阅读说明：本技术 一种吸附卷烟烟气中正己酸的复合过滤嘴及卷烟 (Composite filter tip for adsorbing n-hexanoic acid in cigarette smoke and cigarette ) 是由 周骏 徐同广 蒋成勇 矫海楠 刘德水 芦楠 郑晓曼 白若石 解晓翠 周昭娟 于 2021-09-02 设计创作，主要内容包括：本发明涉及烟气中有害成分的去除技术领域,具体涉及一种吸附卷烟烟气中正己酸的复合过滤嘴及卷烟。本发明所述的过滤嘴包括通用吸附段和特异吸附段；所述特异吸附段上负载有氧化石墨烯键合硅胶、改性活性炭和亚油酸修饰的纳米硅基氧化物的混合物；所述普通吸附段和特异吸附段通过串联的方式共轴排列。本发明所述的复合过滤嘴对于卷烟烟气中的正己酸有非常理想的去除效果,可有效地降低卷烟的刺激性酸败气味,同时不会对烟气中的呈香物质造成损失,提升卷烟整体的口感。(The invention relates to the technical field of removal of harmful components in smoke, in particular to a composite filter tip for adsorbing n-hexanoic acid in cigarette smoke and a cigarette. The filter tip comprises a general adsorption section and a specific adsorption section; the specific adsorption section is loaded with a mixture of graphene oxide bonded silica gel, modified activated carbon and linoleic acid modified nano silicon-based oxide; the common adsorption section and the specific adsorption section are coaxially arranged in a serial connection mode. The composite filter tip has an ideal effect of removing the n-hexanoic acid in the smoke of the cigarette, can effectively reduce the pungent rancid smell of the cigarette, does not cause loss of aroma substances in the smoke, and improves the overall taste of the cigarette.)

1. A composite filter tip for adsorbing n-hexanoic acid in cigarette smoke is characterized by comprising a general adsorption section and a specific adsorption section;

the specific adsorption section is loaded with a mixture of graphene oxide bonded silica gel, modified activated carbon and linoleic acid modified nano silicon-based oxide;

the common adsorption section and the specific adsorption section are coaxially arranged in a serial connection mode.

2. The composite filter according to claim 1, wherein the mass ratio of the graphene oxide bonded silica gel to the modified activated carbon to the linoleic acid modified nano silicon based oxide is 2: 0.8-1.2: 0.2 to 0.5.

3. A composite filter according to claim 1 or 2, wherein the graphene oxide-bonded silica gel is prepared by a process comprising:

1) dispersing graphene oxide in a dimethylformamide solution, performing ultrasonic treatment, adding silica gel and dicyclohexylcarbodiimide, and reacting the suspension at 40-60 ℃;

2) and (3) cleaning and drying the product by using water and methanol, wherein the prepared brown sample is graphene oxide bonded silica gel.

4. A composite filter according to claim 1, wherein the modified activated carbon is prepared by a process comprising:

placing activated carbon in a reactor, adding concentrated acid, heating in a water bath for reflux, performing hot suction filtration to remove acid liquor, washing the activated carbon with water to be neutral, and drying to obtain modified activated carbon;

preferably, the concentrated acid is concentrated sulfuric acid, concentrated nitric acid or concentrated phosphoric acid.

5. The composite filter according to claim 1, wherein the linoleic acid modified nano silicon based oxide is prepared by the following method: adding linoleic acid and nano SiO into n-hexane solvent₂Carrying out ultrasonic oscillation on the powder, and stirring for reaction to obtain the powder; preferably, the linoleic acid and the nano SiO₂The mass ratio of the powder is 9: 100.

6. The composite filter according to claim 1, wherein the ratio of the length of the general adsorbent section to the length of the specific adsorbent section is 1:1 to 1.5.

7. A composite filter according to claim 1 or 6, wherein the mixture is added in an amount of 32 to 38 mg/filter.

8. The composite filter of claim 1, wherein the material of the general adsorbent section and the specific adsorbent section is acetate fiber.

9. A cigarette comprising a composite filter according to any one of claims 1 to 8.

10. The cigarette of claim 9, wherein the specific adsorbent section of the composite filter is proximate to a tobacco cut filler portion of the cigarette.

Technical Field

The invention relates to the technical field of removal of harmful components in smoke, in particular to a composite filter tip for adsorbing n-hexanoic acid in cigarette smoke and a cigarette.

Background

The sensory quality evaluation of the cigarette by the smoker is carried out by evaluating the comprehensive reflecting effect of the smoke generated after the cigarette is burnt, namely, the aroma components in the smoke generated after the cigarette is burnt, on the feeling of the smoker. The function of the oral cavity during smoking evaluation is to judge the irritation (pungency degree) of the smoke, roughness or fineness, hardness or softness of the smoke, thickness or lightness of the smoke, plumpness and aftertaste of the smoke. The cigarette evaluation depends on the throat, and the throat has the functions of judging the irritation of smoke (when the smoke flows to the front edge of the throat) and the strength of the smoke (when the smoke passes through the throat).

