EP2937001A1 - Aluminosilicate sab-15 utilisé comme additif pour la réduction des composés toxiques et cancérigènes présents dans la fumée du tabac - Google Patents

Aluminosilicate sab-15 utilisé comme additif pour la réduction des composés toxiques et cancérigènes présents dans la fumée du tabac Download PDF

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Publication number
EP2937001A1
EP2937001A1 EP13865181.5A EP13865181A EP2937001A1 EP 2937001 A1 EP2937001 A1 EP 2937001A1 EP 13865181 A EP13865181 A EP 13865181A EP 2937001 A1 EP2937001 A1 EP 2937001A1
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EP
European Patent Office
Prior art keywords
tobacco
additive
sba
toxic
aluminosilicate
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Withdrawn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
EP13865181.5A
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German (de)
English (en)
Other versions
EP2937001A4 (fr
Inventor
Antonio Francisco Marcilla Gomis
Amparo GÓMEZ SIURANA
María Isabel BELTRÁN RICO
Isabel MARTÍNEZ CASTELLANOS
Deseada BERENGUER MUÑOZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidad de Alicante
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Universidad de Alicante
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Publication date
Application filed by Universidad de Alicante filed Critical Universidad de Alicante
Publication of EP2937001A1 publication Critical patent/EP2937001A1/fr
Publication of EP2937001A4 publication Critical patent/EP2937001A4/fr
Withdrawn legal-status Critical Current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
    • A24B15/28—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

