WO2007032433A1 - Method for production of recycled tobacco material - Google Patents

Method for production of recycled tobacco material Download PDF

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Publication number
WO2007032433A1
WO2007032433A1 PCT/JP2006/318254 JP2006318254W WO2007032433A1 WO 2007032433 A1 WO2007032433 A1 WO 2007032433A1 JP 2006318254 W JP2006318254 W JP 2006318254W WO 2007032433 A1 WO2007032433 A1 WO 2007032433A1
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WIPO (PCT)
Prior art keywords
extract
adsorbent
amount
tobacco material
tobacco
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PCT/JP2006/318254
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French (fr)
Japanese (ja)
Inventor
Shigenobu Tatsuoka
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Japan Tobacco Inc.
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Publication of WO2007032433A1 publication Critical patent/WO2007032433A1/en

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    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/10Chemical features of tobacco products or tobacco substitutes
    • A24B15/12Chemical features of tobacco products or tobacco substitutes of reconstituted tobacco
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/24Treatment of tobacco products or tobacco substitutes by extraction; Tobacco extracts

Definitions

  • the present invention relates to a method for producing a recycled tobacco material.
  • Tobacco materials such as natural tobacco leaves, chopped bones, bones, stems and roots contain various components such as nicotine, nitrosamines, hydrocarbons and proteins.
  • these components extracted from natural tobacco materials are applied back to the recycled tobacco web made from the extracted residue.
  • Some components of these natural tobacco materials may be desirable to eliminate the power to reduce their amount for taste or other reasons, while others may not be desirable or increased.
  • U.S. Pat. No. 5810020 discloses the removal of trosamines by liquid-liquid extraction using a large amount of crown ether.
  • Trosamine, particularly TSNA, contained in natural tobacco materials is a desirable material to remove.
  • TSNA has a structure similar to that of nicotine, which is a useful component, and it is difficult to selectively remove TSNA without removing nicotine. Therefore, in the conventional method, a regenerated tobacco material that contains a significant amount of nicotine but is substantially free of TSNA is produced using an extract obtained from natural tobacco material and a fiber component that is an extraction residue. It was difficult.
  • the present invention is a comparatively simple operation, and the extract liquid power obtained from the natural tobacco material also reduces TSNA without significantly reducing the amount of cotin, and thus contains a significant amount of nicotine.
  • an object of the present invention is to provide a method for producing a recycled tobacco material from which TSNA is substantially removed.
  • the present invention (a) natural tobacco material is extracted with an aqueous extraction solvent to obtain an extract and an extraction residue containing the components of the natural tobacco material, and (b) the extract or its concentrated solution Subjecting to an adsorptive separation operation using an adsorbent exhibiting interpolarity-reducing trosamine; (c) preparing a regenerated tobacco web using the extraction residue; and (d) an extract with reduced trosamine.
  • the manufacturing method of the regenerated tobacco material which includes adding at least one part of a concentrate to the said regenerated tobacco web is provided.
  • the adsorbent is a porous adsorbent composed of an acrylic or methacrylic resin, a porous adsorbent composed of a hydrophobic resin having a hydrophilic functional group on the surface, and a hydrophilic adsorbent having a hydrophobic functional group on the surface.
  • Porous adsorbent power made of functional resin can be selected.
  • adsorption separation can be performed by tip chromatography separation using a column packed with an adsorbent.
  • the tobacco extract or its concentrate is passed through a column to obtain an effluent, and then the water eluate is combined with the effluent through three times or less of the volume of the adsorbent packed in the column. Can be added to the regenerated tobacco web.
  • FIG. 1 is a flow diagram for explaining a method of producing a regenerated tobacco material according to an embodiment of the present invention.
  • FIG. 2A is a graph showing the elution concentrations of nicotine and total TSNA in Example 66 described in detail below.
  • FIG. 2B is a graph showing the cumulative dissolution rate of nicotine and total TSNA in Example 66.
  • FIG. 3A is a graph showing the elution concentrations of total TSNA, sugar (glucose, fructose and sucrose) and amino acids in Example 67, which will be described in detail later.
  • FIG. 3B is a graph showing the cumulative elution rates of total TSNA, sugars (glucose, fructose and sucrose) and amino acids in Example 67.
  • the method of the present invention uses an adsorbent exhibiting an intermediate polarity, and the TSNA (N ′ -Nitrosonornicotine (NNN), 4- (Methylnitrosamino)-1-(3-Pyridyl)-1-Butanone (NNK), N'--Trosoanatabine (NAT))
  • TSNA N ′ -Nitrosonornicotine
  • NNK 4- (Methylnitrosamino)-1-(3-Pyridyl)-1-Butanone
  • NAT N'--Trosoanatabine
  • FIG. 1 shows a flow diagram for explaining a method of producing a recycled tobacco material according to one embodiment of the present invention.
  • the natural tobacco material 11 and the extraction solvent 12 are mixed and stirred to subject the natural tobacco material 11 to the extraction treatment S1.
  • the natural tobacco material 11 tobacco leaves, chopped, medium bones, stems, roots, and mixtures thereof can be used.
  • an aqueous solvent can be used.
  • the 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. Examples of such organic solvents are alcohols such as ethanol.
  • inorganic salts such as sodium hydroxide can be dissolved.
  • the extraction treatment S1 is usually performed at a temperature of 50 to: LOO ° C for about 5 minutes to 6 hours.
  • the obtained extraction mixture is subjected to a separation operation S2 by, for example, filtration, and divided into an extraction liquid 13 and an extraction residue 14.
  • the extract 13 contains water-soluble components in the natural tobacco material, such as nicotine and TSNA.
  • the extraction residue 14 consists essentially of fibers.
  • a regenerated tobacco web 15 is produced by a conventional method.
  • the regenerated tobacco web 15 may be partially constituted by the extraction residue 14 or may be entirely constituted by the extraction residue 14.
  • the extract 13 obtained from the separation operation S2 is concentrated by an ordinary method such as a centrifugal thin film method, or the adsorption solution operation S4 using an adsorbent having intermediate polarity without being concentrated is used.
  • the adsorption separation operation S4 can be performed, for example, by bringing the extract 13 into contact with an adsorbent having intermediate polarity.
  • An adsorbent having an intermediate polarity is generally an adsorbent having an intermediate polarity between high polarity and low polarity, and is a highly porous resin based on acrylic or methacrylic resin, or styrene.
  • Hydrophobic rosin and other hydrophobic sorbents on the surface highly porous rosin having a hydrophilic functional group such as quaternary ammonium group, dalkamine group, iminodiacetic acid group, polyamine group and tertiary amine group, or silica
  • the highly porous resin having a hydrophobic functional group such as octadecyl group on the surface of hydrophilic resin such as fat.
  • the contact between the extract 13 and the adsorbent having intermediate polarity can be performed, for example, by adding particles of the adsorbent having intermediate polarity to the extract 13 and stirring (batch type).
  • the contact between the extract 13 and the adsorbent having an intermediate polarity can also be made by passing the extract through an adsorbent bed filled with particles of an adsorbent having an intermediate polarity.
  • a so-called advanced chromatography separation method can also be used.
  • tobacco extract or its concentrate is passed through a column packed with an adsorbent, and TSNA does not contain TSNA in the column effluent, but liquid containing nicotine begins to flow out. It is a technique to collect the fraction until the start.
  • the separation target liquid is adsorbed by an adsorbent in the column, and then a solvent (for example, water) different from the separation target liquid is used as a mobile phase to separate components during elution.
  • the liquid to be separated (in the present invention, the tobacco extract or its concentrated liquid) itself is used as the mobile phase, and the components can be separated from the time when the liquid to be separated is loaded onto the column. is there. Furthermore, in normal chromatography, the separation target When the liquid load is increased, the resolution decreases, but in the advanced chromatographic separation, since the separation target liquid itself is used as the mobile phase, the mobile phase is different from the case of elution with a mobile phase such as water. Since the hydrogen ion concentration (pH) of each column is different, the resolution is rarely reduced even when a large amount of separation target liquid is loaded onto the column.
  • the tobacco extract used for separation is concentrated by a conventional method such as a centrifugal thin film method so that the concentration of soluble components is about 10 to 20% by weight. It is preferable.
  • the amount of the intermediate polar adsorbent used is preferably an amount corresponding to 50% or more of the weight of the soluble component in the extract 13. If the amount of the intermediate polar adsorbent is less than 50%, it becomes difficult to sufficiently remove TSNA in the extract.
  • the amount of the tobacco extract or its concentrate to be subjected to the separation is about 20 times or less, preferably about 12 times or less the volume of the adsorbent packed in the column.
  • Nicotine can be recovered almost completely (over 90% in total) by passing the entire amount of tobacco extract or its concentrate through the column and then passing water through the column. In that case, it is desirable to use water in an amount of about 3 times or more, preferably about 5 times or more the volume of the adsorbent packed in the column.
  • the amount of the soluble component in the extract can be determined by a freeze-drying method.
  • the extract thus separated by adsorption is separated from the intermediate polar adsorbent (used adsorbent 17) (S5).
  • This separation can be performed by filtration when the contact between the extract and the intermediate polar adsorbent is carried out by adding the intermediate polar adsorbent to the extract and stirring.
  • the contact between the extract and the intermediate polar adsorbent is carried out by passing the extract through the intermediate polar adsorbent bed, or when using advanced chromatographic separation, the extract after the adsorption treatment is Needless to say, it flows out from the intermediate polar adsorbent bed in a state separated from the intermediate polar adsorbent.
  • an eluate from water can be used in combination.
  • the adsorption-treated extract 16 obtained in this way is concentrated by a conventional method, or a part or all of it is added to the regenerated tobacco web 15 without being concentrated (S5). Is obtained. Cigarettes made using the recycled tobacco material 18 thus obtained are TSNA in smoke generated during firing is significantly reduced.
