DE1792740C3 - Method of making a combustible material - Google Patents

Description

Strong mineral acids and salts of such strong acids with weak bases can be used as catalysts. Examples of such catalysts are sulfamic acid and ammonium sulfamic acid. Phosphoric acid, p; _ammonium lyte | rogue phosphate. Ammoniumu · -Jro · ■ _hjl , sulfuric acid, ammoniumuslf; .., alz-

gi μ ζ ,. 'errichlorid. Other catalysts are sau "· - _{d wic} , _ _n sodium hydroxide, oikv a

λ κ. , ^ weak acid, such as B. Sodium I ₁ ...... _The alkaline catalysts should, however

ca " _abc structural carbohydrate washed out before it is incorporated into _{a smoking product, uen ο n jst in an amount of} , _{to 2} () (; _c .

, based on the carbohydrate, present

Subject of the turn -st cn process for the * ₅ production of a combustible material by hermetically breaking down a carbohydrate. The material is suitable as a smoking product for cigarettes, cigars and pipes.

Smoking products usually consist of or contain a high ante of natural tobacco. It is generally believed that smoking tobacco, particularly cigarettes, can cause lung cancer. This has been attributed to the fact that carcinogenic compounds such as / B. ^^ 'P ^ are present; however, experiments in which the tar from tobacco smoke is spread on the skin of mice indicate this. that this tar also contains other harmful ingredients. It is assumed that the harmful effects of smoking are correspondingly reduced by the depletion of the tar content. It is already known to replace the tobacco in smoking products at least partially with wood pulp cells, resulting in smoke mixtures whose smoke unites However, smoke products do not have a lower content of earc.nogenic material

ne? 3ige _n rSfindung, the task ag to-creating grunde, a combustible material which acts as a complete or partial lirsat /. for the tobacco can be used in smoking products and which gives a smoke which has a pleasant aroma and a lower content of harmful components than the smoke of tobacco.

The method according to the invention is characterized in that carbohydrates, cellulose, cellulose derivatives, Mono- and polysaccharides, starches, alginates,

At; "Sf C ^C LT AnweSSrrrrS at ^h :> Crozem bez .: e ^" aTdas Koi.ehydrat, an acid, a salt of a strong acid with a weak base, an alkali hydroxide or an alkali salt of a weak acid as a catalyst "5 heated so long until the remaining black solid weighs less than 90 percent by weight of the starting dry carbohydrate.

ilen. " _Cc j" _ne tc carbohydrates are among other things

"., Cellulose, cellulose derivatives, such as / as Melhyl -.!.., ^ ,, loose mono- and polysaccharides such as Cilucosc""""'U. _irose starches such B rice, Kartoffclumi.. ^ .J ^1. ^ ' _Alpmatc . Pectin and natural vegetable gum, such as gum tragacanth, (iummi • uabiuim and (iummi from carob fries. " The quality of smoke is better than the corresponding '"of the au. _linbc " _a ndelten carbohydrates.

R-uthpn .Ov ^ _r ^^ ^

^ e _t en _{auücrdcm VV} narrower tar than tobacco can be the smoke products in the / usetung and thus in the smoking properties ^ i ^^ _{dcn aK (icml} sche. the untreatedc - _{d only} contain Tahak. Hcispicls-JJJ ^ JJ _{h / abe of} cicschmat-ksmiltcln the wise ^ j "Raudis in several (ieschmacksrich-C tstl ^ima ^ .J ^{cs Kd} _{rdcn [) ic Mcngc dcs} Nicotine, the 1 mgu ^^ ^^ Sandten of smoking products

^ Z Un »cltcn Frenzen Iu-I, eb, g set

miuci, iwuin

^wc ™haben " _crrill junusgemäücn method can the Hern _t rf ndun _fc jtn. ^ _m ^^