  • the present invention relates to the use of aluminosilicates, particularly SAB-15, as an additive for reducing the toxic and carcinogenic compounds present in tobacco smoke.
  • mainstream corresponds to smoke which is generated when burning the tobacco and goes through the cigarette from the lit end to leave through the filter end.
  • Patent document EP2092838 describes the use of certain zeolites and other aluminosilicates and mesoporous solids, in different forms and with various compositions, adding them and mixing them directly with tobacco in the form of powder, without having to use any type of special technology or adhesive, as tobacco additives for drastically reducing the amount of toxic and/or carcinogenic compounds that are generated when smoking and are found in the mainstream and sidestream of tobacco smoke.
  • Patent application US2005133052 describes the use of mesoporous aluminosilicate molecular sieves modified with aminoalkylsilyl groups in filters for retaining specific compounds.
  • Patent application US20050133051 proposes the use of filters containing materials formed by a porous alumina or aluminosilicate matrix containing adsorbent activated carbon and zeolite particles for selectively removing specific compounds from tobacco smoke.
  • Patent application WO 2004110183 A2 describes filters containing a catalyst dispersed in a porous aluminosilicate matrix, for the purpose of converting the CO in cigarette smoke into CO 2 .
  • Patent application WO 2004086888 describes a filter including at least 2 porous monolithic adsorbent segments that are capable of selectively removing components from the smoke stream, and a mixing segment between both.
  • Patent application CN 102242527 proposes the use of a cigarette paper containing a microencapsulated adsorbent which allows reducing the content of toxic substances in tobacco smoke.
  • the different adsorbent materials used include, among others, one or more oxides of Cu, Mn, Zn, Fe, Al, Ti, etc., as well as composite materials where the oxides are supported by zeolites, MCM-48, or SBA-15.
  • Patent application WO 2011015861 proposes the use of a filter containing an adsorbent material which is capable of removing phenol from tobacco smoke.
  • the material is formed by a porous solid (with micro- or mesopores) containing an adsorption promoter which is a hydrophilic organic proton donor or acceptor substance.
  • Patent application CN 101433818 claims the use of a mesoporous material consisting of SBA-15 for adsorbing particulate matter, tar, phenol and nitrosamines in mainstream tobacco smoke.
  • Patent applications US2006130855-A1 and US2005133047-A1 explicitly mention the possibility of using SBA-15-based substrates.
  • Different types of equipment that facilitate and can even improve incorporating the additive to fine-cut tobacco such as for example, speed mixers or orbital mixers, fluidized beds and entrained beds, among others, as well as sieves for separating and recirculating the additive that did not attach onto tobacco fibers, can be used for preparing cigarettes.
  • the present invention relates to aluminosilicate SAB-15 or the acidic or sodium forms thereof, interchanged with Fe, Na, K, Ca, Ce, Zr, the oxides of Fe, Na, K, Ca, Ce, Zr and mixtures thereof as an additive for reducing the toxic and carcinogenic substances present in tobacco smoke, both in mainstream and sidestream tobacco smoke, particularly, toxic substances such as tars, carbon monoxide and nicotine, as well as the components of the liquids and gases generated when burning tobacco in the smoking process.
  • the aluminosilicate SAB-15 has a spherical morphological shape, tubular morphological shape or rod shape, or any other shape obtained by various synthesis processes and different degrees of acidity obtained by incorporating aluminum in its structure, in a pressurized autoclave that is under stirring or standing still and under reflux at different temperatures, and where it has been interchanged with the cations of metals: Fe, Na, K, Ca, Ce, Zr.
  • the aluminosilicate SAB-15 has a pore size comprised between 4-10 nm and a mesopore volume preferably greater than 2.2 cm 3 /g, although the mesopore volume can be less.
  • the present invention relates to a mixture comprising dry tobacco and aluminosilicate SAB-15, or the acidic or sodium forms thereof, interchanged with Fe, Na, K, Ca, Ce, Zr, the oxides of Fe, Na, K, Ca, Ce, Zr and mixtures thereof as an additive and not comprising adhesive agents.
  • Dry tobacco refers to a bright tobacco, dark tobacco, fine-cut tobacco, roll-your-own tobacco, pipe tobacco and any other type of tobacco that can be smoked.
  • agent adhesive refers to compounds with the capacity to bind or adhere to tobacco or substances incorporated therein, for example, guar gum, alginates or other compounds having similar characteristics.
  • the additive is at a concentration comprised between 0.5-10% by weight with respect to the dry tobacco, in another more particular aspect, the additive is at a concentration comprised between 2-7% by weight with respect to the dry tobacco.
  • Example 1 Method for synthesizing the different materials
  • the SBA-15 was synthesized according to the following method: a pluronic P 123 solution in acidic medium was first prepared to which an amount of tetraethyl orthosilicate (TEOS) was added. The resulting solution was aged under stirring at 38°C for 20 hours. It was then transferred to an autoclave with a Teflon liner and kept at 100°C for 24 hours. The resulting suspension was washed with water, dried overnight at 100°C and finally burned at 550°C for 5 hours ( F. Zhang, Y. Yan, H. Yang, Y. Meng, C. Yu, B. Tu, D. Zhao, Journal of Physical Chemistry B.109 (18), (2005), 8723 ).
  • TEOS tetraethyl orthosilicate
  • the SBA-15 spherical was obtained under the following conditions. An amount of pluronic P 123 was dissolved in HCl. A second suspension with CTABr and water was prepared and added to the first suspension. A small amount of ethanol was then added, followed by addition of TEOS. The resulting solution was aged at 35°C for 45 minutes. It was then transferred to an autoclave with a Teflon liner at 75°C for several hours and finally treated at 105°C. The resulting suspension was washed with water, dried overnight at 100°C and finally burned at 550°C, ( A. Katiyar, S. Yadav, PG. Smirniotis, NG. Pinto, Journal of Chromatography A, 1122 (1-2), (2006), 13 ).
  • the SBA-15 reflux material was obtained under conditions similar to SBA-15, but a flask containing the obtained suspension connected to a reflux condenser at 100°C was used in the final step. The resulting solid was washed with water, dried overnight at 100°C and finally burned at 550°C.
  • the SBA-15 material at 125°C was prepared similarly to SBA-15 but modifying the temperature at which it is kept throughout the final temperature of the process, 125°C instead of 100°C.
  • the AISBA-15 material was prepared by means of a gel having a molar composition: 1 TEOS: 0.02 Al 2 O 3 : 0.016 P123: 0.46 HCl: 190 H 2 O, according to the method described by Vinu A., Hartmann M., Devassy B.M., Halligudi S.B., Bohlmann W., Applied Catalysis A: General, 281, (2005), 207 .
  • the Na-AlSBA-15 material was prepared by means of ion exchange from the AISBA-15 material, in which 1 gram of material is stirred for 24 hours with a 1 M NaCl solution. The resulting material is filtered, washed with water and dried in an oven at 100°C.