  • the amount of TSNA is calculated according to Arista's time-lapse TSNA measurement method (Official Method T-309, Determination of Nitrosamines in Whole Tobacco, made by the Department or Health, dated December 31, 1999). Measured accordingly. That is, the sample solution (tobacco extract, adsorbent treatment solution, or column effluent) was subjected to LC MSZMS for measurement.
  • the amount of nicotine was measured by a method in accordance with DIN 10373, a German standardization organization. In other words, sodium hydroxide was added to the sample solution to make it alkaline, then hexane was added and mixed, nicotine was transferred to the hexane phase, and only the hexane phase was subjected to GCZFID for measurement.
  • the amount of sugar is measured by subjecting the sample solution to LC-RI.
  • Tobacco leaf was extracted by mixing tobacco leaf (X-KLl OOg with water lOOOOmL and stirring for 1 hour at a temperature of 25 ° C. The resulting extraction mixture was filtered, and the extract and the extraction residue were filtered. Paper from the extracted residue was obtained to obtain a regenerated tobacco web.
  • methacrylic resin in the extract in the amount (%) shown in Table 1 with respect to the weight of soluble components.
  • the total TSNA amount was significantly decreased by using an adsorbent in an amount of 50% or more of the amount of soluble components in the extract, while the decrease rate of the nicotine amount was It can be seen that even if the treatment time is increased, it can be suppressed to less than 25%. In particular, if the amount of adsorbent used is equivalent to 500% of the amount of soluble components in the extract, it is obvious that the total TSNA amount is reduced by more than 90%.
  • Table 2 shows acrylic resin (trade name XAD7H P, manufactured by Rohm and Haas; average particle size: 350 to 900 ⁇ m; specific surface area: 400 m 2 Zg or more, no functional group) as an intermediate polar adsorbent
  • acrylic resin trade name XAD7H P, manufactured by Rohm and Haas; average particle size: 350 to 900 ⁇ m; specific surface area: 400 m 2 Zg or more, no functional group
  • the total TSNA amount was significantly reduced by using an adsorbent in an amount of 50% or more of the amount of soluble components in the extract. It can be seen that even if the length is increased, it can be suppressed to less than 30%.
  • the amount of adsorbent used is the extract. The amount equivalent to 500% of the amount of soluble components in the mixture is said to reduce the total TSNA amount by more than 90%.
  • Each of the adsorption-treated extracts of Examples 12 to 20 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
  • styrene-based resin having iminodiacetic acid type functional group (trade name Diaion CR11 manufactured by Mitsubishi Chemical Co., Ltd .: average particle size 355 to 1180 ⁇ m) is used in the amount shown in Table 3, and shown in Table 3 The same operation as in Examples 1 to 11 was performed except that the mixture was stirred with the time extract.
  • Table 3 shows the analysis results of the total TSNA and nicotine contained in the extract (filtrate) after the adsorption treatment.
  • results shown in Table 3 While using an adsorbent in an amount of 250% or more of the amount of soluble components in the extract, the total TSNA amount is significantly reduced, while the rate of decrease in the nicotine amount is less than the treatment time. It can be seen that even if it is made longer, it can be suppressed to 35% or less.
  • the amount of adsorbent used is extracted If the amount of soluble components in the liquid is equivalent to 500%, the total TSNA amount will decrease by up to 80%.
  • Each of the adsorption-treated extracts of Examples 21 to 29 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
  • a styrene-based resin having a darucamine functional group (trade name Diaion CRB02 manufactured by Mitsubishi Chemical Co., Ltd .: average particle size of 300 m or more) is used in the amount shown in Table 4, and the time extract shown in Table 4 The same operation as in Examples 1 to 11 was performed except that stirring was performed.
  • the analysis results of the total TSNA and nicotine contained in the extract (filtrate) after the adsorption treatment are also shown in Table 4.
  • Each of the adsorption-treated extracts of Examples 30 to 38 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
  • styrene resin having a quaternary ammonium functional group (trade name Diaion HPA25 manufactured by Mitsubishi Chemical Co., Ltd .: average particle size of 250 ⁇ m or more) is used in the amount shown in Table 5, and in Table 5 The same operations as in Examples 1 to 11 were carried out except that the extract was stirred for the indicated time.
  • Table 5 shows the results of analysis of total TSNA and nicotine contained in the extract (filtrate) after the adsorption treatment.
  • results shown in Table 5 The use of adsorbent in an amount of 250% or more of the amount of soluble components in the extract significantly decreases the total TSNA amount, while the decrease rate of the nicotine amount decreases the processing time. It can be seen that even if it is lengthened, it can be suppressed to about 10% or less.
  • the amount of adsorbent used is If the amount of soluble components in the extract is equivalent to 500%, the total TSNA amount will decrease by 70% or more.
  • Each of the adsorption-treated extracts of Examples 39 to 47 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
  • silica-based rosin having a octadecyl group (trade name Bondpak C18 manufactured by Waters Co., Ltd .: average particle size: 37 to 55 / zm) is used in the amount shown in Table 6, and the time extract shown in Table 6 is used. The same operation as in Examples 1 to 11 was performed except that stirring was performed. Table 6 shows the results of analysis of total TSNA and nicotine contained in the extract (filtrate) after adsorption treatment.
  • Each of the adsorption-treated extracts of Examples 48 to 56 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
  • Example 66 Tobacco leaf was extracted by mixing tobacco leaf (X-KLl OOg with water lOOOmL at a temperature of 25 ° C and stirring for 1 hour. The resulting extraction mixture was filtered, Paper from the extracted residue was obtained to obtain a regenerated tobacco web.
  • This concentrated solution (temperature 25 ° C) was subjected to advanced chromatographic separation under the following conditions.
  • Adsorbent Methacrylic resin (trade name Diaion HP2MG manufactured by Mitsubishi Chemical Corporation; average particle size: 250 ⁇ m or more; specific surface area: 470 m 2 Zg, no functional group)
  • the concentrated extract was first applied to the column in an amount of about 14 times or less the adsorbent packed volume. Subsequently, the cotin was completely eluted with about 5 times the volume of the adsorbent filling volume. Then, TSNA was eluted with 1% acetic acid aqueous solution.
  • FIGS. 2A and 2B show the elution patterns of nicotine and total TSNA.
  • Fig. 2A is a graph plotting the concentrations of nicotine and TSNA (stock standard values) in the eluate against the amount of liquid that passed through the force ram.
  • Fig. 2B is a graph plotting the cumulative elution rates of nicotine and total TSNA against the amount of liquid passed through the column.
  • V the drift dull
  • curve a is for nicotine
  • curve b is for total TSNA.
  • Table 8 shows the amounts of nicotine and total TSNA eluted by each elution treatment, and the total amount and recovery rate of each elution treatment.
  • Extraction was performed by mixing 30 kg of tobacco raw material (mixture of lamina and medium bone of yellow and burre each) with 150 L of water and stirring for 20 to 30 minutes at a temperature of about 60 ° C.
  • the obtained extraction mixture was filtered and divided into an extract and an extraction residue. Paper from the extraction residue was obtained to obtain recycled tapaco web.
  • Adsorbent Methacrylic resin (trade name Diaion HP2MG manufactured by Mitsubishi Chemical Corporation; average particle size: 250 ⁇ m or more; specific surface area: 470 m 2 Zg, no functional group)
  • the concentrated extract was applied to the column in an amount of about 14 times or less the adsorbent packed volume. Subsequently, the cotin was completely eluted with about 5 times the volume of the adsorbent filling volume. Then, TSNA was eluted with 1% acetic acid aqueous solution.
  • FIGS. 3A and 3B show the elution patterns of nicotine, total TSNA, sugars (glucose, fructose and sucrose) and total amino acids.
  • FIG. 3A is a graph plotting the concentrations of nicotine, total TSNA, sugar (glucose, fructose and sucrose) and total amino acids (stock solution standard values) in the eluate against the amount of liquid passed through the column.
  • Figure 3B is a graph that plots the cumulative elution rates of nicotine, total TSNA, sugars (glucose, fructose, and sucrose) and amino acids against the volume of fluid that passed through the column. In both graphs, curve a is for nicotine, curve b is for total TSNA, curve c is for sugar, and curve d is for total amino acids. Is.
  • Table 9 shows the total amount of nicotine, total TSNA, sugar (glucose, fructose and sucrose) and total amino acid eluted by each elution treatment, and the total amount and recovery rate of each elution treatment. Show.
  • TSNA can be separated without significantly reducing the amount of nicotine by a relatively simple method using the extractive force obtained from the natural tobacco material. Recycled tobacco material containing a significant amount of nicotine and substantially free of TSNA can be produced.

Abstract

A method for production of a recycled tobacco material comprising the steps of extracting a natural tobacco material with an aqueous extraction solvent to give an extract containing a component of the natural tobacco material and an extraction residue, subjecting the extract or a concentrated solution of the extract to adsorption/separation with an adsorbent having a neutral polarity to reduce the content of nitrosoamine in the extract or concentrated solution, preparing a recycled tobacco web using the extraction residue, and adding at least a portion of the extract or concentration solution having a reduced nitrosoamine content to the recycled tobacco web.

Description

明 細 書  Specification
再生タバコ材の製造方法  Method for producing recycled tobacco material
技術分野  Technical field
[0001] 本発明は、再生タバコ材の製造方法に関する。  [0001] The present invention relates to a method for producing a recycled tobacco material.
背景技術  Background art
[0002] 天然のタバコの葉、刻、中骨、茎、根等のタバコ材には、ニコチン、ニトロソァミン類 、炭化水素類、タンパク質等種々の成分が含まれている。再生タバコ材の製造プロセ スでは、天然のタバコ材カも抽出したこれらの成分を、同抽出残渣から作製した再生 タバコウェブに掛け戻すことが行われている。これら天然タバコ材の成分には、喫味 または他の理由から、その量を減少させる力 除去することが望ましいものがある一 方、除去しないか、あるいは増加させることが望ましいものもある。  [0002] Tobacco materials such as natural tobacco leaves, chopped bones, bones, stems and roots contain various components such as nicotine, nitrosamines, hydrocarbons and proteins. In the process of manufacturing recycled tobacco materials, these components extracted from natural tobacco materials are applied back to the recycled tobacco web made from the extracted residue. Some components of these natural tobacco materials may be desirable to eliminate the power to reduce their amount for taste or other reasons, while others may not be desirable or increased.