Carbohydrates in jcuu t,

his ^ sol. ^ «N ^ blat ^ ™ * _as j _through , _alsoen

or syringing with egg. ^ r

imprägn «« «nd then ^

Carbohydrate can with cmer lo

verm.scht and then ge ro _t k nc ^^ ^

hy ^ at K Jt, ^ or-Gun isch ^, r ^ v .jr ^ swc-s c ^ M,

JLmgsze.t judge. ^ »^^» ^ Z- ratur, the catalyst con / enlr.U.on and the ange

strived (i loss of weight.,

The catalytic degradation process. b the carbohydrate m black, which iur / μ r Ucn and cigars can be undesirable. Durdi I chandhinfc des degraded KoWehydrats η t Sa peic acid Was sers.offpcroxyd or ammonia ^l ^ ^wu ^ ^c J ^ ¹ elevated temperature can now dc I a. hey it Kohe hydrate another so that tobacco EMC, 1 arbe ^Cr lor the production of Rauchproduk.cn, the degraded carbohydrate also be provided with fiteren, rwunsdUen ingredients »P ¹ ^« ^ ann one Ghmmkatalysa.oren M.tle / cohesion Ashes and flavors or pharmaceuticals / uBebci y Al glow catalysts, alkali metal compounds are preferred.

i 792 740

As substances / uv improving cohesion of the ash salts of ammonia, alkali metals or Hrdalkalimetallen can be used, wherein the salts of magnesium, calcium or ammonium are preferred.

Numerous useful cosmetic ingredients can be added, such as: H. Tobacco extracts, organic L-ster, essential oils, menthol, tonka bean or vanillin · Glycerin is useful as a moistener or cilycols, such as. B. ethylene glycol or Di-, Triodcr Tetraäthylcng'ykol, used.

Other substances, such as B. carbonates or porous inert fillers, can improve the combustion properties can be added. Such substances give the product a loose structure, so that the Oxygen / entry is favored.

Smoke products should preferably simulate tobacco. The degraded carbohydrate is therefore preferred converted into leaf form and then crushed to use as a cigarette or pipe filling. For the production of a smoking product one can use sheet-shaped carbohydrate with the desired additives treat and then crush. If the broken down carbohydrate is present or is in a different form the leaf-shaped carbohydrate after the treatment according to the invention is too weak to cut properly so you can pulverize it and then with a solution of a film-forming agent, such as. B. a solution of a water-soluble cellulose derivative, Polyvinyl alcohol, starch. Mix pectin, vegetable gum or slime and process into an I-him and then dry. Water-soluble methyl cellulose is preferably used as the film-forming agent or sodium carboxymethyl cellulose is used. Is such celluloses to be used, of which a 2 "strength aqueous solution at 25 ° C. has a viscosity of at least 1500 cP. Became an acidic catalyst, like λ Β. Sulfuric acid, used so it is advantageous if the possible residual acidity of the broken down carbohydrates is increased by adding the appropriate Amount of ammonia is neutralized. This measure leads to an improvement in the smoke quality of the final product. This improvement also occurs. when ammonia is used to improve oxygen is used as described above. The other components of the smoking product can be used together incorporated with the carbohydrate in the [restructuring agent will. If necessary, soluble additives can be sprayed onto the sheet-like smoke mixture will. For use in cigarettes or pipes, the crushed mixture is preferably used in brought to a moisture content of 5 to 15 percent by weight in a humid atmosphere.

The invention is illustrated in more detail by the following examples, in which all quantities refer to the By weight.

Example I.

1.0 part of ri-cellulose paper was placed in a 6.0% igc dipped aqueous solution of ammonium sulfamate and then / wiped absorbent pad so that 1.0 part of the Solution remained in the paper. The paper was air dried at 55 "C and then left on for 4 hours 200 "C until the weight of the degraded material is 57.6% of the original weight of the (/ -Cellulose and ammonium sulfamate together. The paper turned black. After that The paper was cooled with an aqueous solution containing 2 "" potassium carbonate and 4 "; ', glycerin, splashed and pressed again between absorbent pads, so that 1.0 part of the solution remained in the paper. The paper was air dried at room temperature. 1.0 part of an oxygenated methyl chloride extract was then applied to the leaf sprayed with tobacco as a cooking agent. The sheet then became a replica a cigarette filling and then conditioned at 25 C and 86 "" relative humidity so that the

ίο final moisture content was 7 "". The obtained Product was made into cigarettes in conventional cigarette paper tubes. The average weight the cigarette was 1.0 g.

The side and main streams of smoke generated with the cigarettes were milder and less irritating to the eyes and throat than conventional tobacco cigarettes.

