RU2336789C1 - Method of manufacturing recovered tobacco material - Google Patents

Abstract

FIELD: food industry.

SUBSTANCE: method relates to manufacturing recovered tobacco material. The method involves extraction of natural tobacco material by water extraction solvent to produce extraction solution containing natural tobacco material components and extraction residue. The extraction solution is subject to adsorptive fractionation using adsorbent to reduce nitrosamine quantity. Recovered tobacco material is prepared with using extraction residue. At least part of extraction solution with reduced nitrosamine quantity is introduced to the recovered tobacco material. High hydrophobic adsorbent is used as adsorbent. Adsorptive fractionation is carried out during 60 minutes using high hydrophobic adsorbent in the amount of 10-110% of the weight of soluble components in the extraction solution.

EFFECT: controlling content of nitrosamines and nicotine in the extraction solution.

6 cl, 1 dwg, 6 tbl, 47 ex

Description

The invention relates to a method for producing reconstituted tobacco material.

Tobacco materials such as natural tobacco leaves, cut tobacco, middle leaf veins, stems and roots contain various components, including nicotine, nitrosoamines, hydrocarbons and proteins. In the process of producing reconstituted tobacco material, these components extracted from natural tobacco material are again introduced into the reconstituted tobacco web made from the extraction residue. Some of these components of the natural tobacco material are desirable to be reduced or removed, while others are not only not required to be removed, but it is even desirable to increase their amount for smoke aroma or other reasons.

For example, in WO 02/28209, a method is disclosed whereby an extraction solution obtained by extracting tobacco using a solvent is contacted with an adsorbent such as activated carbon or zeolite to lower the content of tobacco nitrosoamines (TNAs). Also according to this patent document 1, an extraction solution with a reduced content of nitrosoamines is introduced into the reduced tobacco material.

For example, US Pat. No. 5,810,020 suggests removing nitrosoamines using liquid-liquid extraction treatment using a large amount of corona ether.

According to international publication WO 01/65954, tobacco is treated with supercritical carbon dioxide to extract nitrosoamines and nitrosoamine is removed from the extract.

Nitrosoamines, for example TNA, in natural tobacco materials are substances that it is desirable to remove. But TNAs are similar in structure to nicotine, a useful component, and therefore it is very difficult to selectively remove TNAs and not remove nicotine. Therefore, using conventional methods, it is difficult to prepare reconstituted tobacco material with a significant nicotine content, but essentially without TNA, using an extract solution obtained from natural tobacco material and a fibrous component such as an extraction residue.

In particular, using the method according to international publication WO 02/28209, it is possible to separate TNA from nitric acid and saccharides, but nicotine is adsorbed and removed together with TNA adsorbent.

The method according to US patent No. 5810020 is undesirable for security reasons, because requires the use of a large amount of corona ether. The method according to the international publication WO 01/65954 offers an expensive method of supercritical extraction and therefore its practical application is negligible.

Description of the invention

The purpose of the invention is to provide a method for the relatively simple manufacture of reconstituted tobacco material containing a significant amount of nicotine, but essentially without TNA, by separating nicotine and TNA in an extraction solution derived from natural tobacco material.

The invention provides a method of manufacturing a reconstituted tobacco material using an extraction solution obtained by extraction from a natural tobacco material using an aqueous extraction solvent and an extraction residue.

The inventors drew attention to such an adsorbent with increased hydrophobicity as activated carbon, from the point of view of its use as a simple means for separating nicotine and TNA in an extraction solution obtained from natural tobacco material by means of an aqueous extraction solvent. Such a highly hydrophobic adsorbent as activated carbon adsorbs TNA along with nicotine. But the inventors found that TNA can be largely removed while reducing the amount of nicotine adsorption to a minimum by adjusting the adsorption time and the amount of adsorbent used. The present invention is based on these findings.

