Smoking mixture
United States Patent Gibson et al.  
 SMOKING MIXTURE Inventors: James Gibson; Colin James Webster, both of Manchester, England Imperial Chemical Industries Limited, London, England Filed: Aug. 24, 1972 Appl. No: 283,290  
 Assignee:  
 Foreign Application Priority Data Sept, 8, 1971 United Kingdom 41921/71 US. Cl 131/2; 131/144; 131/17 R Int. Cl A2411 15/00 Field of Search 131/2, 140-144,  
 References Cited UNITED STATES PATENTS 3/1935 Seaman 131/4 A l Yl v 1 Apr. 22, 1975 Abbott, Jr l3l/140C Koree 131/2 Grunwald 131/2 Hind etal.... 131/17 R Kirkland 131/2 Hind et a1. .4 131/2 Troon et al 131/2 Primary Examiner-Melvin D. Rein Attorney, Agent, or Firm-Cushman, Darby &amp;  
 Cushman ABSTRACT A smoking mixture comprising a smoke-producing substrate (particularly a tobacco substitute or a blend with tobacco) fortified by nicotine and a substance producing acidic matter in the smoke to counteract chokiness. Volatile acids, or substances pryolysing to volatile acids or weak base salts may be used.  
 4 Claims, 6 Drawing Figures TOBACCO PATENTEDAPRZZIQYS sum 1 or g Om Om PATENTEUAPRZZIQYS 2,878,850  
 saw 3 o FIG.  
 PATENTEDAPRZZISTS 3,878.850 snmsggg SMOKING MIXTURE This invention relates to smoking mixtures and more particularly to smoking mixtures fortified with nicotine.  
  The smoke produced by smoking mixtures fortified with nicotine, particularly when used in cigarettes is unacceptably irritant. To distinguish from the type of irritancy produced by acrolein and similar substances in cigarette smoke the irritancy caused by nicotine fortification will hereinafter be referred to as &#34;chokiness. Nicotine in the smoke from flue-cured Virginia tobacco alone does not have this defect of chokiness.  
  A method of measuring the pH of whole tabacco smoke is disclosed in a paper by Sensabaugh and Cundiff in Tabacco Science VI page 25 and a similar method may be used for smoke from other substrates. Through investigations using such a method we have now come to associate a choky&#34; flavour effect when nicotine is added to smoking substrates eith an alkaline trend in the pH of the smoke therefrom and we have discovered that if this choky smoke is rendered more acid a decrease or disappearance of the choky effect is observed.  
  According to the invention therefore an improved smoking mixture comprises a smoke-producing substrate fortified by nicotine and containing also a substance which upon smoking of the mixture produces acidic matter in the smoke, whereby to reduce the chokiness thereof.  
  The invention is of value with natural or artificial smoke-producing substrates or mixtures thereof. it is particularly valuable with smoke-producing substrates containing modified carbohydrate manufactured by the process described and claimed in our United Kingdom Pat. No. l,l l3,979, i.e. by subjecting carbohydrate to a catalysed degradation process, for example at a temperature of l to 250C until the weight of the degraded carbohydrate is less than 90 percent of the weight of the original carbohydrate. More particularly the invention is of especial value with smoke-producing substrates containing modified cellulose manufactured by heating a-cellulose at l00-250C in presence of ammonium sulphamate. Another valuable substrate for use in the invention is that described and claimed in our United Kingdom Patent application No. 2270/69 comprising a solid condensate produced by acid or base catalysed condensation of a compound of the formula R COCH CH COR (l) (optionally produced in situ from a precursor thereof) wherein R and R which may be the same or different. each represents hydrogen or an alkyl, hydroxyalkyl or formyl group said condensate being fabricated with the aid of a filmforming agent into a form from which a tobacco simulating material can be produced. Other smokeproducing substrates which may be used in the invention are those based on various carbohydrates e.g. cellulose or on carboxymethyl cellulose or oxidised cellulose as the fuel. Tobaccos fortified by additional nicotine can similarly be employed.  
  The invention is of particular value with substrates comprising blends of tobacco with artificial smokeproducing substrates since these frequently require fortification with nicotine in order that the smoker may receive a degree of satisfaction comparable to that received from tobacco itself. Blends containing up to 80 percent of tobacco are particularly amenable.  