Example 2

1.0 egg: the cigarette filling according to Example I. was mixed with 1.0 part of crushed cigarette tobacco, and the resulting mixture was made into cigarettes. The average weight of the Cigarettes weigh 1.0 g.

The side and air smoke flows generated with the cigarettes were very mild and less irritating to the eyes and throat than an ordinary tobacco cigarette.

Example 1

A cigarette filling as in Example I was used produced, with the exception that instead of the 6.0 "strength aqueous ammonium sulfamic solution, a 2.5 "ige solution of the same was used and that impregnated paper was heated to 246 ° C. for 2 minutes and not to 200 ° C. for 4 hours. The weight of the degraded material was 58.6 "" the initial weight of the i-cellulose / ammonium sulfamate mixture. This filling was made into cigarettes with an average weight of 1.0 g.

• v The rope and llauptrauchstiömc were those according to example I very similar.

Example 4

A cigarette filling was produced as in Example IS, with the difference that instead of the aqueous one Ammonium sulfamate solution is a 5.0 ", aqueous Sulphamic acid solution was applied. The weight of the degraded material was 62 "" of the initial weight of the II-Ccllulose / Sulphamic acid mixture. the The filling was made into cigarettes with an average weight of 1.0 g each.

The side and main streams of smoke generated with the cigarettes were very mild and less irritating Eyes and throat than a normal tobacco cigarette.

Example 5

For example, a cigar filling was produced as in Example I, with the difference that instead of the aqueous Ammonium sulfamate solution is an 8.6% aqueous solution

Ammonium sulfate solution was used and the Heat treatment was not carried out at 200 C but at 175 ° C. The weight of the mined Material was 68% of the initial weight of the fi-cellulose / ammonium sulfate mixture. The filling

was made into cigarettes with an average weight of 1.0 g.

The side and main smoke flows were very similar to those of Example 1.

Example ύ

1.5 parts of cellulose (SuIfilv: rfahren-Holzpulpc with 92% cellulose) were whipped as a slurry in 100 parts of water in the usual way. then 0.38 parts of calcium carbonate and 4 (K) parts of water were added, whereupon the material was slurried was processed in a manner known per se into a sheet of paper, which was placed between absorbent pads at room temperature was dried. The sheet containing 10% by weight calcium carbomite was placed in a 5.6% sge aqueous ammonium sulfamate solution immersed and pressed between suction pads so that 1.5 parts of the solution remained in the sheet. The sheet was then at Dried room temperature and heated to 200 C for 2 hours. The weight of the material mined was then 61% of the initial weight of the Ccllulose / Calciumcarbonat / Ammoniumsulfamal-Gcmischs. The degraded material was then treated further as in Example I, with the difference that a 4 "igen an aqueous glycerin solution was used. The filling obtained was made into cigarettes with an average weight of 1.0 g.

The side and mouth smoke generated with the cigarettes were milder and less irritating to the eyes and throat than an ordinary tobacco ciga save.

Example 7

One cigarette was tilled as in Example 6 manufactured, with the exception that the sheet instead Calcium carbonate contained 12.8 parts magnesium carbonate and the slurry contained 0.008 parts cationic Strength were increased to increase retention Magnesium carbonate? t improve. After the heat treatment, the weight of the dismantled was Material 63 ", ', the initial weight of the mixture of cellulose, magnesium carbonate and ammonium sulfamate.

The side and main smokers produced with cigarettes made from this filling were much milder and less irritating to the eyes and throat than a standard tobacco cigarette.

Example 8

A cigarette filling was produced as in Example I, with the difference that a 5% aqueous solution of ammonium dihydrogen phosphate was used instead of the aqueous ammonium sulfamate solution and a 10% strength glycerin solution was used instead of a 4% strength. In this example, the weight of the degraded material betrtg 75% of the initial weight of the "- Cellulose / ammonium dihydrogen phosphate - mixture.

The side and main smoke rhymes produced with cigarettes from this filling were milder and less irritating to the eyes and throat than a conventional tobacco cigarette.