The invention provides a method of manufacturing a reconstituted tobacco material according to which: (a) the natural tobacco material is extracted with an aqueous extraction solvent to obtain an extraction solution containing components of a natural tobacco material and an extraction residue; (b) carry out the adsorption separation of the extraction solution using an adsorbent to reduce the amount of nitrosoamines; (c) preparing a reconstituted tobacco web using an extraction residue; (d) introducing at least a portion of the extraction solution with a reduced amount of nitrosoamines into the reconstituted tobacco web; wherein the adsorbent is a highly hydrophobic adsorbent, and adsorption separation is performed for 60 minutes using a highly hydrophobic adsorbent in an amount of 10-110% by weight of the soluble components in the extraction solution.

Brief Description of the Drawings

The drawing shows a flow diagram of the manufacture of reconstituted tobacco material according to an embodiment of the invention.

Optimum Embodiment

The invention is described in more detail below with reference to various implementations.

The invention is a method for the manufacture of reconstituted tobacco material by substantially removing TNA: (N'-nitrozonornicotine) (IUH), 4- (methylnitrosoamino) -1- (3-pyridyl) -1-butanone (NNC), N'-nitrosoanatabine (NAT) ), etc., from an extraction solution obtained by extracting natural tobacco material with an aqueous extraction solvent, while at the same time suppressing the loss of nicotine as much as possible; introducing the extraction solution into the reconstituted tobacco web prepared using the extraction residue.

The drawing shows a flow diagram of a method of manufacturing a reconstituted tobacco material according to an embodiment of the invention.

According to the drawing, first the natural tobacco material 11 is treated with S1 by extraction by mixing and mixing the natural tobacco material 11 and the extraction solvent 12.

As natural tobacco material 11, natural tobacco leaves, cut tobacco, medium leaf veins, stems, and roots, and a mixture thereof can be used. As the extraction solvent, an aqueous solvent can be used. An aqueous extraction solvent, such as water, may be alkaline or acidic. A mixture of water and a water-miscible organic solvent can also be used as an aqueous extraction solvent. Examples of this organic solvent are alcohols, for example ethanol. An inorganic salt, for example sodium hydroxide, can be dissolved in these extraction solvents. Treatment S1 extraction is usually carried out at a temperature of 50-100 ^{° C} for from 5 minutes to 6 hours.

Upon completion of the treatment with S1 by extraction, the resulting extraction mixture is separated by S2, for example by filtration, to separate it into the extraction solution 13 and the extraction residue 14. The extraction solution 13 contains water-soluble components in a natural tobacco material such as nicotine and TNA.

The extraction residue 14 essentially consists of fibers. The reconstituted tobacco web 15 is produced in a conventional manner using an extraction residue 14. The reconstructed tobacco web 15 can be partially or completely composed of an extraction residue 14.

On the other hand, the extraction solution 13 obtained by separating S2 undergoes adsorption treatment of S4 using a highly hydrophobic adsorbent. In the present invention, the adsorption separation of S4 can be accomplished by contacting the extraction solution 13 with a highly hydrophobic adsorbent. Highly hydrophobic adsorbent is an adsorbent with a high level of hydrophobicity. Examples thereof are: activated carbon, a styrene-based porous plastic, and an adsorbent in which a hydrophobic modifying group (hydrophobic group), for example bromine, is introduced into styrene-based porous plastic. Using a highly hydrophobic adsorbent, TNA can be largely removed, while suppressing the loss of nicotine from tobacco extract.

The contact between the extraction solution 13 and the highly hydrophobic adsorbent can be achieved by introducing particles of the highly hydrophobic adsorbent into the extract 13, followed by mixing.

Or, the contact between the extraction solution 13 and the highly hydrophobic adsorbent can be achieved by passing the extraction solution 13 through the adsorbent layer filled with particles of the highly hydrophobic adsorbent.

