US3924642A - Tobacco and tobacco substitute material including metal chelate compounds - Google Patents

Tobacco and tobacco substitute material including metal chelate compounds Download PDF

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US3924642A
US3924642A US306655A US30665572A US3924642A US 3924642 A US3924642 A US 3924642A US 306655 A US306655 A US 306655A US 30665572 A US30665572 A US 30665572A US 3924642 A US3924642 A US 3924642A
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ammonium
aluminum
iron
weight
iii
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Theo Eicher
Friedemann Muller
Klaus-Werner Krebs
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Bayer AG
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Haarmann and Reimer GmbH
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Priority claimed from DE2157370A external-priority patent/DE2157370A1/de
Priority claimed from DE19722215412 external-priority patent/DE2215412A1/de
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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

Definitions

  • ABSTRACT In a smokable product comprising a cellulose-based combustible material, the improvement which comprises incorporating therein at least one chelate compound of the stoichiometric formula.
  • K is an alkaline earth metal or divalent manganese
  • Me is trivalent iron or aluminum
  • R is the radical of a chelate-forming organic carboxylic acid
  • w, x, y, and z are integers up to about 5
  • R is the radical of an organic dicarboxylic acid containing 2 to 8 carbon atoms or a hydroxyor keto-substituted carboxylic acid.
  • the product may also contain fillers, compounds which split off ammonia, oxidizing agents, ammonium salts of polymeric acids, low sulfur-content proteins and/or tobacco extracts. The product may be used as such or in blends with tobacco as cigarettes, cigars or pipe tobacco.
  • a smokable material which is not natural tobacco, from tobacco waste products or mixtures thereof with other plant materials, as well as from natural or synthetic non-tobacco products, which are made up into paper-like webs or foils or fibres.
  • smoking materials can be produced from cellulose, cellulose derivatives or starch using certain inorganic fillers which keep the material glowing.
  • hydrated magnesium citrate and calcium tartrate may be added to certain cellulose derivatives to assist the combustion process.
  • non-tobacco smokable products produced by the previously known processes do not have satisfactory organoleptic properties but on the contrary organoleptic properties which are unpleasant to a greater or lesser degree, e.g. sharpness and poor aroma in the main and side streams.
  • organoleptic properties which are unpleasant to a greater or lesser degree, e.g. sharpness and poor aroma in the main and side streams.
  • tobacco substitute products with only a low sulphur content e.g. in the form of sulfates, are found to produce a smoke with an unpleasant sulfidic flavor.
  • Tobacco substitute products with a high cellulose content which contain the alkali metal, alkaline earth metal and iron salts normally present in smokable products give rise, when allowed to glow, to a sharp and biting smoke with a cellulosic flavor and leave behind a persisting astringent effect in the mouth.
  • the known nontobacco smoking products generally manifest an organoleptic incompatibility with numerous sorts of tobacco when blended with them.
  • a cellulose-based combustible material having incorporated therein trivalent metal chelate compounds of alkaline earth metals and/or of manganese, the trivalent metal chelate compounds being complex anions which contain trivalent iron or aluminum as the central atom and the anions of chelate-forming organic carboxylic acids as ligands.
  • a smokable product comprising a combustible material based on cellulose has now been found characterised in that the smokable product contains metal (111) chelate of alkaline earth metals and/or of manganese (II), the metal (111) chelate compounds being complex anions which contain trivalent iron or aluminium as the central atom and the anions of chelate-forming organic carboxylic acids as ligands.
  • metal (111) chelate of alkaline earth metals and/or of manganese (II) the metal (111) chelate compounds being complex anions which contain trivalent iron or aluminium as the central atom and the anions of chelate-forming organic carboxylic acids as ligands.
  • the alkaline earth metal-metal (I1I)-chelate compounds used in the products according to the invention may be, for example, the calcium or magnesium compounds.
  • chelate compounds used in the products according to the invention will hereinafter be referred to simply as chelates.
  • chelate is therefore used to denote complex salts with a chelate structure which contain alkaline earth metal ions or manganese (11) ions as the cation, and as the anion, a chelate-complex consisting of iron (III) ions or aluminium ions as the central atom and chelate-forming organic carboxylic acids as ligands (see, e.g., A. E. Martell, M. Calvin, Die Chemie der Metall-Chelat-Veritatien, page 204, Verlag Chemie, Weinheim (1958)).
  • Smokable products according to the invention may preferably contain at least one chelate compound of the stoichiometric formula I [Mer 1..
  • K is an alkaline earth metal or divalent manganese
  • Me is trivalent iron or aluminum
  • R is the radical of a chelate-forming organic carboxylic acid
  • w, x, y and z are integers up to about 5,
  • x denotes l or 2 and y denotes integers of from 1 to 4, and z resp. w denote the number of divalent cations K resp. anions and depend on the number of free negative valencies'remaining in the anion complex.
  • the cations of the chelates contained in the products according to the invention may be calcium, magnesium or manganese (11), preferably magnesium or manganese (11).
  • Chelate-forming organic carboxylic acids hereinafter referred to as Chelate formers" (see A. E. Martell, M. Calvin, Die Chemie der Metallchelatucunin (pages 462-517) Verlag Chemie, Weinheim (1958), are, for example, organic carboxylic acids which contain 2 to 8 carbon atoms and in addition to the carboxylic group contain at least one hydroxyl group, keto group or additional carboxyl group.
  • Chelate formers may therefore for example be dicarboxylic acids.
  • dicarboxylic acids oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and itaconic acid.
  • Particularly preferred dicarboxylic acids are oxalic acid, malonic acid and succinic acid.
  • Hydroxy acids such as hydroxymonocarboxylic acids, hydroxydicarboxylic acids and hydroxytricarboxylic acids may also be chelate formers. Examples of such hydroxymonocarboxylie acids are: lactic acid, glycolic acid, B-hydroxypropionic acid, glyceric acid and hydroxypivalic acid.
  • Glycolic acid and glyceric acid are particularly preferred hydroxymonoearboxylic acids.
  • hydroxydicarboxylic acids and hydroxytricarboxylic acids hydroxymalonic acid, malic acid, tartaric acid, 2-hydroxglutaric acid, 3-hydroxyglutaric acid, 3-methylmalic acid, 2,5-dihydroxyadipic acid, 2,4-dihydroxyadipic acid and citric acid, among which malic acid, tartaric acid and citric acid are preferred
  • Monoand dicarboxylic acids derived from pentoses and hexoses may also be chelate formers.
