US20140020699A1 - Smoking articles - Google Patents

Smoking articles Download PDF

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Publication number
US20140020699A1
US20140020699A1 US13/985,869 US201213985869A US2014020699A1 US 20140020699 A1 US20140020699 A1 US 20140020699A1 US 201213985869 A US201213985869 A US 201213985869A US 2014020699 A1 US2014020699 A1 US 2014020699A1
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Prior art keywords
tobacco
yields
smoke
blend
smoking article
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US13/985,869
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English (en)
Inventor
David John Dittrich
Peter James Branton
Michael Arthur John Bevan
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British American Tobacco Investments Ltd
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British American Tobacco Investments Ltd
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Priority claimed from GBGB1102785.1A external-priority patent/GB201102785D0/en
Priority claimed from GBGB1113614.0A external-priority patent/GB201113614D0/en
Application filed by British American Tobacco Investments Ltd filed Critical British American Tobacco Investments Ltd
Assigned to BRITISH AMERICAN TOBACCO (INVESTMENTS) LIMITED reassignment BRITISH AMERICAN TOBACCO (INVESTMENTS) LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BEVAN, MICHAEL ARTHUR JOHN, BRANTON, PETER JAMES, DITTRICH, DAVID JOHN
Publication of US20140020699A1 publication Critical patent/US20140020699A1/en
Abandoned 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
    • A24B15/10—Chemical features of tobacco products or tobacco substitutes
    • A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
    • 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
    • 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
    • A24B15/245—Nitrosamines
    • 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
    • A24B15/248—Heavy metals
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D1/00—Cigars; Cigarettes
    • A24D1/18—Selection of materials, other than tobacco, suitable for smoking
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/12—Use of materials for tobacco smoke filters of ion exchange materials
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/163—Carbon

Definitions

  • the present invention relates to smoking articles and, in particular, to smoking articles which combine two or more technological applications that individually reduce the machine measured yields of specific constituents or groups of constituents in mainstream smoke.
  • Tobacco smoke is a complex, dynamic mixture of more than 5000 identified constituents of which approximately 150 have been documented as being undesirable.
  • the constituents are present in the mainstream smoke (MS) which is inhaled by a smoker and are also released between puffs as constituents of sidestream smoke (SS).
  • the IOM and other groups (Life Sciences Research Office (LSRO) 2007; World Health Organization (WHO) 2007) describe a number of stages of activity which are likely to be required for a combustible tobacco product to be recognised as a PREP; however, the detailed approach and stages required to provide relevant data have yet to be agreed amongst the scientific community. For example, some groups have proposed MS yield limits for specific smoke constituents and others have suggested that biomonitoring should play a role in this assessment
  • a further issue to be addressed is the importance of producing a product which is acceptable to the consumer.
  • Much of the sensory impact of a conventional smoking article is based upon the constituents of the MS. Removing some of these has the potential to provide the smoker with an unsatisfactory smoking experience.
  • Increasing filter ventilation has varied effects on the smoke constituents.
  • the absolute yields of all the smoke constituents are reduced, but, relative to tar or nicotine, yields of most of the particulate phase constituents are unchanged or may even be increased.
  • the yields of some of the volatile constituents, such as ammonia and carbon monoxide, are reduced relative to both tar and nicotine, while the relative yields of some of the semivolatile constituents such as phenols are increased.
  • volatile vapour phase components such as the volatile aldehydes and hydrogen cyanide may be selectively reduced using adsorbent materials in the filter such as activated charcoal or certain resins.
  • adsorbent materials such as activated charcoal or certain resins.
  • permanent gases such as carbon monoxide and nitric oxide, are not amenable to adsorption at room temperature, and toxicants in the particulate phase cannot be selectively reduced by filtration since they are largely bound into the aerosol particles.
  • Adsorbents also need to function at the gas-solid interface (i.e. not in solution) and in the presence of thousands of other chemicals in both vapour and particulate phases. Adsorbent surfaces are also susceptible to blocking by condensing smoke aerosol particles. For permanent gases, and smoke constituents with high vapour pressures at ambient temperatures such as formaldehyde, acetaldehyde or HCN, physical adsorption has been found to be less effective and alternative routes are required.
  • Cigarette smoke contains a number of volatile aldehydes, both saturated compounds such as formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde, and unsaturated compounds such as acrolein and crotonaldehyde.
  • Carbonyls in cigarette smoke are mainly generated by combustion of a number of tobacco constituents, mostly carbohydrates.
  • sugars are major sources of formaldehyde in cigarette smoke.
  • Cellulose has been suggested to be the major precursor of mainstream smoke acetaldehyde.
  • glycerol a material sometimes added to tobacco as a humectant, is an additional precursor for acrolein.
  • a promising approach to achieving substantial specific reductions in particulate constituents from a conventionally structured cigarette is to modify the tobacco.
  • Substitution of different tobacco varieties into the blend can have an impact on yields of several smoke constituents. For example there are higher yields of the nitrogen containing smoke constituents from burley tobacco than from flue cured or oriental, and higher yields of formaldehyde and catechol from flue-cured tobaccos.
  • decreases in one constituents or set of constituents are often offset by increases in other constituents. To avoid this it would be useful to be able to identify and remove precursors to smoke constituents from the tobacco leaf.
  • the tobacco specific nitrosamines such as NAT and NAB
  • the major precursors for the volatile carbonyls benzo(a)pyrene, carbon monoxide, benzene and toluene are the structural carbohydrates such as pectin and cellulose as well as the sugars.
  • the nitrogenous smoke constituents are formed from nitrogenous precursors in the leaf, and there is considerable evidence that protein and amino acid combustion contributes to the generation of several nitrogen containing smoke constituents on the Health Canada list.
  • Tobacco protein is also strongly correlated with the formation of mutagenic heterocyclic amines and the resulting mutagenicity of smoke condensate in the TA98 Ames assay.
  • the polyphenols in tobacco are major precursors for phenolic smoke compounds.
  • Chlorogenic acid the most abundant polyphenol in flue-cured tobacco, is a major precursor for phenol, catechol and the substituted catechols, while hydroquinone has also been reported as a chlorogenic acid pyrolysis product.
  • Rutin and caffeic acid also generate catechol and substituted catechols on pyrolysis but because of their low concentrations in tobacco and because of their lower pyrolytic yields their contributions to catechol in flue-cured tobacco smoke are much less than chlorogenic acid.
  • Resorcinol is known to be a major product from pyrolysis of rutin.
  • the present invention provides combinations of bespoke tobacco blends with bespoke adsorbent filter additives, which result in a smoking article having a significant reduction in mainstream smoke constituents considered to be undesirable.
  • the present invention provides a smoking article comprising at least two of:
  • the smoking articles according to the invention have a reduction in at least 75%, preferably at least 90% and more preferably in all of the key constituents of mainstream smoke, as defined herein.
  • the so-called “key constituents” of MS referred to in connection with the present invention are those smoke constituents which have been identified in the literature as being undesirable (see, for example, The Scientific Basis of Tobacco Product Regulation: Report of a WHO Study Group (2007) WHO Technical Report Series 945, Geneva) and/or those whose yields have been analysed in the data provided herein (see, for example, Tables 6, 7 and 8).
  • the reduction is preferably determined using one of the smoking machine conditions set out in Table 3.
  • the reduced yields are measured under Health Canada Intense smoking machine conditions.
  • the reduction in yield of the key constituents is preferably at least 5% or at least 10% or more.
  • the smoking articles of the present invention include a tobacco blend comprising one or more tobaccos or tobacco grades with low TSNA and/or metal content, they further comprise two or more other technologies listed as (b) to (e).
  • FIG. 1 shows Table 2, setting out the cigarette construction details.
  • FIG. 2 shows Table 4, setting out the major constituent yields of test cigarettes to using different smoking machine condition.
  • FIG. 3 shows Table 5, setting out the blend metal and tobacco-specific nitrosamine contents.
  • FIG. 4 shows Table 6, setting out the MS yields of metals and TSNAs measured under Health Canada Intense smoking machine conditions.
  • FIGS. 5A , 5 B and 5 C show Table 7, setting out the MS yields of other smoke constituents measured under Health Canada Intense smoking machine conditions.