[0003] 例えば、国際公開 WO 02Z28209は、タバコ固有の-トロソァミン (TSNA)を減 少させるために、タバコを溶媒で抽出して得られた抽出液を活性炭、ゼォライト等の 吸着剤と接触させることを開示している。この文献は、ニトロソァミンが減少した抽出 液を再生タバコ材に添加することも開示している。 [0003] For example, International Publication WO 02Z28209 discloses that an extract obtained by extracting tobacco with a solvent is brought into contact with an adsorbent such as activated carbon or zeolite in order to reduce tobacco-specific trosamine (TSNA). Is disclosed. This document also discloses the addition of an extract with reduced nitrosamine to the regenerated tobacco material.
米国特許第 5810020号は、多量のクラウンエーテルを用いた液—液抽出処理に より-トロソァミン類を除去することを開示して 、る。  U.S. Pat. No. 5810020 discloses the removal of trosamines by liquid-liquid extraction using a large amount of crown ether.
[0004] 国際公開 WO 01Z65954は、タバコを超臨界二酸ィ匕炭素で処理して-トロソアミ ンを抽出し、その抽出物を-トロソァミン除去プロセスに供することを開示して 、る。 発明の開示  [0004] International publication WO 01Z65954 discloses that tobacco is treated with supercritical carbon dioxide to extract trosoamin and the extract is subjected to a trosamine removal process. Disclosure of the invention
[0005] 天然タバコ材に含まれる-トロソァミン、特に TSNAは、除去することが望ましい物 質である。しかしながら、 TSNAは、有用成分であるニコチンと類似した構造を有して おり、ニコチンを除去することなく TSNAを選択的に除去することは困難である。その ため、従来の手法では、天然タバコ材から得た抽出液と抽出残渣である繊維成分を 用いて有意量のニコチンを含有するが、 TSNAが実質的に除去された再生タバコ材 を製造することが困難であった。  [0005] Trosamine, particularly TSNA, contained in natural tobacco materials is a desirable material to remove. However, TSNA has a structure similar to that of nicotine, which is a useful component, and it is difficult to selectively remove TSNA without removing nicotine. Therefore, in the conventional method, a regenerated tobacco material that contains a significant amount of nicotine but is substantially free of TSNA is produced using an extract obtained from natural tobacco material and a fiber component that is an extraction residue. It was difficult.
国際公開 WO 02Z28209の手法では、 TSNAと硝酸や糖類との分離は可能で あるが、吸着剤により TSNAとともにニコチンも吸着除去されてしまう。 International publication WO 02Z28209 allows separation of TSNA from nitric acid and sugars. There is an adsorbent that adsorbs and removes nicotine along with TSNA.
[0006] また、米国特許第 5810020号の手法では、多量のクラウンエーテルを使用するた め、安全性の面力も好ましくない。さらに、国際公開 WO 01Z65954の手法では、 超臨界抽出処理のコストが高 、ため、実用性に乏 、と 、える。 [0006] Further, in the method of US Pat. No. 5810020, since a large amount of crown ether is used, the safety aspect is not preferable. Furthermore, the method disclosed in International Publication WO 01Z65954 is not practical because of the high cost of the supercritical extraction process.
[0007] 従って、本発明は、比較的簡便な操作で、天然タバコ材カも得た抽出液力も-コチ ンの量を有意に減じることなぐ TSNAを低減させ、もって有意量のニコチンを含有 するが、 TSNAが実質的に除去された再生タバコ材を製造する方法を提供すること を目的とする。 [0007] Therefore, the present invention is a comparatively simple operation, and the extract liquid power obtained from the natural tobacco material also reduces TSNA without significantly reducing the amount of cotin, and thus contains a significant amount of nicotine. However, an object of the present invention is to provide a method for producing a recycled tobacco material from which TSNA is substantially removed.
本発明によれば、(a)天然タバコ材を水系抽出溶媒で抽出し、前記天然タバコ材の 成分を含む抽出液と抽出残渣を得ること、(b)前記抽出液またはその濃縮液を、中 間極性を示す吸着剤を用いた吸着分離操作に供して-トロソァミンを減少させること 、(c)前記抽出残渣を用いて再生タバコウェブを調製すること、(d)前記-トロソァミン が減少した抽出液または濃縮液の少なくとも一部を前記再生タバコウェブに添加す ることを包含する再生タバコ材の製造方が提供される。  According to the present invention, (a) natural tobacco material is extracted with an aqueous extraction solvent to obtain an extract and an extraction residue containing the components of the natural tobacco material, and (b) the extract or its concentrated solution Subjecting to an adsorptive separation operation using an adsorbent exhibiting interpolarity-reducing trosamine; (c) preparing a regenerated tobacco web using the extraction residue; and (d) an extract with reduced trosamine. Or the manufacturing method of the regenerated tobacco material which includes adding at least one part of a concentrate to the said regenerated tobacco web is provided.
本発明において、吸着剤は、アクリル系またはメタクリル系樹脂からなる多孔質吸着 剤、表面に親水性官能基を有する疎水性榭脂からなる多孔質吸着剤、および表面 に疎水性官能基を有する親水性樹脂からなる多孔質吸着剤力 選ぶことができる。  In the present invention, the adsorbent is a porous adsorbent composed of an acrylic or methacrylic resin, a porous adsorbent composed of a hydrophobic resin having a hydrophilic functional group on the surface, and a hydrophilic adsorbent having a hydrophobic functional group on the surface. Porous adsorbent power made of functional resin can be selected.
[0008] また、本発明において吸着分離を、吸着剤を充填したカラムを用いる先端クロマトグ ラフィー分離により行うことができる。その場合、カラムに充填された吸着剤の体積の 20倍以下の量のタバコ抽出液またはその濃縮液をカラムに通じることが好ましい。ま た、タバコ抽出液またはその濃縮液をカラムに通じて流出液を得た後、カラムに充填 された吸着剤の体積の 3倍以下の量の水を通じてその水溶出液を前記流出液と合 わせ、これを再生タバコウェブに添加することもできる。 [0008] Further, in the present invention, adsorption separation can be performed by tip chromatography separation using a column packed with an adsorbent. In that case, it is preferable to pass the tobacco extract or the concentrated solution thereof in an amount not more than 20 times the volume of the adsorbent packed in the column through the column. In addition, the tobacco extract or its concentrate is passed through a column to obtain an effluent, and then the water eluate is combined with the effluent through three times or less of the volume of the adsorbent packed in the column. Can be added to the regenerated tobacco web.
図面の簡単な説明  Brief Description of Drawings
[0009] [図 1]図 1は、本発明の一態様により再生タバコ材を製造する方法を説明するための フロー図である。  [0009] FIG. 1 is a flow diagram for explaining a method of producing a regenerated tobacco material according to an embodiment of the present invention.
[図 2A]図 2Aは、以後詳述する例 66におけるニコチンおよび総 TSNAの溶出濃度を 示すグラフである。 [図 2B]図 2Bは、例 66におけるニコチンおよび総 TSNAの累積溶出率を示すグラフ である。 FIG. 2A is a graph showing the elution concentrations of nicotine and total TSNA in Example 66 described in detail below. FIG. 2B is a graph showing the cumulative dissolution rate of nicotine and total TSNA in Example 66.
[図 3A]図 3Aは、以後詳述する例 67における総 TSNA、糖 (グルコース、フルクトース およびシユークロース)およびアミノ酸の溶出濃度を示すグラフである。  FIG. 3A is a graph showing the elution concentrations of total TSNA, sugar (glucose, fructose and sucrose) and amino acids in Example 67, which will be described in detail later.
[図 3B]図 3Bは、例 67における総 TSNA、糖(グルコース、フルクトースおよびシユー クロース)およびアミノ酸の累積溶出率を示すグラフである。  FIG. 3B is a graph showing the cumulative elution rates of total TSNA, sugars (glucose, fructose and sucrose) and amino acids in Example 67.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0010] 以下、本発明を種々の態様に沿ってより詳しく説明する。 Hereinafter, the present invention will be described in more detail along various aspects.
[0011] 本発明の方法は、中間極性を示す吸着剤を用いて、天然タバコ材カも水系抽出溶 媒による抽出で得られた抽出液から、ニコチンの損失を極力抑えて、 TSNA(N' - ニトロソノルニコチン(NNN)、 4— (メチルニトロソァミノ)— 1— (3—ピリジル)—1— ブタノン (NNK)、 N'— -トロソアナタビン (NAT)等)を実質的に除去し、その抽出 液の少なくとも一部を、抽出残渣を用いて調製された再生タバコウェブに添加するこ とにより、再生タバコ材を製造するものである。  [0011] The method of the present invention uses an adsorbent exhibiting an intermediate polarity, and the TSNA (N ′ -Nitrosonornicotine (NNN), 4- (Methylnitrosamino)-1-(3-Pyridyl)-1-Butanone (NNK), N'--Trosoanatabine (NAT)) The regenerated tobacco material is produced by adding at least a part of the extracted liquid to a regenerated tobacco web prepared using the extraction residue.
[0012] 図 1は、本発明の 1つの態様により再生タバコ材を製造する方法を説明するための フロー図を図 1に示す。  [0012] FIG. 1 shows a flow diagram for explaining a method of producing a recycled tobacco material according to one embodiment of the present invention.
[0013] 図 1に示すように、まず、天然タバコ材 11と抽出溶媒 12を混合し、撹拌することによ り天然タバコ材 11を抽出処理 S1に供する。  As shown in FIG. 1, first, the natural tobacco material 11 and the extraction solvent 12 are mixed and stirred to subject the natural tobacco material 11 to the extraction treatment S1.
