JP2010193718A - Activated carbon for cigarette filter and cigarette with filter - Google Patents

Activated carbon for cigarette filter and cigarette with filter Download PDF

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JP2010193718A
JP2010193718A JP2007159068A JP2007159068A JP2010193718A JP 2010193718 A JP2010193718 A JP 2010193718A JP 2007159068 A JP2007159068 A JP 2007159068A JP 2007159068 A JP2007159068 A JP 2007159068A JP 2010193718 A JP2010193718 A JP 2010193718A
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activated carbon
cigarette
filter
adsorption
nitric acid
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Noritoshi Fujita
憲俊 藤田
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Japan Tobacco Inc
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Japan Tobacco Inc
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Priority to PCT/JP2008/060223 priority patent/WO2008152948A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/163—Carbon

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  • Materials Engineering (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an activated carbon for cigarette filters which selectively and effectively removes an aldehyde, a ketone, and nitrile in cigarette smoke, and to provide a cigarette with a filter comprising a filter which contains the activated carbon. <P>SOLUTION: The activated carbon for cigarette filters is composed of an activated carbon processed with an inorganic acid. The cigarette with a filter comprises the filter which contains the activated carbon. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、シガレットフィルタ用活性炭およびフィルタ付シガレットに関する。   The present invention relates to activated carbon for a cigarette filter and a cigarette with a filter.

シガレット煙中の揮発性有機化合物（ＶＯＣ）を除去するために、シガレットフィルタには、主として、炭化、賦活された活性炭が添加されている。活性炭は、アルデヒド、ケトン、ニトリル類等の吸着除去に有効であるが、その吸着現象は物理吸着が主体であるため、シガレット煙中のＶＯＣをほぼ無差別に吸着する。そのため、香喫味成分までも活性炭により吸着され、シガレットの香喫味が損なわれるという問題が生じている。   In order to remove volatile organic compounds (VOC) in cigarette smoke, carbonized and activated activated carbon is mainly added to the cigarette filter. Activated carbon is effective for adsorption and removal of aldehydes, ketones, nitriles, etc., but since the adsorption phenomenon is mainly physical adsorption, VOC in cigarette smoke is adsorbed almost indiscriminately. Therefore, even the flavor component is adsorbed by the activated carbon, causing a problem that the flavor of cigarette is impaired.

そこで、シガレット煙中の有害成分を選択的に除去し得る活性炭の研究が行われている。例えば、特許文献１には、特定の活性炭素材に特定の脂肪族第１級または第２級アミンを添着させたアルデヒド類の吸着剤が開示されている。しかしながら、従来の活性炭系タバコフィルタ用吸着剤は、シガレット煙中のアルデヒド類と、ケトン類と、ニトリル類とを選択的かつ効果的に除去し得るものではなかった。
特開昭６３−２４４１４号公報 Therefore, research on activated carbon that can selectively remove harmful components in cigarette smoke has been conducted. For example, Patent Document 1 discloses an adsorbent for aldehydes obtained by attaching a specific aliphatic primary or secondary amine to a specific activated carbon material. However, conventional adsorbents for activated carbon-based tobacco filters cannot selectively and effectively remove aldehydes, ketones, and nitriles in cigarette smoke.
JP-A-63-24414

したがって、本発明は、シガレット煙中のアルデヒド類と、ケトン類と、ニトリル類とを選択的かつ効果的に除去し得るシガレットフィルタ用活性炭およびかかる活性炭を含むフィルタを備えたフィルタ付シガレットを提供することを目的とする。   Therefore, this invention provides the cigarette with a filter provided with the activated carbon for cigarette filters which can selectively and effectively remove the aldehydes, ketones, and nitriles in cigarette smoke, and the filter containing such activated carbon. For the purpose.

