DE2342196A1 - SMOKE MATERIAL - Google Patents

Description

PATENT'.NWÄLTE

DI PL. -ING. H. BOHR.
DIPL. -ING .. p. 37 EG ER ₁

8 MUNICH 5,
'MÜLLERSTRASSE 3 \

Folder 23 292 '.

Case Dt. 25 414-2 i.Auq. 1973

IMPERIAL GHiSMICAL INDUSTRIES LIMITED London, United Kingdom

SMOKE MATERIAL

Priority: Great Britain 8/31/1972 - 40324/72 -

The invention relates to the production of Rauchinet er ial for cigarettes, cigars, and pipes like that.

It is known that carbohydrates lose weight when heated, with the formation of simpler ones anhydrous types of sugar and / or a complete breakdown into small organic molecules, such as acetaldehyde, formaldehyde, formic acid, methane, carbon oxides, water and other compounds. Cellulose in particular releases anhydroglycose units, especially laevoglucosan.

GB-PS 1.113-979 describes a method of manufacture of a modified carbohydrate which is suitable for smoking mixtures and in which a carbohydrate

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is subjected to a catalyzed degradation process at a temperature of 100 to 25O ° C until the weight of the degraded carbohydrate is less than 90% of the weight of the starting carbohydrate. The degradation in such a process is completely different from that which occurs when a carbohydrate is ^{heated in / in the} absence of a catalyst and the products obtained in the two processes are completely different from each other.

It has previously been considered that if a carbohydrate is heated to a temperature above 250 ° even in the presence of a catalyst, the degradation will at least partially lead to the formation of smaller molecules such as those obtained in the absence of a catalyst. However, this is not the case. It has now been found that degradation does not take place to anhydrous sugar and smaller units in a significant cost scale when a carbohydrate is heated in the presence of a catalyst itself to a temperature above 250 ⁰ G.

In the accompanying drawings, curve A shows the weight loss achieved when heating

^ -Cellulose on increasing temperatures and curve B shows the weight loss achieved by heating a DG cellulose to the same temperatures in the presence of a catalyst, for example from 5% by weight Ammonium sulfamate.

According to the present invention, a method of preparing a smoke material is now proposed, which consists in that a carbohydrate material katalytisch.beeinflußten a thermal degradation at a temperature above 250 ⁰ C, is preferably subjected to 250 to 300 ⁰ C,

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until the weight of the solid residue is 30 to 90%, preferably 65 to 90 % of the weight of the starting carbohydrate material, whereupon the residue is bleached, mixed with a binder and further processed, if desired, to give a tobacco-like material.

When operating at the relatively high temperatures employed in the present process, it is particularly important to limit the duration of the heating so that the weight of the residue does not drop below 50%, and preferably not below 65%, of the weight of the starting carbohydrate material . The duration of the heating will depend to a very large extent on the effectiveness of the degradation catalyst used. In general, only short Erhitzungs · times are required see _f of a few minutes (eg, about 5 minutes at 250 ° C) up to a few seconds at 500 ⁰ C vary. Short heating times represent a technical advance over the processes of GB-PS 1,115 · 979, in that higher production speeds of an equally satisfactory material can be obtained in a continuous mode of operation. At the higher temperatures, for example those above 270 ^° C., it may be desirable to work in the absence of oxygen.

The carbohydrate material used in the present process is preferably cellulose. Besides cellulose per se, other examples of carbohydrate material can also be used, such as cellulose derivatives, eg methyl cellulose. Starch, eg rice, potato and corn starch, alginates, pectin, faturgumrai such as tragacanth, gum arabic and locust bean gum and similar carbohydrates, including mono - and disaccharides, for example glucose and r> ucro. ~ e are examples of further carbon hydrate material, C.rir, related : t woi ^v .len k-jnxi.

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SAO ORIOiNAt

Catalysts that can be used for the heat degradation treatment can be more basic or more acidic iftur, although acidic catalysts are preferred. Preferred catalysts are strong acids and salts of strong acids with weak bases. Such catalysts are for example sulfamic acid, phosphoric acid, Sulfuric acid, hydrochloric acid, perchloric acid, trichloroacetic acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, Ammonium sulfate, ferric chloride, zinc chloride, Stannous chloride, aluminum chloride and especially ammonium sulf amat.

-Basic catalysts are alkali hydroxides, such as Sodium and potassium hydroxides, as well as alkali salts of weak acids, such as sodium and potassium carbonates, Acetates and lactates.

To ensure that there is no substantial degradation of the types represented by curve A of the drawings, should expediently be present at least 1 wt .-% catalyst, and preferably the amount of catalyst is from 2.5 to 20% by weight of the carbohydrate material.

The carbohydrate material can be the subject of the invention, forming processes in any form, for example in 'powder or sheet form. As In the process of GB-PS 1.113-979, the carbohydrate material present in sheet form can initially with a Solution of the catalyst are impregnated, which is applied by dipping or spraying and then dried will. A powdered carbohydrate material can also be mixed with a solution of the catalyst and then dried will.