Example 9

The result was a cigarette filling as in Example 8 produced, with the difference that instead of the aqueous ammonium dihydrogen phosphate solution one 5% aqueous solution of diammonium hydrogen phosphate was used. The weight of the mined Material amounted to 74% of the initial weight of the (icmisehs from -cellulose and diammonium hydrogen phosphide.

The side and laue smoke currents produced with cigarettes from this filling were milder and less irritating to eyes and throat than a conventional tobacco / igaretle.

Example 10

A cigarette filling was produced as in Example 3, with the difference that instead of the aqueous one Ammonium sulfamate solution is a 5.6 "strength aqueous

ίο acid solution was used. The weight of the degraded material was 53 "" of the initial weight of the cellulose / weak acid mixture Filling was processed into cigarettes with an average weight of 1.0 g.

The side and main smoke flows were very similar to those of Example I.

Example Il

A cigarette filling was produced as in Example 3, with the difference that instead of the aqueous ammonium sulfamate solution a 6.5 "strength aqueous solution of phosphoric acid was used. In this example the heat treatment Carried out for 4 minutes at 225 ° C and not 2 minutes at 246 ° C. The weight of the material being mined was 73 "" of the initial weight of the -cellulose / phosphoric acid cicmiseh. The filling turned into cigarettes processed with an average weight of 1.0 g.

The ropes and main streams of smoke were much less pungent tasting and less irritating to Eyes and throat than an ordinary tobacco cigarette.

Example 12

1.0 part of cellulose pulp in sheet form was poured into a Dipped 10, 0 "ige aqueous black acid solution and pressed between rollers so that 1.0 part of the solution remained in the BIaU. The sheet was exposed to air at 45 C dried and then heated to 225 C for 4 minutes, whereupon it turned black. The weight of the mined Material was 75% of the initial weight of the "-Cllulose / Schwerclsäurc-Mixture". The black leaf was then cooled and ground to a powder,

which passed through a 0.12 mm mesh sieve. Then there were 11.4 parts of the black Powder mixed intimately with 2.0 parts of calcium carbonate and then 100 parts of a stirred aqueous Solution added, the 2.0 parts of sodium

5 "carboxymethyl cellulose, 2.8 parts glycerin, 0.8 parts Citric acid and 1.0 part potassium citrate. The resulting slurry was measured as a 0.381 mm thick film spread on a running endless steel conveyor belt and then gctrock-

^rc nel. The dried film was splashed with water so that the film had a water content of 25%, whereupon the film was removed from the steel belt and conditioned at 20 ° C. in a 70% relative humidity atmosphere to make the final

"" Water content was 13%. The film became a replica a cigarette filling and crushed using conventional cigarette paper tubes Cigarettes processed. The average weight of the cigarettes was 1.0 g.

^fi 5 The side and produced with the cigarettes 1 lauptrauchströme were milder and less irritating to the eyes and throat than in a normal tobacco cigarette.

U c i s ο i c I I λ

1.0 part of H-Cclluloscpulpc in sheet form was poured into cine IO, O% igc aqueous solution of sulfuric acid gctuuchl and bruised between rollers, then 1.0 part of the Solution looking back. The sheet was at 45 C on the Air dried and then heated to 225 C for 4 minutes, during which it turned black. The weight of the degraded Material was 75 "of the initial weight of the (i-Ccllulosc / black acid mixture. The black Leaf was cooled and then ground to a powder that passed through a sieve of mesh 0.12 mm passed through. Then 11.4 parts of the black powder was added to 30 parts of water, and the resulting slurry was 1.6 ml a 0.88 η solution of ammonium hydroxide in water. That black slurry was added to a solution containing 70 parts of water, 2.0 parts of sodium arboxymethyl chloride, 2.8 parts Glycerin, 0.8 parts of citric acid, 1.0 part of potassium citrate and 2.0 parts of calcium carbonate. the The resulting slurry was treated as in Example 12. Thereby were cigarettes with average weight of 1.0 g.

The side and main tract streams, which with the Cigarettes produced were milder and less irritating to the eyes and throat than an ordinary one Tabakz.igarctte, and the taste quality was better than that of a cigarette made from the material which was made without adding ammonia to the slurry.