本発明の第１の側面によると、無機酸で処理された活性炭からなることを特徴とするシガレットフィルタ用活性炭が提供される。本発明の第２の側面によると、温度２９８Ｋの水の吸着等温線から求めた吸着特性エネルギーが１０００ｋＪ／ｇ以上、２３００ｋＪ／ｇ未満の活性炭からなることを特徴とするシガレットフィルタ用活性炭が提供される。また、本発明の第３の側面によると、親水性官能基を１０〜４０ミリモル／グラムの割合で含む活性炭からなることを特徴とするシガレットフィルタ用活性炭が提供される。さらに、本発明の第４の側面によると、シガレット本体と、前記シガレット本体の一端に設けられたフィルタとを備え、前記フィルタが、本発明のシガレットフィルタ用活性炭を含むことを特徴とするフィルタ付シガレットが提供される。   According to a first aspect of the present invention, there is provided an activated carbon for a cigarette filter, comprising activated carbon treated with an inorganic acid. According to a second aspect of the present invention, there is provided an activated carbon for a cigarette filter, characterized in that the adsorption characteristic energy obtained from the adsorption isotherm of water at a temperature of 298K is composed of activated carbon having a viscosity of 1000 kJ / g or more and less than 2300 kJ / g. The Moreover, according to the 3rd side surface of this invention, the activated carbon for cigarette filters characterized by consisting of activated carbon which contains a hydrophilic functional group in the ratio of 10-40 mmol / gram is provided. Furthermore, according to the 4th side surface of this invention, it is provided with the cigarette main body and the filter provided in the end of the said cigarette main body, The said filter contains the activated carbon for cigarette filters of this invention. Cigarettes are provided.

本発明によると、シガレット煙中のアルデヒド類と、ケトン類と、ニトリル類とを選択的かつ効果的に除去し得るシガレットフィルタ用活性炭およびかかる活性炭を含むフィルタを備えたフィルタ付シガレットが提供される。   ADVANTAGE OF THE INVENTION According to this invention, the cigarette with a filter provided with the filter containing the activated carbon for cigarette filters which can selectively and effectively remove the aldehydes in a cigarette smoke, ketones, and nitriles, and such activated carbon is provided. .

以下、本発明をさらに詳しく説明する。   Hereinafter, the present invention will be described in more detail.

本発明は、無機酸で処理された活性炭からなることを特徴とするシガレットフィルタ用活性炭を提供する。   The present invention provides activated carbon for a cigarette filter, comprising activated carbon treated with an inorganic acid.

本発明において、原料となる活性炭は、その由来、形状に特に制限はない。粒状、球状、繊維状の活性炭を用いることができる。   In the present invention, the activated carbon used as a raw material is not particularly limited in its origin and shape. Granular, spherical, and fibrous activated carbon can be used.

活性炭を処理する無機酸は、処理により活性炭に親水性を付与し得るものであり、例えば、液相処理には、硝酸、硫酸、塩酸、過酸化水素水等を用いることができ、気相処理にはオゾンをも用いることができる。   The inorganic acid for treating the activated carbon can impart hydrophilicity to the activated carbon by the treatment. For example, in the liquid phase treatment, nitric acid, sulfuric acid, hydrochloric acid, hydrogen peroxide water, etc. can be used. Ozone can also be used.

液相処理では、原料活性炭を無機酸中に入れ、室温（２０℃）から無機酸の沸点までの温度で攪拌することにより、活性炭を処理することができる。気相処理では、気相にある無機酸を活性炭に接触させることにより、活性炭を処理することができる。   In the liquid phase treatment, the activated carbon can be treated by placing the raw material activated carbon in an inorganic acid and stirring at a temperature from room temperature (20 ° C.) to the boiling point of the inorganic acid. In the gas phase treatment, the activated carbon can be treated by bringing the inorganic acid in the gas phase into contact with the activated carbon.

液相の無機酸の濃度に特に制限はないが、硝酸としては、０．１Ｎ〜１Ｎの濃度の硝酸を用いることが特に好ましい。   Although there is no restriction | limiting in particular in the density | concentration of a liquid phase inorganic acid, It is especially preferable to use nitric acid with a density | concentration of 0.1N-1N as nitric acid.

上記無機酸による処理により、活性炭による温度２９８Ｋの水の吸着等温線からＤｕｂｉｎｉｎ−Ａｓｔａｋｈｏｖ式により求めた吸着特性エネルギーＥが１０００ｋＪ／ｇ以上、２３００ｋＪ／ｇ未満の活性炭が得られる。吸着特性エネルギーＥは、１０００〜２０００ｋＪ／ｇであることが好ましい。   By the treatment with the inorganic acid, activated carbon having an adsorption characteristic energy E of 1000 kJ / g or more and less than 2300 kJ / g obtained from the adsorption isotherm of water at a temperature of 298 K by activated carbon by the Dubinin-Astakhov equation is obtained. The adsorption characteristic energy E is preferably 1000 to 2000 kJ / g.