  • FIG. 6 shows Table 8, setting out the MS yields of carbonyl and miscellaneous volatile and vapour phase smoke constituents in control and triple stage filter EC measured under Health Canada Intense smoking machine conditions.
  • FIG. 7 shows Table 9, setting out the MS yields of carbonyl and miscellaneous volatile and vapour phase smoke constituents in control and dual stage filter EC measured under Health Canada Intense smoking machine conditions.
  • FIG. 8 shows Table 10, setting out the sidestream smoke yields under ISO smoking machine conditions
  • FIG. 9 shows a comparison of HCI machine toxicant yields from ECs (1 mg ISO) with those from published data sources.
  • FIG. 10 shows a comparison of HCI machine toxicant yields from ECs (6 mg ISO) with those from published data sources.
  • FIG. 11 shows a comparison of Total Toxicant Yields (TTY) between EC yields and published HCI yield data.
  • FIG. 12 shows a comparison of total yields from a subset of toxicants (TSY) between EC yields and published HCI yield data.
  • FIG. 13 shows a comparison of total normalised toxicant yields (NTT) between ECs and published HCI yield data.
  • FIG. 14 shows a summary of the process by which high activity polymer-derived carbon is prepared.
  • FIG. 15 shows Table 15, setting out the smoke and biomarker changes for test products as compared with a control cigarette.
  • FIG. 16 shows the in vivo study design.
  • FIGS. 17 and 18 show the results of the in vivo study.
  • FIG. 19 shows a smoking article design according to an embodiment of the invention.
  • ECs Three low toxicant tobacco blends, featuring a tobacco substitute sheet (TSS) or a tobacco blend treatment (BT), were combined with filters containing an amine functionalised resin material (CR20L) and/or a high activity carbon adsorbent (HAC) to generate three experimental cigarettes (ECs).
  • MS Mainstream smoke
  • HCI Health Canada Intense
  • Constituent yields from the ECs were compared with those from two commercial comparator (CC) cigarettes, three scientific control (SC) cigarettes and published data on 120 commercial cigarettes. The ECs were found to generate some of the lowest machine yields of constituents from cigarettes for which HCI smoke chemistry is available; these comparisons therefore confirm that the ECs generate reduced MS machine constituent yields in comparison to commercial cigarettes.
  • the first stage in the design of a cigarette-based PREP involved the development of technologies which reduce the yields of smoke constituents.
  • Experimental cigarettes ECs were assembled using these technologies and then assessed for their constituent yields using smoking machines; comparison to relevant control and reference products indicated the effectiveness of the cigarette design in generating reduced yields of constituents.
  • Those ECs which are found to reduce smoking machine measured yields of smoke constituents, in comparison to reference products, are termed “reduced machine-yield prototypes” (RMYPs).
  • the inventors have described different individual technological approaches to the reduction of constituents in cigarette smoke, one of which involves the selection of tobacco blend components to provide a blend with reduced levels of the known precursors of undesirable smoke constituents, two of which modify the tobacco and two of which modify the cigarette filter.
  • the tobacco blend (TB), the tobacco-substitute sheet material (TSS) and the tobacco blend treatment (BT) reduce the generation of constituents at source within the burning cigarette.
  • the two filter technologies an amine functionalised resin material (CR20L) and a high activity, polymer-derived, carbon adsorbent (HAC), remove volatile species from the smoke stream after formation. These technologies are discussed in greater detail below (in Section 2.1).
  • TSNAs smoke constituents
  • metals such as a metal
  • the levels of TSNAs may be reduced by using specific (such as lighter) tobacco blends and by selecting parts of the tobacco plant that are low in nitrate, a precursor of TSNAs.
  • specific tobacco blends such as lighter
  • parts of the tobacco plant that are low in nitrate, a precursor of TSNAs.
  • the person skilled in the art would be well aware of the ways in which the blending process may be adapted to provide a tobacco blend having these desired properties.
  • the tobacco blend may also comprise expanded tobacco, which is cut tobacco that has been expanded to reduce the mass of tobacco burnt in a cigarette.
  • expanded tobacco is cut tobacco that has been expanded to reduce the mass of tobacco burnt in a cigarette.
  • the expansion processes are similar to those used to make puffed rice snack food.
  • One process used is called dry-ice expanded tobacco (DIET) and involves permeating the tobacco leaf structure with liquid carbon dioxide before warming. The resulting carbon dioxide gas forces the tobacco to expand.
  • DIET dry-ice expanded tobacco
  • Some of the commercially available tobacco brands with low ISO tar yields use some proportion of expanded tobacco in the overall blend.
  • Treated tobacco blends are described herein which have been treated by processes that allow the removal of protein and polyphenols from tobacco, with a beneficial effect on the smoke toxicant yields.
  • the tobacco treatment was carried out on cut, flue-cured tobacco, and involved extraction of the tobacco with water followed by treatment with an aqueous protease enzyme solution. After treatment of the tobacco extract with adsorbents and concentration, the solubles were re-applied to the extracted tobacco.
  • the treated tobacco retained the structure of the original tobacco and was made into cigarettes using conventional cigarette making equipment, without the need for reconstitution into a sheet material.
  • Another approach to reducing smoke toxicant yields is to dilute the smoke with glycerol and it is proposed to include up to 60% of a glycerol-containing “tobacco substitute” sheet in cigarettes. Analysis of mainstream smoke from such experimental cigarettes showed reductions in yields of most measured constituents, other than some volatile species.
  • chemisorption is capable of removing high volatility aldehydes and HCN from mainstream cigarette smoke.
  • the material, manufactured by Mitsubishi Chemical Corporation is normally supplied in bead form in an aqueous environment and sold under the trade name Dialon®CR20 (hereafter referred to as CR20). This material offers the potential for the nucleophilic capture of aldehydes from mainstream smoke, and due to its weakly basic nature it may also be used for the removal of HCN from MS.
  • the amine-functionalised chelating resin material may be incorporated into the filter of a smoking article in a cavity, or dispersed (dalmation style) throughout the filter material (such as cellulose acetate) in the whole or a section of the filter.
  • a high activity material comprising spherical particles of polymer-derived carbon was prepared by a propriety process (Von Bl ⁇ dot over (u) ⁇ cher and De Ruiter 2004; Von Blucher et el 2006; Bschreibinger and Fichtner 2008) and was available from Blücher GmbH (Germany).
  • the polymer-derived material is approximately twice as effective, in general, at removing volatile cigarette smoke toxicants than the coconut shell-derived carbon commonly used in contemporary carbon filtered cigarette products.
  • the polymer-derived carbon performed well at both ISO and HCI smoking regimes and with regular and smaller circumference cigarettes. Limitations were also observed under higher flow-rate smoking conditions in the removal of acetaldehyde.
  • the high activity carbon may be incorporated into the filter of a smoking article in a cavity, or dispersed (dalmation style) throughout the filter material (such as cellulose acetate) in the whole or a section of the filter.
  • the present invention provides ECs made using combinations of the blend and filter technologies described.
  • the goal of the study of these ECs was to assess whether these technologies could be combined into prototypes which reduce machine yields of toxicants in comparison to commercial products, and have the potential to reduce exposure of smokers to toxicants in human smoking.
  • the ECs were constructed from combinations of blend and filter technologies that were developed to reduce specific chemical classes of smoke toxicants or their precursors in tobacco (Table 1). For each EC individual tobacco grades with low TSNA and metal contents were selected and blended to provide a low toxicant starting point for the design of experimental cigarettes.
  • the tobacco blend is subjected to an aqueous extraction step and the extract is subsequently passed through two stages of filtration to remove polyphenols and soluble peptides.
  • the residual tobacco solids are treated with protease to remove insoluble proteins.
  • the tobacco solids and filtered aqueous extract are re-combined.
  • the treatment process results in reduced smoke yields of phenolics, aromatic amines, HCN, and a number of other nitrogenous smoke constituents; however, there are also increases in the yields of formaldehyde and isoprene.
  • the tobacco material to be extracted may be strip, cut, shredded or ground tobacco.
  • the tobacco is shredded tobacco.