[0014] 天然タバコ材 11としては、タバコの葉、刻、中骨、茎、根およびそれらの混合物を用 いることができる。抽出溶媒としては、水系溶媒を用いることができる。水等の水系抽 出溶媒は、アルカリ性であっても、酸性であってもよい。水系抽出溶媒として、水と水 混和性有機溶媒との混合物も使用し得る。そのような有機溶媒の例を挙げると、エタ ノールのようなアルコール類である。これら抽出溶媒には、水酸ィ匕ナトリウムのような 無機塩を溶解させることもできる。抽出処理 S1は、通常、 50〜: LOO°Cの温度で、 5分 〜6時間程度行われる。  [0014] As the natural tobacco material 11, tobacco leaves, chopped, medium bones, stems, roots, and mixtures thereof can be used. As the extraction solvent, an aqueous solvent can be used. The aqueous extraction solvent such as water may be alkaline or acidic. As an aqueous extraction solvent, a mixture of water and a water-miscible organic solvent can also be used. Examples of such organic solvents are alcohols such as ethanol. In these extraction solvents, inorganic salts such as sodium hydroxide can be dissolved. The extraction treatment S1 is usually performed at a temperature of 50 to: LOO ° C for about 5 minutes to 6 hours.
[0015] 抽出処理 S1の終了後、得られた抽出混合物を、例えばろ過等による分離操作 S2 に供し、抽出液 13と抽出残渣 14に分ける。抽出液 13は、天然タバコ材中の水溶性 成分、例えばニコチン、 TSNA等を含む。 抽出残渣 14は、実質的に繊維からなる。この抽出残渣 14を用いて、常法により、再 生タバコウェブ 15を製造する。この再生タバコウェブ 15は、その一部が抽出残渣 14 により構成されるものでもよいし、その全部が抽出残渣 14により構成されるものでもよ い。 [0015] After completion of the extraction treatment S1, the obtained extraction mixture is subjected to a separation operation S2 by, for example, filtration, and divided into an extraction liquid 13 and an extraction residue 14. The extract 13 contains water-soluble components in the natural tobacco material, such as nicotine and TSNA. The extraction residue 14 consists essentially of fibers. Using this extraction residue 14, a regenerated tobacco web 15 is produced by a conventional method. The regenerated tobacco web 15 may be partially constituted by the extraction residue 14 or may be entirely constituted by the extraction residue 14.
[0016] 他方、分離操作 S2から得られた抽出液 13は、これを例えば遠心薄膜法等の常法 により濃縮し、あるいは濃縮することなぐ中間極性を示す吸着剤を用いた吸着処理 操作 S4に供する。本発明において、この吸着分離操作 S4は、例えば、抽出液 13を 、中間極性を示す吸着剤と接触させることにより行うことができる。中間極性を示す吸 着剤とは、一般に高極性と低極性との中間の極性を示す吸着剤であり、アクリル系ま たはメタクリル系榭脂を基材とする高多孔質榭脂、またはスチレン系榭脂等の疎水性 榭脂表面に、 4級アンモニゥム基、ダルカミン基、イミノジ酢酸基、ポリアミン基、 3級ァ ミン基等の親水性官能基を有する高多孔質榭脂、あるいはシリカ系榭脂等の親水性 榭脂表面にォクタデシル基等の疎水性官能基を有する高多孔質榭脂を例示するこ とができる。中間極性の吸着剤を用いることにより、タバコ抽出液力もニコチンの損失 を極力抑えて TSNAを有意に除去することができる。  [0016] On the other hand, the extract 13 obtained from the separation operation S2 is concentrated by an ordinary method such as a centrifugal thin film method, or the adsorption solution operation S4 using an adsorbent having intermediate polarity without being concentrated is used. Provide. In the present invention, the adsorption separation operation S4 can be performed, for example, by bringing the extract 13 into contact with an adsorbent having intermediate polarity. An adsorbent having an intermediate polarity is generally an adsorbent having an intermediate polarity between high polarity and low polarity, and is a highly porous resin based on acrylic or methacrylic resin, or styrene. Hydrophobic rosin and other hydrophobic sorbents on the surface, highly porous rosin having a hydrophilic functional group such as quaternary ammonium group, dalkamine group, iminodiacetic acid group, polyamine group and tertiary amine group, or silica Examples of the highly porous resin having a hydrophobic functional group such as octadecyl group on the surface of hydrophilic resin such as fat. By using an adsorbent with a medium polarity, TSNA can be significantly removed by reducing the nicotine loss as much as possible in the tobacco extract.
[0017] 抽出液 13と中間極性を示す吸着剤との接触は、例えば、抽出液 13に中間極性を 示す吸着剤の粒子を添加し、撹拌することによって行うことができる (バッチ式)。ある いは、抽出液 13と中間極性を示す吸着剤との接触は、中間極性を示す吸着剤の粒 子を充填した吸着剤床に抽出液を通じることによつても行うことができる。  [0017] The contact between the extract 13 and the adsorbent having intermediate polarity can be performed, for example, by adding particles of the adsorbent having intermediate polarity to the extract 13 and stirring (batch type). Alternatively, the contact between the extract 13 and the adsorbent having an intermediate polarity can also be made by passing the extract through an adsorbent bed filled with particles of an adsorbent having an intermediate polarity.
[0018] また、いわゆる先端クロマトグラフィー分離法を用いることもできる。この先端クロマト グラフィー分離法は、吸着剤を充填したカラムにタバコ抽出液もしくはその濃縮液を 通じ、カラム流出液の TSNAはほとんど含まないがニコチンを含む液が流出し始めた 点から TSNAが流出し始めるまでの画分を採取する手法である。先端クロマトグラフ ィー分離法は、分離対象液をカラム内の吸着剤に吸着させた後、分離対象液と異な る溶媒 (例えば水)を移動相として用い、溶離時に成分を分離する通常のクロマトダラ フィー技術と異なり、分離対象液 (本発明においては、タバコ抽出液またはその濃縮 液)自体を移動相として用いるものであり、分離対象液をカラムに負荷した時点から 成分を分離することが可能である。さらに、通常のクロマトグラフィーでは、分離対象 液の負荷量を増カロさせると分離能が低下するが、先端クロマトグラフィー分離では、 分離対象液自体を移動相として用いて 、るため、水等の移動相により溶出させる場 合とでは移動相の水素イオン濃度 (pH)が異なるので、多量の分離対象液をカラム に負荷しても分離能を低下させることが少な 、。 [0018] A so-called advanced chromatography separation method can also be used. In this advanced chromatographic separation method, tobacco extract or its concentrate is passed through a column packed with an adsorbent, and TSNA does not contain TSNA in the column effluent, but liquid containing nicotine begins to flow out. It is a technique to collect the fraction until the start. In the advanced chromatographic separation method, the separation target liquid is adsorbed by an adsorbent in the column, and then a solvent (for example, water) different from the separation target liquid is used as a mobile phase to separate components during elution. Unlike the fee technology, the liquid to be separated (in the present invention, the tobacco extract or its concentrated liquid) itself is used as the mobile phase, and the components can be separated from the time when the liquid to be separated is loaded onto the column. is there. Furthermore, in normal chromatography, the separation target When the liquid load is increased, the resolution decreases, but in the advanced chromatographic separation, since the separation target liquid itself is used as the mobile phase, the mobile phase is different from the case of elution with a mobile phase such as water. Since the hydrogen ion concentration (pH) of each column is different, the resolution is rarely reduced even when a large amount of separation target liquid is loaded onto the column.
[0019] 本発明にお 、て用いる先端クロマトグラフィー分離法では、分離に供するタバコ抽 出液を遠心薄膜法等の常法により、可溶性成分濃度が約 10〜20重量%となるよう に濃縮することが好ましい。  [0019] In the advanced chromatographic separation method used in the present invention, the tobacco extract used for separation is concentrated by a conventional method such as a centrifugal thin film method so that the concentration of soluble components is about 10 to 20% by weight. It is preferable.
[0020] 用いる中間極性吸着剤の量は、抽出液 13中の可溶性成分の重量の 50%以上に 相当する量が好ましい。中間極性吸着剤の量が 50%未満であると、抽出液中の TS NAを十分に除去することが困難になる。  [0020] The amount of the intermediate polar adsorbent used is preferably an amount corresponding to 50% or more of the weight of the soluble component in the extract 13. If the amount of the intermediate polar adsorbent is less than 50%, it becomes difficult to sufficiently remove TSNA in the extract.
[0021] 先端クロマトグラフィー分離法では、分離に供するタバコ抽出液またはその濃縮物 の量をカラムに充填した吸着剤体積の約 20倍量以下、好ましくは約 12倍量以下とす ることが望ましい。タバコ抽出液またはその濃縮物の全量をカラムに通じた後、カラム の水を通じることにより、ニコチンをほぼ完全に (合計で 90%以上)回収することがで きる。その場合、水は、カラムに充填した吸着剤体積の約 3倍量以上、好ましくは約 5 倍量以上の量で用いることが望まし 、。  [0021] In the advanced chromatographic separation method, it is desirable that the amount of the tobacco extract or its concentrate to be subjected to the separation is about 20 times or less, preferably about 12 times or less the volume of the adsorbent packed in the column. . Nicotine can be recovered almost completely (over 90% in total) by passing the entire amount of tobacco extract or its concentrate through the column and then passing water through the column. In that case, it is desirable to use water in an amount of about 3 times or more, preferably about 5 times or more the volume of the adsorbent packed in the column.
[0022] なお、抽出液中の可溶性成分の量は、凍結乾燥法によって知ることができる。  [0022] The amount of the soluble component in the extract can be determined by a freeze-drying method.