吸着特性エネルギーＥは、活性炭表面の親水性の指標であり、その値が大きくなるほど親水性が高いことを示すものである。吸着特性エネルギーＥは、上に述べたように、活性炭による温度２９８Ｋの水の吸着等温線からＤｕｂｉｎｉｎ−Ａｓｔａｋｈｏｖ式により求められるものであり、Ｄｕｂｉｎｉｎ−Ａｓｔａｋｈｏｖ式は、
ｌｏｇＷ＝ｌｏｇＷ0−２．３０３m-1（ＲＴ／Ｅ）mｌｏｇm（Ｐ0／Ｐ）
（ここで、Ｒは、気体定数（８．３１４５１Ｊ／ｍｏｌ・Ｋ）、Ｔは、吸着温度（２９８Ｋ）、Ｐ0は、飽和蒸気圧（３．１８０ｋＰａ）、Ｐは、吸着圧、ｍは、吸着剤指数（定数であり、通常２〜６）、Ｗは、相対圧Ｐ／Ｐ0のときに満たされているミクロ孔の容積（ｃｃ／ｇ）、Ｗ0は、全ミクロ孔容積（ｃｃ／ｇ））で示される。ここで、活性炭による２９８Ｋの水の吸着等温線は、例えば、ＢＥＬｓｏｒｐ−１８（日本ベル社製）を用いて求めることができる。また、全ミクロ孔容積は、例えば、Ａｕｔｏｓｏｒｂ−１−ＭＰ（Ｑｕａｎｔａｃｈｒｏｍｅ社製）に付属しているソフトウェアにより密度関数理論（ＤＦＴ）法で解析することによって求めることができる。 The adsorption characteristic energy E is an index of hydrophilicity on the activated carbon surface, and indicates that the larger the value, the higher the hydrophilicity. As described above, the adsorption characteristic energy E is obtained by the Dubinin-Astakhov equation from the adsorption isotherm of water at a temperature of 298 K by activated carbon, and the Dubinin-Astakhov equation is
logW = logW 0 -2.3303 m-1 (RT / E) m log m (P 0 / P)
(Where R is a gas constant (8.31451 J / mol · K), T is an adsorption temperature (298 K), P 0 is a saturated vapor pressure (3.180 kPa), P is an adsorption pressure, and m is Adsorbent index (constant, usually 2-6), W is the volume of micropores filled at relative pressure P / P 0 (cc / g), W 0 is the total micropore volume (cc / G)). Here, the adsorption isotherm of 298K water by activated carbon can be determined using, for example, BELsorb-18 (manufactured by Nippon Bell Co., Ltd.). Further, the total micropore volume can be determined by analyzing the density function theory (DFT) method using software attached to Autosorb-1-MP (manufactured by Quantachrome), for example.

また、上記無機酸による処理により、親水性官能基を１０〜４０ミリモル／グラムの割合で含む活性炭が得られる。ここで、親水性官能基の含有率は、ＢＥＬ−ＣＡＴ−Ｓ（日本ベル社製）を用い、活性炭を、ヘリウム雰囲気下、５Ｋ／分の昇温速度で２９８Ｋから６７３Ｋまで加熱した際に発生する一酸化炭素（ＣＯ）および二酸化炭素（ＣＯ2）をＴＣＤ検出器（ＨＯＲＩＢＡ製）で定量し、一酸化炭素量（重量）をヒドロキシル基量（重量）として換算し、二酸化炭素量（重量）をカルボキシル基量（重量）として換算し、両換算値を合算することによって得ることができる。 Moreover, the activated carbon which contains a hydrophilic functional group in the ratio of 10-40 mmol / gram is obtained by the process by the said inorganic acid. Here, the content rate of the hydrophilic functional group is generated when BEL-CAT-S (manufactured by Nippon Bell Co., Ltd.) is used and the activated carbon is heated from 298 K to 673 K at a heating rate of 5 K / min in a helium atmosphere. Carbon monoxide (CO) and carbon dioxide (CO 2 ) are quantified with a TCD detector (manufactured by HORIBA), the amount of carbon monoxide (weight) is converted as the amount of hydroxyl groups (weight), and the amount of carbon dioxide (weight) Can be obtained as a carboxyl group amount (weight), and both converted values can be added together.