Example 14

A black, heat-coated pulp in the form of a sheet was obtained by treatment of cellulose with Sulfuric acid produced as in Example 12. Then were 20 parts of this black pulp in 20 parts of a 35% strength aqueous nitric acid solution at 90 ° C. during Immersed for 30 seconds. The product thus obtained was washed free of nitric acid with water and then dried at 50 ° C. Thus, 15 parts of a sheet having an orange-brown color was obtained similar to that of cigarette tobacco.

The sheet was treated as in Example 12 and made into cigarettes. The side and main streams of smoke were milder and less irritating to the eyes and throat than a standard cigarette.

Example 15

A black heat-treated pulp in sheet form was produced by treating -cellulose with sulfuric acid as in Example 12. Then, 20 parts of this black pulp were immersed in 40 parts of a ¹ 5 / o'gen aqueous hydrogen peroxide solution for 6 hours. The product thus obtained was washed with water free from hydrogen peroxide and dried at 40 ⁰ C. Thus, there were obtained 16 pieces of a sheet with an orange color similar to that of cigarette tobacco.

The sheet was treated as in Example 12 further. The cigarettes obtained produced side and main streams of smoke when smoked, the milder and less were irritating to the eyes and throat than conventional tobacco cigarettes.

Example 16

20 parts of a black heat-treated pulp in sheet form produced by treating «« -cellulose with sulfuric acid as in Example 12 was exposed to gaseous ammonia for 60 minutes under atmospheric pressure and at ambient temperature. Then the excess ammonia was evaporated off under reduced pressure, whereby 21.4 parts of a dark brown pulp powder in the form of a leaf were obtained.

The pulp material was continued as in Example 12

treated, and produced the resulting cigarettes

ίο when smoking side and llauptrauchströmc that were milder and less irritating to the eyes and throat than a conventional tobacco / igarcttc.

Example 17

19.0 parts of tragacanth gum were mixed with 20.0 parts of an aqueous ammonium sulfamic solution. The resulting wet paste was dried at 60.degree. C. and heated at 225.degree. C. for 18 minutes, resulting in a black powder

The weight was 60 "of the initial weight of the gum / ammonium sulfamate mixture . The black powder was stirred with a 35% strength aqueous nitric acid solution for 3 minutes at 90 ° C., washed free of acid with water and dried at 50 ° C.

A powder with an orange-brown color resulted. The powder was ground so that it would pass through a sieve of mesh size 0.12 mm . Then 11.4 parts of the powder were intimately mixed with 2.0 parts of calcium carbonate and added to 100 parts of a stirred aqueous solution containing 2.0 parts of sodium carboxymethylcellulose, 2.8 parts of glycerol, 0.8 parts of citric acid and 1.0 part of potassium citrate. The resulting slurry was treated as in Example 12 and the resulting cigarettes produced side and main streams of smoke when smoked which were milder and less irritating to the eyes and throat than a conventional tobacco cigarette.

Example 18

Cigarettes were produced as in Example 17, with the difference that instead of gum tragacanth Locust bean gum was used and the heat treatment was carried out at 225 ° C. for 60 minutes became. In this example the weight of the black powder was 70% of the initial weight of the Mixture of locust bean gum and ammonium sulfamate.

The side and main streams of smoke generated with the cigarettes were very mild and less irritating to the eyes and throat than a conventional tobacco cigarette.

Example 19

Cigarettes were made as in Example 17, with the exception that gum arabic was used instead of tragacanth gum and the heat treatment was carried out at 225 ° C. for 30 minutes. That The weight of the black powder was 74% of the initial weight of the gum arabic mixture and ammonium sulfamate.

The side and main streams of smoke generated with the cigarettes were very mild and less irritating to Eyes and throat than an ordinary tobacco cigarette.

Example 20

Cigarettes were made as in Example 17, with the difference that instead of gum tragacanth

509615/105

D-glucose used and the heat treatment Was carried out at 225 ° C. for 12 minutes. The weight The actual powder was 63% of the initial weight the mixture of D-glueose and amnionium sulfamal.

Oic with the cigarettes generated side and Main streams of smoke were very mild and less irritating to the eyes and throat than from a usual one Tobacco cigarette.