The sensory quality of the cigarettes is closely related to the types and concentrations of chemical components in smoke, the taste is also related to the threshold value of the chemical components, the types of compounds distributed in gas phase and particle phase substances of aerosol of the smoke of the cigarettes are thousands, and the compositions and the contents of the compounds have important influence on the sensory quality of the cigarettes. Some cigarettes often generate unpleasant sour taste, bitter taste, spicy taste, astringent taste and the like, researches show that volatile carbonyl compounds, phenolic compounds, ammonia and other substances with low molecular weight in smoke have stimulating effect, non-volatile organic acids have strong spicy, burning and rancidity smell at higher concentration, and the substances not only stimulate taste acceptance and sensory nerves of oral cavity, but also stimulate sensory nerve endings and have negative effect on the sensory quality of the cigarettes. The n-hexanoic acid has the irritation similar to that of the n-butyric acid and the rancid cream smell, and shows stronger irritation and obvious offensive odor on the sensory quality of the mainstream smoke of the cigarettes.

At present, cigarette products with lower irritation, mellow mouthfeel and clean aftertaste are more and more popular with consumers for pursuing comfort, so that how to reduce the content of hexanoic acid in cigarette smoke becomes a hot point of current research.

Disclosure of Invention

The invention provides a composite filter tip for adsorbing n-hexanoic acid in cigarette smoke, which comprises a general adsorption section and a specific adsorption section;

the specific adsorption section is loaded with a mixture of graphene oxide bonded silica gel, modified activated carbon and linoleic acid modified nano silicon-based oxide;

the common adsorption section and the specific adsorption section are coaxially arranged in a serial connection mode.

The invention discovers that the mixture of graphene oxide bonded silica gel, modified activated carbon and linoleic acid modified nano silicon-based oxide is used as a specific adsorption material, and the structure of the composite filter tip is matched, so that the n-hexanoic acid in cigarette smoke can be effectively adsorbed, loss of other aroma components cannot be caused, and the taste of the cigarette is improved.

Preferably, the mass ratio of the graphene oxide bonded silica gel to the modified activated carbon to the linoleic acid-modified nano silicon-based oxide is 2: 0.8-1.2: 0.2 to 0.5. Under the relative dosage, the adsorbing material can play a better synergistic role, has a better adsorbing effect on the hexanoic acid, and can not adsorb and remove other aroma substances.

Preferably, the graphene oxide bonded silica gel is prepared by the following method:

1) dispersing graphene oxide in a dimethylformamide solution, performing ultrasonic treatment, adding silica gel and dicyclohexylcarbodiimide, and reacting the suspension at 40-60 ℃;

2) and (3) cleaning the product by using water and methanol, and drying the product to obtain a brown sample, namely graphene oxide bonded silica gel.

Preferably, the modified activated carbon is prepared by the following method:

placing activated carbon in a reactor, adding concentrated acid, heating in a water bath for reflux, performing hot suction filtration to remove acid liquor, washing the activated carbon with water to be neutral, and drying to obtain modified activated carbon;

preferably, the concentrated acid is concentrated sulfuric acid, concentrated nitric acid or concentrated phosphoric acid.

Preferably, the linoleic acid modified nano silicon-based oxide is prepared by the following method: adding linoleic acid and nano SiO into n-hexane solvent₂And (3) carrying out ultrasonic oscillation on the powder, and stirring for reaction to obtain the powder.

Further preferably, the linoleic acid and the nano SiO₂The mass ratio of the powder is 8-10: 100.

The graphene oxide bonded silica gel and the acid-treated active carbon can increase oxygen-containing functional groups such as hydroxyl, carboxyl and the like on the surface of the material so as to be beneficial to generating intermolecular electrostatic interaction with micromolecular acidity; the hydroxyl number on the surface of the nano silicon-based oxide modified by linoleic acid is reduced, the nano silicon-based oxide is favorably dispersed in triacetyl glycerine serving as a filter stick plasticizer and is conveniently and uniformly added into acetate fibers, and the three modified substances are mixed for use, so that the n-hexanoic acid in the cigarette smoke can be effectively adsorbed and removed.

Preferably, the length ratio of the general adsorption section to the specific adsorption section is 1: 1-1.5. Under the condition of the relative length, the adsorption effect of the specific adsorption section on the n-hexanoic acid can be ensured, and the influence on the whole aroma of the smoke can be avoided.

Preferably, the addition amount of the mixture is 32-38 mg/count. The better adsorption effect can be ensured under the addition amount.

