DE1792740B2 - Process for the preparation of a combustible material excretion from: 1692921 - Google Patents

Description

The invention relates to a method for producing a combustible material by thermal Breakdown of a carbohydrate. The material is suitable as a smoking product for cigarettes, cigars and whistles.

Smoking products are usually made from or contain high levels of natural tobacco. There is a general opinion that smoking tobacco, especially in the form of Cigarettes can cause lung cancer. This has been attributed to the fact that tobacco smoke contains carcinogens Connections such as B. 3,4-benzopyrene are present; however, attempts at which the tar from tobacco smoke is spread on the skin of mice, suggests that this tar too contains other harmful ingredients. It is believed that by reducing the tar content the harmful Effect of smoking is reduced accordingly.

It is already known that tobacco in smoking products can be at least partially replaced by wood pulp cellulose replace, whereby smoke mixtures are obtained, the smoke of which has a lower content of carcinogenic material contains. However, such smoking products do not have the desired aroma.

The present invention had the object to provide a combustible material that as complete or partial substitute for tobacco can be used in smoking products and that gives a smoke which has a pleasant aroma and a lower level of harmful ones Ingredients than the smoke of tobacco.

The inventive i; The method is characterized in that, used starches, alginates, pectin or natural gum as carbohydrate cellulose, cellulose derivatives, mono- and polysaccharides and at 100 to 250 ⁰ C in the presence of 1 to 20 weight percent, based on the carbohydrate, an acid, Salt of a strong acid with a weak base, an alkali hydroxide or an alkali salt of a weak acid as a catalyst are heated until the remaining black solid weighs less than 90 percent by weight of the dry starting carbohydrate.

The catalysts are strong mineral acids and salts of such strong acids with weak bases usable. Examples of such catalysts are sulfamic acid, ammonium sulfamate, phosphoric acid, Diammonium hydrogen phosphate, ammonium dihydrogen phosphate. Sulfuric acid, ammonium sulphate, hydrochloric acid and ferric chloride. Other catalysts are alkali hydroxide, such as. B. sodium hydroxide, or a Alkali salt of a weak acid, such as. B. sodium carbonate. The alkaline catalysts should, however be washed out of the broken down carbohydrate before it is incorporated into a smoking product. The catalyst is in an amount of 1 to 20 percent by weight, based on the carbohydrate.

Particularly suitable carbohydrates are inter alia cellulose, cellulose derivatives, such as. B. methyl cellulose. Mono- and polysaccharides, such as B. glucose and sucrose, starches, such as. B. rice, potato and corn starch, alginates, pectin and natural vegetable gum, such as. B. gum tragacanth. rubber carob arabic and gum.

Smoking products that contain the carbohydrate modified according to the invention are in taste and The quality of the smoke is better than the corresponding smoke products made from untreated carbohydrates. They make a smoother, less irritating smoke. The smoke also contains less tar than tobacco smoke. The composition and thus the smoking properties of the smoke products can also change can be varied better than mixtures containing untreated carbohydrates or just tobacco. For example By adding flavoring agents, the taste of the smoke can be made into several flavors can be varied. The amount of nicotine, which is an undesirable component of smoking products can be set as desired within wide limits.

In the method according to the invention, the carbohydrates can be treated in any form. So you can z. B. be powder or leaf-shaped. If a sheet-shaped carbohydrate is to be treated, it is expediently impregnated with a solution of the catalyst by dipping or spraying and then dried. A powdered carbohydrate can be mixed with a solution of the catalyst and then dried. The carbohydrate / catalyst mixture is preferably ^{heated to 150 to 250 °} C. for 1 minute to 4 hours. The heating time depends on the treatment temperature, the catalyst concentration and the desired weight loss.

The catalytic degradation process turns the carbohydrate black, which is good for cigarettes and Cigars can be undesirable. By treating the broken down carbohydrate with nitric acid, hydrogen Peroxide or ammonia, preferably at elevated temperature, can change the color of the carbohydrate change it so that it gets a tobacco brown color.

For the production of smoking products, the broken down carbohydrate can also be combined with other desired ones Components are provided. For example, glow catalysts, means for improving the Ashes and color cohesion, add nicotine, flavorings or medicines. as Corona catalysts are preferred to alkali metal compounds.

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As substances to improve the cohesion of the ashes can be salts of ammonia, alkali metals or alkaline earth metals are used, the salts of magnesium, calcium or ammonium to be favoured.

Numerous useful flavoring agents can be added, such as: B. Tobacco extracts, organic Esters, essential oils, menthol, tonka bean or vanillin. Glycerin is useful as a humidifier or glycols, such as. B. ethylene glycol or di-, tri- or tetraethylene glycol is 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 access is favored.