The amount of highly hydrophobic adsorbent used corresponds to 10-110% of the weight of the soluble components in the extraction solution 13. If the amount of highly hydrophobic adsorbent is less than 10%, then the TNA in the extraction solution cannot be removed sufficiently. On the other hand, if the amount of adsorbent exceeds 110%, the amount of nicotine adsorbed increases significantly. Preferably, the amount of highly hydrophobic adsorbent corresponds to 10-50% by weight of the soluble components in the extract 13. It should be noted that the amount of soluble components in the extract can be determined by lyophilization.

Contact time between extraction solution 13 and highly hydrophobic adsorbent: within 60 minutes Upon contact within 60 minutes TNA can be removed while significantly suppressing nicotine adsorption. A preferred contact time is 5-60 minutes and more preferably 5-30 minutes.

In order to suppress the adsorption of nicotine and increase the adsorption of TNA according to the invention, the pH of the extract in contact with the highly hydrophobic adsorbent is preferably higher than 2, but lower than 10, and more preferably higher than 4, but lower than 10. The pH value can be adjusted by the addition of acid or alkali. The preferred extraction temperature is 0-100 ^{° C} and a solution, more preferably 20-60 ° ^C.

The adsorbed / separated extract is separated (S5) from the highly hydrophobic adsorbent (spent adsorbent 17). If the contact between the extract and the highly hydrophobic adsorbent is carried out by introducing the adsorbent into the extract and mixing, then this separation operation is performed by filtration. And if the contact between the extract and the highly hydrophobic adsorbent is carried out by passing the extract through the highly hydrophobic adsorbent layer, then the extract after adsorption, of course, flows from the highly hydrophobic adsorbent layer in a state separated from the adsorbent. Extract 16 thus obtained, which has already undergone adsorption treatment, is introduced (S5) completely or partially into the reconstituted 5 tobacco web - after or without concentration of the extract; in this way, reduced tobacco material can be obtained 18. A cigarette obtained using the thus obtained reduced tobacco material 18 has a significantly reduced amount of TNA in the smoke during combustion.

The foregoing description is set forth as embodiments of the invention, but is not limited to them. Of course, the above-mentioned embodiments can be combined.

The invention will now be described with reference to various non-limiting examples.

In the examples below, the amount of TNA was measured by the method of measuring TNA in chopped tobacco of the Arista variety (Regulatory method T-309: Determination of nitrosoamines in whole tobacco, developed by the Ministry of Health, December 31, 1999). In particular, to measure tobacco extract or adsorbent-treated liquid, liquid chromatography — mass spectrometry / mass spectrometry — examined. The amount of nicotine was measured according to the standard DIN 10373 of the German Institute for Normalization. In particular, sodium hydroxide was added to the tobacco extract or to the adsorbent-treated liquid to make it alkaline, and then hexane was also added thereto. The resulting substance was mixed to direct nicotine into the hexane phase and then only the hexane phase, for measurement, it was studied by gas chromatography / chromatographic method of structural group analysis using fluorescent indicators.

Examples 1-8

At a temperature of 25 ^C. 100 g of the shredded leaf tobacco (X-KL1) was mixed with 1000 ml of water and the mixture was stirred, thereby performing extraction of shredded tobacco. The extraction mixture thus obtained was filtered to separate it into an extraction solution and an extraction residue. A web of reconstituted tobacco was made from the extraction residue.

Other data: activated carbon (with an average particle diameter of 1100 μm, with a specific surface area of 1638 sq. M / g) was introduced into the extraction solution (pH: 6.0) in quantities (%) indicated in Table 1 in relation to the amount soluble components of the extraction solution; stirring is performed for a time (adsorption treatment time) listed in Table 1, at ²⁵ ° C, followed by filtration. Were analyzed: the total amount of TNA and the amount of nicotine in the extraction solution (filtrate) after adsorption treatment. The results are presented in Table 1. Table 1 also shows the degree of change in the total contents of TNA and nicotine. In Table 1, the term “no treatment” indicates that the extract did not undergo adsorption treatment (The same applies to Tables 2-6).