Preferably, the mixture is dispersed in the filter tip in an amount of 2-3 mg/mm.

Preferably, the materials of the general adsorption section and the specific adsorption section are both acetate fibers.

In another aspect, the invention provides a cigarette comprising a composite filter according to the invention.

Preferably, the specific adsorption section of the composite filter is close to the tobacco shred part of the cigarette.

The invention has the following beneficial effects:

1) the composite filter tip has ideal removal effect on the n-hexanoic acid in the smoke of the cigarette, and can effectively improve the taste of the cigarette and reduce the pungent rancid smell of the cigarette.

2) The composite filter tip only has obvious adsorption effect on the orthocaproic acid, has no obvious adsorption effect on other components in the cigarette, can keep the original style of the cigarette unchanged, improves and enhances the taste absorption quality to a certain extent, meets the physiological requirements of consumers, and enhances the competitiveness of products.

Drawings

FIG. 1 is a schematic structural view of a cigarette according to the present invention;

in the figure, 1 is a composite filter tip, 2 is a cigarette body, 3 is a general adsorption section, and 4 is a specific adsorption section.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

The graphene oxide bonded silica gel is prepared by the following method:

1) dispersing 0.2g of graphene oxide in a dimethylformamide solution for ultrasonic treatment, adding 5g of silica gel and 0.5g of dicyclohexylcarbodiimide, and reacting the suspension at 50 ℃;

2) and (3) sequentially cleaning and drying the product by using water and methanol, wherein the prepared brown sample is graphene oxide bonded silica gel.

The modified activated carbon referred to in the examples was prepared by the following method:

putting the activated carbon into a reactor, adding 98% sulfuric acid, heating and refluxing in a water bath, carrying out hot suction filtration to remove acid liquor, washing the activated carbon with water to be neutral, and drying to obtain the modified activated carbon.

The linoleic acid modified nano silicon-based oxide related in the embodiment is prepared by the following method:

adding linoleic acid and nano SiO into n-hexane solvent₂And (3) carrying out ultrasonic oscillation on the powder, and stirring for reaction to obtain the powder.

The linoleic acid and the nano SiO₂The mass ratio of the powder is 9: 100.

During the use process, the linoleic acid modified nano silicon-based oxide is firstly dispersed in triacetyl glycerine according to the mass fraction of 10%.

Example 1

The embodiment relates to a composite cigarette filter, which has the following structure:

the composite filter tip comprises a general adsorption section and a specific adsorption section;

the specific adsorption section is loaded with a mixture of graphene oxide bonded silica gel, modified activated carbon and linoleic acid modified nano silicon-based oxide;

the common adsorption section and the specific adsorption section are coaxially arranged in a serial connection mode.

The mass ratio of the graphene oxide bonded silica gel to the modified activated carbon to the linoleic acid modified nano silicon-based oxide is 2: 1: 0.3.

the preparation method of the composite filter tip comprises the following steps:

dispersing the linoleic acid modified nano silicon-based oxide in plasticizer glyceryl triacetate, wherein the addition amount of the plasticizer is 8% of the total mass of the filter stick, adding graphene oxide bonded silica gel, modified activated carbon and glyceryl triacetate dispersed with the linoleic acid modified nano silicon-based oxide into tobacco bundle to prepare a specific adsorption section, and compounding the specific adsorption section with acetate fibers to prepare the functional composite cigarette filter.

The length of the specific adsorption section in the composite filter tip is 15mm, and the length of the general adsorption section is 10 mm;

the addition amount of the graphene oxide bonded silica gel, the modified activated carbon and the linoleic acid modified nano silicon-based oxide in the acetate fiber is 3 mg/mm.

The added mass of the mixture was 32 mg/piece.

The embodiment also relates to a cigarette provided with the composite cigarette filter, and the structural schematic diagram is shown in figure 1, wherein 1 is the composite filter, 2 is a cigarette body, 3 is a general adsorption section, and 4 is a specific adsorption section. Wherein the length of the cigarette is 84mm +/-0.5 mm, the circumference is 24.35 +/-0.2 mm, and the specific adsorption section of the filter tip is close to the cut tobacco of the cigarette.

Example 2

The embodiment relates to a composite cigarette filter, which has the following structure:

the composite filter tip comprises a general adsorption section and a specific adsorption section;

the specific adsorption section is loaded with a mixture of graphene oxide bonded silica gel, modified activated carbon and linoleic acid modified nano silicon-based oxide;

the common adsorption section and the specific adsorption section are coaxially arranged in a serial connection mode.