  • the FeNa-AlSBA-15 material was prepared by means of ion exchange from the Na-AISBA-15 material, in which in 1 liter of distilled water with 1.26 g of Fe(NO 3 )9H 2 O and 4.5 g of Na-AISBA-15 is added. The resulting solution is stirred for 24 hours and then filtered, washed with water and dried in an oven at 100°C.
  • Table 1 shows the chemical and structural characteristics of some of the additives that are studied in this application as representative examples of such materials, corresponding to SBA-15 samples prepared under different synthesis conditions or subjected to post-synthesis modifications.
  • Figure 2 shows the corresponding N 2 adsorption isotherms at 77 K.
  • the nomenclature refers to SBA-15 materials prepared with different synthesis conditions or subjected to post-synthesis modifications.
  • Nicotine standards of different concentrations were prepared for quantifying the compounds present in the condensed phase of tobacco smoke. They were injected in the equipment and the value of the corresponding response factor was obtained from the slope of the straight line obtained from the graphs representing the amount of injected compound vs. peak area. The response factor obtained for nicotine was used for the rest of the analyzed compounds since nicotine was the main compound. Quantification was carried out in a similar manner for the gases, in which a mean response factor was used in the cases in which the corresponding response factor was not available.
  • Table 2 shows the mixtures made in the different tests conducted. Table 2: tobacco mixtures Mixtures 3R4F+SBA-15 (4%) 3R4F+SBA-15 (6%) 3R4F+SBA-15 (8%) 3R4F+SBA-15 spherical 3R4F+Na-SBA-15 3R4F+FeNa-SBA 3R4F+AlSBA-15 (autoclave) 3R4F+Na-AISBA-15 (autoclave) 3R4F+SBA-15 spherical (125°C) 3R4F+SBA-15 (reflux)
  • Tables 3, 4, 5 and 6 show the results obtained when smoking the cigarettes using the cigarette preparation conditions, the smoking conditions and the conditions for analyzing the generated products and the examples corresponding to different tobacco-additive mixtures. The values obtained for the following are shown:
  • Tables 3 to 6 clearly show that, generally, the proposed additives, mixed with tobacco in the described proportions, provided a significant reduction in the amount of most of the toxic compounds in tobacco smoke. This reduction in turn entailed a decrease of the potential negative effects caused by tobacco smoke in smokers and in passive smokers, without causing significant changes in the organoleptic properties, taste and consistency of the tobacco, and without the apparent generation of other undesired compounds.
  • the toxic compounds were reduced, but also the total amount of gases and liquids that are formed when smoking the cigarette (total particulate matter, TPM, plus the liquids retained in the filter) also generally decreased in a significant manner, whereas solid residue together with ash increased. When the process of smoking the cigarette ended, the additives were retained in the ash or in the tobacco that has not been smoked.
  • Table 3 shows the yields obtained for CO and CO 2 when smoking cigarettes prepared with the described mixtures. As can be seen, reductions are generally obtained in the amount of CO present in the mainstream tobacco smoke as a result of the presence of almost all the studied materials. As will be seen below, these reductions are particularly interesting for the additive referred to as SBA-15 when it is used in nominal proportions of 6 and 8%.
  • SBA-15 spherical , SBA-15 spherical and SBA-15 at 125°C materials also provide significant reductions in CO. That is particularly interesting since CO is one of the substances regulated by laws applicable to commercial cigarettes.
  • the rest of the additives also provide a reduction, although less, in CO, with the only exception of FeNa-SBA-15, which causes a slight increase.
  • Table 5 shows, by way of example, the results obtained for the production of some toxic and carcinogenic compounds in tobacco smoke.
  • all the additives provided a reduction in the formation of propionaldehyde with respect to the reference cigarette.
  • interesting reductions were also observed in the case of toluene, with the only exception of the NaFe-SBA-15 material, which caused a slight increase.
  • Similar considerations can be made for benzene and acetaldehyde: reductions are observed for benzene in all cases, except for SBA-15 spherical and SBA-15 spherical at 125°C, causing a slight increase.
  • the only additive which causes reductions with respect to the reference cigarette is SBA-15.
  • the sample of the SBA-15 material has an excellent behavior from the viewpoint of applying same as an additive for reducing the toxicity of the mainstream tobacco smoke since, in addition to reducing the generation of CO and TPM, it separately reduces all the analyzed toxic compounds.
  • Table 6 shows the results obtained for other compounds present in tobacco smoke in the case of the reference tobacco and with 4 of the studied additives.
  • the excellent behavior shown by the SBA-15 sample can again be confirmed, with reductions ranging between 95% for phenol and 39% for nicotine.
  • the SBA-15 spherical material also caused reductions in 7 studied compounds, whereas FeNa-SBA-15 caused an increase in all of said compounds, except benzaldehyde.
  • All the described mixtures can also be prepared by means of using speed mixers, fluidized beds or entrained beds and any other type of equipment which favors mixing the tobacco fiber and additive. Sieves can also be used for separating and recirculating the additive that did not attach onto the tobacco fibers.
  • a dispenser providing the suitable amount of catalyst can be used for preparing bright tobacco, dark tobacco, fine-cut tobacco, roll-your-own tobacco, pipe tobacco and any other product that can be smoked.
  • This dispenser can consist of a blister, in which each cavity contains the selected amount (between 5 and 70 mg, such that between 0.5 and 7% is obtained with respect to the tobacco which will usually be consumed in portions of about 1 g of tobacco), individual capsules containing said amounts, a container including a calibrated or graduated spoon or any another calibrated dispenser.
  • a ready-to-smoke product MYO, RYO, pipe or other forms
  • the content of the calibrated dispenser is poured onto the tobacco fiber and carefully mixed by hand. This method assures excellent results which are as good as those shown in Tables 3 to 6.
  • the additive used in all the cases was SBA-15.
  • the percentages by weight of catalyst are indicated.
  • the cigarettes were prepared using the method described in "cigarette preparation conditions” and using nominal concentrations (percentage by weight) of 4.6 and 8%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Catalysts (AREA)
EP13865181.5A 2012-12-21 2013-12-05 Aluminosilicate sab-15 utilisé comme additif pour la réduction des composés toxiques et cancérigènes présents dans la fumée du tabac Withdrawn EP2937001A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES201201266A ES2482490B1 (es) 2012-12-21 2012-12-21 Aluminosilicato SAB-15 como aditivo para la reducción de los compuestos tóxicos y cancerígenos presentes en el humo del tabaco
PCT/ES2013/070848 WO2014096486A1 (fr) 2012-12-21 2013-12-05 Aluminosilicate sab-15 utilisé comme additif pour la réduction des composés toxiques et cancérigènes présents dans la fumée du tabac