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BAD ORIQfNAL

When the carbohydrate material is subjected to the method of the invention is subjected, it is broken down into a black material. Should be the black color for smoking materials considered unsuitable, however, the color can be bleached brown so that it becomes a Cigarette tobacco resembles, namely by treatment with nitric acid, ammonia or hydrogen peroxide, whereby this treatment preferably takes place at an elevated temperature. ,

The thermally degraded carbohydrate material can then be further processed after bleaching to take on a shape similar to tobacco with the aid of a binder. This step in the process can be carried out by the procedure described in GB-PS 1,113,979. For example, the material can be ground to a powder, mixed with a solution of a binder, for example a water-soluble cellulose derivative such as methyl or ethyl cellulose, carboxymethyl cellulose or a salt thereof, starch, alginate, pectin, natural gum such as guar gum or locust bean gum, whereupon the Material is formed into a film and dried. ^u egebenenfalls a mixture can the degraded by heat. Carbohydrate material and the binder as a thread or tape · are extruded. This film, thread or tie can be shredded or cut to give a tobacco-like material. It is advantageous to condition such a material in a humid atmosphere to a moisture content of 5 to 15% by weight in order to make it more suitable for use in filling cigarettes or pipes.

Smoking materials produced by the process forming the subject of the invention are similar to those obtained according to the procedure of GB-PS 1,113,979

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and they are concerning, the smoke quality and the smoky taste of the corresponding room materials consider which ones are made from untreated carbohydrates, and they yield a softer, less lovely smoke. The resulting smoke contains less tar than tobacco smoke. These smoke mixtures can also with regard to their composition and accordingly also theirs Smoking properties are changed much more extensively than mixtures containing untreated carbohydrates contain and even compared to mixtures which only contain tobacco contain. For example, by incorporating flavors and odor additives, the taste and smell of tobacco are changed to meet a wide need to meet consumer needs. The level of nicotine, which is a desirable component of smoking mixtures can also be largely set as desired.

It should be noted that the smoking materials according to the invention may contain, in addition to the modified carbohydrate, other materials which are normal constituents of smoking materials, such as tobacco, untreated carbohydrate or other smoke-producing organic material and, if desired, any of the other modifying agents which usually used in such mixtures. For example, the smoking materials may contain smoldering catalysts, materials to improve ash cohesion and color, nicotine, odor improvers, or medicaments. Various useful odor enhancing agents can be incorporated into the smoking material. These are tobacco extracts, organic esters, essential oils, menthol, tonka beans or vanillin. Glycerine and glycol, such as ethylene glycol and di-, tri- and tetraethylene glycol oind ^; Common humectants.

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Desired failures can be assigned to the puff materials according to the Invention also, inorganic fillers of fe are added. It is particularly useful to give them from 4-0 to 65% by weight inorganic fillers to be added and these fillers are selected to give the mixture an acceptable rate of burn to be granted as described in GB-PS 1.299.296. Through these means the Amount of harmful smoke components that the smoker reach, further reduced. The usual mixtures of calcium and magnesium carbonate can be used for this purpose be used.

The invention is explained in more detail in the following examples, without being restricted thereto, which relate to parts focus on the weight.

EXAMPLE 1

"3.0 parts of oO -cellulose pulp in sheet form was immersed in a 5% aqueous solution of ammonium sulfamate and the pulp then pressed between rollers to leave 1 part of solution in the pulp. The pulp was dried and for 100 seconds heat-treated at 270 ^° G. This process turned the pulp black. The weight of the degraded material was 75 % of the initial weight of the ^ -cellulose and the ammonium sulfamate. The degraded material then became a film according to Example 12 of G3-PS 1,113,979 and processed cigarettes.

The secondary and mainstream smoke that arose from such cigarettes was milder and less irritating to the eyes and throat as the smoke from an ordinary tobacco cigarette.

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BATH ORIGINAL

/? 34? 196

EXAMPLE 2

1.0 part of * O -cellulose pulp was impregnated with 7.0% of an aqueous solution of ammonium sulfamate and squeezed to leave 1 part of the solution in the cellulose. The cellulose was dried at 155 ⁰ C and then for 2 minutes in air at 265 ⁰ C heated until the weight of the material was 73% the Criginalgewichtes. The color of the material turned black.

26.9 parts of the black material became 6.7 parts Glycerine, 9.6 parts hatter ^^ carboxymethyl cellulose, 21.3 parts calcium carbonate and 35.3 parts magnesite gel, and the mixture., According to Example 6 of the G3-F3 1.299-295 / one film processed. This movie was crushed, and cigarettes were made from it. The IT side stream and main stream smoke was milder and less irritating to the eyes and throat than that of ordinary tobacco cigarettes.

If the black material of the heating process was ^{pyrolyzed in the usual way at 600 °} C and the pyrolysis products were fed to a gas chromatograph, the yields of acetaldehyde and acrolein, i.e. of two particularly irritating compounds, were significantly lower than the yields of the starting cellulose. Comparative yields of arbitrary units (peak heights of the recording curves) of acetaldehyde and acrolein were:

Cellulose product example 2

Acetaldehyde more than 250 80

Acrolein

148

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A similar black iiaterial arose when heated according to Example 2 1 1/2 min to 50C ⁰ C instead of 2 minutes at 165 ° C.