[0023] こうして吸着分離を行つた抽出液を中間極性吸着剤 (使用済吸着剤 17)から分離( S5)する。この分離は、抽出液と中間極性吸着剤との接触を抽出液中に中間極性吸 着剤を添加し撹拌することによって行った場合には、ろ過により行うことができる。また 、抽出液と中間極性吸着剤との接触を、抽出液を中間極性吸着剤床に通じること〖こ よって行った場合あるいは先端クロマトグラフィー分離を用いた場合には、吸着処理 後の抽出液は、いうまでもなぐ中間極性吸着剤から分離された状態で、中間極性吸 着剤床から流出する。先端クロマトグラフィー分離を用いた場合、水による溶出液を 合わせて用いることができる。  [0023] The extract thus separated by adsorption is separated from the intermediate polar adsorbent (used adsorbent 17) (S5). This separation can be performed by filtration when the contact between the extract and the intermediate polar adsorbent is carried out by adding the intermediate polar adsorbent to the extract and stirring. In addition, when the contact between the extract and the intermediate polar adsorbent is carried out by passing the extract through the intermediate polar adsorbent bed, or when using advanced chromatographic separation, the extract after the adsorption treatment is Needless to say, it flows out from the intermediate polar adsorbent bed in a state separated from the intermediate polar adsorbent. When using advanced chromatographic separation, an eluate from water can be used in combination.
[0024] こうして得られる吸着処理済抽出液 16を常法により濃縮し、または濃縮することなく 、その一部または全部を再生タバコウェブ 15に添カ卩(S5)することにより、再生タバコ 材 18が得られる。こうして得られる再生タバコ材 18を用いて作製したシガレットは、燃 焼時に生成する煙中の TSNAが有意に低減したものとなる。 [0024] The adsorption-treated extract 16 obtained in this way is concentrated by a conventional method, or a part or all of it is added to the regenerated tobacco web 15 without being concentrated (S5). Is obtained. Cigarettes made using the recycled tobacco material 18 thus obtained are TSNA in smoke generated during firing is significantly reduced.
[0025] 以上、本発明を実施の形態に沿って説明したが、本発明は上記実施の形態に限 定されるものではない。いうまでもなぐ上記種々の実施の形態を組み合わせることも できる。 As described above, the present invention has been described according to the embodiment, but the present invention is not limited to the above embodiment. Needless to say, the various embodiments described above can be combined.
実施例  Example
[0026] 以下本発明を種々の例により説明する力 本発明はそれらに限定されるものではな い。  [0026] Hereinafter, the present invention will be described with reference to various examples. The present invention is not limited to these examples.
[0027] 以下の例にお 、て、 TSNA量は、 Aristaの刻中 TSNA測定法(Official Method T- 309, Determination of Nitrosamines in Whole Tobacco, made by the Department or Health, dated December 31, 1999)に準じて測定した。すなわち、試料液(タバコ抽出 液、吸着剤処理液またはカラム流出液)を LC MSZMSに供して測定した。  [0027] In the following example, the amount of TSNA is calculated according to Arista's time-lapse TSNA measurement method (Official Method T-309, Determination of Nitrosamines in Whole Tobacco, made by the Department or Health, dated December 31, 1999). Measured accordingly. That is, the sample solution (tobacco extract, adsorbent treatment solution, or column effluent) was subjected to LC MSZMS for measurement.
[0028] また、ニコチン量は、ドイツ標準化機構 DIN 10373に準ずる方法で行った。すな わち、試料液に水酸ィ匕ナトリウムを加えアルカリ性にし、ついでへキサンをカ卩えて混 合し、ニコチンをへキサン相に移行させ、へキサン相のみを GCZFIDに供して測定 した。  [0028] The amount of nicotine was measured by a method in accordance with DIN 10373, a German standardization organization. In other words, sodium hydroxide was added to the sample solution to make it alkaline, then hexane was added and mixed, nicotine was transferred to the hexane phase, and only the hexane phase was subjected to GCZFID for measurement.
[0029] 糖(グルコース、フルクトース、シユークロース)量は、試料液を LC— RIに供して測 し 7こ。  [0029] The amount of sugar (glucose, fructose, sucrose) is measured by subjecting the sample solution to LC-RI.
[0030] さらに、アミノ酸量は、全自動アミノ酸分析装置(日本電子 (株)衡 LC— 500)を用 いて測定した。  [0030] Furthermore, the amount of amino acids was measured using a fully automatic amino acid analyzer (JEOL Co., Ltd. Heng LC-500).
[0031] 例 1〜11 [0031] Examples 1-11
温度 25°Cで、タバコ葉刻 (X— KLl OOgを水 lOOOmLと混合し、 1時間撹拌する ことによりタバコ刻の抽出を行った。得られた抽出混合物をろ過し、抽出液と、抽出残 渣に分けた。抽出残渣を抄紙して、再生タバコウェブを得た。  Tobacco leaf was extracted by mixing tobacco leaf (X-KLl OOg with water lOOOOmL and stirring for 1 hour at a temperature of 25 ° C. The resulting extraction mixture was filtered, and the extract and the extraction residue were filtered. Paper from the extracted residue was obtained to obtain a regenerated tobacco web.
[0032] 他方、抽出液に、その可溶性成分重量に対し表 1に示す量(%)でメタクリル系榭脂 [0032] On the other hand, methacrylic resin in the extract in the amount (%) shown in Table 1 with respect to the weight of soluble components.
(三菱化学社製商品名ダイヤイオン HP2MG;平均粒径: 250 μ m以上;比表面積: 470mVg,官能基なし)をカ卩え、温度 25°Cで、表 1に示す時間(処理時間)撹拌した 後、ろ過した。吸着処理後の抽出液 (ろ液)中に含まれる総 TSNA量とニコチン量を 分析した。結果を下記表 1に併記する。表 1には、総 TSNA増減率とニコチン増減率 も示す。表 1中、未処理とは、吸着処理を行っていない抽出液を指す (以下の表にお いて同じ)。 (Mitsubishi Chemical's product name Diaion HP2MG; average particle size: 250 μm or more; specific surface area: 470 mVg, no functional group), stirring at the temperature (25 ° C) shown in Table 1 (treatment time) And then filtered. The total TSNA amount and nicotine amount contained in the extract (filtrate) after the adsorption treatment were analyzed. The results are also shown in Table 1 below. Table 1 shows the total TSNA change rate and nicotine change rate. Also shown. In Table 1, untreated refers to the extract that has not been adsorbed (the same applies to the following table).
[表 1] | ¥ §VN S丄 V N S上  [Table 1] | ¥ §VN S 丄 on V N S
着処時量吸理チチンンニニココ s ty- m CD 0) CO (Μ ID 寸 CO o O  Absorbing amount at the time of dressing nicotine s ty- m CD 0) CO (Μ ID size CO o O
1 I CNJ CO 寸 in CD  1 I CNJ CO inch in CD
1 1 [ 1 I 1 1 1 1 1 1  1 1 [1 I 1 1 1 1 1 1
CD CD CO CO 寸 CD CD CO CO
褂 1 〇 CVJ CM N CNJ  褂 1 〇 CVJ CM N CNJ
1 1  1 1
細 1 1 1 1 1 1 1 1 as &- 0s Fine 1 1 1 1 1 1 1 1 as &-0 s
O 〇 寸 W IT) 〇 0) 00 ( 寸  O ○ Dimension W IT) 〇 0) 00 (Dimension
1  1
褂 寸 If) (D CO 00 00 σ>  寸 Dimension If) (D CO 00 00 σ>
锾 i 1 1 1 1 1 1 1 1 I 1 tuO 〇 〇 卜 σ> 00 00 < i O 0) 00  锾 i 1 1 1 1 1 1 1 1 I 1 tuO ○ ○ 卜 σ> 00 00 <i O 0) 00
\  \
ω r- CO 10 CO VJ 〇 〇 〇  ω r- CO 10 CO VJ ○ ○ ○
Ε M <M CNJ NJ (M CNJ CM CM CM CM (M  Ε M <M CNJ NJ (M CNJ CM CM CM CM (M
O) LO 00 o O) LO 00 o
tuO 寸  tuO size
(NJ 寸 ID 0) 1Λ 卜 〇  (NJ size ID 0) 1Λ 〇 〇
\  \
eg eg
JO CO CD 寸  JO CO CD size
00 O CO CVJ CM 00 O CO CVJ CM
O <  O <
Yes
IT) O o in 〇 O in 〇 O o  IT) O o in ○ O in ○ O o
1 CO CD O <D r— CO (D  1 CO CD O <D r— CO (D
〇 O O 〇 〇 O 〇 〇 ○ O O ○ ○ O ○ ○
〇 o 〇  ○ o ○
1 ID in in 〇 o O 〇 〇  1 ID in in ○ o O ○ ○
ID ΙΩ  ID ΙΩ
劇 vJ to ID  Play vJ to ID
m mriil  m mriil
 Yes
CM CO 寸 ΙΩ CD O  CM CO Dimension ΙΩ CD O
軍 軍 [0033] 表 1に示す結果から、抽出液中の可溶性成分量の 50%以上の量の吸着剤を用い ることにより、総 TSNA量が有意に減少する一方で、ニコチン量の減少率は、処理時 間を長くしても 25%未満に抑制できることがわかる。特に、吸着剤の使用量が抽出液 中の可溶性成分量の 500%相当量であると、総 TSNA量がほぼ 90%以上減少する ことがわ力ゝる。 Army army [0033] From the results shown in Table 1, the total TSNA amount was significantly decreased by using an adsorbent in an amount of 50% or more of the amount of soluble components in the extract, while the decrease rate of the nicotine amount was It can be seen that even if the treatment time is increased, it can be suppressed to less than 25%. In particular, if the amount of adsorbent used is equivalent to 500% of the amount of soluble components in the extract, it is obvious that the total TSNA amount is reduced by more than 90%.
[0034] 例 1〜: L 1の吸着処理済抽出液のそれぞれを再生タバコウェブに添加してそれぞれ 再生タバコ材を調製した。  [0034] Examples 1 to: Each of the L 1 adsorption-treated extracts was added to a regenerated tobacco web to prepare a regenerated tobacco material.