The mass ratio of the graphene oxide bonded silica gel to the modified activated carbon to the linoleic acid modified nano silicon-based oxide is 2: 1: 0.5.

the preparation method of the composite filter tip comprises the following steps:

dispersing the linoleic acid modified nano silicon-based oxide in plasticizer glyceryl triacetate, wherein the addition amount of the plasticizer is 8% of the total mass of the filter stick, adding the plasticizer into tobacco bundle to prepare a specific adsorption section, and compounding the specific adsorption section with acetate fibers to prepare the functional composite cigarette filter tip.

The length of the specific adsorption section in the composite filter tip is 20mm, and the length of the general adsorption section is 10 mm.

The addition amount of the graphene oxide bonded silica gel, the modified activated carbon and the linoleic acid modified nano silicon-based oxide in the acetate fiber is 2 mg/mm.

The added mass of the mixture in the cut tobacco is 38 mg/cigarette.

The embodiment also relates to a cigarette provided with the composite cigarette filter, the length of the cigarette is 94mm plus or minus 0.5mm, the circumference of the cigarette is 21.80 plus or minus 0.2mm, and the specific adsorption section of the filter is close to the cut tobacco of the cigarette.

Comparative example 1

Compared with the embodiment 1, the method is characterized in that the mixture added into the composite filter tip is replaced by a mixture of coarse silica gel (with the pore diameter of 5-10 nm) activated carbon and linoleic acid modified nano silicon-based oxide, and the mass ratio of the mixture to the coarse silica gel is 2: 1: 0.3.

comparative example 2

Compared with the example 1, the cigarette is different in that the cigarette does not adopt a composite filter tip, adopts a common filter tip prepared by acetate fiber, and has the same specification as the example 1.

Comparative example 3

Compared with the example 2, the cigarette is different in that the cigarette does not adopt a composite filter tip, adopts a common filter tip prepared from acetate fiber, and has the same specification as the example 2.

Experimental example 1

The experimental example relates to detection of effective components in cigarette smoke in the example:

the method for detecting the content of the n-hexanoic acid in the cigarette smoke by the GC-MS method comprises the following specific steps: ultrasonically extracting the Cambridge filter disc for trapping the smoke by using 12ml of dichloromethane for 20 minutes, standing for 5 minutes, taking 1.5ml of supernatant, filtering by using a microporous filter membrane, transferring into a chromatographic flask, adding 60ul of derivatization reagent N, O-bis (trimethylsilyl) trifluoroacetamide, performing derivatization reaction for 50 minutes under the water bath condition at the temperature of 60 ℃, taking out, and sampling for GC-MS analysis. The analysis conditions were: a chromatographic column: HP-5MS quartz capillary column (30m × 0.25um i.d. × 0.25um d.f.); pre-column: DB-5 quartz capillary column (2m x 0.25um i.d. x 0.25um d.f.); column temperature: the initial temperature was maintained at 40 ℃ for 3 minutes, then ramped up to 210 ℃ at a rate of 4 ℃/min, ramped up to 230 ℃ at a rate of 2 ℃/min, ramped up to 280 ℃ at a rate of 4 ℃/min, and maintained for 50 minutes; sample inlet temperature: 250 ℃; carrier gas: he, 1.0 mL/min; the split ratio is as follows: 10: 1; sample introduction amount: 1.0 uL; transmission line temperature: 250 ℃; quadrupole temperature: 150 ℃; ion source temperature: 230 ℃; ionization energy: 70 eV; mass number range: 30-400 amu.

The results are shown in tables 1 and 2:

TABLE 1

TABLE 2

From the above data, it can be seen that the use of the composite filter according to the present invention can effectively adsorb hexanoic acid.

Experimental example 2

The sensory evaluation of the cigarettes of the examples and comparative examples was carried out in accordance with tobacco industry Standard YC/T138-1998 sensory evaluation methods for tobacco and tobacco products, and the results are shown in Table 3.

TABLE 3

Note: taste Activity Value (TAV) ═ C_{Measurement of Release amount}/TPM/C_{Threshold value}Reflecting the contribution of the compound component to the sensory quality of the cigarette, when the value is more than 1, the compound is shown to contribute to the sensory system, and the higher the value is, the greater the contribution is.

The n-hexanoic acid has strong pungent, burning and rancidity smell when the concentration is higher, and reflects that stronger irritation and obvious miscellaneous gas appear on the sensory quality of the main stream smoke of the cigarette, which is consistent with the sensory quality evaluation result of the cigarette, and the irritation of the cigarette adopting the functional composite filter stick is reduced, and the miscellaneous gas and aftertaste are superior to those of a control cigarette. By combining the sensory evaluation result of the cigarettes, the use of the functional composite filter stick can obviously reduce the irritation and the miscellaneous gas of the smoke, improve the comfort of the oral cavity and totally does not influence the integral fragrance quantity and the style characteristics of the mixed type cigarettes.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.