwendung in einem Raucherartikel und Verfahren zur Herstellung

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US (1) US20020195115A1 (de)
EP (1) EP1234512A3 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10070664B2 (en) 2014-07-17 2018-09-11 Nicoventures Holdings Limited Electronic vapor provision system

Families Citing this family (8)

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Publication number Priority date Publication date Assignee Title
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
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
US20070131038A1 (en) * 2005-12-09 2007-06-14 Qiang Wei Real-time particulate matter measuring system
WO2012047348A1 (en) * 2010-10-06 2012-04-12 Celanese Acetate Llc Smoke filters for smoking devices with porous masses having a carbon particle loading and an encapsulated pressure drop
JP6159470B2 (ja) 2013-03-13 2017-07-05 セラニーズ アセテート，エルエルシー 煙流中の成分を低減するための煙フィルター
CN105266203A (zh) * 2014-07-05 2016-01-27 刘先忠 一种吸收二手烟的设备
CN105249534A (zh) * 2014-07-20 2016-01-20 刘先忠 一种不需明火的抽烟器
WO2018029536A1 (en) * 2016-08-10 2018-02-15 Gary Stephen Shuster Vaporization improvements

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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
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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
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10070664B2 (en) 2014-07-17 2018-09-11 Nicoventures Holdings Limited Electronic vapor provision system

Also Published As

Publication number Publication date
US20020195115A1 (en) 2002-12-26
EP1234512A3 (de) 2003-08-06

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