  • chelate formers examples include the isomeric monocarboxylic acids known as uronic acids, for example, glucuronic acid, galacturonic acid and mannuronic acid, the compounds known as saccharic acids, e.g. saccharic acid itself, manosaccharic acid and idosaccharic acid, as well as the isomeric mucic acids (galactaric acids).
  • the pentaric acids derived from pentoses, ribotrihydroxyglutaric acid and xylotrihydroxyglutaric acid may also be mentioned as examples.
  • Ketocarboxylic acids containing 3 to 8 carbon atoms may be used as chelate formers which contain a keto group. Examples of keto carboxylic acids are: pyroracemic acid, acetoacetic acid. laevulinic acid and mesoxa lic acid.
  • the preferred chelate formers used are diearboxylic acids and hydroxycarboxylic acids, in particular oxalic acid, glyceric acid, glycolic acid, malic acid, tartaric acid, galactaric acid, saccharic acid and citric acid.
  • chelates of the general formula (I) which have the following composition: magnesium-iron(lll)- glycolate, magnesium-iron-(lll)-oxalate, magnesiumiron-(III)-citrate, magnesium-iron-Ill)-tartrate, magnesium-iron-(lll)-galactarate, magnesiumiron-(lll)' saccharate, magnesium-aluminum glycolate, magnesiumaluminum oxalate, magnesium-aluminum citrate, magnesiumaluminum tartrate, magnesium-aluminum galactarate, magnesium-aluminum saccharate, man ganese-iron-(III)-glycolate, manganese-iron-(Ill)-oxalate, manganese-iron-(llI)-citrate, manganese-iron- (lll)-tartrate, manganese-iron-(lll)-galactarate, manganese-iron-([ID-saccharate,
  • the chelates used in the smokable products according to the invention may, for example, have the composition indicated in Table (l).
  • the compounds shown in Table (1) correspond to the general formula (1) (K,[Me, R,,],,.), in which K represents magnesium, calcium or manganese (11), Me represents iron (111) or aluminum and R represents the chelate-forming carboxylic acid.
  • K represents magnesium, calcium or manganese (11)
  • Me represents iron (111) or aluminum
  • R represents the chelate-forming carboxylic acid.
  • the values indicated for x, y, w and z are substituted in the general formula (1) in each case to give the summation formula of the given example of chelate.
  • Particularly preferred chelate formers are tartaric acid, citric acid and galactaric acid.
  • Particularly preferred chelates are magnesium-iron- ([ll)-tartrate, magnesium-iron-(lll) citrate, magnesium-aluminium tartrate, magnesium-aluminum citrate, manganese-iron-(IlI)-galactarate and manganese-iron- (IIl)-citrate.
  • the chelates contained in the smokable products according to the invention may be prepared in known manner in aqueous solution, e.g. by reacting the iron or aluminum salts of the desired chelate-forming carboxylic acids with calcium magnesium or manganese salts, which may be added as hydroxides, carbonates or salts of the corresponding chelate-forming carboxylic acids (see DRP 514,504; Hanus and Quadrate Z Anorg. Chem. 63, page 314 (1909) and W. Franke, Liebig Ann. Chem. 486, page 248 (1931)).
  • combustible materials based on cellulose are: cellulose-containing plant materials, particularly tobacco, tobacco waste products, e.g. stalks, ribs or fragments, decomposed cellulose-containing plant material such as for example hay, straw, lupins or fern, as well as cellulose or wood pulp or cellulose derivatives, alone or as mixtures.
  • cellulose derivatives used may be. for example, carboxymethyl cellulose, hydroxyethylcellulose or methyl cellulose.
  • the combustible materials used may also be polymerlike lower molecular weight fragments of cellulose obtained by thermal degradation of cellulose, or they may be cellulose derivatives prepared by chemical processes, particularly by alkaline or acid oxidation.
  • the smolaable products according to the invention generally contain about 0.5 to by weight of chelate, based on the total weight of combustible material used in the products. It has been found advantageous to adjust the quantity of chelate according to the cellulose content of the combustible material used. lf, for example, the cellulose content ofthe combustible material is about 10% by weight, then the quantity of chelate used is preferably about 1 to 15% by weight, based on the total weight, and in particular about 5 to 10% by weight. If the cellulose content of the combustible material is higher than 70% by weight, the quantity of chelate used, based on the total weight, is about 10 to 70% by-weight, preferably 25 to 50% by weight.
  • the smokable products contain a filler.
  • fillers are meant minerals, inorganic salts and oxides which have no effect on the flavor under smoking conditions, for example silica, silicates, mica, alumina, dolomite, magnesite and chalk or carbonates, phosphates and oxides of aluminum iron, magnesium and calcium.
  • Inert fillers which split off water under smoking conditions may also be used. This elimination of water may be due to the presence of a large quantity of water of crystallization in the filler or it may be due to chemical decomposition, e.g. from metal hydroxides.
  • Fillers which have been found to be particularly advantageous are the hydroxides and hydrated oxides of aluminum and iron, natural silicates such as vermiculite and kaolin, precipitated silicates such as silicic acid, silica gel, silica sol and alkaline earth metal and alkali metal silicates, the hydrated oxides of aluminum and/or silicic acid being preferred. It is generally suitable to use about 1 to 70% by weight of fillers, based on the total quantity of smokable product. The quantity used is preferably about to 50% by weight.
  • the smokable products contain compounds which split off ammonia under smoking conditions, in particular,-ammonium salts of inorganic acids and organic carboxylic acids, salts of amino acids and acid amides.
  • the preferred compounds which split off ammonia under smoking conditions are the acid and neutral ammonium salts of inorganic acids such as carbonic acid, nitric acid and phosphoric acid, particularly the ammonium salts of phosphoric acid.
  • Suitable ammo nium salts are therefore, for example the ammonium of monocarboxylic acids such as formic acid and acetic acid, ammonium salts of dicarboxylic acids such as oxalic acid, malonic acid and succinic acid, ammonium salts of hydroxymono-, hydroxydiand hydroxytricarboxylic acids such as glycolic acid, lactic acid, B- hydroxypropionic acid, glyceric acid, malic acid, tartaric acid and citric acid, and the ammonium salts of monoand di-carboxylic acids derived from pentoses and hexoses, such as glucuronic acid, galacturonic acid and mannuronic acid, saccharic acid and the isomeric mucic acids.
  • ammonium salts corresponding to the chelates according to the invention (1(" representing ammonium in the general formula (I) are also very advantageous to use as compounds which split off ammonia.