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EP2937001A1 true EP2937001A1 (fr) 2015-10-28
EP2937001A4 EP2937001A4 (fr) 2016-08-03

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EP13865181.5A Withdrawn EP2937001A4 (fr) 2012-12-21 2013-12-05 Aluminosilicate sab-15 utilisé comme additif pour la réduction des composés toxiques et cancérigènes présents dans la fumée du tabac

Country Status (8)

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US (1) US20150320108A1 (fr)
EP (1) EP2937001A4 (fr)
JP (1) JP2016502847A (fr)
CN (1) CN105072930A (fr)
BR (1) BR112015014886A2 (fr)
ES (1) ES2482490B1 (fr)
RU (1) RU2015125372A (fr)
WO (1) WO2014096486A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2528338B1 (es) * 2014-10-31 2015-11-12 Universidad De Alicante Productos susceptibles de ser fumados con sistema de liberación controlada de nicotina y catalizador para la reducción de los compuestos tóxicos
CN107551831B (zh) * 2017-08-30 2021-02-23 山东大学 一种用于过滤烟草烟雾颗粒物的金属-有机骨架纤维膜及其应用

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Publication number Priority date Publication date Assignee Title
DE69524059T2 (de) 1995-05-03 2002-07-18 British American Tobacco (Investments) Ltd., London Rauchartikel
US6814786B1 (en) 2003-04-02 2004-11-09 Philip Morris Usa Inc. Filters including segmented monolithic sorbent for gas-phase filtration
US7165553B2 (en) 2003-06-13 2007-01-23 Philip Morris Usa Inc. Nanoscale catalyst particles/aluminosilicate to reduce carbon monoxide in the mainstream smoke of a cigarette
US9107452B2 (en) * 2003-06-13 2015-08-18 Philip Morris Usa Inc. Catalyst to reduce carbon monoxide in the mainstream smoke of a cigarette
US9107455B2 (en) * 2003-11-21 2015-08-18 Philip Morris Usa Inc. Cigarette filter
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US7448392B2 (en) 2003-12-22 2008-11-11 Philip Morris Usa Inc. Smoking articles and filters with carbon-coated molecular sieve sorbent
US20060130855A1 (en) 2004-09-28 2006-06-22 Philip Morris Usa Inc. Smoking article with mercaptopropyl functionalized sorbent and method
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ES2301392B1 (es) * 2006-11-07 2009-06-09 Universidad De Alicante Mezclas tabaco-catalizador para la reduccion de los compuestos toxicos presentes en el humo del tabaco.
CN101669677B (zh) * 2008-09-12 2011-08-03 湖北中烟工业有限责任公司 加有复合麦饭石的滤嘴棒及其制作方法
CN101433818A (zh) 2008-12-04 2009-05-20 南京大学 用于吸附烟草主流烟气里粒相物、焦油、苯酚和亚硝胺的介孔新材料
GB0913509D0 (en) 2009-08-04 2009-09-16 British American Tobacco Co Filter for a smoking article
GB201005547D0 (en) * 2010-04-01 2010-05-19 British American Tobacco Co Composite additive materials
CN102242527A (zh) 2011-05-13 2011-11-16 民丰特种纸股份有限公司 一种功能卷烟纸及制备方法
CN102429318B (zh) * 2011-09-06 2014-08-27 湖北中烟工业有限责任公司 一种能够降低烟气中有害物质的烟草薄片的制备方法

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RU2015125372A (ru) 2017-01-30
WO2014096486A1 (fr) 2014-06-26
ES2482490A1 (es) 2014-08-01
ES2482490B1 (es) 2015-05-19
BR112015014886A2 (pt) 2017-07-11
US20150320108A1 (en) 2015-11-12
CN105072930A (zh) 2015-11-18
JP2016502847A (ja) 2016-02-01
EP2937001A4 (fr) 2016-08-03

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