Example 21

1. cigarettes were made as in Example 17, with the exception that instead of gum tragacanth methylcellulose used and the heat treatment 10 minutes at 225 ° C was carried out. The weight of the black powder thus obtained was 63 "" the initial weight of the mixture of Methylccllulosc and ammonium sulfamate.

The ropes and main streams produced by the cigarettes were very mild and less irritating for the eyes and throat than with a conventional tobacco cigarette.

Example 22

Cigarettes were produced as in Example 17, with the exception that instead of gum tragacanth rice starch is used and the heat treatment 35 minutes at 225 ° C was carried out. The weight of the black powder thus obtained was 66% the initial weight of the mixture of rice starch and ammonium sulfamate.

The side and Ilaupira smoke currents generated with the cigarettes were very mild and less irritating for the eyes and throat than with a conventional tobacco cigarette.

Example 23

Ils cigarettes were made as in Example 17, with the exception that instead of gum tragacanth pectin is used and the heat treatment is 20 minutes was carried out at 225 C. The weight of the black powder thus obtained was 60% of the initial weight the mixture of pectin and ammonium sulfamate.

The side and main currents from the cigarettes were very mild and less irritating to the eyes and Throat ak in an ordinary tobacco cigarette.

Example 24

Cigarettes were produced as in Example 17, Slightly different, that instead of gum tragacanth, alginic acid and the heat treatment was carried out at 225 ° C. for 23 minutes. The weight of the black powder thus obtained was 60% of the initial weight of the mixture of alginic acid and Ammonium sulfamate.

The side and main streams of smoke from the cigarettes were very mild and less irritating to the eyes and throat than a conventional tobacco cigarette.

Example 25

The flake sheet was refluxed over the surface of a concentrated hydrochloric acid solution for 2 hours (at about HO C) and then at 60 "C dried. The weight of the black-brown material thus obtained was 75% of the initial weight the cellulose. The degraded material was ground to a powder that passed through a mesh size sieve

ίο 0.12 mm passed, and then to cigarettes with Average weight of 1.0 g each processed as in Example 21.

The side and smoke streams from the cigarettes were milder and less irritating to the eyes and Throat than usual tobacco cigarettes.

Example 26

Cigarettes were produced as in Example 12, with the difference that instead of sulfuric acid a 10.0% igc trichloride solution is used and the heat treatment Was carried out at 230 ° C. for 20 minutes. The weight of the black thus obtained Material was 75% of the initial weight of the mixture of cellulose and fluoride.

The side and smoke streams from the cigarettes were milder and less irritating than usual Tobacco cigarcites.

Example 27

Cigarettes were produced as in Example 12, with the difference that instead of sulfuric acid, a 10.0 "strength sodium carbonate solution is used and the Heat treatment carried out at 230 "C for 20 minutes and that the degraded pulp sheet was washed substantially free of sodium carbonate. The weight of the dark brown material so obtained was 73% of the initial weight of the mixture made of u-cellulose and sodium carbonate.

The side and main streams of smoke from the cigarettes contained less "tar" than the smoke streams from usual tobacco cigarettes, but were not as pleasant as the smoke streams from the product according to example 12.

Example 28

There were cigarette as prepared in Example 12 with the exception that instead of sulfuric acid used is a <7.5 "" strength sodium hydroxide solution and dii Runaway heat treatment for 15 minutes at 230 ¹ C was leads, and that the pulp sheet has been degraded in gewaschei substantially free of sodium hydroxide The weight of the dark brown so obtained!

Material was 72% of the initial weight of the mixture of cellulose and sodium hydroxide.

The side and main smoke streams from the cigarettes were similar to those of Example 27.

Claims (2)

1 Ai claims: 1. Process / ur production of a combustible material by thermal decomposition of a carbohydrate, characterized, including cellulose as the carbohydrate. Cellulose derivatives, mono- and polysaccharides, starches, alginates, pectin or natural vegetable gum are used and at 100 to 250 C in the presence of 1 to 20 percent by weight, based on the carbohydrate, an acid, a salt of a strong acid plus one weak base, an alkali hydroxide or an alkali salt of a weak acid as a catalyst be heated until the remaining black solid is less than 90 percent by weight of the dry initial cabbage hydrate. 2. The method according to claim I, characterized in that that ammonium sulfamate as a catalyst is used. " 740