  • the following ammonium chelate compounds are preferably used: ammonium-iron-(IlI)-glycolate, ammonium-iron-(llI)-oxalate, ammonium-iron-(I1I)-citrate, ammonium-iron-(lII)-tartrate, ammonium-iron (III)- galactarate and ammonium-iron-(IIl)-saccharate as well as ammonium-aluminum glycolate, ammoniumaluminum oxalate, ammonium-aluminum citrate, ammonium-aluminum tartrate, ammonium-aluminum galactarate and ammonium-aluminum saccharate.
  • Ammonium-iron-(III)-citrate, ammonium-iron-(Ill)- tartrate, ammonium-iron-(lII)-galactarate, ammoniumaluminium citrate and ammonium-aluminum tartrate are particularly preferred.
  • acid amides as compounds which split off ammonia
  • acid amides for example acetamide, propionamide, succinic acid monoamide and diamide and particularly urea.
  • Ammonium, magnesium or manganese (II) salts of aminoacids may also be used as compounds which split off ammonia, the aminoacids being preferably glycine, serine, lysine, arginine, leucine, proline, valine, aspartic acid or glutamic acid.
  • Magnesium glutamate and manganese glutamate are particularly preferred as compounds which split off ammonia.
  • the compounds which split off ammonia are used, for example, in quantities of about 1 to 25% by weight, based on the smokable product, preferably about 5 to 15% by weight.
  • the smokable products contain about 0.01 to 7% by weight, preferably about 1 to 5% by weight based on the total weight of the smoking product, of an oxidizing agent.
  • oxidizing agent is meant a substance which improves the glowing of the smoking product.
  • the oxidizing agents used may be, for example, salts of nitric acid, particularly alkali metal or alkaline earth metal nitrates.
  • the nitrates preferably used are potassium nitrate and/or sodium nitrate.
  • Oxidizing agents which have been found to be particularly advantageous in the smokable products according to the invention are compounds of manganese (VII), in particular alkali metal permanganates, e.g. potassium permanganate.
  • the smokable products contain about 0.01 to 10% by weight, preferably about 0.1 to 5% by weight, based on the smokable product, of ammonium salts of polygalacturonic acids such as pectin, alginic acid or gum arabic and/or ammonium salts of carboxymethyl cellulose.
  • Satisfactory organoleptic properties are also obtained when using about 0.01 to 5% by weight, preferably about 0.1 to 3% by weight, based on the smokable product, of proteins which have a low sulfur content, e.g. zein, hordein or gliadin, as well as the alcoholic extracts of these proteins, e.g. the ethanol extracts. Apart from liberating ammonia in the smokable products, these compounds impart a pleasant plant flavor with a tobacco-like note.
  • the smokable products obtained by this method are completely compatible in their aroma with any tobacco with which they may be blended.
  • the smokable products contain about 0.1 to 50% by weight, based on the total weight of smokable product, of tobacco constituents.
  • tobacco constituents are substances or groups of substances which can be obtained from tobacco by known processes, e.g. by pressing, distillation or extraction. It is preferred to use tobacco constituents which have been obtained by extraction carried out, for example, with water or organic solvents.
  • the combustible material which forms the basis of the smokable products according to the invention may be in the form of a paper-like-web, a fleece, a foil or a thread or strand, cut or uncut.
  • Th e'paper-like webs, fleeces or the like may be produced by known technical processes (see Ullmanns Enzyklopadie der techn. Chemie, 3rd Edition, Volume 13, pages 122-130 (1962) and ibid. Volume 17, pages 288 to 296 (1966)).
  • the smokable products according to the invention may be produced, for example, by applying the chelates used according to the invention in the form of a solution, preferably an aqueous solution, to the combustible material based on cellulose which is in the form of a paper-like web, a fleece, a foil or a thread or strand, cut or uncut.
  • Application of the chelate solution may be carried out, for example, by immersing the combustible material in a bath of the solution of chelate compounds and then drying it, advantageously at temperatures of about 50 to 120C.
  • the material may be sprayed or painted with the solution of chelates.
  • the chelates may be introduced directly into the starting mixture from which the combustible material is produced, e.g. in the form of paperlike webs, fleeces, foils, threads or strands.
  • the chelates may, for example, be introduced directly into a casting solution containing the combustible material.
  • These casting solutions may advantageously contain about 0.1 to 20% by weight of a binder, in addition to optional fillers compounds which split off ammonia, oxidizing agents and tobacco constituents.
  • the binders may be for example polysaccharides or their derivatives, gum arabic, starch, carboxymethylcellulose with a low alkaline content and/or ammonium-carboxymethylcellulose. If the binder comprises a combustible material based on cellulose, it may, of course, take over the function of combustible material in the products according to the invention.
  • the products according to the invention may be produced, for example, by pouring the casting solution on to an endless band and by drying at 50C to 120C.
  • the smokable products according to the invention are preferably produced using paper-like webs or fleeces.
  • the amount of chelates taken up by the foil or fleece may be controlled not only by the various operating conditions but also by the structure of the foil and the viscosity and concentration of the chelate solution. Adjustment of the viscosity can be achieved for example by varying the concentration of the solution of chelates or by adding thickeners such as a carboxymethylcellulose which has a low alkaline content, a hydroxyethyl, cellulose, pectins, gum arabic, alginates, galactomanan, starch and derivatives thereof. A high uptake of salts into the smokable product is possible, for example, by using concentrated, highly viscous solutions.
  • the fillers which may be used according to a preferred embodiment of the invention may be incorporated into the combustible material at the same time as the chelates. Alternatively, they may be incorporated partly or completely in a separate stage of the process before or after the treatment with chelates. Incorporation of the fillers may be carried out by known technical methods employed for producing paper-like webs, fleeces or foils which contain fillers.
  • the compounds which split off ammonia may be introduced into the combustible material either together with the chelates or in a separate stage of the process before or after incorporation of the chelates.
  • Introduction of the compounds which split off ammonia is carried out e.g. by spraying or painting the combustible material with aqueous solutions of the compounds which split off ammonia, or by immersing the material in such solutions, and then drying the material.
  • the oxidizing agents used according to a preferred embodiment of the invention may be introduced into the combustible material at the same time as the chelates or before or after their incorporation into the material.
  • oxidizing agents are carried out e.g. byspraying or painting the combustible material with an aqueous, alcoholic or acetonic solution of the oxidizing agent or by immersing the material in such a solution.
  • ammonium salts of polygalacturonic acids used according to another preferred embodiment of the invention may be introduced together with the chelates or before or after the latter are incorporated into the combustible material. They are preferably incorporated into the combustible material together with or after the chelates.
