MOF-based composite particle, preparation method thereof and cigarette

Abstract

The invention provides a preparation method of composite particles based on MOF (Metal Organic Fragrance), which comprises the following steps: A) carrying out crushing, solvent extraction and solid-liquid separation on spicy plant raw materials to obtain an extracting solution and a solid product; b) drying the solid product, and mixing the dried solid product with an adhesive and an MOF material to obtain a mixture; the MOF material is MIL-101-NH2 (Fe), and the molecular weight of the MOF material is 100-200; and C) adding an extracting solution into the mixture to obtain a wet material, and granulating the wet material to obtain the composite granules. According to the granules provided by the invention, the selective adsorption MOF is compounded with the spicy plant extract, so that the synchronous release of aroma and the adsorption of harmful gas in a filter stick are realized, and the effects of aroma enhancement and harm reduction are achieved.

Description

Technical Field

[0001] This invention relates to the field of tobacco technology, and in particular to a method for preparing MOF composite particles and cigarettes. Background Technology

[0002] In recent years, with the increasing health awareness of consumers and the advancement of the major project to reduce tar and harm in cigarettes, the functions of additives used in cigarette filters are often relatively singular, focusing either on supplementing and modifying aroma or on retaining some particulate matter in the smoke. Traditional adsorbent materials such as activated carbon, while possessing a certain broad-spectrum adsorption capacity, inevitably trap aroma molecules along with harmful components due to their lack of selectivity, making it difficult to simultaneously achieve the dual goals of enhancing aroma and reducing harm.

[0003] Metal-organic frameworks (MOFs), a novel class of porous crystalline materials, are self-assembled from metal ions or clusters and organic ligands. Their advantages lie in their extremely high specific surface area, tunable pore structure, and functionalizable pore environment. These properties enable MOFs to transcend the physical adsorption limitations of traditional materials, achieving selective adsorption based on molecular size, polarity, and interaction forces. Through precise design and screening of metal nodes and organic ligands, MOFs with specific binding capabilities to particular small-molecule harmful gases can be constructed. For example, some MOFs containing unsaturated metal sites exhibit strong complexing ability for carbon monoxide (CO) (CIESC Journal, 2025, 76(5): 2279-2293); MOFs with specific pore sizes and surface polarities can preferentially capture phenolic substances such as phenol (Chemical Industry and Engineering Progress, 2021, 40(8): 4525-4539); while some amino-functionalized MOFs, such as UIO-66-NH2, have efficient chemisorption effects on carbonyl compounds such as formaldehyde.

[0004] Therefore, developing an innovative composite particle that combines the precise selective adsorption characteristics of MOF materials (targeting specific harmful components such as carbon monoxide, phenol, and formaldehyde) with the aroma release of natural plants to construct a filter additive system with synergistic effects of enhancing aroma and reducing harm is of vital importance for fundamentally improving the smoking safety and sensory quality of cigarettes. Summary of the Invention

[0005] In view of this, the present invention provides a MOF-based composite particle, which combines selective adsorption of MOF with pungent plant extracts to achieve simultaneous release of aroma and adsorption of harmful gases in the filter rod, thereby achieving the effect of "enhancing aroma and reducing harm".

[0006] This invention discloses a spice-derived aroma-enhancing and harm-reducing composite particle based on a metal-organic framework (MOF), its preparation method, and its application. The method uses natural spice plants as raw materials, employing a reduced-pressure internal boiling extraction technique to separate the spice extract from the solid product. The dried solid product is used as a carrier, mixed with a binder and a selectively adsorbing MOF material, and then backfilled with the spice extract. The resulting composite particles are obtained through wet granulation. These particles possess both aroma-releasing and harmful gas-adsorbing functions, selectively adsorbing harmful components such as formaldehyde and acrolein in cigarette smoke while stably releasing aroma. Applying them to cigarette filters significantly improves smoking quality and reduces harm, making them suitable for the development of functional cigarettes. The process of this invention is simple to operate, has high raw material utilization, low processing intensity, and is easy to industrialize.

[0007] This invention provides a method for preparing MOF-based composite particles, comprising the following steps:

[0008] A) The aromatic plant raw materials are crushed, extracted with solvent, and separated into solid and liquid components to obtain an extract and a solid product;

[0009] B) The solid product is dried and then mixed with a binder and MOF material to obtain a mixture; the MOF material is MIL-101-NH2 (Fe);

[0010] C) Add the extract to the mixture to obtain a wet material; granulate the wet material to obtain composite particles.

[0011] Preferably, the method for synthesizing MIL-101-NH2(Fe) specifically includes:

[0012] Dissolve FeCl3·6H2O and 2-aminoterephthalic acid in a solvent, heat to react, cool, wash and dry to obtain the product;

[0013] The molar ratio of FeCl3·6H2O to 2-aminoterephthalic acid is 2:1; the solvent is N,N-dimethylformamide; and the reaction conditions are heating at 110~150 °C for 1~20 h.