Table 1 The amount of adsorbent (%) Adsorption time. processing (min) Total number TNA (μg / g) Kolich. nicotine (mg / g) The degree of change in the total number of TNA (a) The degree of change in nicotine (b) Difference (a-b) No processing - - 30.5 23,4 - - - Project 1 13 fifteen 11.8 17,2 -61% -26% -35% Project 2 13 thirty 10.0 16,4 -67% -thirty% -37% Project 3 13 60 8.9 14.1 -71% -39% -31% Project 4 13 120 8.5 14.0 -72% -40% -32% Ex.5 25 fifteen 7.7 21.3 -75% -9% -66% Ex.6 25 thirty 4.1 17.6 -86% -25% -62% Ex 7 25 60 2.6 15.0 -91% -36% -56% Ex 8 fifty 5 6.2 15,5 -80% -34% -46%

According to the results of Table 1 it is seen that when using an adsorbent (activated carbon) in an amount of 10-50% of the amount of soluble components in the extract and when the adsorption treatment was carried out from 5 to 60 minutes, the TNAs decreased by 60% or more, while suppressing the degree reduction of nicotine in the range of less than 40% (Examples 1-3 and 5-8). In particular, when the amount of adsorbent used was equal to 25% of the amount of soluble components in the extract, and when the adsorption treatment was carried out for 15-30 minutes, the difference between the degree of change in the total amount of TNA and the degree of change in the amount of nicotine was from -62 to -66 %; and this indicates an increase in TNA-selective removal (Examples 5-6).

The extracts that underwent adsorption treatment according to Examples 1-3 and 5-6 were introduced into the reconstituted tobacco web, respectively, to obtain reconstituted tobacco material.

Examples 9-11

The same operations were performed as in Examples 1-8, except that an artificial adsorbent based on styrene plastic with bromine chemical bonding (SP 207 manufactured by Mitsubishi Chemical Corp.) was used as a highly hydrophobic adsorbent in the respective amounts indicated in Table 2, and it was mixed together with the extract for the corresponding periods indicated in Table 2. The results of the analysis of the total amount of TNA and the amount of nicotine in the extract (filtrate) after adsorption treatment are also indicated us in Table 2.

table 2 The amount of adsorbent (%) Adsorption time (min) Total TNA (μg / g) The amount of nicotine (mg / g) The degree of change in the total number of TNA (a) The degree of change in nicotine (b) Difference (a-b) No processing - - 32,3 20,4 - - - Project 9 fifty fifteen 8.7 18.9 -73% -7% -66% Project 10 fifty thirty 7.2 18.1 -78% -eleven% -66% Project 11 fifty 60 5.9 15.9 -82% -22% -60%

The results of Table 2 show that the total amount of TNA was reduced by 70% while suppressing the degree of reduction in the amount of nicotine within 25% in each example. In particular, when the amount of adsorbent used was equal to 50% of the amount of soluble components in the extract, and when the adsorption treatment was carried out for 15-30 minutes, the difference between the degree of change in the total amount of TNA and the degree of change in the amount of nicotine was from -66%, and this indicates an increase in TNA-selective removability (examples 9-10).

The extracts that underwent adsorption processing according to examples 9-11 were introduced into the reconstituted tobacco web, respectively, to obtain reconstituted tobacco material.

Examples 12-14

The same operations were performed as in examples 1-8, except that activated carbon with an average particle diameter of 150 μm and with a specific surface area of 1140 sq / g was used as a highly hydrophobic adsorbent in the corresponding the amounts indicated in Table 3, and it was mixed with the extract for the corresponding periods indicated in Table 3. The results of the analysis of the total amount of TNA and the amount of nicotine in the extract (filtrate) after adsorption treatment are also shown in Table 3.