  In one embodiment of the invention the substance producing acidic matter in the smoke is an organic acid which is either volatile or steam-volatile and thus passes into the smoke directly, or pyrolyses on heating to produce a volatile or steam-volatile acid. Volatile acids are for example formic, acetic, propionic. ncaproic, iso-caproic and n-heptylic acids. Acids which pyrolyse to produce volatile acids are for example lactic, malic and maleic acids. The pyrolyses of lactic and malic acids are disclosed in a paper by K. R. Geisinger, T. C. Jones and l. Schmeltz, Tobacco Science 89. p.65-66, June [970.  
  In a second embodiment of the invention the substance producing acidic matter is a neutral substance which pyrolyses to produce acidic matter. Examples of such neutral substances are starch. fructose, glucose and esters particularly glyceryl esters e.g. glycerol mono-. dior tri-acetate, tributyrate, trioleate. tripalmitate.  
  In a third embodiment of the invention the substance producing acidic matter is a salt of a weak nitrogenous base (e.g. ammonia) with a strong acid (e.g. sulphuric or hydrochloric acid).  
  Although all substances which upon smoking of the mixture produce acid material in the smoke are effective in reducing the chokiness caused by nicotine used to fortify the substrate, it is sometimes advantageous to employ as the said substance a mixture containing combinations in order to avoid the introduction of other unpleasant taste/odour properties. Thus mixtures of am monium sulphate and lactic acid can advantageously be used.  
  For full effectiveness the quantity of the substance producing acidic matter should be sufficient to counteract the effect of the nicotine in producing chokiness and it will be clear that the necessary quantity will depend directly upon the amount of added nicotine in the smoking mixture and, in cases where pyrolysis is necessary, upon the extent to which this occurs in the process of smoking. Generally the proportion of the substance producing acidic matter will not exceed twice the proportion by weight of the fortifying nicotine. Proportions by weight of fortifying nicotine will not usually exceed 5 percent.  
  The smoking mixtuze of the invention may, if desired. contain other materials which are common constituents of smoking mixtures, for example glow-promoting catalysts, materials to improve ash coherence and colour, flavourants and medicaments.  
  Cigarettes, cigars and pipe-fillings from the improved smoking mixture of the invention produce less chokiness than corresponding smoking articles from comparable smoking mixtures which do not contain the substance producing acidic matter in the smoke. By using the preferred combinations of substances the chokiness may be completely eliminated without introduction of other unpleasant flavour characteristics.  
  The invention is illustrated but not limited by the following Examples in which all parts and percentages are by weight.  
  In the accompanying drawings FIGS. 1-6 each provide graphical illustrations of the puff-by-puff pH protiles during smoking of cigarettes made from smoking mixtures described in particular examples. The method employed for production of these graphical illustra tions is described by Sensabaugh and Cundiff in Tobacco Science Vl pages 25 to 30. This procedure is an empirical one and the results are comparative only. For this reason no absolute pH scale is marked on the figures. The horizontal line represents in each case the equilibrium pH of the electrode. Acidity increases upwardly.  
  Some of the Examples also include measurements of absolute pH carried out on collected smoke volatiles by the method of Y. Mikami et al.. Science Papers of Japan Monopoly Corporation 1967 Volume III, pages l73-l77. Distilled water was used in these measurements.  
 EXAMPLE l [[60 Parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with l6,l60 parts of water and ground in a disintegrator; 388 parts of glycerol followed by 227 parts of nicotine in 2000 parts water were added to the stirred mix. A dry mixture consisting of 708 parts of calcium carbonate, 2 16 parts of bentonite and 91 parts of ammonium sulphate was then added, followed by 5 l 7 parts of sodium carboxymethyl cellulose and 1,230 parts of magnesite and the resultant slurry stirred for at least 1 hour. The slurry was then cast on a drier to give a film with a dry basis weight of 48-52 g./sq. metre.  
  The film was shredded and the shred blended with flue-cured tobacco to give blends containing 70, 60 and 50% of tobacco. The blends were made up in cigarette form and these cigarettes were flavour assessed. No chokiness was reported.  
  FIG. 1 shows comparative puff-by-puff pH profiles of the smoke from the three blends described above, and the tobacco itself.  
  Similar blends were made from the same tobacco and an otherwise identical composition which did not contain ammonium sulphate. These blends all gave choky irritant smokes.  
  FIG. 2 shows comparative puff-by-puff pH profiles of the smoke from these three blends. By comparing FlG. l with H6. 2 it may be seen that the ammonium sulphate renders the smoke more acidic, thus counteracting alkalinity due to the added nicotine.  