本発明に従う無機酸による処理では、原料活性炭の物理的構造特性、特にＢＥＴ比表面積、細孔径分布が、当該処理後も実質的に維持される。すなわち、原料活性炭のＢＥＴ比表面積は、無機酸による処理後でも、その８５％以上の値を示し、細孔径分布の傾向は、処理の前後で同様である。ここで、ＢＥＴ比表面積は、例えば、活性炭による温度７７Ｋでの窒素吸着等温線を、Ａｕｔｏｓｏｒｂ−１−ＭＰ（Ｑｕａｎｔａｃｈｒｏｍｅ社製）を用いて求め、その窒素吸着等温線を用いて、相対圧Ｐ／Ｐ0＝０．０１〜０．１間でのＭｕｌｔｉＰｏｉｎｔＢＥＴ法により算出したものである。また、細孔径分布は、上記活性炭による温度７７Ｋでの窒素吸着等温線を用い、上記Ａｕｔｏｓｏｒｂ−１−ＭＰに付属しているソフトウェアによりＤＦＴ法で解析して得たものである。 In the treatment with the inorganic acid according to the present invention, the physical structural characteristics of the raw material activated carbon, in particular, the BET specific surface area and the pore size distribution are substantially maintained even after the treatment. That is, the BET specific surface area of the raw material activated carbon shows a value of 85% or more even after the treatment with the inorganic acid, and the tendency of the pore size distribution is the same before and after the treatment. Here, the BET specific surface area is obtained, for example, by using an autosorb-1-MP (manufactured by Quantachrome) for a nitrogen adsorption isotherm at a temperature of 77 K by activated carbon, and using the nitrogen adsorption isotherm, the relative pressure P / It is calculated by the MultiPoint BET method between P 0 = 0.01 to 0.1. The pore size distribution was obtained by analysis by the DFT method using software attached to the Autosorb-1-MP using a nitrogen adsorption isotherm at a temperature of 77 K by the activated carbon.

本発明によるフィルタ付シガレットは、シガレット本体と、シガレット本体の一端に設けられたフィルタとを備える。フィルタは、上記本発明のシガレットフィルタ用活性炭を含む。本発明のフィルタ付シガレットは、活性炭として本発明の活性炭を用いる以外は、通常のチャコールフィルタ付シガレットと同様の構造を有する。フィルタは、例えば、本発明の活性炭を分散させたセルロースアセテート繊維トウからなる単一フィルタ構造、または本発明の活性炭を分散させたセルロースアセテート繊維トウからなるフィルタセクションと、その後段に設けられた、セルロースアセテート繊維トウからなるプレーンフィルタセクションとからなるデュアルフィルタ構造を取ることができる。また、フィルタは、空隙を隔てて設けられた２つのプレーンフィルタセクションからなり、その空隙に本発明の活性炭を充填することによって構成することもできる。フィルタに含まれる本発明の活性炭は、シガレット１本につき、３０〜５０ｍｇの割合で用いることが好ましい。   The cigarette with a filter according to the present invention includes a cigarette main body and a filter provided at one end of the cigarette main body. The filter includes the activated carbon for cigarette filter of the present invention. The cigarette with a filter of the present invention has the same structure as a cigarette with a normal charcoal filter except that the activated carbon of the present invention is used as the activated carbon. The filter is provided, for example, in a single filter structure composed of cellulose acetate fiber tow dispersed with activated carbon of the present invention, or a filter section composed of cellulose acetate fiber tow dispersed with activated carbon of the present invention, and a subsequent stage. A dual filter structure comprising a plain filter section made of cellulose acetate fiber tow can be taken. The filter can also be constituted by two plain filter sections provided with a gap between them, and filling the gap with the activated carbon of the present invention. The activated carbon of the present invention contained in the filter is preferably used at a rate of 30 to 50 mg per cigarette.

本発明の活性炭は、原料活性炭の物理的構造特性、特にＢＥＴ比表面積および細孔径分布を維持しながら、シガレット煙中のアルデヒド類と、ケトン類と、ニトリル類とを選択的かつ効果的に除去し得る。いいかえると、本発明の活性炭は、原料活性炭の全体的な吸着能を実質的に維持しながら、そのアルデヒド類、ケトン類およびニトリル類に対する吸着能が向上しているものである。したがって、通常の活性炭を用いた場合のシガレットの香喫味の低下を有意に抑制することができる。   The activated carbon of the present invention selectively and effectively removes aldehydes, ketones and nitriles in cigarette smoke while maintaining the physical structural characteristics of the raw material activated carbon, particularly the BET specific surface area and pore size distribution. Can do. In other words, the activated carbon of the present invention has improved adsorption capacity for aldehydes, ketones and nitriles while substantially maintaining the overall adsorption capacity of the raw material activated carbon. Therefore, the fall of the flavor of a cigarette at the time of using normal activated carbon can be suppressed significantly.