  • Other forms of tobacco may, however, be extracted using the methods described herein.
  • the tobacco material may be mixed with a solvent for extraction to form a slurry.
  • the solvent may be added to the tobacco material in a ratio of between 10:1 and 50:1, preferably between 20:1 and 40:1 and most preferably between 25:1 and 30:1 by weight. In a particularly preferred embodiment, the solvent is added to the tobacco material in a ratio of 27:1 by weight.
  • the solvent may be an organic solution, but preferably is an aqueous solution or is water.
  • the solvent is usually water, but it can also contain alcohols such as ethanol or methanol, or it can contain a surfactant.
  • Other solvents could be used, depending on the particular constituents to be extracted from the tobacco.
  • the extraction may be performed at 15-85° C., and preferably is performed at 65° C. It is preferable for the slurry to be continually stirred during extraction, such that the tobacco remains in suspension. Extraction should be performed for between 15 minutes and two hours. In a preferred embodiment, extraction is performed for approximately 20 minutes.
  • soluble tobacco components are removed from the tobacco material and enter solution. These include nicotine, sugars, some proteins, amino acids, pectins, polyphenols and flavours. Up to about 55% of the initial tobacco weight may become solubilised. It is important that the pectins in the tobacco fibre remain cross-linked throughout the extraction and treatment process in order to maintain the fibrous structure of the tobacco. Accordingly, calcium may be added to the solvent used to extract the tobacco and to any solutions used in the downstream processing procedures.
  • the slurry may be drained to allow the liquid filtrate (the “mother filtrate”) to be collected. Meanwhile, the insoluble tobacco residue may be further extracted by counter-current washing as it is conveyed, so that as many soluble constituents as possible are removed from the tobacco.
  • Fresh solvent may be applied to the tobacco and the filtrate (the “wash filtrate”) is collected.
  • the wash filtrate may be recycled by being applied to the incoming tobacco residue traveling on the belt at an upstream point.
  • the collection and upstream reapplication of wash filtrate to incoming tobacco residue may be repeated a number of times, preferably three, four or even five times.
  • the final wash filtrate that is collected at the head of the belt may be concentrated in those soluble tobacco constituents that have been removed from the tobacco residue as it travels the length of the filter.
  • the final wash filtrate may be further recycled by being added to fresh tobacco to form a tobacco slurry, ready for extraction. For example, the final wash filtrate may be added into the tobacco mix tank where a tobacco slurry is formed prior to extraction.
  • the extraction process may thus be a continual process in which fresh tobacco is extracted using recycled wash filtrate. Only at start-up of this extraction process is tobacco extracted with fresh solvent. Once the extraction process has begun, no fresh solvent is used in the extraction, but the solvent is solely made up of recycled wash filtrate.
  • the extract thus becomes more concentrated in soluble tobacco constituents.
  • These constituents include those that entered solution during primary extraction in the extraction tank (forming the mother filtrate), as well as those that entered solution during secondary extraction on the horizontal belt filter (forming the wash filtrate).
  • the final filtrate thus comprises both the mother and wash filtrates.
  • the tobacco residue that results after filtration is devoid of those constituents that are soluble in the solvent used for extraction.
  • the extracted tobacco may be squeezed at the end of filtration, so as to remove any excess liquid from it.
  • the extracted tobacco emanating from the horizontal belt filter is thus typically in the form of a dewatered mat.
  • the final filtrate hereinafter referred to as the tobacco extract, may be subsequently processed to remove those constituents not desired in the final tobacco product.
  • Undesirable constituents include proteins, polypeptides, amino acids, polyphenols, nitrates, amines, nitrosamines and pigment compounds.
  • the levels of constituents which may be considered desirable, such as sugar and nicotine, may, however, remain unaffected so that the flavour and smoking properties of the extracted tobacco are comparable to those of the original material.
  • the tobacco extract is treated to remove proteins, polypeptides and/or amino acids.
  • Up to 60% of the proteins contained in the original tobacco material may be removed using an insoluble adsorbent such as hydroxyapatite or a Fuller's Earth mineral such as attapulgite or bentonite.
  • the tobacco extract is preferably treated with bentonite, to remove polypeptides therefrom. Bentonite may be added to the extract in an amount of 2-4% of the weight of tobacco initially extracted.
  • the tobacco extract may be fed into a tank containing a slurry of bentonite in water.
  • a suitable slurry contains approximately 7 kg of bentonite in approximately 64 kg water (quantities per hour), for example, 7.13 kg bentonite in 64.18 kg water (quantities per hour).
  • the bentonite concentration should be high enough to substantially reduce the protein content of the tobacco extract, but not so high as to additionally adsorb nicotine from it.
  • Bentonite treatment may also be effective in the removal of pigment compounds found in tobacco extract which, if not removed, tend to darken the extract after concentration. When sufficient bentonite is used to treat the extract, the reduced amount of pigment compounds may result in a product that is not overly darkened in appearance.
  • the tobacco extract may be purified from the slurry by centrifugation and/or filtration.
  • the tobacco extract may also, or alternatively, be treated to remove polyphenols therefrom.
  • PVPP Polyvinylpolypyrrolidone
  • PVPP Polyvinylpolypyrrolidone
  • PVPP is an insoluble adsorbent for polyphenols, traditionally used in the brewing industry to remove polyphenols from beer.
  • PVPP in an amount of 5-10% of the weight of tobacco initially extracted may be added to the extract. This amount of PVPP is capable of removing between 50 and 90% of the polyphenols in solution.
  • the optimum pH for removal of polyphenols from the tobacco extract by PVPP is believed to be about 3.
  • the efficiency of adsorption by PVPP may therefore be increased by reducing the pH of the extract via the addition of a suitable acid, such as hydrochloric acid.
  • one or more enzymes may be added to the tobacco extract to degrade the polyphenols therein.
  • a suitable enzyme is laccase (urishiol oxidase).
  • laccase urishiol oxidase
  • the invention is not, however, limited to methods for removing only proteins and/or polyphenols from tobacco.
  • Alternative or additional enzymes, agents or adsorbents may be used to remove other undesirable tobacco constituents from the tobacco extract. Examples of further undesirable tobacco constituents that could be removed from the extract include nitrates, amines and nitrosamines.
  • a number of tanks may be set up in series, each one comprising a different enzyme, agent or adsorbent, in order for a chosen complement of undesirable constituents to be removed.
  • a single tank may contain a plurality of enzymes, agents or adsorbents so that the undesirable constituents may be removed min a single step.
  • a bentonite or PVPP holding tank could comprise one or more additional enzymes, agents or adsorbents so as to remove not only protein or phenols from the tobacco, but one or more further undesirable constituents also.
  • the extract is preferably concentrated to a solids concentration of between 20 and 50% by weight. Concentrations of up to 10% solids are most efficiently achieved using reverse osmosis. A further concentration to approximately 40% solids may be achieved by means of a falling film evaporator. Other methods of concentration can be used and will be known to a person skilled in the art.
  • the concentrated tobacco extract may be subsequently recombined with the extracted tobacco.
  • the tobacco having been extracted in an aqueous solution as discussed above, however, is preferably further extracted to remove one or more further undesirable constituents before being recombined with the concentrated tobacco extract.
  • the enzyme is a proteolytic enzyme for removal of protein from the tobacco.
  • the enzyme is preferably a bacterial or fungal enzyme and, more preferably, is an enzyme used commercially in the food and detergent industries.
  • the enzyme may be selected from the group consisting of SavinaseTM, NeutraseTM, EnzobakeTM and AlcalaseTM, which are all available from Novozymes A/S.
  • the proteolytic enzyme is preferably added to the tobacco in an amount of between 0.1 and 5% by weight of the tobacco material. For example, SavinaseTM may be added to the tobacco in an amount of approximately 1% by weight.
  • the tobacco may be reslurried in a solution of the chosen enzyme.
  • the ratio of water to tobacco in the slurry should be between 10:1 and 50:1, preferably between 20:1 and 40:1 and most preferably between 25:1 and 30:1 by weight. In a particularly preferred embodiment, the ratio of water to tobacco is 27:1 by weight.