Table 3 The amount of adsorbent (%) Adsorption time (min) Total TNA (μg / g) The amount of nicotine (mg / g) The degree of change in the total number of TNA (a) The degree of change in nicotine (b) Difference (a-b) No processing - - 30.5 23,4 - - - Project 12 fifty fifteen 3.9 22.6 -87% -3% -84% Project 13 fifty thirty 2,8 19.3 -91% -17% -73% Project 14 fifty 60 1.9 15.3 -94% -35% -59%

The results of Table 3 show that the total amount of TNA was reduced by 70% or more, while suppressing the degree of decrease in the amount of nicotine within 35% in each example. In particular, when the amount of adsorbent used was equal to 50% of the amount of soluble components in the extract and when the adsorption treatment was carried out for 15-30 minutes, the difference between the degree of change in the total amount of TNA and the degree of change in the amount of nicotine was from -73 to -84% , and this indicates an increase in TNA-selective removal (examples 12-13).

The extracts that underwent adsorption processing according to examples 12-14 were introduced into the reconstituted tobacco web, respectively, to obtain reconstituted tobacco material.

Examples 15-20

The cut tobacco was extracted according to the procedures of Examples 1-8, and the extracts thus obtained were adjusted to pH 2.0 or 10.0 by the addition of acid (acetic acid) or alkali (sodium hydroxide). The extracts were treated with activated carbon, used in examples 12-14 under the appropriate conditions indicated in Table 4. The results of the analysis of the total amount of TNA and nicotine in the extract (filtrate) after adsorption treatment are shown in Table 4.

Table 4 pH ext. solution The amount of adsorbent (%) Adsorption time (min) Total TNA (μg / g) The amount of nicotine (mg / g) The degree of change in the total number of TNA (a) The degree of change in nicotine (b) Difference (a-b) No processing - - 30.5 23,4 - - - Project 15 2.0 fifty fifteen 23.8 23.3 -22% -0% -22% Project 16 2.0 fifty thirty 23,4 22.9 -23% -2% -21% Project 17 2.0 fifty 60 24.1 22.5 -21% -four% -17% Project 18 10.0 fifty fifteen 1.3 3.0 -96% -87% -9% Project 19 10.0 fifty thirty 0.8 1,5 -97% -93% -four% Project 20 10.0 fifty 60 0.9 1,1 -97% -95% -2%

According to Table 4, when the pH of the solution was 2.0, both TNA and nicotine were difficult to adsorb (examples 15-17), but when the pH of the solution was 10.0, about 90% or more of TNA and nicotine were removed (examples 18-20). In the case of examples 12 to 14, in which the pH of the extract was 6.0 and the TNA-selective adsorption was good: the pH of the solution is preferably higher than 2 but less than 10. That is, for increased TNA-selective removal, it is preferable that the pH of the extract was above 4.0, in which TNAs are ionized, but below 10, in which nicotine is ionized.

Examples 21-38

The same procedures were performed as in Examples 1-8, except that activated carbon was used under other conditions that are listed in Table 5. The results of the analysis of the total amount of TNA and nicotine in the extract (filtrate) after adsorption treatment are also indicated in Table 5.

Table 5 The amount of adsorbent (%) Adsorption time (min) Total TNA (μg / g) The amount of nicotine (mg / g) The degree of change in the total number of TNA (a) The degree of change in nicotine (b) Difference (a-b) No processing - - 30.5 23,4 - - - Project 21 2 fifteen 26.2 20,4 -fourteen% -13% -2% Project 22 2 thirty 27.9 19.6 -9% -16% 7% Project 23 2 60 27.7 19.3 -9% -eighteen% 8% Ex 24 2 120 24.8 19.1 -19% -eighteen% 0% Ex.25 5 fifteen 27.4 18.2 -10% -22% 12% Project 26 5 thirty 24.5 18.1 -twenty% -22% 3% Project 27 5 60 22.3 16,2 -27% -31% four% Project 28 5 120 16.6 16.1 -45% -31% -fourteen% Ex.29 fifty 120 3,7 3.3 -88% -86% -2% Project 30 125 thirty 2.2 0.2 -93% -99% 7% Project 31 250 5 0.1 4.2 -one hundred% -82% -eighteen% Project 32 250 fifteen 1.8 1.7 -94% -93% -one% Project 33 250 thirty 1,1 0.6 -96% -98% one% Project 34 250 60 1,0 0.7 -97% -97% 0% Project 35 500 5 0,0 1.4 -one hundred% -94% -6% Project 36 500 fifteen 0.4 0.5 -99% -98% -one% Project 37 500 thirty 0,0 0,0 -one hundred% -one hundred% 0% Project 38 500 60 0,0 0,0 -one hundred% -one hundred% 0%