次に、本発明を実施例により説明するが、本発明はこれら実施例により限定されるものではない。   EXAMPLES Next, although an Example demonstrates this invention, this invention is not limited by these Examples.

実施例１
（Ａ）ヤシガラ活性炭を、０．１Ｎ硝酸、１Ｎ硝酸または３Ｎ硝酸中に入れ、温度３７３Ｋで硝酸が活性炭による吸収と蒸発によりすべて消失するまで攪拌した後、活性炭を取り出し、余剰の硝酸を除去するために、ヘリウム雰囲気下、温度６７３Ｋで２時間加熱した。 Example 1
(A) Coconut husk activated carbon is placed in 0.1N nitric acid, 1N nitric acid or 3N nitric acid and stirred at a temperature of 373K until all nitric acid disappears due to absorption and evaporation by the activated carbon, and then the activated carbon is taken out to remove excess nitric acid. Therefore, it was heated at a temperature of 673 K for 2 hours in a helium atmosphere.

（Ｂ）原料のヤシガラ活性炭（未処理活性炭）と、０．１Ｎ硝酸、１Ｎ硝酸および３Ｎ硝酸で処理したヤシガラ活性炭による温度７７Ｋでの窒素吸着等温線を、Ａｕｔｏｓｏｒｂ−１−ＭＰ（Ｑｕａｎｔａｃｈｒｏｍｅ社製）を用いて求めた。得られた窒素吸着等温線を図１に示す。図１に示すように、０．１Ｎ〜１Ｎの硝酸で処理したヤシガラ活性炭は、未処理ヤシガラ活性炭に比べ、吸着量は向上するが、３Ｎ硝酸で処理したヤシガラ活性炭は吸着量が減少する。   (B) Nitrogen adsorption isotherm at a temperature of 77 K by coconut shell activated carbon (untreated activated carbon) as raw material and coconut shell activated carbon treated with 0.1 N nitric acid, 1 N nitric acid and 3 N nitric acid, Autosorb-1-MP (manufactured by Quantachrome) Was determined using. The obtained nitrogen adsorption isotherm is shown in FIG. As shown in FIG. 1, the amount of adsorption of coconut husk activated carbon treated with nitric acid of 0.1N to 1N is improved as compared with that of untreated coconut husk activated carbon, but the amount of adsorption of coconut husk activated carbon treated with 3N nitric acid is decreased.

（Ｃ）各活性炭について、図１に示す窒素吸着等温線を用いて、相対圧Ｐ／Ｐ0＝０．０１〜０．１間でのＭｕｌｔｉＰｏｉｎｔＢＥＴ法により算出したＢＥＴ比表面積を表１に示す。 (C) For each activated carbon, Table 1 shows the BET specific surface area calculated by the MultiPoint BET method between relative pressure P / P 0 = 0.01 to 0.1 using the nitrogen adsorption isotherm shown in FIG.

Figure 2010193718
Figure 2010193718

表１に示すように、ＢＥＴ比表面積は、０．１Ｎ〜１Ｎの硝酸で処理したヤシガラ活性炭では、未処理活性炭と実質的に同じ（未処理活性炭の比表面積の８５％以上を維持）であるのに対し、３Ｎ硝酸で処理したヤシガラ活性炭では、未処理活性炭の比表面積より大きく減少している。   As shown in Table 1, the BET specific surface area is substantially the same as that of untreated activated carbon treated with 0.1N to 1N nitric acid (maintaining 85% or more of the specific surface area of untreated activated carbon). On the other hand, in the coconut shell activated carbon treated with 3N nitric acid, the specific surface area of untreated activated carbon is greatly reduced.

（Ｄ）また、各活性炭について、図１に示す窒素吸着等温線を用いて、上記Ａｕｔｏｓｏｒｂ−１−ＭＰに付属しているソフトウェアにより密度関数理論（ＤＦＴ法）で解析した細孔分布（ＤＦＴ細孔分布）を図２に示す。図２において、線ａは、未処理活性炭、線ｂは、０．１Ｎ硝酸処理活性炭、線ｃは、１Ｎ硝酸処理活性炭、線ｄは、３Ｎ硝酸活性炭についてのものである。図２に示すように、硝酸による処理の有無にかかわらず、ミクロ細孔（直径２ｎｍ以下）の分布の傾向は、同様である。   (D) Moreover, about each activated carbon, the pore distribution (DFT fine) analyzed by the density functional theory (DFT method) with the software attached to the said Autosorb-1-MP using the nitrogen adsorption isotherm shown in FIG. The pore distribution is shown in FIG. In FIG. 2, line a is for untreated activated carbon, line b is for 0.1N nitric acid-treated activated carbon, line c is for 1N nitric acid-treated activated carbon, and line d is for 3N nitric acid activated carbon. As shown in FIG. 2, the tendency of the distribution of micropores (diameter 2 nm or less) is the same regardless of the presence or absence of treatment with nitric acid.