  • the usual additives employed in tobacco processing e.g. moisturizing agents, flavor and nicotine, may be introduced in the same or separate process steps.
  • the products according to the invention are organoleptically less acrid. they have a pleasant, mild flavor without any astringent effect the aroma is improved.
  • the smokable products according to the invention are added to tobaccos which have a cellulosic sharpness or when such tobaccos are treated by the process according to the invention, then not only is the sharpness reduced but the aroma of these tobaccos is greatly enhanced.
  • the smokable products according to the invention are not only distinguished by their exceptionally low condensate value but also have excellent glowing properties.
  • the smokable products according to the invention are particularly distinctive in producing a smoke which has no cellulose flavor and therefore no organoleptically irritating components.
  • Smoke analyses of smokable products according to the invention show in part a considerable reduction in physiologically harmful substances as compared with those found in tobacco.
  • a cigarette containing the products according to the invention is found to have a substantially lower phenol content and hydrocyanic acid content as well as substantially lower condensate values than a cigarette comprising tobacco.
  • the phenol content in each cigarette was found to be reduced by more than 90%, the hydrocyanic acid content by about 40% and benzpyrene content by about 25%.
  • the quantity of dry condensate could be reduced by about 80 to 90% compared with that in tobacco.
  • the addition of the smokable products according to the invention to tobacco can have an advantageous influence on the burning properties of tobacco, especially in that the amount of physiologicallyharmful substances in the smoke is substantially reduced, as was to be expected from the individual components of these mixtures.
  • the aroma and flavor of the smokable products can be varied and if desired, for example, the flavor can be neutralized, by varying the chelates used as well as the other components which are added according to various preferred embodiments of the invention, e.g. by adjusting the ratios of the quantity of chelate compounds to the quantity of compounds which split off ammonia under smoking conditions.
  • the char acteristics of the smokable products can easily be adjusted to those of various synthetic aromatic components or aromatic components obtained by extraction from tobacco as well as to those of various kinds of tobacco such as Burley, Virginia or Oriental with which the smokable products may be blended.
  • a harmonious blend of tobacco aromas and flavors can therefore be obtained in every case and constantly reproduced.
  • chelates contained in the products according to the invention is found to be particularly advantageous because these compounds are generally readily soluble in water. Homogeneous distribution of the chelates in the smokable products can therefore easily be achieved in one step. Due to their low tendency to crystallization and their hygroscopic properties, the products obtained by the process according to the invention are smooth and elastic and therefore particularly easy to work with.
  • the bulk volume can be increased to a value higher than that of an equal quantity of tobacco by adjusting the surface weight of the support, for example to a value of about l to 60 g/m so that, by blending tobacco with such smokable products, the individual smokable article, such as a cigarette, cigar or pipeful of tobacco, is reduced in weight, and consequently the total quantity of substance smoked, and hence the quantity of condensate produced, is still'further reduced.
  • the smokable products according to the invention may be used alone or as components of blends of cigarette tobacco, cigar tobacco and pipe tobacco. They are also suitable for use as cigar wrappers or binders or as cigarette paper.
  • the smokable products produced according to the Examples were made up into filter cigarettes with cellulose acetate filters.
  • the filter cigarettes had a length of 82 mm, a diameter of 8 mm and a'butt length of 15 mm. They were smoked down to average butt length of 23 mm.
  • the density of packing of the cigarettes was measured in terms of the draft resistance.
  • the draft resistance was determined for individual cigarettes by using a draft resistance measuring instrument supplied by Filtrona, London, which indicated the pressuredrop in mm H O. i
  • the filter cigarettes produced from the smokable products generally had draft resistances of from to mm H O.
  • the quantities of condensate given in the examples were quantities of dry condensate in mg/cig.. They were determined in accordance with Coresta Standard No. 10. The test cigarettes were smoked with a puff volume of 35 ml a puff time of 2 seconds and a puff frequence of 60 seconds. The condensate formed was deposited on a Cambridge filter and weighed. The water content was determined by titration using the Karl-Fischer method and was subtracted from the total condensate.
  • Example 1a 100 g of a paper-like foil of bleached sulfate cellulose having a surface weight of 58 g/m a thickness of 60 p. and an ash content of 0.06% were sprayed with a 25% aqueous solution of magnesium-aluminum citrate, Mg [Al (citrate) and dried so that the resulting dry foil contained 20% by weight of the chelate.
  • the foil was cut up into strips of various lengths about 0.9 mm in width (fine cigarette cut), and made up into cigarettes with an average draft resistance of l 13 mm H O using ordinary commercial cigarette paper tubes with cellulose acetate filters.
  • the cigarettes When smoked, the cigarettes glowed uniformly without ignition of the smoking product,, and the ash was gray white and self-supporting.
  • the treated foil was cut up into strips of various lengths about 0.9 mm in width (fine cigarette cut) and made up into cigarettes with an average draft resistance of 102 mm H O using ordinary commercial cigarette paper tubes with cellulose acetate filters.
  • Sharpness Smoking flavor Condensate 5.0 mg.
  • the resulting product was cut up and made into filter cigarettes as in Example 1a.
  • the cigarettes had an average draft resistance of 109 mm H O.
  • Example 2 A product was produced as described in Example la but with the addition of magnesium citrate instead of magnesium-aluminium citrate. This was obtained as follows:
  • Example 1 100 g of a paper-like foil as described in Example In consisting of bleached sulfate cellulose, having a surface weight of 58 g/m and a thickness of 60 p, and containing 1 1.3% by weight of magnesium carbonate as a filler, were immersed in a aqueous citric acid solution at 30C. so that the product contained magnesium citrate produced in situ. When the excess citric acid had been washed out and the foil dried, the weight increase of the foil was found to be 19 g, which corresponds to a magnesium citrate content of 22% by weight. The resulting product was cut up and made into filter cigarettes as in Example la. The cigarettes had an average draft resistance of 102 mm H O. Organoleptic assessment:
  • Example 3a 100 g of a paper-like foil according to Example lb were sprayed with a 25% aqueous solution of magnesium-iron-(lII)-citrate, Mg [Fe(citrate) and dried so that the dried foil contained by weight of chelate. The resulting product was cut up into strips of various lengths about 0.9 mm in width and made up into cigarettes with a draft resistance of 115 mm H O by the method described in Example la.
  • the cigarettes When smoked, the cigarettes glowed like tobacco without ignition of the smoking product.
  • the ash was brownish gray and self-supporting.