  • the pH of the tobacco/enzyme mixture should be that which promotes optimal enzyme activity. Accordingly, it may prove convenient to feed the dewatered mat of tobacco into a tank in which the pH is adjusted, for example, by the addition of a base such as sodium hydroxide.
  • the pH-adjusted tobacco may then be fed into an enzyme dosing tank for mixing with the enzyme of choice.
  • the tobacco/enzyme mixture may subsequently be fed into a plug flow reactor, where the enzymic extraction is performed.
  • the enzymic extraction should be carried out at the temperature promoting optimal enzyme activity. Preferably, a narrow temperature range, such as 30-40° C., should be used to avoid denaturing the enzyme.
  • the optimum working conditions when SavinaseTM is the chosen enzyme are 57° C. and pH 9-11.
  • the enzymic extraction should be carried out for at least 45 minutes; any shorter duration is believed to be insufficient for a proteolytic enzyme to degrade tobacco proteins.
  • multiple enzymic extractions could be carried out if there are multiple constituents to be removed from the tobacco. These could be performed in series or multiple enzymes could be added to the tobacco in a single treatment step.
  • the enzyme prefferably included in the very first extraction step in the treatment process, rather than forming a subsequent separate extraction step.
  • the insoluble tobacco residue may be washed with a salt solution, preferably a sodium chloride solution, to rinse it free of enzyme. Salt rinsing may be performed in a sequential, counter-current fashion.
  • a salt solution preferably a sodium chloride solution
  • Salt and water rinsing may not be sufficient to remove all of the enzyme from the tobacco.
  • the washed tobacco may also be treated to deactivate any residual enzyme remaining in the tobacco following the salt and water rinses. This may be done by steam treating the tobacco sufficiently to deactivate the enzyme, but not so much that the tobacco loses its fibrous form. In an embodiment, steam treating is carried out at 98° C. for four minutes, but the residence time may be increased to 10 minutes or so if desired.
  • the tobacco may be heat treated to deactivate the enzyme, for example by microwaving or baking the tobacco.
  • the enzyme may be deactivated by chemical denaturation; steps should however be taken to remove the chemical from the tobacco.
  • the processed tobacco may then be recombined with the concentrated tobacco extract. Adding the treated extract back to the extracted tobacco ensures retention of water soluble flavour components of tobacco and nicotine in the final product. Recombination therefore results in a tobacco product that has similar physical form and appearance, taste and smoking properties to the original material, but with substantially reduced levels of protein, polyphenols or other constituent(s) of choice. Recombination may be achieved by spraying the tobacco extract onto the tobacco. The amount of the original extract being recombined with the processed tobacco depends upon the amount that was lost during treatment of the extract to remove selected constituents, and will vary from one type of tobacco to the next.
  • a standard drying process may be used to dry the treated tobacco, either before, during or after recombination with the treated tobacco extract.
  • the starting moisture content of the treated tobacco is typically approximately 70-80%. In a preferred embodiment, the moisture content after drying should be approximately 14%.
  • a heated dryer such as an apron dryer, may be used to reduce the starting moisture content in the tobacco to approximately 30%.
  • a second heated dryer, such as an air dryer, may then be used to further reduce the moisture content to approximately 14%.
  • the final dried product may subsequently be processed into a finished form, such as a sheet, which, when shredded, can form all or part of a cigarette filler.
  • a finished form such as a sheet
  • the concentration of remaining constituents per unit weight of tobacco is increased in the finished product compared to the original material.
  • These constituents include cellulose, which, together with sugars and starches, may produce harmful volatile materials such as acetaldehyde and formaldehyde in smoke when combusted.
  • TSS tobacco substitute sheet
  • NFDPM nicotine-free dry particulate matter
  • incorporation of glycerol into the smoke stream effectively results in a reduced contribution of the tobacco combustion products to the overall NFDPM value: this process is termed “dilution.”
  • the incorporation of TSS into cigarettes results in reductions in a wide range of smoke constituents, including both particulate and vapour phase toxicants.
  • In vitro toxicological tests showed reductions in the activity of smoke particulates in proportion to their glycerol content. Human exposure to nicotine was reduced by a mean of 18% as determined by filter studies and by 14% using 24 hour urinary biomarker analysis.
  • Smoke particulate exposures were reduced by a mean of 29% in filter studies and by similar amounts based on urinary 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol concentrations. These results show that reducing exposure to some smoke toxicants is possible using a tobacco substitute sheet.
  • a smoking article may be prepared including a tobacco substitute sheet material comprising a non-combustible inorganic filler material, an alginic binder and aerosol generating means.
  • the tobacco substitute sheet material comprises as the main components thereof, non-combustible inorganic filler, binder and aerosol generating means, with these three components together preferably comprising at least 85% by weight of the tobacco substitute sheet material, preferably greater than 90%, and even more preferably total about 94% or more by weight of the tobacco substitute sheet material.
  • the three components may even be 100% of the tobacco substitute sheet material.
  • the remaining components are preferably one or more of colourant, fibre, such as wood pulp, or flavourant, for example. Other minor component materials will be known to the skilled man.
  • the tobacco substitute sheet material is therefore a very simple sheet in terms of its constituents.
  • tobacco substitute sheet material means a material which can be used in a smoking article. It does not necessarily mean that the material itself will necessarily sustain combustion.
  • the tobacco substitute sheet material is usually produced as a sheet, then cut.
  • the tobacco substitute sheet material may then be blended with other materials to produce a smokable filler material.
  • the present invention further provides a smoking article comprising a wrapped rod of a smokable filler material, the smokable filler material consisting of a blend which incorporates tobacco substitute sheet material comprising a non-combustible inorganic filler, an alginic binder and aerosol generating means, the smoking article having an aerosol transfer efficiency ratio of greater than 4.0.
  • the aerosol transfer efficiency is measured as the percentage aerosol in the smoke divided by the percentage aerosol in the smokable filler material.
  • the aerosol transfer efficiency is greater than 5, and more preferably greater than 6.
  • the smokable filler material used in the smoking articles of the present invention may comprise a blend consisting of not more than 75% by weight of the tobacco substitute sheet material.
  • the inorganic filler material is present in the range of 60-90%, and is more preferably greater than 70% of the final sheet material.
  • the inorganic filler material is present at about 74% by weight of the final sheet material, but may be present at higher levels, for example, 80%, 85% or 90% by weight of the final sheet material.
  • the non-combustible filler advantageously comprises a proportion of material having a mean particle size in the range of 500 ⁇ m to 75 ⁇ m.
  • the mean particle size of the inorganic filler is in the range of 400 ⁇ m to 100 ⁇ m, and is more than 125 ⁇ m, and preferably more than 150 ⁇ m.
  • the mean particle size is at or about 170 ⁇ m, and may be in the range of 170 ⁇ m to 200 ⁇ m. This particle size is in contrast to that conventionally used for food grade inorganic filler materials in alternative tobacco products, namely a particle size of about 2-3 ⁇ m.
  • the range of particle size seen for each inorganic filler individually may be from 1 ⁇ m-1 mm (1000 ⁇ m).
  • the inorganic filler material may be ground, milled or precipitated to the desired particle size.
  • the inorganic filler material is one or more of perlite, alumina, diatomaceous earth, calcium carbonate (chalk), vermiculite, magnesium oxide, magnesium sulphate, zinc oxide, calcium sulphate (gypsum), ferric oxide, pumice, titanium dioxide, calcium aluminate or other insoluble aluminates, or other inorganic filler materials.
  • the density range of the materials is suitably in the range of 0.1 to 5.7 g/cm 3 .
  • the inorganic filler material has a density that is less than 3 g/cm 3 , and preferably less than 2.5 g/cm 3 , more preferably less than 2.0 g/cm 3 and even more preferably less than 1.5 g/cm 3 .
  • An inorganic filler having a density of less than 1 g/cm 3 is desirable.
  • a lower density inorganic filler reduces the density of the product, thus improving the ash characteristics.
  • one or more of the fillers may suitably be of a small particle size and another may be of a larger particle size, the proportions of each filler being suitable to achieve the desired mean particle size.