（Ｅ）次に、未処理活性炭、および硝酸処理活性炭の親水性官能基含有率を測定した。その測定には、ＢＥＬ−ＣＡＴ−Ｓ（日本ベル社製）を用い、各活性炭を、ヘリウム雰囲気下、５Ｋ／分の昇温速度で２９８Ｋから６７３Ｋまで加熱した際に発生する一酸化炭素（ＣＯ）および二酸化炭素（ＣＯ2）ＴＣＤ検出器（ＨＯＲＩＢＡ製）で定量し、一酸化炭素量（重量）をヒドロキシル基量（重量）として換算し、二酸化炭素量（重量）をカルボキシル基量（重量）として換算した。結果を表２に示す。 (E) Next, the hydrophilic functional group content of untreated activated carbon and nitric acid-treated activated carbon was measured. For the measurement, BEL-CAT-S (manufactured by Nippon Bell Co., Ltd.) was used, and carbon monoxide (CO generated when each activated carbon was heated from 298 K to 673 K at a heating rate of 5 K / min in a helium atmosphere. ) And carbon dioxide (CO 2 ) by a TCD detector (manufactured by HORIBA), the amount of carbon monoxide (weight) is converted as the amount of hydroxyl groups (weight), and the amount of carbon dioxide (weight) is the amount of carboxyl groups (weight) As converted. The results are shown in Table 2.

Figure 2010193718
Figure 2010193718

表２に示すように、未処理活性炭には親水性官能基はほとんど含まれておらず、他方硝酸で処理した活性炭は、酸強度が高いほど、親水性官能基の含有率が増加している。   As shown in Table 2, the untreated activated carbon contains almost no hydrophilic functional groups, while the activated carbon treated with nitric acid has a higher content of hydrophilic functional groups as the acid strength is higher. .

（Ｆ）また、各活性炭について、２９８Ｋの水の吸着等温線を、ＢＥＬｓｏｒｐ−１８（日本ベル社製）を用いて求めた。結果を図３に示す。図３に示すように、硝酸の強度が高いほど、より低い相対圧で吸着等温線が立ち上がり、親水性が増大する。   (F) Moreover, about each activated carbon, the adsorption isotherm of 298K water was calculated | required using BELsorb-18 (made by Nippon Bell Co., Ltd.). The results are shown in FIG. As shown in FIG. 3, as the strength of nitric acid is higher, the adsorption isotherm rises at a lower relative pressure, and the hydrophilicity increases.

（Ｇ）また、各活性炭について、吸着特性エネルギーＥを、図３に示す水の吸着等温線より、上記Ｄｕｂｉｎｉｎ−Ａｓｔａｋｈｏｖ式にて算出した。結果を表３に示す。   (G) For each activated carbon, the adsorption characteristic energy E was calculated from the water adsorption isotherm shown in FIG. 3 according to the above Dubinin-Astakhov equation. The results are shown in Table 3.

Figure 2010193718
Figure 2010193718

表３に示す結果からも、硝酸の強度が高いほうが、親水性が増大することがわかる。   From the results shown in Table 3, it can be seen that the higher the strength of nitric acid, the higher the hydrophilicity.