Smoking products should preferably simulate tobacco. The degraded carbohydrate is therefore preferred transferred into leaf form and then ready for use Crushed as a cigarette or pipe filling. Sheet-shaped ones can be used to make a smoking product Treat the carbohydrate with the desired additives and then chop it up. That falls degraded carbohydrate in another form or is the leaf-shaped carbohydrate according to the invention Treatment too weak to be 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, Mix polyvinyl alcohol, starch, pectin, vegetable gum or slime and process into a film and then dry. Water-soluble methylcellulose is advantageously used as the film-forming agent or sodium carboxymethyl cellulose used. Such celluloses should be used, of which a 2% aqueous solution at 25 ° C has a viscosity of at least 1500 cP. Got a sour Catalyst, such as B. sulfuric acid is used, then e:> is advantageous if the possible residual acidity of the degraded carbohydrate is neutralized by adding the appropriate amount of ammonia. These Measure leads to an improvement in the smoke quality of the end product. ! This improvement occurs also when ammonia is used for color enhancement as described above. The others Components of the smoking product can be incorporated into the film-forming agent together with the carbohydrate will. If necessary, soluble additives can be sprayed onto the sheet-like smoke mixture will. For use in cigarettes or arrows, 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 explained in more detail by the following examples, in which all quantities refer to the By weight.

example 1

1.0 part of a-cellulose paper was immersed in a 6.0% strength aqueous solution of ammonium sulfamate and then pressed between absorbent pads so that 1.0 part of the solution remained in the paper. The paper was air-dried at 55 ° C. and then ^{heated to 200 °} C. for 4 hours until the weight of the degraded material was 57.6% of the original weight of the α-cellulose and the ammonium sulfamate combined. The paper turned black After cooling, the paper was sprayed with an aqueous solution containing 2 "; potassium carbonate and 4% glycerol and again pressed 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 a 6% strength methylene chloride extract of tobacco was then sprayed onto the sheet as a flavoring agent. The leaf was then comminuted to simulate a cigarette filling and then conditioned at 25'X and 86% relative humidity so that the

ίο final moisture content was 7%. The received 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 produced by the cigarettes were milder and for the eyes and for themselves Throat less irritating than conventional tobacco cigarettes.

Example 2

One part of 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 was 1.0 g.

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 3

A cigarette filling was produced as in Example 1, with the difference that a 2.5% solution of the same was used instead of the 6.0% strength aqueous ammonium sulfamate solution and the impregnated paper was heated to 246 ^° C. for 2 minutes and not

Was heated to 200 ° C. for 4 hours. The weight of the degraded material was 58.6% of the initial weight des (Z-cellulose / ammonium sulfamate mixture. This filling was made into cigarettes with an average weight of 1.0 g.

4 "The side and main streams of smoke were those very similar to example 1.

Example 4

A cigarette filling was produced as in Example 1, with the difference that instead of the aqueous one Arr ^ oniumsulfamatlösung a 5.0% aqueous sulfamic acid solution was applied. The weight the degraded material was 62% of the initial weight of the µ-cellulose / sulfamic 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 to Eyes and throat than a normal tobacco cigarette.

Example 5

A cigarette filling was produced as in Example I, with the difference that instead of the aqueous Ammonium sulfamate solution an 8.6% strength aqueous

Ammonium sulfate solution was used and the heat treatment was not carried out at 200 ⁰ C but at 175 ° C. The weight of the degraded material was 68% of the initial weight of the µ-cellulose / ammonium sulfate mixture. The filling

⁶ S 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 6

1.5 parts of cellulose (sulfite process wood pulp with 92% cellulose) were whipped as a slurry in 100 parts of water in the usual way. then were 0.38 parts calcium carbonate and 400 parts ·; Water was added, whereupon the slurried material 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 carbonate was placed in a Immersed 5.6% aqueous ammonium sulfamate solution and pressed between suction pads, so that 1.5 parts of the Solution remained in the leaf. The sheet was then dried at room temperature and at 200 ° C. for 2 hours heated. The weight of the degraded material was then 61% of the initial weight of the cellulose / calcium carbonate / ammonium sulphate mixture. The degraded material was then treated as in Example 1, with the exception that a 4% strength was started a 10% aqueous glycerol solution was used. The resulting filling was made into cigarettes with an average weight of 1.0 g.

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

Example 7

It became a cigarette filling like with ßciipie! 6th produced, with the exception that the leaf contained 12.8 parts of magnesium carbonate instead of calcium carbonate, and that 0.008 parts of cationic starch was added to the slurry for retention to improve the magnesium carbonate. After the heat treatment, the weight of the dismantled was Material 63% of the initial weight of the mixture of cellulose, magnesium carbonate and ammonium sulfamate.