[0035] 例 12〜20  [0035] Examples 12-20
中間極性吸着剤としてアクリル系榭脂(ローム ·アンド ·ハース社製商品名 XAD7H P;平均粒径: 350〜900 μ m;比表面積: 400m2Zg以上、官能基なし)を表 2に示 す量で用 、、表 2に示す時間抽出液と撹拌した以外は例 1〜 11と同様の操作を行つ た。吸着処理後の抽出液 (ろ液)中に含まれる総 TSNA量とニコチン量の分析結果 を表 2に併記する。 Table 2 shows acrylic resin (trade name XAD7H P, manufactured by Rohm and Haas; average particle size: 350 to 900 μm; specific surface area: 400 m 2 Zg or more, no functional group) as an intermediate polar adsorbent The same operation as in Examples 1 to 11 was carried out except that the amount was used and stirring with the extract solution for the time shown in Table 2. The analysis results of the total TSNA and nicotine contained in the extract (filtrate) after the adsorption treatment are also shown in Table 2.
[表 2] [Table 2]
Figure imgf000011_0001
Figure imgf000011_0001
表 2に示す結果から、抽出液中の可溶性成分量の 50%以上の量の吸着剤を用い ることにより、総 TSNA量が有意に減少する一方で、ニコチン量の減少率は、処理時 間を長くしても 30%未満に抑制できることがわかる。特に、吸着剤の使用量が抽出液 中の可溶性成分量の 500%相当量であると、総 TSNA量がほぼ 90%以上減少する ことがわ力ゝる。 From the results shown in Table 2, the total TSNA amount was significantly reduced by using an adsorbent in an amount of 50% or more of the amount of soluble components in the extract. It can be seen that even if the length is increased, it can be suppressed to less than 30%. In particular, the amount of adsorbent used is the extract. The amount equivalent to 500% of the amount of soluble components in the mixture is said to reduce the total TSNA amount by more than 90%.
[0037] 例 12〜20の吸着処理済抽出液のそれぞれを再生タバコウェブに添加してそれぞ れ再生タバコ材を調製した。  [0037] Each of the adsorption-treated extracts of Examples 12 to 20 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
[0038] 例 21〜29  [0038] Examples 21-29
中間極性吸着剤として、イミノジ酢酸型官能基を有するスチレン系榭脂 (三菱化学 社製商品名ダイヤイオン CR11:平均粒径 355〜1180 μ m)を表 3に示す量で用い 、表 3に示す時間抽出液と撹拌した以外は例 1〜11と同様の操作を行った。吸着処 理後の抽出液 (ろ液)中に含まれる総 TSNA量とニコチン量の分析結果を表 3に併 記する。  As an intermediate polar adsorbent, styrene-based resin having iminodiacetic acid type functional group (trade name Diaion CR11 manufactured by Mitsubishi Chemical Co., Ltd .: average particle size 355 to 1180 μm) is used in the amount shown in Table 3, and shown in Table 3 The same operation as in Examples 1 to 11 was performed except that the mixture was stirred with the time extract. Table 3 shows the analysis results of the total TSNA and nicotine contained in the extract (filtrate) after the adsorption treatment.
[表 3] [Table 3]
Figure imgf000013_0001
Figure imgf000013_0001
表 3に示す結果力 抽出液中の可溶性成分量の 250%以上の量の吸着剤を用い ることにより、総 TSNA量が有意に減少する一方で、ニコチン量の減少率は、処理時 間を長くしても、 35%以下に抑制できることがわかる。特に、吸着剤の使用量が抽出 液中の可溶性成分量の 500%相当量であると、総 TSNA量が最大で 80%減少する ことがわ力ゝる。 Results shown in Table 3 While using an adsorbent in an amount of 250% or more of the amount of soluble components in the extract, the total TSNA amount is significantly reduced, while the rate of decrease in the nicotine amount is less than the treatment time. It can be seen that even if it is made longer, it can be suppressed to 35% or less. In particular, the amount of adsorbent used is extracted If the amount of soluble components in the liquid is equivalent to 500%, the total TSNA amount will decrease by up to 80%.
[0040] 例 21〜29の吸着処理済抽出液のそれぞれを再生タバコウェブに添カ卩してそれぞ れ再生タバコ材を調製した。  [0040] Each of the adsorption-treated extracts of Examples 21 to 29 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
[0041] 例 30〜38  [0041] Examples 30-38
中間極性吸着剤として、ダルカミン官能基を有するスチレン系榭脂 (三菱化学社製 商品名ダイヤイオン CRB02 :平均粒径 300 m以上)を表 4に示す量で用い、表 4に 示す時間抽出液と撹拌した以外は例 1〜 11と同様の操作を行った。吸着処理後の 抽出液 (ろ液)中に含まれる総 TSNA量とニコチン量の分析結果を表 4に併記する。  As an intermediate polar adsorbent, a styrene-based resin having a darucamine functional group (trade name Diaion CRB02 manufactured by Mitsubishi Chemical Co., Ltd .: average particle size of 300 m or more) is used in the amount shown in Table 4, and the time extract shown in Table 4 The same operation as in Examples 1 to 11 was performed except that stirring was performed. The analysis results of the total TSNA and nicotine contained in the extract (filtrate) after the adsorption treatment are also shown in Table 4.
[表 4] [Table 4]
Figure imgf000015_0001
Figure imgf000015_0001
表 4に示す結果力 抽出液中の可溶性成分量の 250%以上の量の吸着剤を用い ることにより、総 TSNA量が有意に減少する一方で、ニコチン量の減少率は、処理時 間を長くしても、 10%以下に抑制できることがわかる。特に、吸着剤の使用量が抽出 液中の可溶性成分量の 500 %相当量であると、総 TSNA量が 70%以上減少するこ とがわかる。 The results shown in Table 4 While using an adsorbent in an amount of 250% or more of the amount of soluble components in the extract, the total TSNA amount is significantly reduced, while the reduction rate of the nicotine amount is less than the treatment time. It can be seen that even if it is made longer, it can be suppressed to 10% or less. In particular, the amount of adsorbent used is extracted It can be seen that when the amount of soluble components in the liquid is equivalent to 500%, the total TSNA amount decreases by 70% or more.
[0043] 例 30〜38の吸着処理済抽出液のそれぞれを再生タバコウェブに添加してそれぞ れ再生タバコ材を調製した。  [0043] Each of the adsorption-treated extracts of Examples 30 to 38 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
[0044] 例 39〜47  [0044] Examples 39-47
中間極性吸着剤として、 4級アンモニゥム官能基を有するスチレン系榭脂 (三菱ィ匕 学社製商品名ダイヤイオン HPA25:平均粒径 250 μ m以上)を表 5に示す量で用い 、表 5に示す時間抽出液と撹拌した以外は例 1〜11と同様の操作を行った。吸着処 理後の抽出液 (ろ液)中に含まれる総 TSNA量とニコチン量の分析結果を表 5に併 記する。  As an intermediate polar adsorbent, styrene resin having a quaternary ammonium functional group (trade name Diaion HPA25 manufactured by Mitsubishi Chemical Co., Ltd .: average particle size of 250 μm or more) is used in the amount shown in Table 5, and in Table 5 The same operations as in Examples 1 to 11 were carried out except that the extract was stirred for the indicated time. Table 5 shows the results of analysis of total TSNA and nicotine contained in the extract (filtrate) after the adsorption treatment.
[表 5] [Table 5]
Si Si
LO 寸 寸 〇 CO 寸 〇  LO Dimension 〇 CO Dimension 〇
m 1 1 「 「 寸 in 寸 in (0 CD  m 1 1 `` Dimension in Dimension in (0 CD
(0  (0
1 1 1 1 1 1 1 1 1  1 1 1 1 1 1 1 1 1
-Q -Q
1時着総量総量吸処理チチンNA A丁 Sン T S Nニニココ 〇 寸  1 o'clock arrival total amount absorption treatment titin NA A Ding Sun T S N Ninikoko ○ inch
褂 1 LO  LO 1 LO
锾 1 1 1 I 1  锾 1 1 1 I 1
1 1 1 1  1 1 1 1
Ρ3 Ρ3
CD 寸 (D LD ID  CD dimension (D LD ID
!  !
褂 寸 LD ιο  寸 inch LD ιο
1 1 I 1 1 1 1 1 1  1 1 I 1 1 1 1 1 1
10 CO 寸 〇 J 寸 CD r- CM 10 CO Dimension 〇 J Dimension CD r- CM
\  \
寸 寸 CO O CM  Dimension CO O CM
£ CM (M CVJ OJ J CvJ CM CJ  £ CM (M CVJ OJ J CvJ CM CJ
tlfl 00 〇 O 00 CO O 00 tlfl 00 ○ O 00 CO O 00
 Size
\  \
do CO 卜 lf> 寸 寸 O 〇  do CO 卜 lf> Dimension O 〇
00  00
CO CvJ  CO CvJ
ID o 〇 LD o o 10 o O ID o 〇 LD o o 10 o O
1 O O CD C CD o o 〇 o o 〇  1 O O CD C CD o o ○ o o ○
O 〇 〇  O ○ ○
镧 1 If) LO o 〇 O  镧 1 If) LO o ○ O
io t LO  io t LO
OJ <NI (M ΙΩ ID IT)  OJ <NI (M ΙΩ ID IT)
DH  DH
〇 CM 寸 in CD  〇 CM dimension in CD
CO 寸 寸 寸 寸 寸 寸 寸 寸  CO Dimension Dimension Dimension Dimension Dimension Dimension
 伥
Figure imgf000017_0001
Figure imgf000017_0001
表 5に示す結果力 抽出液中の可溶性成分量の 250%以上の量の吸着剤を用い ることにより、総 TSNA量が有意に減少する一方で、ニコチン量の減少率は、処理時 間を長くしても、ほぼ 10%以下に抑制できることがわかる。特に、吸着剤の使用量が 抽出液中の可溶性成分量の 500%相当量であると、総 TSNA量が 70%以上減少 することがゎカゝる。 Results shown in Table 5 The use of adsorbent in an amount of 250% or more of the amount of soluble components in the extract significantly decreases the total TSNA amount, while the decrease rate of the nicotine amount decreases the processing time. It can be seen that even if it is lengthened, it can be suppressed to about 10% or less. In particular, the amount of adsorbent used is If the amount of soluble components in the extract is equivalent to 500%, the total TSNA amount will decrease by 70% or more.