実施例２
実施例１で調製した各活性炭によるシガレット煙中成分の吸着率を測定した。この測定に用いた試験シガレット試料１０の概略を図４に示す。図４に示すように、シガレット試料１０は、日本たばこ産業（株）製マイルドセブンスーパーライトのシガレット本体１１を有する。シガレット本体１１の一端には、フィルタ１２がチップペーパー１３により取り付けられている。フィルタ１２は、シガレット本体１１の端に接した第１のプレーンフィルタセクション１２１と、第１のプレーンフィルタセクション１２１から空隙１２３を隔てて設けられた第２のプレーンフィルタ１２２からなる。第１および第２のプレーンフィルタセクションは、それぞれ、断面Ｙ型で、５．０デニール、総繊維度３５０００のセルロースアセテートトウからなり、長さは５．０ｍｍである。チップペーパー１３には、ベンチレーション孔は設けられていない。空隙１２３には、各活性炭１２４を５０ｍｇ充填した。また、対照シガレット試料として、第１および第２のプレーンフィルタを直接接して設けた以外は試験シガレット試料１０と同様の構成を有するシガレット（活性炭なし）を作製した。 Example 2
The adsorption rate of the components in cigarette smoke by each activated carbon prepared in Example 1 was measured. An outline of the test cigarette sample 10 used for this measurement is shown in FIG. As shown in FIG. 4, the cigarette sample 10 has a cigarette body 11 of Mild Seven Superlite manufactured by Japan Tobacco Inc. A filter 12 is attached to one end of the cigarette body 11 with a chip paper 13. The filter 12 includes a first plane filter section 121 in contact with the end of the cigarette main body 11 and a second plane filter 122 provided with a gap 123 from the first plane filter section 121. Each of the first and second plain filter sections is Y-shaped in cross section, made of cellulose acetate tow having 5.0 denier and a total fiber degree of 35000, and has a length of 5.0 mm. The tip paper 13 is not provided with ventilation holes. The gap 123 was filled with 50 mg of each activated carbon 124. In addition, a cigarette (without activated carbon) having the same configuration as that of the test cigarette sample 10 was prepared as a control cigarette sample except that the first and second plain filters were provided in direct contact.

各シガレット試料を用いて、定容量型自動喫煙器（ボルグワルド社製）により、吸引流量１７．５ｍＬ／秒、喫煙時間２秒／回、喫煙頻度１回／分の条件で吸煙を行い、フィルタ１２を通過したシガレット主流煙を、ガラス繊維フィルタ（ケンブリッジフィルタ）に通じ、その煙をアルミニウム製バッグ（容量３Ｌ）に捕集し、ＶＯＣをＧＣ−ＦＩＤ（Ａｇｉｌｅｎｔ社製）で測定した。シガレット試料の喫煙頻度は７回とした。   Using each cigarette sample, smoke was absorbed by a constant-volume automatic smoker (manufactured by Borgwald) under the conditions of a suction flow rate of 17.5 mL / second, a smoking time of 2 seconds / time, and a smoking frequency of 1 time / minute. The cigarette mainstream smoke that passed through was passed through a glass fiber filter (Cambridge filter), and the smoke was collected in an aluminum bag (capacity 3 L), and VOC was measured with GC-FID (manufactured by Agilent). The cigarette sample was smoked seven times.

活性炭によるシガレット主流煙中成分の吸着率を、ＧＣ−ＦＩＤの面積値を定量して以下の式より求めた。
吸着率＝（各成分における試験シガレット試料の７回吸煙の面積値の合計）／（各成分における対照シガレット試料の７回吸煙の面積値の合計）
結果を表４に示す。また、表４に示す結果をグラフにして図５に示す。さらに、表４に示す吸着率を、活性炭の性能の比較の基準としてケトン類の吸着率を１．００としたときの各成分の吸着率の比を表５に示し、その吸着率比をグラフにして図６に示す。図５および図６において、棒グラフＡは、未処理活性炭についてのものであり、棒グラフＢは、０．１Ｎ硝酸処理活性炭についてのものであり、棒グラフＣは、１Ｎ硝酸処理活性炭についてのものであり、棒グラフＤは、３Ｎ硝酸処理活性炭についてのものである。 The adsorption rate of components in cigarette mainstream smoke by activated carbon was determined from the following formula by quantifying the area value of GC-FID.
Adsorption rate = (sum of area values of 7 smoke absorptions of test cigarette samples in each component) / (sum of area values of 7 smoke absorptions of control cigarette samples in each component)
The results are shown in Table 4. Further, the results shown in Table 4 are shown as a graph in FIG. Further, the adsorption rate shown in Table 4 is a standard for comparing the performance of activated carbon, and the adsorption rate ratio of each component when the adsorption rate of ketones is 1.00 is shown in Table 5. The adsorption rate ratio is a graph. This is shown in FIG. 5 and 6, bar graph A is for untreated activated carbon, bar graph B is for 0.1N nitric acid-treated activated carbon, bar graph C is for 1N nitric acid-treated activated carbon, Bar graph D is for 3N nitric acid treated activated carbon.