  • EXAMPLE 3b 300 g of dried, cut stalks of shield fern (Dryopteris filix-mas) were heated to 105C. with 6 litres of a Spercent aluminum sulfate solution for 4 hours in a 10 1 pressure vessel. The decomposed plant material was then filtered and washed free from sulphate with water. It was then pulped up in a Hollander and made up into a web with a surface weight of 68 glm and a.thickness of 60 on a Fourdrinier machine. g of the resulting foil were sprayed with a l0percent magnesium-iron citrate solution and dried so that the foil contained l0percent by weight of chelate. The resulting product was then cut up and made into filter cigarettes as in Example la. The cigarettes had an average draft resistance of 120 mm H O. They were mild in the main stream smoke and had a pleasant, plant-like flavor. Organoleptic assessment:
  • Smoking flavor Condensate 5.2 mg/Cig
  • the cigarettes produced in accordance with Example la which had a draft resistance of 1 15 mm H O, glowed uniformly. The ash was brownish red and self-supporting.
  • the product When smoked, the product had a light, aromatic flavor without cellulosic sharpness.
  • Example 4 A paper-like foil similar to that described in Example lb was repeatedly dipped alternately into a saturated calcium hydroxide solution and then into a l0percent tartaric acid solution and then washed and dried until the weight increase was 25.3percent by weight, i.e. the foil contained about 20percent by weight of calcium tartrate.
  • the product produced in this way was cut up as in Example 1 (fine cigarette cut), and made up into filter cigarettes with a draft resistance of l 17 mm H O.
  • the cigarettes had a dull, musty after-taste and very pronounced cellulosic sharpness.
  • Example la A paper-like foil according to Example la was treated in an aqueous immersion bath containing 12.6percent by weight of magnesium-aluminum tartrate Mg [Al(tartrate) squeezed off between steel rollers and dried so that the impregnated web showed a weight increase of 24.8percent, which corresponded to a chelate content of percent by weight.
  • the resulting product was cut up as in Example la and made up into filter cigarettes which had an average draft resistance of 115 mm H O. The cigarettes glowed slowly and constantly and formed a pale, self-supporting ash.
  • Example 6 100 g of a paper-like foil according to Example 1a were sprayed with a percent manganese-iron-(lll) oxalate solution, Mn [Fe(oxalate) and dried so that the treated foil contained 20percent by weight of the chelate. The resulting product was cut up and made up into filter cigarettes in a manner analogous to Example la. Draft resistance: 123 mm H O. The cigarettes glowed very uniformly and formed a brown, self-supporting ash.
  • EXAMPLE 7 100 g of a paper-like foil according to Example la were sprayed several times with a total of 250 ml of a IOpercent magnesium-aluminum glycolate solution, Mg [Al(glycolate) and dried so that the chelate content was 20percent by weight.
  • the resulting product was made up into filter cigarettes as in Example 1a.
  • the cigarettes had a draft resistance of 122 mm H O. They glowed uniformly and formed a light white ash.
  • EXAMPLE 8 100 g of a paper-like foil according to Example lbwere sprayed with a l2percent solution of manganese-iron galactarate, Mn [Fe(galactarate) and dried. The foil contained 19.5percent by weight of the chelate.
  • Example la The material cut up as in Example la and made up into filter cigarettes having a draft resistance of 121 mm H O glowed uniformly and formed a brownish gray ash.
  • EXAMPLE 9 A mixture of percent weight of the impregnated foil from Example la, and 70percent by weight of an American Virginia tobacco having a condensate of 28 mg/Cig. was made up into filter cigarettes with a draft resistance of 126 mm H O. The aromatic substances and the characteristic sweetness of Virginia tobacco were found to be completely preserved when the mixture was smoked. The nicotine reaction on the respiratory tract was considerably attenuated; Organoleptic assessment:
  • Smoking flavor Condensate: l5 mg/Cig.
  • EXAMPLE 10 A mixture of 30percent by weight of the foil from Example 3aand percent by weight of an Italian Burley tobacco having a condensate of 22 mg/Cig. was made up into filter cigarettes with an average draft resistance of 121 mm H O. The cigarettes were found when smoked to have the complete characteristic cigar-like flavour of Burley tobacco. Organoleptic assessment:
  • EXAMPLE 1 l A mixture of 30percent by weight of the foil from Example 6 and 70percent by weight of a commercial tobacco mixture with a light note (American blend type flavor having a condensate of 15 mg/Cig. was made up into filter cigarettes. The cigarettes were found when smoked to have a pleasant, mild flavor. The smoke appeared much thinner than that produced by the tobacco mixture alone. The glowing process was similar to that of natural tobacco in its uniformity and rate. Draft resistance: 1 18 mm H O Organoleptic assessment:
  • EXAMPLE 12 The combustible material used as a tobacco which was characterized as rough Burley with a strong cigar note. This tobacco was sprayed with a solution of ammonium-iron (lll) citrate, (Nl-l [Fe(citrate) and acid magnesium-aluminum tartarate, Mg H [Al (tart) in a ratio by weight of 1:1, so that the amount of dry substance taken up was 2.5percent by weight, i.e. the amount of each compound present in the treated tobacco material is 1.25percent by weight.
  • the Burley tobacco which has been treated by the process according to the invention was less sharp when smoked but with an overall spicy aromatic flavor.
  • the Burley note was completely preserved.
  • Example 13 The combusticle material used was a paper-like foil produced from a 1:1 mixture of ground tobacco ribs and sulfate cellulose and having a surface weight of 45 g/mand a thickness of 55 This material was treated in an immersion bath containing 15 parts by weight of magnesium-aluminum citrate, Mg [Al (citrate) 6 parts of ammonium aluminum citrate, (NH [Al (citrate) 4 parts of aluminum hydroxide, 4 parts of silicic acid, 1 1 parts of tobacco extract and 60 parts of water. The treated foil was squeezed off and dried in a stream of air at 95C. A weight increase of 55% by weight was obtained. The components dissolved in the immersion bath were incorporated in the foil at the same concentration ratio, i.e.
  • the foil contained 13.6% by weight of Mg [Al (citrate) and by weight of (NI-l [Al (citrate) Compared with a product obtained without the addition of chelate, the smokable product obtained had no astringent effect, was free from sharpness and produced a light, aromatic smell. It was found to be completely compatible with commercial cigarette tobaccos with which it was blended.
  • Table III summarizes for Examples 14 to 22 the nature of the foil used as combustible material, the composition of the immersion bath, the increase in dry weight of the treated foil.(total weight increase and increase due to chelate content) and the assessment of the organoleptic properties of the resulting smokable products as well as the condensate values.