[0046] 例 39〜47の吸着処理済抽出液のそれぞれを再生タバコウェブに添カ卩してそれぞ れ再生タバコ材を調製した。  [0046] Each of the adsorption-treated extracts of Examples 39 to 47 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
[0047] 例 48〜56  [0047] Examples 48-56
中間極性吸着剤として、ォクタデシル基を有するシリカ系榭脂(ウォーターズ社製商 品名 Bondpak C18 :平均粒径 37〜55 /z m)を表 6に示す量で用い、表 6に示す時 間抽出液と撹拌した以外は例 1〜 11と同様の操作を行つた。吸着処理後の抽出液( ろ液)中に含まれる総 TSNA量とニコチン量の分析結果を表 6に併記する。  As an intermediate polar adsorbent, silica-based rosin having a octadecyl group (trade name Bondpak C18 manufactured by Waters Co., Ltd .: average particle size: 37 to 55 / zm) is used in the amount shown in Table 6, and the time extract shown in Table 6 is used. The same operation as in Examples 1 to 11 was performed except that stirring was performed. Table 6 shows the results of analysis of total TSNA and nicotine contained in the extract (filtrate) after adsorption treatment.
[表 6] [Table 6]
O CD CD 〇 O <D CD O CD CD 〇 O <D CD
m 1 1 寸 寸 寸 ΙΩ CD CD  m 1 1 inch size ΙΩ CD CD
― ca 1 1 1 1 1 I 1 1 総総量時量着処理吸チンチン TSNA TS N Aニニココ ΙΩ  ― Ca 1 1 1 1 1 I 1 1
1 C ID 寸 (D 寸 寸  1 C ID dimension (D dimension
o Ο  o Ο
1減増率増減率(()間(分))ba 1 1 1 1 1 1 1 1 Increase / decrease rate change rate (between () (minutes)) ba 1 1 1 1 1 1 1
% ε -% ε-
CD 00 CD 10 寸 CD 00 CD 10 inch
1 o 寸 O 〇  1 o Dimension O ○
CNJ CO 寸 ΙΛ ID  CNJ CO dimension ΙΛ ID
1 1 1 I 1 1 1 1 1 寸 CD O m 寸 ο CO io 寸 1 1 1 I 1 1 1 1 1 dimension CD O m dimension ο CO io dimension
O CM CvJ CVJ O OJ ο CO CvJ Csl  O CM CvJ CVJ O OJ ο CO CvJ Csl
CM CvJ CM CM CvJ OJ CVJ CM OJ  CM CvJ CM CM CvJ OJ CVJ CM OJ
00 00 CO O 00 〇 CM 00 00 CO O 00 〇 CM
CVJ 寸  CVJ size
〇 OJ ΙΌ <D CO 寸 寸 〇 OJ ΙΌ <D CO Dimension
O CM CNJ <  O CM CNJ <
10 Ten
1 O O IO 〇 ο ID 〇 〇  1 O O IO 〇 ο ID 〇 〇
CO CO O  CO CO O
〇 〇 Ο 〇 〇 O 〇 〇 Ο 〇 〇 O
O O 〇  O O ○
颧 - 1 ID Ιί) O o O  颧-1 ID Ιί) O o O
lO ID  lO ID
CM CvJ CvJ LD in IO  CM CvJ CvJ LD in IO
¾ 瞷  ¾ 瞷
00 〇 OJ CO 寸 i CD  00 〇 OJ CO inch i CD
寸 寸 LO LO 10 to 10 IO  Dimension LO LO 10 to 10 IO
 伥
Figure imgf000019_0001
Figure imgf000019_0001
表 6に示す結果力 抽出液中の可溶性成分量の 250%以上の量の吸着剤を用い ることにより、総 TSNA量が有意に減少する一方で、ニコチン量の減少率は、処理時 間を長くしても、ほぼ 10%以下に抑制できることがわかる。特に、吸着剤の使用量が 抽出液中の可溶性成分量の 500%相当量であると、総 TSNA量が 70%以上減少 することがゎカゝる。 The results shown in Table 6 While using an adsorbent in an amount of 250% or more of the amount of soluble components in the extract, the total TSNA amount decreased significantly, while the rate of decrease in nicotine amount decreased with the treatment time. It can be seen that even if it is lengthened, it can be suppressed to about 10% or less. In particular, the amount of adsorbent used is If the amount of soluble components in the extract is equivalent to 500%, the total TSNA amount will decrease by 70% or more.
[0049] 例 48〜56の吸着処理済抽出液のそれぞれを再生タバコウェブに添カ卩してそれぞ れ再生タバコ材を調製した。  [0049] Each of the adsorption-treated extracts of Examples 48 to 56 was added to a regenerated tobacco web to prepare a regenerated tobacco material.
[0050] 例 57〜65 (比較例) [0050] Examples 57-65 (comparative examples)
吸着剤として親水性の吸着剤である活性アルミナを表 7に示す量で用い、表 7に示 す時間抽出液と撹拌した以外は例 1〜 11と同様の操作を行った。吸着処理後の抽 出液 (ろ液)中に含まれる総 TSNA量とニコチン量の分析結果を表 7に併記する。  The same operation as in Examples 1 to 11 was performed except that activated alumina, which is a hydrophilic adsorbent, was used as the adsorbent in the amount shown in Table 7 and the mixture was stirred with the extract for the time shown in Table 7. Table 7 also shows the results of analysis of the total TSNA and nicotine contained in the extract (filtrate) after adsorption.
[表 7] [Table 7]
Figure imgf000021_0001
Figure imgf000021_0001
表 7に示すように、親水性吸着剤を用いた場合、 TSNAの除去がほとんど行えない 例 66 温度 25°Cで、タバコ葉刻 (X— KLl OOgを水 lOOOmLと混合し、 1時間撹拌する ことによりタバコ刻の抽出を行った。得られた抽出混合物をろ過し、抽出液と、抽出残 渣に分けた。抽出残渣を抄紙して、再生タバコウェブを得た。 As shown in Table 7, when a hydrophilic adsorbent is used, TSNA can hardly be removed. Example 66 Tobacco leaf was extracted by mixing tobacco leaf (X-KLl OOg with water lOOOmL at a temperature of 25 ° C and stirring for 1 hour. The resulting extraction mixture was filtered, Paper from the extracted residue was obtained to obtain a regenerated tobacco web.
[0052] 他方、抽出液を、減圧下、約 60°Cで遠心薄膜法により可溶性成分が約 15重量% となるまで濃縮し、濃縮抽出液 (pH = 6. 0)を得た。この濃縮液 (温度 25°C)を以下 の条件で先端クロマトグラフィー分離に供した。 On the other hand, the extract was concentrated under reduced pressure at about 60 ° C. by a centrifugal thin film method until the soluble component became about 15% by weight to obtain a concentrated extract (pH = 6.0). This concentrated solution (temperature 25 ° C) was subjected to advanced chromatographic separation under the following conditions.
[0053] カラム:直径 1. 5cm、長さ 25cm [0053] Column: diameter 1.5 cm, length 25 cm
吸着剤:メタクリル系榭脂(三菱化学社製商品名ダイヤイオン HP2MG;平均粒径: 250 μ m以上;比表面積: 470m2Zg、官能基なし) Adsorbent: Methacrylic resin (trade name Diaion HP2MG manufactured by Mitsubishi Chemical Corporation; average particle size: 250 μm or more; specific surface area: 470 m 2 Zg, no functional group)
充填吸着剤体積:約 44mL  Filled adsorbent volume: Approximately 44mL
流速: 8mLZ分。  Flow rate: 8mLZ min.
[0054] 先端クロマトグラフィー分離操作では、最初に上記濃縮抽出液を吸着剤充填体積 の約 14倍以下の量でカラムに供した。続いて、吸着剤充填体積の約 5倍量の水で- コチンを完全に溶出させた。し力る後、 1%酢酸水溶液を用いて TSNAを溶出させた  [0054] In the advanced chromatography separation operation, the concentrated extract was first applied to the column in an amount of about 14 times or less the adsorbent packed volume. Subsequently, the cotin was completely eluted with about 5 times the volume of the adsorbent filling volume. Then, TSNA was eluted with 1% acetic acid aqueous solution.
[0055] 図 2Aおよび 2Bは、ニコチンおよび総 TSNAの溶出パターンを示す。図 2Aは、力 ラムを通過した液量に対し、溶出液中のニコチンおよび TSNAそれぞれの濃度 (原 液規格値)をプロットしたグラフである。図 2Bは、カラムを通過した液量に対し、ニコチ ンおよび総 TSNAそれぞれの累積溶出率をプロットしたグラフである。 V、ずれのダラ フでも、曲線 aは、ニコチンについてのものであり、曲線 bは、総 TSNAについてのも のである。 [0055] FIGS. 2A and 2B show the elution patterns of nicotine and total TSNA. Fig. 2A is a graph plotting the concentrations of nicotine and TSNA (stock standard values) in the eluate against the amount of liquid that passed through the force ram. Fig. 2B is a graph plotting the cumulative elution rates of nicotine and total TSNA against the amount of liquid passed through the column. In V, the drift dull, curve a is for nicotine and curve b is for total TSNA.
[0056] 表 8に、それぞれの溶出処理により溶出したニコチンと総 TSNAの量を示すとともに 、各溶出処理でのそれらの合計量と回収率を示す。  [0056] Table 8 shows the amounts of nicotine and total TSNA eluted by each elution treatment, and the total amount and recovery rate of each elution treatment.
[表 8] 表 8 [Table 8] Table 8
Figure imgf000023_0001
Figure imgf000023_0001
[0057] 表 8に示す結果から、水で溶出させた画分までを再生タバコの製造に利用するとす ると、ニコチンを損失することなぐ総 TSNAを約 80%低減した画分が得られることが ゎカゝる。  [0057] From the results shown in Table 8, if the fraction eluted with water is used for the production of recycled tobacco, a fraction with about 80% reduction in total TSNA without nicotine loss can be obtained.ゎ ゎ.