 EXAMPLE 2 1160 Parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with l6,l60 parts of water and ground in a disintegrator. 388 Parts of glycerol followed by 227 parts of lactic acid and 227 parts of nicotine in 2,000 parts water, which had been previously mixed were added to the mix. A dry mixture consisting of 626 parts of calcium carbonate, 216 parts of bentonite and 91 parts of ammonium sulphate was then added, followed by 5l7 parts of sodium carboxymethyl cellulose and 1,088 parts of magnesite and the resultant slurry stirred for at least l hour. The slurry was then cast on a drier to give a film with a dry basis weight of 48-52 g./sq. me-  
  The film was shredded and the shred blended with flue-cured tobacco to give a blend containing 50 percent of tobacco. The blend was made into cigarettes and these cigarettes were flavour assessed. No chokiness was reported.  
  FIG. 3 shows a puff-by-puff pH profile of the smoke from this blend. Absolute pH values determined on portions of the smoke were Particulate phase Gas phase side stream EXAMPLE 3 Parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with l6,l60 parts of water and ground in a disintegrator. 388 Parts of glycerol followed by 227 parts of lactic acid and 227 parts of nicotine in 2,000 parts water which had been previously mixed were added to the mix. A dry mixture consisting of 663 parts of calcium carbonate, 2 l 6 parts of bentonite was added followed by 5 l7 parts of sodium carboxymethyl cellulose and H39 parts of magnesite and the resultant slurry stirred for at least 1 hour. The slurry was then cast on a drier to give a film with a dry basis weight of 48-52 g./sq. metre.  
  The film was shredded and the shred blended with flue-cured tobacco to give a blend containing 50 percent tobacco. The blend was made into cigarettes and these cigarettes were flavour assessed. No chokiness was reported.  
  A similar 50:50 blend of tobacco with an otherwise identical composition without lactic acid gave a choky irritant smoke.  
 EXAMPLE 4 51 Parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with 60 parts of water and ground in a disintegrator, 1.7 Parts of glycerol followed by 1 part of nicotine and l part glycerol triacetate in 20 parts of water were added to the stirred mix. A dry mixture consisting of 2.92 parts of calcium carbonate, 0.95 parts bentonite was then added followed by 2.3 parts of sodium carboxymethyl cellulose and 5.0 parts magnesite and the resultant slurry stirred for at least I hour. The slurry was then cast to give a film with a dry basis weight of 48-52 g./sq. metre.  
  The film was shredded and the shred blended with flue-cured tobacco to give a blend containing 50 percent of tobacco. The blend was made up in cigarette form and the cigarettes flavour assessed. No chokiness was reported.  
  FIG. 4 shows a puff-by-puff pH profile of the smoke from this blend. Absolute pH values determined on portions of the smoke were:  
 Particulate phase 6 EXAMPLE 5 5.02 Parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with 60 parts of water and ground in a disintegrator. l.7 Parts of glycerol followed by l part of nicotine in parts water were added to the stirred mix. A dry mixture consisting of 2.92 parts of calcium carbonate, 0.95 parts of bentonite and 2 parts of starch was then added followed by 2.3 parts of sodium carboxymethyl cellulose and 4.12 parts magnesite and the resultant slurry stirred for at least 1 hour. The. slurry was then cast to give a film with a dry basis weight of 48-52 g./sq. metre.  
  The film was shredded and the shred blended with flue-cured tobacco to give a blend containing 50 percent of tobacco. The blend was made up in cigarette form and the cigarettes flavour assessed. No chokiness was reported.  
  The same composition without starch gave a choky irritant smoke.  
 EXAMPLE 6 98.8 parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with 1,600 parts of water and ground in a disintegrator. 22.0 Parts of glycerol followed by 14 parts nicotine and 18 parts malic acid in 200 parts water were added to the mix. A dry mixture consisting of 60.4 parts of calcium carbonate, 18.4 parts of hentonite and 0.8 parts of ammonium sulphate was added, followed by 55.2 parts of sodium carboxymethyl cellulose and 105.2 parts of magnesite and the resultant slurry stirred for at least 1 hour.  
  The slurry was then cast on a drier to give a film with a dry basis weight of 48-52 g./sq. metre.  
  The film was shredded and the shred blended with equal parts of flue-cured tobacco and made into cigarettes. These cigarettes were flavour assessed. No chokiness was reported.  
  FIG. 5 shows a puff-by-puff pH profile of the smoke from this blend.  