  • the quantity of solids taken up by the foil is obtained from the weight increase, the individual constituents being taken up into the foil in the same ratio by weight as that found in the immersion bath.
  • the quantity of chelates taken up is indicated separately.
  • Examples 23-25 Tobacco mixtures The cut foils from Examples 15, 16 and 18 were mixed with a commercial cigarette tobacco with'a light note and made up into filter cigarettes.
  • Example 23 A 30% mixture of the foil from Example 15 and a commercial cigarette tobacco with a light note resalted in a round, soft aroma without any cellulosic sharpness. The only effect of the low nicotine content in the total mixture was an attenuation of the reaction to inhalation of the main stream smoke. Assessment:
  • Example 24 A 30% mixture of the foil from Example 16 resulted in a slightly attenuated aromatic impression in the tobacco mixture with a low residual sharpness
  • the nicotine reaction on inhalation of the main stream smoke was the same as in Example 13.
  • Example 25 Examples 2631 Foils from Examples 14-22 were immersed in accordance with the following Examples 26-31 in a solution of aqueous tobacco extract containing about 30% by weight of soluble tobacco constituents or sprayed with this solution so that the dry weight increase was up to 50% by weight. Drying was carried out using hot air at 60C. to 100C.
  • Example 26 of the constituents of commercial tobacco mixture with an American Blend type flavor were extracted using a cold methanol/water solution (70 vol/30 vol). This aqueous-methanolic extract was sprayed on the smoking product produced according to Example 17 so that the dry weight increase was 30% by weight.
  • the resulting product was made up into filter cigarettes which gave an aromatic overall impression without sharpness in the main stream (assessment and no cellulosic after-taste (assessment: on inhalation, with a distinctly perceptible nicotine reaction and a fully aromatic side stream.
  • the resulting smokable product was compatible when mixed in any proportion with Virginia, Burley and Orient type tobaccos and mixtures of such tobaccos (Condensate: 9.8 mg).
  • Example 27 The foil obtained according to Example 19 was treated with the same extract of tobacco constituents as in Example 26 to result in a dry weight increase of 29% by weight.
  • the flavor of the product made up into filter cigarettes was assessed as inert with little aroma and with only a slight sharpness (assessment: when the cigarette was lit up.
  • the side stream smoke was aromatic and mild (assessment of smoking flavor: condensate: 10.7 mg).
  • Example 28 The foil obtained according to Example 20 was treated with the same extract of tobacco constituents as in Example 26 so that the increase in dry. weight was about 25% by weight. Compared with Example 27, a fuller flavor was obtained with a good reaction, and even when lighting up the cigarette no sharpness (assessment: and no cellulosic after-taste (assessment: were experienced. The side stream smoke was pleasantly aromatic. (Condensate: 9.0 mg).
  • Example 29 The constituents of American Virginia tobacco were completely extracted with hot water. The aqueous extract was sprayed onto the smokable product produced according to Example 20 so that the increase in dry weight was 31%. When this cigarette was smoked, it was found to have an unmistakable, typical Virginia flavor the spiciness of which was not impaired by the foil. Assessment:
  • Example 30 The soluble constituents were completely extracted from Italian' Burley tobacco by means of a cold methanol/water solution (60 vol/40 vol). The extract was sprayed onto the smokable product obtained according to Example 22 so that the weight increase was 20%. The flavor was that of a good quality, characteristic Burley tobacco with a sweetish note. The smokable product was less sharp than the Burley tobacco used for extraction. The smokable product obtained was compatible in any proportions with Virginia, Burley and Orient type tobaccos and mixtures thereof. Assessment:
  • Example 31 Foil C indicated in Table 11 was treated in an immersion bath which contained 160 g of ammonium citrate, g of magnesium-aluminum citrate, Mg [Al (citrate) and 280 g of the tobacco constituents obtained by extraction with water in accordance with Example 19 and which had been adjusted to pH 7 with ammonia.
  • the increase in dry weight of the foil was 50% and the resulting smokable product contained 5.1% by weight of chelate. When smoked, the product was light, aromatic and practically free from any after-taste or sharpness. It was compatible with all the usual sorts of tobacco in any proportions.
  • Example 32 15 parts of ground, pure linters (99.8% a-cellulose), 15 parts of aluminum hydroxide, 5 parts of magnesiumaluminum citrate, Mg [Al (citrate) and 5 parts of magnesium-iron citrate, Mg [Fe(citrate) were added to a 5% aqueous casting solution of sodium car- 20 boxymethylcellulose/ammonium carboxymethylcellu-
  • Table V shows examples of the preparation of smoklose (3:1 able products by the process according to the invention The solution was cast onto a polytetrafluorethyleneand quantities of condensate formed by these products. coated band using a pressure casting tool and dried at Table VI shows the production of smokable products 130C. The cast foil weighed 15 g/m.
  • a 30% by weight 5 according to Table V which in addition contain potasmixture of this product with a Virginia-Burley mixture sium permanganate as an oxidizing agent and the quan- (proportion by weight: 3:1) had a slightly weaker tities of condensate formed by these products.
  • a commercial cigarette paper was sprayed with a 6% lf t A] (OH)3 by weight solution of 2 parts of magnesium-aluminum cellulose 102% by Weight citrate, Mg [Al citrate) and 1 part of ammonium- B do. 44.6% by weight 50 62 aluminum citrate, (Nl-1 [Al (citrate ]and dried at A] on 1 90C.
  • the amount of salt taken up was 9% by weight.
  • Cigarettes produced using this paper were improved in m ht flavor and aroma compared with cigarettes produced with untreated paper because the treated paper was D d 31.1% by weight 38 45 free from sharpness and had no unpleasant cellulosic h after-taste.
  • a'mminium-iron citrate (NH,) [Fe(citrate) 20 urea 20 ammonium citrate B as in Example 34 16.8 8.9 3.7 36 C as in Example 34 17.4 9.3 4.1 37 D as in Example 34 26.6 14.0 4.3 38 'E 120 Magnesium-iron citrate Mg [Fe(citrate) 27.5 18.7 6.6
  • ammonium-iron citrate (NH ),,[Fe(citrate)-,]' 20 urea 20 ammonium citrate 75 water-soluble tobacco constituents "lncrease in by weight after drying, based on the foil used as starting material "Obtained by complete extraction of Burley tobacco with hot water as combustible starting material are shown in Table IV.