Who produce from this filling with cigarettes Side and main streams of smoke were much milder and less irritating to the eyes and throat than from a common tobacco cigarette.

Example 8

A cigarette filling was produced as in Example I, with the difference that instead of the aqueous Ammonium sulfamate solution is a 5% aqueous solution of ammonium dihydrogen phosphate and instead a 4% a 10% glycerol solution is used. In this example the weight of the demoted was Material 75% of the initial weight of the cellulose / ammonium dihydrogen phosphate mixture.

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

Example 9

A cigarette filling was produced as in Example 8, with the difference that instead of the aqueous one Ammonium dihydrogen phosphate solution a 5% aqueous solution of diammonium hydrogen phosphate was used. The weight of the mined Material was 74% of the initial weight of the mixture of -cellulose and diammonium hydrogen phosphate.

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

Example 10

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

ίο sulfuric acid solution was used. The weight of the degraded material was 53% of the initial weight of the -cellulose / sulfuric acid mixture. the Filling was made into cigarettes with an average weight of 1.0 g.

The side and main smoke streams were those according to the example! very similar.

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% aqueous solution of phosphoric acid was used. In this example the heat treatment was 4 minutes at 225 ° C and not 2 minutes at 246 ° C carried out. The weight of the degraded material was 73% of the initial weight of the «cellulose / Phosphoric acid mixture. The filling was made into cigarettes with an average weight of 1.0 g.

The side 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 10.0 ″ aqueous sulfuric acid solution dipped and pressed between rollers so that 1.0 part of the solution remained in the sheet. The sheet was exposed to air at 45'C dried and then heated to 225 ° C. for 4 minutes, during which it turned black. The weight of the mined Material was 75% of the initial weight of the cellulose / sulfuric acid mixture. The black sheet was then cooled and ground to a powder which passed through a 0.12 mm sieve. Then 11.4 parts of the black powder were intimately mixed with 2.0 parts of calcium carbonate and then added to 100 parts of a stirred aqueous solution containing 2.0 parts of sodium carboxymethyl cellulose, Contained 2.8 parts of glycerin, 0.8 parts of citric acid and 1.0 part of potassium citrate. the resulting slurry appeared as a 0.381 mm thick film on a running endless steel conveyor belt spread out and then dried at 130 C

^rc net. 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

⁶ⁿ water content was 13%. The film was crushed to simulate a cigarette filling and made into cigarettes using conventional cigarette paper sleeves. The average weight of the cigarettes was 1.0 g.

The side and main streams of smoke generated with the cigarettes were milder and less irritating to them Eyes and throat than in a common tobacco cicarettc.

Example 13

1.0 part of α-cellulose pulp in sheet form was put into a 10.0% aqueous solution of sulfuric acid immersed and pressed between rollers, so that 1.0 part of the Solution remained. The sheet would be air dried at 45 ° C and then heated to 225 ° C for 4 minutes, where it turned black. The weight of the degraded material was 75% of the initial weight of the u-cellulose / sulfuric acid mixture. The black one 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 carboxymethyl cellulose, 2.8 parts Glycerin, 0.8 parts citric acid, 1.0 part potassium citrate and 2.0 parts 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 streams of smoke generated with the cigarettes were milder and less irritating to eyes and throat than an ordinary tobacco cigarette, and the quality of taste was better than a cigarette made from the material made without adding ammonia to the slurry was produced.

Example 14

Black heat-treated pulp in sheet form was produced by treating α-cellulose with sulfuric acid as in Example 12. Then, 20 parts of this black pulp was immersed in 20 parts of a 35% strength aqueous nitric acid solution at 90 ° C. for 30 seconds. The product thus obtained was washed with water free from nitric acid, and then at 50 ⁰ C dried. Thus, 15 parts of a sheet with an orange-brown color similar to that of cigarette tobacco were obtained.

The sheet was treated as in Example 12 further and processed into cigarettes. The side and main streams of smoke were milder and less irritating to Eyes and throat than a normal cigarette.

Example 15

It became a black heat-treated pulp in sheet form by treating α-cellulose with Sulfuric acid produced as in Example 12. Then were 20 parts of this black pulp in 40 parts of a 15% aqueous hydrogen peroxide solution during Dived for 6 hours. The product thus obtained was washed free of hydrogen peroxide with water and dried at 40 ° C. Thus, there were obtained 16 parts of a sheet with an orange color similar to that of the Cigarettes 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 obtained by treating u-cellulose was produced with sulfuric acid as in Example 12, were exposed to ammonia gas for 60 minutes at atmospheric pressure and at ambient temperature. Then the excess ammonia was evaporated under reduced pressure, with 21.4 Parts of a dark brown pulp material in sheet form were obtained.