  • the static burn rate required in the finished smoking article may be achieved using an appropriate blend of tobacco and tobacco substitute sheet material in the smokable filler material.
  • the inorganic filler material is not in agglomerated form.
  • the inorganic filler material should require little pre-treatment, other than perhaps size gradation, before use.
  • the binder is present in the range of about 5-13%, more preferably less than 10% and even more preferably less than 8%, by weight of the final filler material.
  • the binder is about 7.5% by weight or less of the final sheet material.
  • the binder is a mixture of alginate and non-alginate binders, then preferably the binder is comprised of at least 50% alginate, preferably at least 60% alginate and even more preferably at least 70% alginate.
  • the amount of combined binder required may suitably decrease when a non-alginate binder is utilised.
  • the amount of alginate in a binder combination advantageously increases as the amount of combined binder decreases.
  • Suitable alginic binders include soluble alginates, such as ammonium alginate, sodium alginate, sodium calcium alginate, calcium ammonium alginate, potassium alginate, magnesium alginate, triethanol-amine alginate and propylene glycol alginate.
  • Other organic binders such as cellulosic binders, gums or gels can also be used in combination with alginic binders.
  • Suitable cellulosic binders include cellulose and cellulose derivatives, such as sodium carboxymethylcellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose or cellulose ethers.
  • Suitable gums include gum arabic, gum ghatti, gum tragacanth, Karaya, locust bean, acacia, guar, quince seed or xanthan gums.
  • Suitable gels include agar, agarose, canageenans, furoidan and furcellaran. Starches can also be used as organic binders.
  • Other suitable gums can be selected by reference to handbooks, such as Industrial Gums, E. Whistler (Academic Press). Much preferred as the major proportion of the binder are alginic binders. Alginates are preferred in the invention for their neutral taste character upon combustion.
  • the aerosol generating means is present in the range of 5-20%, more preferably is less than 15%, is even more preferably greater than 7% and even more preferably is greater than 10%.
  • the aerosol generating means is less than 13%.
  • the aerosol generating means is between 11% and 13%, and may advantageously be about 11.25% or 12.5%, by weight of the final sheet material.
  • the amount of aerosol generating means is selected in combination with the amount of tobacco material to be present in the blend comprising the smokable filler material of a smoking article. For example, in a blend comprising a high proportion of sheet material with a low proportion of tobacco material, the sheet material may require a lower loading level of aerosol generating means therein. Alternatively in a blend comprising a low proportion of sheet material with a high proportion of tobacco material, the sheet material may require a higher loading level of aerosol generating means therein.
  • Suitable aerosol generating means include aerosol forming means selected from polyhydric alcohols, such as glycerol, propylene glycol and triethylene glycol; esters, such as triethyl citrate or triacetin, high boiling point hydrocarbons, or non-polyols, such as glycols, sorbitol or lactic acid, for example.
  • aerosol forming means selected from polyhydric alcohols, such as glycerol, propylene glycol and triethylene glycol; esters, such as triethyl citrate or triacetin, high boiling point hydrocarbons, or non-polyols, such as glycols, sorbitol or lactic acid, for example.
  • a combination of aerosol generating means may be used.
  • An additional function of the aerosol generating means is the plasticising of the sheet material.
  • Suitable additional plasticisers include water.
  • the sheet material may suitably be aerated.
  • the cast slurry thereby forms a sheet material with a cellular structure.
  • the or a proportion of the aerosol generating means may be encapsulated, preferably micro-encapsulated, or stabilised in some other way.
  • the amount of aerosol generating means may be higher than the range given.
  • the smoking material comprises a colourant to darken the material and/or a flavourant to impart a particular flavour.
  • Suitable flavouring or colourant materials can include cocoa, liquorice, caramel, chocolate or toffee, for example. Finely ground, granulated or homogenised tobacco may also be used. Industry approved food colorants may also be used, such as E150a (caramel), E151 (brilliant black BN), E153 (vegetable carbon) or E155 (brown HT).
  • Suitable flavourants include menthol and vanillin, for example.
  • Other casing materials may also be suitable.
  • the presence of vermiculite or other inorganic filler materials may give a darker colour to the tobacco substitute sheet material.
  • the colourant is present from 0-10% and may be as much as 5-7% by weight of the final tobacco substitute sheet material.
  • the colourant is less than 7%, preferably less than 6% and more preferably less than 5% of the final tobacco substitute sheet material.
  • Much preferred is use of colourant at less than 4%, less than 3% and less than 2%.
  • Cocoa may suitably be present in a range of 0-5% and liquorice may be present in a range of 0-4%, by weight of the final tobacco substitute sheet material.
  • the colourant is cocoa or liquorice, for example, the minimum amount of cocoa to obtain the desired sheet colour is about 3% and for liquorice is about 2%, by weight of the final tobacco substitute sheet material.
  • caramel may suitably be present in a range of 0-5%, preferably less than about 2% by weight of the final tobacco substitute sheet material, and more preferably about 1.5%.
  • suitable colorants include molasses, malt extract, coffee extract, tea resinoids, St. John's Bread, prune extract or tobacco extract. Mixtures of colorants may also be used.
  • flavourants may also be added to alter the taste and flavour characteristics of the tobacco substitute sheet material.
  • a food dye is utilised in the alternative it is present at 0.5% by weight or less of the final tobacco substitute sheet material.
  • the colourant may alternatively be dusted into the sheet after sheet manufacture.
  • Fibres such as cellulose fibres, for example wood pulp, flax, hemp or bast could be added to provide the sheet material with one or more of a higher strength, lower density or higher fill value. Fibres, if added, may be present in the range of 0.5-10%, preferably less than 5% and even more preferably less than about 3% by weight of the final sheet material. Advantageously there is no fibrous material present in the sheet material, cellulosic or otherwise.
  • the tobacco substitute sheet material is a non-tobacco containing sheet. It shall be understood that at high levels of sheet material inclusion in the blend, e.g. at greater than 75% by weight of the blend, the combustibility of the blend is poor. This may be overcome by, for example, incorporating low levels of up to 5-10% granular carbon in the tobacco substitute sheet material.
  • the carbon is preferably not an agglomerated carbonaceous material, i.e. the carbon is not pre-treated by mixing with another material to produce an agglomerate.
  • the tobacco substitute sheet material is blended with tobacco material to provide smokable filler material.
  • the tobacco material components in the blend are high quality lamina grades.
  • the majority of the tobacco material is cut tobacco.
  • the tobacco material may comprise between 20-100% expanded tobacco of a high order expansion process, such as DIET for example.
  • the filling power of such material is typically in the range of 6-9 cc/g (see GB 1484536 or U.S. Pat. No. 4,340,073 for example).
  • the blend comprises ⁇ 30% of other blend components apart from lamina, the other blend components being stem cut rolled stem (CRS), water treated stem (WTS) or steam treated stem (STS) or reconstituted tobacco.
  • the other components comprise ⁇ 20%, more preferably ⁇ 10% and even more preferably ⁇ 5% of the final weight of the tobacco material.
  • a smoking article according to the invention comprises tobacco material being treated with aerosol generating means.
  • the tobacco material may be treated with aerosol generating means, but this is not essential for all blends of tobacco material and sheet material.
  • the amount of aerosol generating means added to the tobacco is in the range of 2-6% by weight of the tobacco.
  • the total amount of aerosol generating means in the blend of tobacco material and sheet material after processing is advantageously in the range of 4-12% by weight of the smokable material, preferably less than 10% and preferably more than 5%.
  • the polymer-derived, high activity carbon granules used in the dual and triple stage filters possesses a pore structure different from the carbon commonly used in commercial cigarettes, which is typically derived from coconut shells. As a result it has superior adsorption characteristics for a range of volatile smoke toxicants.
  • the spherical particle shape polymer-derived carbon was prepared by a propriety process (Von Blucher and De Ruiter 2004, Von Bl ⁇ dot over (u) ⁇ cher et el 2006, Bohringer and Fichtner 2008), as depicted in FIG. 14 .