  • the foil is passed through an aqueous KMnO. bath 43 36 sprayed from solution in acetone 3.0 1.7 44 37 foil was treated with aqueous KMnO solution 3.0 3.0
  • Example 47a A 1% solution of citrus pectin in the form of the ammonium salt was sprayed onto the product produced according to Example 34 so that the dry weight of citrus pectin taken up by the product was 1.3% by weight.
  • Table VII shows the expected and found condensate contents and nicotine contents for various mixtures. When calculating the expected values, the bulk volumes of the various mixtures were taken into consideration.
  • Example 47b A mixture of by weight of the product according to Example 47a and 70% by weight of a commercial fine cut tobacco mixture with the type of flavor of an American blend was made up into cigarettes. The flavor produced by the pectin in the main stream smoke was completely compatible with the tobacco aroma and rounded off the aroma bouquet.
  • Example 48 A 2% solution of zein in ethanol was sprayed onto the product produced according to Example so that the weight increase due to the zein was 1.7% after drying.
  • the product made up into cigarettes was found when smoked to produce an improved aroma in the main stream and subsidiary stream smoke compared with the product according to Example 35 and had the same condensate value.
  • Example 49 A 2% ethanolic solution of zein was sprayed onto the product made according to Example 39 so that the weight increase due to the zein was 1.5% by weight after drying.
  • Example 50 Mixtures were prepared as indicated in Table V11 from the smoking products according to Example 39
  • the foil produced according to Example 36 was sprayed with an aqueous alcoholic solution of potassium nitrate and dried, the increase in dry weight being 1%.
  • Example 52 The foil produced according to Example 36 was sprayed with an aqueous potassium nitrate solution and dried, the increase in dry weight being 2%. Condensate: 2.5 mg/Cig.
  • Example 53 A foil produced according to Example 38 was sprayed with an aqueous potassium nitrate solution and dried, the increase in dry weight being 2%. Condensate: 3.2 mg/Cig.
  • Example 54 A combustible material in the form of a paper web of bleached sulfate cellulose containing 45% by weight of aluminum hydroxide as a filler and having a surface weight of 50 g/m and a thickness of 38 p. was treated in an immersion bath containing:
  • Example 55 A combustible material as in Example 54 consisting of a foil of bleached sulfate cellulose which contained 45% by weight of aluminum hydroxide as a filler and which had been pretreated with a 2% aqueous potassium permanganate solution was treated in an immersion bath which consisted of:
  • the product obtained by this Example was exceptionally compatible with a commercial tobacco mixture which had a light note.
  • a smokable product comprising a cellulosebased combustible material
  • the improvement which comprises incorporating therein at least one chelate compound of the stoichiometric formula.
  • K is an alkaline earth metal or divalent manganese
  • Me is trivalent iron or aluminum
  • R is the radical of a chelate-forming organic carboxylic acid
  • w, x, y and z are integers up to about 5, the chelate compound being incorporated in an amount ranging from about 0.5 to 70% by weight of the combustible material.
  • organic carboxylic acid is a material selected from the group consisting of oxalic, glyceric, glycolic, malic, tartaric, citric, galactaric and saccharic acids.
  • the chelate compound is a material selected from the group consisting of magnesium-iron (III) glycolate, magnesium-iron (III)-oxalate, magnesium-iron (III) citrate, magnesium-iron (III) tartrate, magnesium-iron (III) galactarate, magnesium-iron (III) saccharate, magnesium-aluminum glycolate, magnesium-aluminum oxalate, magnesium-aluminum citrate, magnesiumaluminum tartrate, magnesium-aluminum galactarate, magnesium-aluminum-saccharate, manganese-iron (III) glycolate, manganese-iron (III) oxalate, manganese-iron (III) citrate, manganese-iron (III) tartrate, manganese-iron (III) galactarate, manganese-iron (III) saccharate, manganese-aluminum glycolate, manganese-aluminum oxalate, manganese-iron (III) citrate, manganese-iron (III) tart
  • a smokable product according to claim 1 containing about 1 to by weight of at least one filler selected from the group consisting of minerals and salts which are inert under conditions of smoking, and hydroxides and hydrated oxides which split off water under conditions of smoking.
  • a smokable product according to claim 8 wherein the filler is at least one material selected from the group consisting of hydrated oxides of aluminum and silicic acid.
  • a smokable product according to claim 1 containing at least one compound which splits off ammonia under conditions of smoking and which is present in an amount such that the smoke has a pH of about 5 to 8.
  • a smokable product according to claim 10, wherein the compound which splits off ammonia is at least one material selected from the group consisting of ammonium salts of inorganic acids, ammonium salts of organic acids, salts of amino acids and acid amides.
  • a smokable product according to claim 10, wherein the compound which splits off ammonia is at least one material selected from the group consisting of acid or neutral ammonium carbonate, nitrate or phosphate, ammonium citrate, ammonium tartrate, ammonium or magnesium glutamate, urea, ammonium-iron (III) glycolate, ammonium-iron (III) oxalate, ammonium-iron (III) citrate, ammonium-iron (III) tartrate, ammonium-iron-(III) galactarate, ammonium-iron (III) saccharate, ammonium-aluminum glycolate, ammonium-aluminum oxalate, ammonium-aluminum citrate, ammonium-aluminum tartrate, ammonium-aluminum galactarate and ammonium-aluminum saccharate.
  • the compound which splits off ammonia is at least one material selected from the group consisting of acid or neutral ammonium carbonate,
  • a smokable product according to claim 1 containing about 0.01 to 7% by weight of at least one oxidizing agent selected from the group consisting of alkali metal or alkaline earth metal nitrates and alkali metal permanganates.
  • a smokable product according to claim 1 containing about 0.01 to 10% by weight of the ammonium salt of at least one polymeric acid selected from the group consisting of pectin, alginic acid, gum arabic or carboxymethylcellulose.
  • a smokable product according to claim 1 containing about 0.01 to 5% by weight of at least one low sulfur-content protein selected from the group consisting of zein, hordein and gliadin.
  • a smokable product according to claim 1 containing about 0.1 to 50% by weight of a tobacco extract.