According to the results of Table 5, in cases where the amount of adsorbent used and the adsorption period go beyond the limits defined by this invention, it is impossible to provide an increase in TNA adsorption while suppressing nicotine adsorption.

Examples 39-47

The same operations were performed as for examples 1-8, with the exception that the active alumina, which is a hydrophilic adsorbent, was used as an adsorbent in the corresponding amounts indicated in Table 6, and it was mixed with the extract for the corresponding period, indicated in Table 6. The results of the analysis of the total amount of TNA and nicotine in the extract (filtrate) after adsorption treatment are also shown in Table 6.

Table 6 The amount of adsorbent (%) Processing adsorbent time (min) Total TNA (μg / g) The amount of nicotine (mg / g) The degree of change in the total number of TNA (a) The degree of change in nicotine (b) Difference (a-b) No processing - - 33.7 25.1 - - - Project 39 fifty fifteen 30.7 22.9 -9% -9% 0% Project 40 fifty thirty 30.7 23.5 -9% -6% -3% Project 41 fifty 60 33.3 24.4 -one% -3% 2% Project 42 250 fifteen 31.8 23,2 -6% -8% 2% Project 43 250 thirty 32.8 22.8 -3% -9% 6%; Project 44 250 60 32.6 23.7 -3% -6% 2% Project 45 500 fifteen 32,2 24.4 -5% -3% -2% Project 46 500 thirty 33.3 24.7 -one% -one% 0% Project 47 500 60 33.1 25.0 -2% 0% -2%

According to the data of Table 6: when using a hydrophilic adsorbent TNAs are not substantially removed.

As mentioned above, according to the invention, it is possible to separate nicotine and TNA from the extraction solution obtained from natural tobacco material in a relatively simple way and to make reconstituted tobacco material essentially without TNA - while suppressing nicotine loss as much as possible.

Claims (6)

1. A method of obtaining a reconstituted tobacco material, comprising: (a) extracting the natural tobacco material with an aqueous extraction solvent to obtain an extraction solution containing components of the natural tobacco material and an extraction residue; (b) adsorption separation of the extraction solution using an adsorbent to reduce the amount of nitrosoamines; (c) manufacturing a reconstituted tobacco web using an extraction residue; and (d) adding at least a portion of the extraction solution, in which the amount of nitrosoamines is reduced, to the reconstituted tobacco web; wherein the adsorbent is a highly hydrophobic adsorbent, and adsorption separation is performed for 60 minutes using a highly hydrophobic adsorbent in an amount of 10-110 wt.% of soluble components in the extraction solution. 2. The method according to claim 1, wherein the adsorbent is a styrene-based porous plastic, activated carbon, or an adsorbent in which a hydrophobic group is bonded to the surface of the adsorbent. 3. The method according to claim 1, in which a highly hydrophobic adsorbent is used in an amount corresponding to 15-60 wt.% Soluble components of the extraction solution. 4. The method according to claim 1, in which the pH of the extraction solution is above 2, but below 10. 5. The method according to claim 1, in which the pH of the extraction solution is higher than 4, but lower than 10. 6. The method according to claim 1, in which the adsorption separation is carried out at a temperature of from 0 to 100 ° C.