  • the polymer-derived active carbon is produced using a batch process with indirect heated rotary kilns, under reduced pressure in an ineit atmosphere. After preparation of the spherical polymer feedstock the material is thermally stabilised using an excess of oleum. Subsequently, the material is slowly heated to 500° C., resulting in the release of predominantly SO 2 and H 2 O and the carbonisation of the polymer.
  • the resulting carbon has an initial pore system which is not accessible for typical adsorptives.
  • the material is further heated to 900 to 1000° C. for activation with oxidising agents (steam).
  • steam oxidising agents
  • This establishes a pore system consisting mainly of micropores with pore sizes between 0.7 and 3 nm.
  • Subsequent activation with CO 2 leads to the formation of predominantly larger mesopores in the range of 3 to 80 nm.
  • Combining the steam and CO 2 activation steps offers a flexible strategy for producing desired pore characteristics.
  • the polymer-derived carbon being a synthetic material, possesses a much more closely defined spherical shape, together with a more uniform particle size.
  • the polymer derived material possesses a lower density, and has a lower ash content reflecting the synthetic nature of the polymer feedstock in comparison to a natural coconut shell as starting materials for the carbonization processes.
  • DIAION® CR20 is a commercially available type of amine-functionalised resin bead which may be used in the present invention (manufactured by Mitsubishi Chemical Corporation). It has polyamine groups as chelating ligands which are bonded onto a highly porous crosslinked polystyrene matrix. CR20 shows large affinity for transition metal ions. The exact type of amine groups produced by functionalization cannot be precisely controlled and several different types could be present on the resins.
  • CR20C Commercial grade CR20
  • CR20L Commercial grade CR20
  • This material possessed a bead size of 600 mm, density of 0.64 g/cm 3 , a 15% by weight water content, and total exchange capacity of 0.92 meq/cm 3 .
  • CR20 Various other types of CR20 are made by Mitsubishi Chemical Corporation, to including CR20D and CR20HD. All of the different types or grades of the ion-exchange resin are encompassed by the term CR20 as used herein.
  • Some CR20 beads are provided in water and, to make them suitable for use in a cigarette filter application, it may be necessary to remove at least some of the water. In one embodiment, the water is removed and the material is dried to approximately 15% or less moisture. In an alternative embodiment, a higher moisture content may be acceptable in the filter of smoking articles.
  • CR20 including specifically CR20L, may be incorporated into cigarette filters.
  • CR20L offers superior reductions for HCN, formaldehyde and acetaldehyde.
  • carbon is more efficient than CR20L in removing other volatile constituents from a smoke stream.
  • Cigarettes were constructed using these technologies targeting ISO NFDPM (tar) yields of 1 and 6 mg.
  • the commercial comparator products were of similar machine smoked constituent yields to the market leading brands at 1 mg and 6 mg (ISO) from Germany in 2007-8.
  • BAT group comparator cigarettes were chosen, rather than the actual market leading brands, in order that full information was available on blend and cigarette design characteristics, and to allow product masking to be conducted for human sensory and exposure evaluations. Samples of both commercial cigarettes were therefore manufactured specially for these studies, without brand marking or other identification, in order to support human smoking studies.
  • the experimental cigarette BT1 combined a Virginia style tobacco blend containing BT treated tobacco (75.4% treated Virginia tobacco, with 4.3% Oriental tobacco and 20.3% untreated Virginia tobacco) with a filter containing a CR20 stage (to reduce formaldehyde, acetaldehyde and HCN yields) and a polymer-derived, high activity carbon filter containing stage (to reduce yields of isoprene and other volatile toxicants).
  • the target NFDPM yield from this cigarette was 1 mg under ISO machine smoking conditions.
  • the experimental cigarette TSS1 was also designed to yield 1 mg of NFDPM under ISO smoking machine conditions and was based on an US style blend containing TSS (a blend of Virginia, Burley and Oriental tobaccos, with the inclusion of approximately 20% TSS and the same filter used in experimental cigarette BT1.
  • the experimental cigarette TSS6 also used 20% TSS in a different US style blend, and was designed to give an NFDPM yield of 6 mg under ISO machine smoking conditions.
  • a different filter construction was used with this cigarette: a dual segment filter containing 80 mg of the high activity carbon interspersed amongst CA fibres adjacent to the tobacco rod with a CA stage at the mouth end.
  • the commercial comparator cigarette CC1 contained a US-blended style of tobacco, including some Maryland tobacco.
  • the design features of the three ECs are summarised and compared with control cigarettes and commercial comparators in Table 2 [shown in FIG. 1 ]. Both commercial comparator cigarettes used single stage cellulose acetate filters.
  • the three “scientific control” (SC) cigarettes had identical construction to the relevant experimental cigarettes BT1, TSS1 and TSS6, with the exception that the filter used in each control cigarette was a single stage 27 mm CA filter without additional filter adsorbent media.
  • Table 2 shows that the cigarette constructions of BT1 and CC1 were very similar, with well matched filter ventilation and paper permeability. There were slight differences in tobacco density and filter pressure drop (the draw resistance or impedence to flow of the filter), with BT1 higher than CC1 for both parameters. The cigarette constructions of TSS1 and CC1 were also very similar. The filter pressure drop was higher from TSS1 than the commercial control, but both tobacco density and filter pressure drop were higher for CC1. For TSS6 and CC6 less filter ventilation was used than with the 1 mg (ISO) products. Comparing the two 6 mg (ISO) products showed slightly higher tobacco densities, pressure drop values and slightly lower filter ventilation for TSS6.
  • cigarettes Prior to smoke chemistry analysis, cigarettes were conditioned according to the specifications of ISO 3402, 1999. Routine chemical analyses were performed according to the smoking conditions specified in ISO 4387, 2000 (i.e., a 35 ml puff of 2 seconds duration taken every 60 seconds, abbreviated as 35/2/60) and ISO 3308, 2000 which was developed for NFDPM and nicotine analysis.
  • the SS emissions from the ECs were also measured using the ISO smoking profile. The tests were conducted on a comparative basis with two commercial cigarettes and with three scientific control cigarettes. As a final step, the overall performance of the ECs was assessed both in comparison to previously published MS yield data on cigarettes from several countries and as ratios of specific toxicant yields to nicotine yields.
  • the yields of the major smoke constituents (NFDPM, nicotine and CO) and glycerol under four smoking machine conditions are shown in Table 4 (shown in FIG. 2 ). Glycerol measurements are included in this table because it has been incorporated into the tobacco-substitute sheet used in the ECs TSS1 and TSS6, to dilute other smoke constituents in the smoke particulate phase.
  • Table 4 shows that BT1 and CC1 were well matched across the four smoking regimes for MS NFDPM and nicotine yields, but that BT1 had lower CO yields than CC1.
  • TSS1 and CC1 were well matched across the four smoking regimes for NFDPM and nicotine yields but TSS1 had lower CO yields than CC1.
  • the higher glycerol yield from TSS1 is consistent with the intended dilution effect due to the glycerol content of TSS.
  • the MS NFDPM and nicotine yields from TSS6 and CC6 were well matched across the four smoking regimes, other than higher CO yields from CC6 and the expected higher glycerol yields from TSS6.
  • the 47 toxicants quantified in this work were also measured under all of the smoking machine conditions shown in Table 3, except that data for the ECs TSS1 and BT1 under ISO machine smoking conditions were not collected because preliminary runs showed the yields of many constituents to be below the LOQ for the methods.
  • the machine smoked yields of these toxicants generally followed the rank order noted for NFDPM, nicotine and CO shown in Table 4 and so, for the remainder of this paper, only the yields obtained under HCI conditions are described. Some consistent exceptions to the general yield trend were observed.
  • HCI smoking regime in this work represents the strictest test of the ECs and the commercial comparator cigarettes. Although these smoking conditions inactivate a design feature used in the ECs and commercial cigarettes (filter ventilation), they address criticism of the machine yield values obtained from ventilated cigarettes.
  • Blend nitrosamine content of BT1 was lower than US-blended commercial comparator CC1, as has been seen previously in comparison of Virginia and US-blended cigarettes.
  • the MS yields of nitrogenous constituents were expected to be lower from BT1 than from CC1 for two reasons: first the tobacco treatment reduces precursors of nitrogenous smoke compounds; and, second, Virginia style tobaccos typically generate lower yields of nitrogenous smoke constituents than US-blended cigarettes.