The pulp material was continued as in Example 12

treated, and produced the resulting cigarettes

ίο when smoking side and main streams of smoke that were milder and less irritating to the eyes and throat than a conventional tobacco cigarette.

Example 17

There were 19.0 parts of gum tragacanth with 20.0 parts of an 10% strength aqueous ammonium sulfamate solution mixed. The resulting wet paste was dried at 60.degree. C. and at 225.degree. C. for 18 minutes heated, producing a black powder, its

ao weight 60 ° / "of the initial weight of the rubber / Ammonium sulfamate mixture was. The black powder was mixed with a 35% aqueous nitric acid solution Stirred for 3 minutes at 90.degree. C., washed free of acid with water and dried at 50.degree.

* 5 A powder with an orange-brown color resulted. The powder was ground so that it passed through a 0.12 mm mesh sieve. then 11.4 parts of the powder were intimately mixed with 2.0 parts of calcium carbonate and 100 parts of a stirred aqueous solution added, the 2.0 parts of sodium carboxymethyl cellulose. 2.8 parts glycerine, Contained 0.8 parts of citric acid and 1.0 part of potassium citrate. The resulting slurry was as in Example 12 treated, and the resulting cigarettes produced side and main fume currents when smoking, which are milder and less irritating to the eyes and Throat than a usual 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 for 60 minutes at 225 ° C 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 is used instead of gum tragacanth and the heat treatment Was carried out at 225 ° C for 30 minutes. The weight of the black powder was 74% Initial weight of the mixture of gum arabic and ammonium sulfamate

The side and main streams of smoke produced by the cigarettes were very mild and less irritating to the eyes and throat than from an ordinary tobacco cigarette.
65

Example 20

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

D-glucose used and the heat treatment 12 minutes at 225'C was carried out. The weight of the black powder was 63% of the initial weight of the mixture of D-glucose and ammonium sulfamate.

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

Example 21

Cigarettes were made as in Example 17, with the exception that instead of gum tragacanth methyl cellulose is used and the heat treatment 10 minutes at 225 "C. The weight the black powder thus obtained was 63% of the initial weight of the mixture of methyl cellulose and ammonium sulfamate.

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

Example 22

Cigarettes were made 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 main streams of smoke generated with the cigarettes were very mild and less irritating for the eyes and throat than with a conventional tobacco cigarette.

Example 23

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 streams from the cigarettes were very mild and less irritating to the eyes and Throat than an ordinary tobacco cigarette.

Example 24

Cigarettes were made as in Example 17, with the exception 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 common tobacco cigarette.

Example 25

A cellulose sheet was maintained for 2 hours under RückfluC over the surface of a concentrated hydrochloric acid solution (at about 11O ⁰ C) and then dried at 60 ° C. The weight of the black-brown material thus obtained was 75% of the initial weight of the cellulose. The degraded material was ground to a powder which passed through a ί0 0.12 mm sieve and then made into cigarettes with an average weight of 1.0 g each as in Example 21.

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

Example 26

Cigarettes were made as in Example 12.

with the exception that a 10.0% strength solution of ferric chloride used in place of sulfuric acid and the heat treatment was durchgeführl 20 minutes at 230 ⁰ C. The weight of the black material thus obtained was 75% of the initial weight of the mixture of α-cellulose and ferric chloride.

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

Example 27

Cigarettes were made as in Example 12, with the difference that a 10.0% sodium carbonate solution is used instead of sulfuric acid and the Heat treatment was carried out for 20 minutes at 230 ° C, and that the pulp sheet degraded substantially washed free of sodium carbonate. The weight of the dark brown material so obtained was 73% of the initial weight of the mixture of α-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 streams of smoke from the produki according to example 12.

Example 28

Cigarettes were made as in Example 12, with the difference that instead of sulfuric acid a 7.5% sodium hydroxide solution is used and the Heat treatment was carried out for 15 minutes at 230 ° C, and that the degraded pulp sheet in washed essentially free of sodium hydroxide. The weight of the dark brown so obtained Material was 72% of the initial weight of the mixture of α-cellulose and sodium hydroxide.

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

Claims (2)

Patent claims: 1. A method for producing a combustible material by thermal degradation of a carbohydrate, characterized in that the carbohydrate used is cellulose, cellulose derivatives, mono- and polysaccharides, starches, alginates, pectin or natural vegetable gum and at 100 to 250 ⁰ C in the presence of 1 to 20 percent by weight, based on the carbohydrate, 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 are heated until the remaining black solid weighs less than 90 percent by weight of the dry exhausted carbohydrate . 2. The method according to claim I, characterized in that that ammonium sulfamate is used as a catalyst.