Figure 2010193718
Figure 2010193718

Figure 2010193718
Figure 2010193718

これらの結果からわかるように、活性炭を硝酸で処理することにより、シガレット主流煙中の代表的な嫌気、有害成分であるアルデヒド類、ケトン類およびニトリル類を選択的が除去される一方、飽和炭化水素類、不飽和炭化水素類の除去は抑制される。   As can be seen from these results, treatment of activated carbon with nitric acid selectively removes typical anaerobic and harmful components such as aldehydes, ketones and nitriles in cigarette mainstream smoke, while saturated carbonization. Removal of hydrogen and unsaturated hydrocarbons is suppressed.

特に、硝酸の濃度が０．１Ｎ〜１Ｎであれば、未処理活性炭と同量で、アルデヒド類、ケトン類、ニトリル類のみを、未処理活性炭を同程度で除去することができる。   In particular, if the concentration of nitric acid is 0.1N to 1N, it is possible to remove only the aldehydes, ketones and nitriles in the same amount as the untreated activated carbon, and the untreated activated carbon to the same extent.

種々の活性炭による温度７７Ｋでの窒素吸着等温線を示すグラフ。The graph which shows the nitrogen adsorption isotherm at the temperature of 77K by various activated carbon. 種々の活性炭のＤＦＴ細孔分布を示すグラフ。The graph which shows DFT pore distribution of various activated carbon. 種々の活性炭による２９８Ｋの水の吸着等温線を示すグラフ。The graph which shows the adsorption isotherm of 298K water by various activated carbon. 試験シガレット試料を示す概略断面図。A schematic sectional view showing a test cigarette sample. 種々の活性炭によるシガレット主流煙中成分の吸着率を示すグラフ。The graph which shows the adsorption rate of the component in a cigarette mainstream smoke by various activated carbon. ケトン類の吸着率を１．００としたときの、種々の活性炭によるシガレット主流煙中成分の吸着率比を示すグラフ。The graph which shows the adsorption rate ratio of the component in a cigarette mainstream smoke by various activated carbon when the adsorption rate of ketones is 1.00.

符号の説明Explanation of symbols

１０…試験シガレット試料
１１…シガレット本体
１２…フィルタ
１２１…第１のプレーンフィルタセクション
１２２…第２のプレーンフィルタセクション
１２３…空隙
１２４…活性炭
１３…チップペーパー DESCRIPTION OF SYMBOLS 10 ... Test cigarette sample 11 ... Cigarette main body 12 ... Filter 121 ... 1st plane filter section 122 ... 2nd plane filter section 123 ... Air gap 124 ... Activated carbon 13 ... Chip paper

Claims (6)

無機酸で処理された活性炭からなることを特徴とするシガレットフィルタ用活性炭。   An activated carbon for a cigarette filter, comprising activated carbon treated with an inorganic acid. 前記無機酸が、硝酸であることを特徴とする請求項１に記載のシガレットフィルタ用活性炭。   The activated carbon for a cigarette filter according to claim 1, wherein the inorganic acid is nitric acid. 活性炭による温度２９８Ｋの水の吸着等温線からＤｕｂｉｎｉｎ−Ａｓｔａｋｈｏｖ式により求めた吸着特性エネルギーが１０００ｋＪ／ｇ以上、２３００ｋＪ／ｇ未満の活性炭からなることを特徴とするシガレットフィルタ用活性炭。   An activated carbon for a cigarette filter, comprising an activated carbon having an adsorption characteristic energy of 1000 kJ / g or more and less than 2300 kJ / g determined from the adsorption isotherm of water at a temperature of 298 K by activated carbon using the Dubinin-Astakhov equation. 前記吸着特性エネルギーが、１０００〜２０００ｋＪ／ｇであることを特徴とする請求項３に記載のシガレットフィルタ用活性炭。   The activated carbon for a cigarette filter according to claim 3, wherein the adsorption characteristic energy is 1000 to 2000 kJ / g. 親水性官能基を１０〜４０ミリモル／グラムの割合で含む活性炭からなることを特徴とするシガレットフィルタ用活性炭。   An activated carbon for a cigarette filter, comprising activated carbon containing a hydrophilic functional group at a rate of 10 to 40 mmol / gram. シガレット本体と、前記シガレット本体の一端に設けられたフィルタとを備え、前記フィルタが、請求項１〜６のいずれか１項に記載のシガレットフィルタ用活性炭を含むことを特徴とするフィルタ付シガレット。   A cigarette with a filter, comprising: a cigarette main body; and a filter provided at one end of the cigarette main body, wherein the filter includes the activated carbon for cigarette filters according to any one of claims 1 to 6.
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