  • yields of the TSNAs were statistically significantly (83-96%) lower from BT1 than from CC1 (Table 6); aromatic amine yields from BT1 were 26-57% lower than from CC1 (Table 7); and the yields of other nitrogenous compounds from BT1 were also substantially lower (HCN by 82%, NO by 79%, ammonia by 75%, pyridine by 97%, quinolene by 67% and acrylonitrile by 69%) than the respective yields from CC1 (Table 7).
  • the BT process also reduces blend polyphenol levels and so reductions in MS phenols yields would be expected; however, higher yields of phenolics are generally expected from Virginia style products than from US-blended products and this tobacco type difference could mitigate any reductions from the BT process.
  • Comparison between phenolic compound yields from CC1 and from BT1 showed a mixed picture: phenol, p-cresol and resorcinol yields were lower from BT1, whereas m-cresol, catechol and hydroquinone yields were higher from BT1 (Table 7).
  • the BT process does not influence benzo(a)pyrene yields and analysis of PAHs in the current study showed comparable yields from BT1 and CC1 for fluorene, phenanthrene, pyrene and benzo(a)pyrene.
  • Lower carbonyl yields (26 to 74% lower) were obtained from cigarette BT1, apart from formaldehyde, which showed a higher (41%) yield from BT1.
  • the volatile hydrocarbon yields from BT1 were lower, with a range from 21 to 78% for isoprene, benzene, toluene and naphthalene, when compared to the respective constituent yields from CC1; however, the 1,3-butadiene yield was 35% higher from BT1 compared to CC1.
  • the 1,3-butadiene yields from CC1 are lower than expected under the HCI regime, and this observation may therefore be unreliable. Most of the observed differences in volatile constituent yields are consistent with the use of an effective vapour phase adsorbent in the filter of BT1. Formaldehyde yields are driven in part by sugar levels, which are normally higher in Virginia blends than in US blends.
  • Formaldehyde yields are also increased by the blend treatment process. Hence the higher formaldehyde yields from BT1 are understandable on the basis of knowledge of formaldehyde generation in cigarettes.
  • the apparent higher yield of 1,3-butadiene from BT1 is possibly due to an error in the yield measurement of CC1 as there is no obvious mechanistic factor to support this difference (the tobacco treatment process does not give statistically significant changes in 1,3-butadiene yields and the use of the vapour phase adsorbent in BT1 filters should result in lower 1,3 butadiene yields from BT1).
  • the contribution of the blend and the selective filter used in BT1 to the overall reductions in smoke toxicants are addressed in Section 3.2 and the results are consistent with the higher yield values for formaldehyde observed in Table 7 being due to blend chemistry factors.
  • the overall blend metal content was higher in TSS1 than in CC1 for some metals (arsenic, chromium and nickel), lower for cadmium content and not different for other metals (Table 5).
  • the TSS contains a high proportion of chalk, which would contribute some portion of the blend metals.
  • Analysis of the TSS showed a higher level of chromium and comparable or lower levels of the other measured metals than the TSS1 blend.
  • the higher chromium content of TSS1 than CC1 most likely reflects the inclusion of TSS material in the blend; whereas, the higher arsenic and nickel levels were most likely due to the different tobacco types used in the blend.
  • the blend metal contents of TSS6 and CC6 were similar, other than statistically significantly higher chromium and cadmium blend levels in TSS6.
  • the higher chromium level was most likely due to the high inorganic content of the TSS; whereas, the higher cadmium content most likely reflects a difference in the tobacco types used between the two blends.
  • the MS yields of cadmium and chromium, determined under HCI smoking machine conditions, were not elevated in TSS6 compared to CC6 (Table 6), which again supports the contention that the chemical form of these metals was different between the EC and the commercial comparator, and less likely to transfer into MS.
  • the three data sources above were compiled into one dataset to provide a reference set of global cigarette yield data with which to compare the toxicant yields from the ECs described in this study.
  • the full dataset was truncated as follows: first, arsenic, methyl ethyl ketone, nickel and selenium yields were removed from the dataset because yields were not provided by all three sources; second, a number of brands were removed from the dataset due to incomplete, duplicated or erroneous data (two brands in the HC dataset appear to have erroneous (exchanged) toluene and styrene yields; tar, nicotine and CO yields were not provided in the HC dataset for Gitanes KS, and multiple instances of the same yield data were observed in the HC dataset).
  • the median value was normalised to 100 for each toxicant, and the yields of toxicants scaled against this value of 100. Totaling the scaled values for all toxicants gave a normalised toxicant total (NTT) for each brand.
  • NTT normalised toxicant total
  • the TTY, TSY and NTT values for the ECs are compared to and ranked against the values for all of the brands in the commercial dataset in FIGS. 10 to 12 . The comparisons show, with each of the approaches, that the ECs were at the low end of the ranking order.
  • the 1 mg ECs were found to have the lowest total toxicant yields under each of the three approaches, and the 6 mg EC was also lower than any of the commercial brands for the TSY and NTT.
  • TTY analysis two of the 120 commercial products have lower TTY values than TSS6 due to their lower tar and nicotine values.
  • the commercial comparator cigarettes CC1 and CC6 were also reasonably low in total toxicant values in comparison with the dataset of commercial brands, falling around the lower quartile of values.
  • SS yields for the expanded list of smoke constituents were measured, under ISO smoking parameters.
  • the ISO smoking parameters were chosen because they generate higher SS yields than any of the other smoking regimes.
  • the quantity of sidestream smoke can be expected to be dependent on the amount of tobacco consumed in the static burn or smoulder phase of cigarette smoking.
  • the SS yield results are presented as a comparison between the ECs BT1 and TSS1 and the commercial cigarette CC1, in Table 10.
  • the cigarettes are of king size format with a filter length of 27 mm and a tobacco rod of 56 mm.
  • the prototypes have a tobacco rod comprising a mix of lamina, Expanded Tobacco and non tobacco sheet or modified tobacco.
  • Conventional cigarette paper is used to form the tobacco rod and ensure the achievement of burn rate and subsequent puff number.
  • the filter for two of the prototypes is a triple filter composed of a CA mouth end segment (7 mm in length), a CA central segment containing CR20 HD ion exchange resin (10 mm in length) and a dalmation style tobacco end segment containing carbon beads with an engineered microstructure (10 mm in length).
  • the filter for the third prototype is a dual filter composed of a CA mouth end segment (15 mm in length) and a dalmation style tobacco end segment containing high activity, polymer-derived carbon beads (12 mm in length).
  • the prototype cigarettes were manufactured to give ISO NFDPM yields of 1 (T562 and H671) and 6 mg (F752). The specification of the prototype cigarettes is described in more detail in Tables 11 to 13.
  • Smoke chemistry indicated good reductions in toxicants compared to control cigarettes of conventional design, see Table 15 ( FIG. 15 ).
  • the non-smoker group provided an indication of background levels of biomarkers.
  • FIG. 17 shows the biomarker results for Group 2 who switched from control cigarette CC6 (Day 14) to test cigarette TSS6 (Day 41). * denotes a statistically significant difference (p ⁇ 0.01) between day 14 and 41 results. Non-smoker biomarker levels are shown for reference. All non-smoker levels were significantly lower than day 14 values
  • FIG. 18 shows the biomarker results for Group 4, who switched from control cigarette CC1 (Day 14) to test cigarette TSS1 (Day 41) and Group 5, who switched from control cigarette CC1 (Day 14) to test cigarette BT1 (Day 41).
  • the blend treated tobacco is a tobacco with reduced protein and polyphenol content which results from the following process: (i) aqueous extraction of a tobacco; (ii) passing the aqueous extract through a clay and a resin; (iii) treatment of the fibre with an enzyme and deactivation; and (iv) recombining the extract and fibre and drying.
  • the leaf is tobacco as is used in conventional commercial cigarettes.
  • the expanded tobacco is a tobacco that has been expanded using a supercritical CO 2 process which is used in conventional commercial cigarettes.
  • the filter 3 is attached to the tobacco rod 2 by a tipping paper which is a non-porous paper.