[0058] 従って、この画分を用いて作製した再生タバコ材は、 TSNAが非常に減少したもの となることは明らかである。  [0058] Therefore, it is clear that the regenerated tobacco material produced using this fraction has a greatly reduced TSNA.
[0059] 例 67 [0059] Example 67
温度約 60°Cで、タバコ原料 (黄色種とバーレ一種それぞれのラミナと中骨の混合物 ) 30kgを水 150Lと混合し、 20〜30分間撹拌することにより抽出を行った。得られた 抽出混合物をろ過し、抽出液と、抽出残渣に分けた。抽出残渣を抄紙して、再生タパ コウェブを得た。  Extraction was performed by mixing 30 kg of tobacco raw material (mixture of lamina and medium bone of yellow and burre each) with 150 L of water and stirring for 20 to 30 minutes at a temperature of about 60 ° C. The obtained extraction mixture was filtered and divided into an extract and an extraction residue. Paper from the extraction residue was obtained to obtain recycled tapaco web.
[0060] 他方、抽出液を、排除限界分子量が約 2万の限外濾過膜を用いた遠心薄膜法によ り高分子量物質を除去した後、逆浸透膜で無機イオン類等を除去した。得られた処 理抽出液を、減圧下、 60°Cで遠心薄膜法により、可溶性成分が約 15重量%となるま で濃縮し、濃縮抽出液 (pH = 6. 0)を得た。この濃縮液 (温度 25°C)を以下の条件で 先端クロマトグラフィー分離に供した。  [0060] On the other hand, after removing high molecular weight substances from the extract by a centrifugal thin film method using an ultrafiltration membrane having an exclusion limit molecular weight of about 20,000, inorganic ions and the like were removed with a reverse osmosis membrane. The obtained processed extract was concentrated under reduced pressure at 60 ° C. by a centrifugal thin film method until the soluble component was about 15% by weight to obtain a concentrated extract (pH = 6.0). This concentrated solution (temperature 25 ° C) was subjected to advanced chromatographic separation under the following conditions.
[0061] カラム:直径 7. 4cm、長さ 150cm  [0061] Column: Diameter 7.4 cm, Length 150 cm
吸着剤:メタクリル系榭脂(三菱化学社製商品名ダイヤイオン HP2MG;平均粒径: 250 μ m以上;比表面積: 470m2Zg、官能基なし) Adsorbent: Methacrylic resin (trade name Diaion HP2MG manufactured by Mitsubishi Chemical Corporation; average particle size: 250 μm or more; specific surface area: 470 m 2 Zg, no functional group)
充填吸着剤体積:約 6. 4L 流速: 200mLZ分。 Filling adsorbent volume: approx.6.4 L Flow rate: 200 mLZ min.
[0062] 先端クロマトグラフィー分離操作では、最初に上記濃縮抽出液を吸着剤充填体積 の約 14倍以下の量でカラムに供した。続いて、吸着剤充填体積の約 5倍量の水で- コチンを完全に溶出させた。し力る後、 1%酢酸水溶液を用いて TSNAを溶出させた  [0062] In the advanced chromatography separation operation, first, the concentrated extract was applied to the column in an amount of about 14 times or less the adsorbent packed volume. Subsequently, the cotin was completely eluted with about 5 times the volume of the adsorbent filling volume. Then, TSNA was eluted with 1% acetic acid aqueous solution.
[0063] 図 3Aおよび 3Bは、ニコチン、総 TSNA、糖(グルコース、フルクトースおよびシユー クロース)および総アミノ酸の溶出パターンを示す。図 3Aは、カラムを通過した液量 に対し、溶出液中のニコチン、総 TSNA、糖(グルコース、フルクトースおよびシユー クロース)および総アミノ酸それぞれの濃度 (原液規格値)をプロットしたグラフである 。図 3Bは、カラムを通過した液量に対し、ニコチン、総 TSNA、糖(グルコース、フル クトースおよびシユークロース)およびアミノ酸それぞれの累積溶出率をプロットしたグ ラフである。いずれのグラフでも、曲線 aは、ニコチンについてのものであり、曲線 bは 、総 TSNAについてのものであり、曲線 cは、糖についてのものであり、曲線 dは、総 アミノ酸につ 、てのものである。 [0063] FIGS. 3A and 3B show the elution patterns of nicotine, total TSNA, sugars (glucose, fructose and sucrose) and total amino acids. FIG. 3A is a graph plotting the concentrations of nicotine, total TSNA, sugar (glucose, fructose and sucrose) and total amino acids (stock solution standard values) in the eluate against the amount of liquid passed through the column. Figure 3B is a graph that plots the cumulative elution rates of nicotine, total TSNA, sugars (glucose, fructose, and sucrose) and amino acids against the volume of fluid that passed through the column. In both graphs, curve a is for nicotine, curve b is for total TSNA, curve c is for sugar, and curve d is for total amino acids. Is.
[0064] 表 9に、それぞれの溶出処理により溶出したニコチン、総 TSNA、糖 (グルコース、 フルクトースおよびシュークロース)および総アミノ酸の量とともに、各溶出処理でのそ れらの合計量と回収率を示す。  [0064] Table 9 shows the total amount of nicotine, total TSNA, sugar (glucose, fructose and sucrose) and total amino acid eluted by each elution treatment, and the total amount and recovery rate of each elution treatment. Show.
[表 9]  [Table 9]
表 9  Table 9
Figure imgf000024_0001
Figure imgf000024_0001
[0065] 表 9に示す結果から、水で溶出させた画分までを再生タバコの製造に利用すると、 ニコチン、糖およびアミノ酸を損失することなぐ総 TSNAを約 95%低減した画分が 得られることがゎカゝる。 [0065] From the results shown in Table 9, when the fraction eluted with water is used for the production of recycled tobacco, It is clear that a fraction with about 95% reduction in total TSNA without nicotine, sugar and amino acid loss is obtained.
[0066] 従って、この画分を用いて作製した再生タバコ材は、 TSNAが非常に減少したもの となることは明らかである。  [0066] Therefore, it is clear that the regenerated tobacco material produced using this fraction has a greatly reduced TSNA.
[0067] 以上述べたように、本発明によれば、天然タバコ材カも得た抽出液力も比較的簡便 な手法によりニコチンの量を有意に減少させることなく TSNAを分離することができ、 有意量のニコチンを含んで、 TSNAが実質的に除去された再生タバコ材を製造する ことができる。 [0067] As described above, according to the present invention, TSNA can be separated without significantly reducing the amount of nicotine by a relatively simple method using the extractive force obtained from the natural tobacco material. Recycled tobacco material containing a significant amount of nicotine and substantially free of TSNA can be produced.

Claims

請求の範囲 The scope of the claims
[1] (a)天然タバコ材を水系抽出溶媒で抽出し、該天然タバコ材の成分を含む抽出液 と抽出残渣を得ること、  [1] (a) Extracting a natural tobacco material with an aqueous extraction solvent to obtain an extract containing the components of the natural tobacco material and an extraction residue;
(b)前記抽出液またはその濃縮液を、中間極性を示す吸着剤を用いた吸着分離操 作に供して-トロソァミンを減少させること、  (b) subjecting the extract or its concentrate to an adsorptive separation operation using an adsorbent exhibiting intermediate polarity to reduce trosamine;
(c)前記抽出残渣を用いて再生タバコウェブを調製すること、  (c) preparing a regenerated tobacco web using the extraction residue;
(d)前記-トロソァミンが減少した抽出液または濃縮液の少なくとも一部を前記再生 タバコウェブに添加すること  (d) adding at least a portion of the -trosomamine-depleted extract or concentrate to the regenerated tobacco web
を包含する再生タバコ材の製造方法。  A method for producing a recycled tobacco material.
[2] 前記吸着剤が、アクリル系またはメタクリル系榭脂からなる多孔質吸着剤、表面に 親水性官能基を有する疎水性榭脂からなる多孔質吸着剤、および表面に疎水性官 能基を有する親水性樹脂からなる多孔質吸着剤から選ばれる請求項 1に記載の再 生タバコ材の製造方法。  [2] The adsorbent comprises a porous adsorbent made of acrylic or methacrylic resin, a porous adsorbent made of hydrophobic resin having a hydrophilic functional group on the surface, and a hydrophobic functional group on the surface. 2. The method for producing a regenerated tobacco material according to claim 1, wherein the method is selected from porous adsorbents comprising a hydrophilic resin.
[3] 前記吸着分離を、前記吸着剤を充填したカラムを用いる先端クロマトグラフィー分 離により行う請求項 1に記載の再生タバコ材の製造方法。  [3] The method for producing a regenerated tobacco material according to [1], wherein the adsorption separation is performed by tip chromatography separation using a column packed with the adsorbent.
[4] 前記カラムに充填された吸着剤の体積の 20倍以下の量のタバコ抽出液またはその 濃縮液を前記カラムに通じる請求項 3に記載の再生タバコ材の製造方法。 [4] The method for producing a regenerated tobacco material according to claim 3, wherein a tobacco extract or a concentrated liquid thereof having an amount of 20 times or less the volume of the adsorbent packed in the column is passed through the column.
[5] 前記タバコ抽出液またはその濃縮液を前記カラムに通じて流出液を得た後、前記 カラムに充填された吸着剤の体積の 3倍以下の量の水を通じてその水溶出液を前記 流出液と合わせ、これを前記再生タバコウェブに添加する請求項 4に記載の再生タ バコ材の製造方法。 [5] After passing the tobacco extract or its concentrate through the column to obtain an effluent, the effluent is discharged through the water in an amount not more than three times the volume of the adsorbent packed in the column. The method for producing a reclaimed octopus material according to claim 4, which is combined with a liquid and added to the regenerated tobacco web.
PCT/JP2006/318254 2005-09-15 2006-09-14 Method for production of recycled tobacco material WO2007032433A1 (en)

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