  • a smokable product according to claim 1 in the form of a cigarette or cigar.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
  • Paper (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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US4296762A (en) * 1977-07-01 1981-10-27 Bayer Aktiengesellschaft Smokable products
US4830028A (en) * 1987-02-10 1989-05-16 R. J. Reynolds Tobacco Company Salts provided from nicotine and organic acid as cigarette additives
US4920990A (en) * 1988-11-23 1990-05-01 R. J. Reynolds Tobacco Company Cigarette
US5031646A (en) * 1990-01-16 1991-07-16 R. J. Reynolds Tobacco Company Cigarette
US5133368A (en) * 1986-12-12 1992-07-28 R. J. Reynolds Tobacco Company Impact modifying agent for use with smoking articles
US5559263A (en) * 1994-11-16 1996-09-24 Tiorco, Inc. Aluminum citrate preparations and methods
RU2358621C2 (ru) * 2004-07-30 2009-06-20 Браун Энд Уилльямсон Холдингс, Инк. Выкуриваемый наполнитель из заменителя табака, обладающий увеличенным удельным объемом, и способ его изготовления
US20150122280A1 (en) * 2004-10-25 2015-05-07 Philip Morris Usa Inc. Synthesis and incorporation of high-temperature ammonia-release agent in lit-end cigarettes
CN109567254A (zh) * 2018-12-20 2019-04-05 陕西科技大学 一种烟草薄片及制备方法及其基片、涂布液的制备方法
CN109788794A (zh) * 2016-10-18 2019-05-21 菲利普莫里斯生产公司 用于提高电子蒸汽烟装置的蒸汽前调配物的稳定性的方法和系统
US10765141B2 (en) 2015-01-07 2020-09-08 British American Tobacco (Investments) Limited Material for inclusion in a smoking article
US11317649B2 (en) 2015-01-07 2022-05-03 British American Tobacco (Investments) Limited Material for inclusion in a smoking article

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US4804002A (en) * 1987-05-29 1989-02-14 P. H. Glatfelter Company Tobacco product containing side stream smoke flavorant
DE4334222C3 (de) * 1993-10-07 2001-07-26 Reemtsma H F & Ph Stabförmiges Rauchprodukt
HRP940578B1 (en) * 1993-10-07 1999-10-31 Hans Noe Rod-shaped smoking article
CN105286078B (zh) * 2015-11-21 2017-05-10 安徽中烟再造烟叶科技有限责任公司 一种棉杆皮纤维代替木浆纤维制备造纸法再造烟叶的方法

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Cited By (19)

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Publication number Priority date Publication date Assignee Title
US4296762A (en) * 1977-07-01 1981-10-27 Bayer Aktiengesellschaft Smokable products
US5133368A (en) * 1986-12-12 1992-07-28 R. J. Reynolds Tobacco Company Impact modifying agent for use with smoking articles
US4830028A (en) * 1987-02-10 1989-05-16 R. J. Reynolds Tobacco Company Salts provided from nicotine and organic acid as cigarette additives
US4836224A (en) * 1987-02-10 1989-06-06 R. J. Reynolds Tobacco Company Cigarette
US4920990A (en) * 1988-11-23 1990-05-01 R. J. Reynolds Tobacco Company Cigarette
US5031646A (en) * 1990-01-16 1991-07-16 R. J. Reynolds Tobacco Company Cigarette
US5662168A (en) * 1994-11-16 1997-09-02 Tiorco, Inc. Process for modifying the water permeability of a subterranean formation
US5654261A (en) * 1994-11-16 1997-08-05 Tiorco, Inc. Permeability modifying composition for use in oil recovery
US5559263A (en) * 1994-11-16 1996-09-24 Tiorco, Inc. Aluminum citrate preparations and methods
RU2358621C2 (ru) * 2004-07-30 2009-06-20 Браун Энд Уилльямсон Холдингс, Инк. Выкуриваемый наполнитель из заменителя табака, обладающий увеличенным удельным объемом, и способ его изготовления
US20150122280A1 (en) * 2004-10-25 2015-05-07 Philip Morris Usa Inc. Synthesis and incorporation of high-temperature ammonia-release agent in lit-end cigarettes
US9668514B2 (en) * 2004-10-25 2017-06-06 Philip Morris Usa Inc. Synthesis and incorporation of high-temperature ammonia-release agent in lit-end cigarettes
US10226065B2 (en) 2004-10-25 2019-03-12 Philip Morris Usa Inc. Synthesis and incorporation of high-temperature ammonia-release agent in lit-end cigarettes
US10765141B2 (en) 2015-01-07 2020-09-08 British American Tobacco (Investments) Limited Material for inclusion in a smoking article
US11317649B2 (en) 2015-01-07 2022-05-03 British American Tobacco (Investments) Limited Material for inclusion in a smoking article
CN109788794A (zh) * 2016-10-18 2019-05-21 菲利普莫里斯生产公司 用于提高电子蒸汽烟装置的蒸汽前调配物的稳定性的方法和系统
CN109788794B (zh) * 2016-10-18 2022-04-01 菲利普莫里斯生产公司 用于提高电子蒸汽烟装置的蒸汽前调配物的稳定性的方法和系统
CN109567254A (zh) * 2018-12-20 2019-04-05 陕西科技大学 一种烟草薄片及制备方法及其基片、涂布液的制备方法
CN109567254B (zh) * 2018-12-20 2021-07-30 陕西科技大学 一种烟草薄片及制备方法及其基片、涂布液的制备方法

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FI58254C (fi) 1981-01-12
NO131152C (enrdf_load_stackoverflow) 1975-04-16
IL40860A0 (en) 1973-01-30
NL7215529A (enrdf_load_stackoverflow) 1973-05-22
DK147252C (da) 1984-12-03
CA978819A (en) 1975-12-02
SE409166B (sv) 1979-08-06
CS164938B2 (enrdf_load_stackoverflow) 1975-11-28
AT334266B (de) 1976-01-10
JPS4861696A (enrdf_load_stackoverflow) 1973-08-29
CH569428A5 (enrdf_load_stackoverflow) 1975-11-28
SU516333A3 (ru) 1976-05-30
EG11093A (en) 1976-12-31
IL40860A (en) 1976-04-30
IE37185B1 (en) 1977-05-25
IN139200B (enrdf_load_stackoverflow) 1976-05-22
DD105716A5 (enrdf_load_stackoverflow) 1974-05-12
HU168783B (enrdf_load_stackoverflow) 1976-07-28
FR2161705A5 (enrdf_load_stackoverflow) 1973-07-06
ATA979472A (de) 1976-04-15
IT1045265B (it) 1980-05-10
FI58254B (fi) 1980-09-30
NO131152B (enrdf_load_stackoverflow) 1975-01-06
LU66490A1 (enrdf_load_stackoverflow) 1973-02-01
NL179967C (nl) 1986-12-16
USB306655I5 (enrdf_load_stackoverflow) 1975-01-28
JPS5715874B2 (enrdf_load_stackoverflow) 1982-04-01

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