  • the filter 3 is made up of three sections, as indicated by the inset.
  • the section 4 adjacent the end of the tobacco rod is 10 mm in length and contains 60 mg of synthetic carbon. This is a form of carbon which has an engineered porous structure.
  • the middle section 5 is 10 mm in length and contains 20 mg (that is, 2 mg/mm) of CR20HD, an amine functionalized resin having a water content of 12-17%.
  • the mouth-end section 6 of the filter is 7 mm in length. This may comprise, for example, cellulose acetate tow as used in conventional commercial cigarettes.
  • the smokable material may further include tobacco substitute sheet.
  • tobacco substitute sheet is a chalk-based sheet containing glycerol that reduces the quantity of tobacco in a cigarette when incorporated into the tobacco blend.
  • the tobacco substitute sheet may replace some or all of any or all of the different materials making up the smokable material of the smoking article design discussed above.
  • CR20D is an amine functionalized resin having a water content of 0-5%.
  • CR20D may partially or completely replace the CR20HD used in the design discussed above.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
  • Manufacture Of Tobacco Products (AREA)
US13/985,869 2011-02-17 2012-02-16 Smoking articles Abandoned US20140020699A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GBGB1102785.1A GB201102785D0 (en) 2011-02-17 2011-02-17 Smoking articles
GB1102785.1 2011-02-17
GB1113614.0 2011-08-08
GBGB1113614.0A GB201113614D0 (en) 2011-08-08 2011-08-08 Smoking articles
PCT/GB2012/050349 WO2012110819A1 (en) 2011-02-17 2012-02-16 Smoking articles

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US20140020699A1 true US20140020699A1 (en) 2014-01-23

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EP (1) EP2675302A1 (ru)
JP (2) JP2014506470A (ru)
KR (1) KR20140004754A (ru)
CN (1) CN103347408A (ru)
AR (1) AR085295A1 (ru)
AU (1) AU2012219223B2 (ru)
BR (1) BR112013020509A2 (ru)
CA (1) CA2824731C (ru)
CL (1) CL2013002357A1 (ru)
MX (1) MX2013009504A (ru)
RU (1) RU2013142175A (ru)
TW (1) TW201247115A (ru)
WO (1) WO2012110819A1 (ru)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10034988B2 (en) 2012-11-28 2018-07-31 Fontem Holdings I B.V. Methods and devices for compound delivery
US10194693B2 (en) 2013-09-20 2019-02-05 Fontem Holdings 1 B.V. Aerosol generating device
WO2021224600A1 (en) * 2020-05-05 2021-11-11 Nicoventures Trading Limited Aerosol generating material
WO2021224604A1 (en) * 2020-05-05 2021-11-11 Nicoventures Trading Limited Aerosol generating material

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201221199D0 (en) * 2012-11-26 2013-01-09 British American Tobacco Co Treatment of tobacco material
GB201221207D0 (en) * 2012-11-26 2013-01-09 British American Tobacco Co Treatment of tobacco material
RU2522082C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной табачной мешки
RU2522087C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной табачной мешки
RU2521802C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной соусированной табачной мешки
RU2530395C1 (ru) * 2013-05-13 2014-10-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кубанский государственный технологический университет Способ получения ароматизированной соусированной табачной мешки
RU2522066C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной табачной мешки
RU2521799C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной табачной мешки
RU2521805C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной соусированной табачной мешки
RU2521804C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной соусированной табачной мешки
RU2522077C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной табачной мешки
RU2521801C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной соусированной табачной мешки
RU2521817C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной табачной мешки
RU2521800C1 (ru) * 2013-05-13 2014-07-10 Олег Иванович Квасенков Способ производства ароматизированной соусированной табачной мешки
RU2530400C1 (ru) * 2013-07-24 2014-10-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кубанский государственный технологический университет Способ получения ароматизированной табачной мешки
RU2530403C1 (ru) * 2013-07-24 2014-10-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кубанский государственный технологический университет Способ получения ароматизированной соусированной табачной мешки
RU2530402C1 (ru) * 2013-07-24 2014-10-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кубанский государственный технологический университет Способ выработки ароматизированной соусированной табачной мешки
WO2015055567A1 (en) 2013-10-14 2015-04-23 Philip Morris Products S.A. Heated aerosol-generating articles comprising improved rods
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GB201711534D0 (en) * 2017-07-18 2017-08-30 British American Tobacco Investments Ltd Tobacco constituent releasing components
CN109007958B (zh) * 2018-09-13 2021-05-25 云南中烟工业有限责任公司 一种烟草烘烤香物质及其制备方法与应用
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GB201917917D0 (en) * 2019-12-06 2020-01-22 British American Tobacco Investments Ltd Tobacco composition
AU2020405996B2 (en) * 2019-12-17 2024-02-29 Philip Morris Products S.A. Aerosol-forming substrate with nitrogen-containing nucleophilic compound
CN117794401A (zh) * 2021-07-08 2024-03-29 日本烟草产业株式会社 含纸的烟草段

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040231684A1 (en) * 2003-05-20 2004-11-25 Zawadzki Michael A. Smoking article and smoking article filter
US20060130862A1 (en) * 2002-04-27 2006-06-22 British American Tobacco Smoking articles and smokable filler materials therefor
US20070258879A1 (en) * 2005-12-13 2007-11-08 Philip Morris Usa Inc. Carbon beads with multimodal pore size distribution
US20110005534A1 (en) * 2007-09-28 2011-01-13 Vector Tobacco, Inc. Reduced risk tobacco products and use thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1031068B (it) 1974-02-05 1979-04-30 Airco Inc Metodo e apparecchiatura per la espansione di sostanze or ganiche
US4340073A (en) 1974-02-12 1982-07-20 Philip Morris, Incorporated Expanding tobacco
US6779529B2 (en) * 2001-08-01 2004-08-24 Brown & Williamson Tobacco Corporation Cigarette filter
JP4882588B2 (ja) * 2005-08-10 2012-02-22 三菱化学株式会社 タバコフィルター用ガス吸着剤
DE202006016898U1 (de) * 2006-10-12 2007-11-22 BLüCHER GMBH Hochleistungsadsorbentien auf der Basis von Aktivkohle mit hoher Mikroporosität
US20100206317A1 (en) * 2007-09-28 2010-08-19 Vector Tobacco, Inc. Reduced risk tobacco products and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060130862A1 (en) * 2002-04-27 2006-06-22 British American Tobacco Smoking articles and smokable filler materials therefor
US20040231684A1 (en) * 2003-05-20 2004-11-25 Zawadzki Michael A. Smoking article and smoking article filter
US20070258879A1 (en) * 2005-12-13 2007-11-08 Philip Morris Usa Inc. Carbon beads with multimodal pore size distribution
US20110005534A1 (en) * 2007-09-28 2011-01-13 Vector Tobacco, Inc. Reduced risk tobacco products and use thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10034988B2 (en) 2012-11-28 2018-07-31 Fontem Holdings I B.V. Methods and devices for compound delivery
US10194693B2 (en) 2013-09-20 2019-02-05 Fontem Holdings 1 B.V. Aerosol generating device
WO2021224600A1 (en) * 2020-05-05 2021-11-11 Nicoventures Trading Limited Aerosol generating material
WO2021224604A1 (en) * 2020-05-05 2021-11-11 Nicoventures Trading Limited Aerosol generating material

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NZ612998A (en) 2015-03-27
KR20140004754A (ko) 2014-01-13
AU2012219223B2 (en) 2015-07-23
JP3201449U (ja) 2015-12-10
CA2824731C (en) 2016-02-09
JP2014506470A (ja) 2014-03-17
CN103347408A (zh) 2013-10-09
RU2013142175A (ru) 2015-03-27
AR085295A1 (es) 2013-09-18
EP2675302A1 (en) 2013-12-25
CA2824731A1 (en) 2012-08-23
CL2013002357A1 (es) 2013-11-08
BR112013020509A2 (pt) 2016-10-18
WO2012110819A1 (en) 2012-08-23
TW201247115A (en) 2012-12-01
AU2012219223A1 (en) 2013-08-01

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