EXAMPLE 3

The procedure described in Example 2 was repeated with the modification that the aqueous solution contained sulfuric acid. The air temperature was 280 ⁰ C, the Heizzjeit. 1 1/2 min and the weight of the material was 75 % -

The cigarettes made from this were less irritating to the eyes and throat.

The comparative yields of acetaldehyde and acrolein were:

Acetaldehyde acrolein

Cellulose more than 250 1 ^ 8

Product example J. 95 40

EXAMPLE 4

The procedure described in Example 2 was repeated with the modification that the aqueous solution contained sodium hydroxide. The air temperature was 275 ° C., the heating time was 3 minutes and the weight of the material was 80 % of the initial weight.

The cigarettes made with this material were also "less irritating to the eyes and throat.

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^BA0

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Comparative yields of acetaldehyde and acrolein in a pyrolysis at 6CO ⁰ C were as follows:

Acetaldehyde acrolein

Cellulose more than 25> C 146

Product example 4 IJO 41

EXAMPLE 5

The procedure described in Example 2 was repeated with the modification that the aqueous solution contained 10% sodium carbonate. The air temperature was -270 ^° C., the heating time was 4 minutes and the weight of the residue material was 70 % of the initial weight of the cellulose.

The cigarettes made with this material were less irritating to the eyes and throat.

Comparative yields of acetaldehyde and acrolein in a pyrolysis at 600 ^° C. were as follows:

Acetaldehyde acrolein

Cellulose 250 148

Product example 5 125 40.

EXAMPLE G

20 parts of sucrose were mixed with 20 parts of a 10% aqueous solution of ammonium sulfam'-t. The wet Pasto obtained was dried at 6O ⁰ unadonn G

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~ -11

r.it air ^{heated to 280 0} C for 5 rain, whereby the liateri ?! 7 ^Λ · Gow .-% of the starting cellulose.

As described in Example 2, cigarettes were produced, and these were also less irritating to the eyes and throat.

Vergleichsausbouten to denreizerzeugenden substances acetaldehyde and acrolein at a pyrolysis at 600 ⁰ C were as follows:

oucrose

Product example 6

Acetaldehyde acrolein more than 250 160

EXAMPLE 7

The procedure described in Example 6 was repeated with the modification that the d-is carbohydrate consisted of glucose. The temperature of the heated air was 280 ⁰ C, the heating time ^ min and the weight was 73% of that of the AungangG weight of cellulose.

The cigarettes made with this material were less irritating to the base and the throat.

Comparative yields of acetaldehyde and acrolein at a p3'rolyse at 600 ⁰ C were as follows:

glucose

Product example 7

Acetaldehyde more than c-50

Acrolein ISO

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EXAMPLE S

The procedure described in Example 6 was repeated with the modification that the carbohydrate consisted of starch. The temperature of the heated air was 275 ⁰ C, cie firhitzunsszeit 5 min, and the weight was 75% of the initial weight of the starch.

Cigarettes made with this material were less cheesy and throaty.

Versrleichsausbeuten of acetaldehyde and acrolein at a pyrolysis of 600 ⁰ C were as follows:

Acetaldehyde / acrolein

Starch product example 8

more than 250

95

155 40.

PATENT CLAIMS j

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Claims (8)

? 34? 196 • PATENT CLAIM Process for the production of an Rguchimterials, characterized in that a carbohydrate material is subjected to a heat dissipation influenced by a catalyst at a temperature above 2_50 ° C, until the weight of the solid residue is from 50 to. Is 90% by weight of the starting carbohydrate material, whereupon the residue is bleached if desired, mixed with a binding agent ', and processed into a tobacco-like nateriai. 2. The method according to claim 1, characterized in that the thermal degradation influenced by catalysis at a temperature between 250 and 300 ⁰ C is performed. 3. Method according to claim 1 or 2, characterized in that that the weight of the solid residue is from 65 to 90% by weight of the starting carbohydrate. 4-, method according to any one of the preceding claims, characterized characterized in that the carbohydrate material consists of cellulose. 5- The method according to any one of claims 1 to 3, characterized in that the carbohydrate material au3. strength consists. 6. The method according to any one of the preceding claims, characterized in that the thermal degradation The catalyst used is a strong acid or a salt of a strong acid with a weak base. 4 098 11/10 77 7 »" Method according to claim 6, characterized in that that the catalyst used consists of ammonium sulfamate. 8. The method according to any one of the preceding claims, characterized in that the catalyst is present in the heat degradation treatment in an amount of 1 to PO Gev.-jo of the carbon / mineral material. 9 · Method according to one of the preceding claims, characterized in characterized that the carbohydrate material, the in sheet or powder form, is first impregnated with a thin catalyst solution and dried. 40981 1/1077