  A similar 50:50 blend of tobacco with an otherwise identical composition without malic acid and ammonium sulphate gave a choky irritant smoke.  
 EXAMPLE 7 98.8 Parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with 1,600 parts of water and ground in a disintegrator. 22.0 parts of glycerol followed by 14 parts of nicotine and 18 parts of maleic acid in 200 parts of water were added to the mix. A dry mixture consisting of 60.4 parts of calcium carbonate, 18.4 parts of bentonite and 8 parts of ammonium sulphate was added followed by 55.2 parts of sodium carboxymethyl cellulose and 105.2 parts of magnesite. The resultant slurry was stirred for at least one hour then cast on a drier to give a film with a dry basis weight of 48-52 g./sq. metre.  
  The film was shredded and the shred blended with an equal part of flue-cured tobacco and made into cigarettes. These cigarettes were flavour assessed. No chokiness reported.  
  FIG. 6 shows a puff-by-puff pH profile of the smoke from this blend.  
  A similar 50:50 blend of tobacco with an otherwise identical composition without maleic acid and ammonium sulphate gave a choky irritant smoke.  
 EXAMPLE 8 5.02 Parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with 60 parts of water and ground in a disin tegrator. 1.7 Parts of glycerol followed by 1 part of nicotine and 1 part of fructose in 20 parts of water were added to the mix. A dry mixture consisting of 2.92 part: of calcium carbonate and 10.95 parts of bentonite was then added followed by 2.3 parts of sodium carboxymethyl cellulose and 4.12 parts magnesite and the re sultant slurry stirred for at least one hour. The slurry was then cast to give a film with a dry basis weight 0: 48-52 g./sq. metre.  
  The film was shredded and the shred blended witl equal part of flue-cured tobacco. The blend was made up in cigarette form and the cigarettes flavour assessed No chokiness was reported.  
  A similar 50:50 blend of tobacco with an otherwise identical composition without fructose gave a choky irritant smoke.  
 EXAMPLE 9 96.8 Parts of alginic acid was mixed with 1600 parts of water and ground in a disintegrator. 24.4 Parts 01 glycerol, 14.4 parts of potassium citrate followed by 20 parts of nicotine and 20 parts of lactic acid were added to the mix. A dry mixture consisting of 69.2 parts 01 calcium carbonate and 120.8 parts of magnesite was then added followed by 34.4 parts of sodium carboxymethyl cellulose and the resultant slurry stirred for at least 1 hour. The slurry was then cast on a drier to give a film with a dry basis weight of 48-52 g./sq. metre.  
  The film was shredded and the shred blended with ar equal weight of flue-cured tobacco shred and made into cigarettes and these cigarettes were flavour assessed. No chokiness was recorded.  
  A similar 50:50 blend of tobacco with an otherwise identical composition without lactic acid gave a choky smoke.  
 EXAMPLE 10 102.4 Parts of a material prepared by heat-treating a-cellulose in the presence of ammonium sulphamate was mixed with 1,600 parts of water and ground in z disintegrator. 34.4 Parts of glycerol followed by 2( parts of nicotine, 20 parts of formic acid in 200 part: of water were added to the mix. A dry mixture consist ing of 58.0 parts of calcium carbonate, 19.2 parts 0&#39; bentonite was then added followed by 45.6 parts of so dium carboxymethyl cellulose and 100.4 parts of mag nesite and the resultant slurry stirred for at least 1 hour The slurry was then cast on a Sandvik drier to give a film with a dry basis weight of 48-52 g./sq. metre.  
  The film was shredded and the shred blended with at equal weight of flue-cured tobacco shred and madi into cigarettes. These cigarettes were flavour assessec and no chokiness was recorded.  
  A similar 50:50 blend of tobacco with an OtllClWlSt identical composition without formic acid gave a chok smoke.  
 We claim:  
  1. A smoking mixture comprising a smoke-producim substrate containing a modified carbohydrate and forti fied by nicotine, said mixture containing also lactic acir present in a quantity sufficient to reduce the chokines or choky flavor effect of the smoke as caused by th nicotine fortification, the quantity of said acid being at more than twice the proportion by weight of the nico tine and the modified carbohydrate being the produc obtained by catalytic thermal degradation of carbohy 3. A smoking material according to claim 1 wherein the smoke-producing substrate contains up to percent by weight of tobacco.  
 4. A smoking mixture according to claim I wherein the mixture also contains ammonium sulphate.