[0014] Preferably, the extraction temperature in step A) is 40 ℃~80 ℃, the extraction time is 30 min~90 min, and the extraction pressure is 20 kPa~50 kPa.

[0015] Preferably, the aromatic plant ingredients include one or more of star anise, cinnamon, cloves, dried plum, fennel, nutmeg, or lemongrass;

[0016] The pulverization is performed to a mesh size of 100-150; the extraction solvent is an ethanol-water mixture with an ethanol content of 40%-60%; and the mass ratio of the pungent plant material to the extraction solvent is 1:5-1:10.

[0017] Preferably, the solid product in step B) is dried to a moisture content of ≤5%; the drying equipment for the solid product is a vacuum drying oven with a drying pressure of ≤0.08 MPa and a temperature of 40-60 ℃ for 1-6 h.

[0018] The binder is at least one of sodium carboxymethyl cellulose, sodium alginate, or guar gum, and its addition amount is 3% to 5% of the mass of the dried solid product; the MOF material is added at 1% to 10% of the mass of the dried solid product.

[0019] Preferably, the granulation time is 5 to 15 minutes; the granulation is performed using a gyratory granulator with a gyratory frequency of 40 Hz to 60 Hz.

[0020] The granulation process is followed by sieving and drying; the sieving is performed through a 20-40 mesh sieve; the drying is carried out at 40-60°C for 50-90 minutes.

[0021] This invention provides a MOF-based composite particle, prepared by any one of the preparation methods described in the above technical solutions.

[0022] This invention provides a flavor-enhancing and harm-reducing composite granule, including the MOF-based composite granules described in the above technical solution.

[0023] This invention provides a cigarette in which MOF-based composite particles as described in the above-mentioned technical solution are added to the cigarette filter rod.

[0024] Preferably, the amount of MOF-based composite particles added to cigarettes is 0.1wt% to 3wt%.

[0025] Compared with existing technologies, this invention provides a method for preparing MOF-based composite particles, comprising the following steps: A) pulverizing, solvent-extracting, and separating the pungent plant raw materials to obtain an extract and a solid product; B) drying the solid product and mixing it with a binder and MOF material to obtain a mixture; wherein the MOF material is MIL-101-NH2 (Fe); C) adding the extract to the mixture to obtain a wet material; granulating the wet material to obtain composite particles. The particles provided by this invention, by selectively adsorbing MOF and combining it with pungent plant extracts, achieve the simultaneous release of aroma and adsorption of harmful gases in the filter rod, thus achieving the effect of "enhancing aroma and reducing harm". Attached Figure Description

[0026] Figure 1 SEM image of MIL-101-NH2 (Fe) crystal;

[0027] Figure 2Release levels of mainstream flue gas components in different samples. Detailed Implementation

[0028] This invention provides a method for preparing MOF composite particles and cigarettes thereof. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and fall within the scope of this invention. The method and application of this invention have been described through preferred embodiments. Those skilled in the art can clearly modify or appropriately change and combine the method and application described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0029] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0030] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0031] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0032] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items.

[0033] This invention provides a method for preparing MOF-based composite particles, comprising the following steps:

[0034] A) The aromatic plant raw materials are crushed, extracted with solvent, and separated into solid and liquid components to obtain an extract and a solid product;

[0035] B) The solid product is dried and then mixed with a binder and MOF material to obtain a mixture; the MOF material is MIL-101-NH2 (Fe);

[0036] C) Add the extract to the mixture to obtain a wet material; granulate the wet material to obtain composite particles.

[0037] The present invention provides a method for preparing spice plant composite particles based on MOF multi-stage sustained release, which first involves pulverizing spice plant raw materials.

[0038] The aromatic plant ingredients described in this invention include, but are not limited to, one or more of star anise, cinnamon, cloves, dried plum, fennel, nutmeg, or lemongrass;

[0039] The pulverization refers to pulverizing to 100-150 mesh; specifically, it can be 100 mesh, 110 mesh, 120 mesh, 130 mesh, 140 mesh, 150 mesh; or any value between the two mentioned above.

[0040] Spicy plant powder and extraction solvent are mixed at a mass ratio of 1:5 to 1:10 and placed in a vacuum internal boiling extraction device. Under certain conditions, the extract and solid product are obtained by vacuum filtration or centrifugation. The mass ratio of the spicy plant raw material to the extraction solvent is specifically 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0041] The extraction solvent described in this invention is an ethanol-water mixed solvent, with an ethanol content of 40% to 60% (volume percentage); specifically, it can be 40%, 45%, 50%, 55%, or 60%.

[0042] The extraction temperature is 40 ℃~80 ℃, specifically 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃;

[0043] The extraction time is 30 min to 90 min, specifically 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, and 90 min.

[0044] The extraction pressure is 20 kPa to 50 kPa. Specifically, it can be 20 kPa, 25 kPa, 30 kPa, 35 kPa, 40 kPa, 45 kPa, or 50 kPa; or any value within the range of any two of the above.

[0045] The present invention preferably dries the obtained solid product to a moisture content of ≤5%; specifically, the solid residue is dried in a vacuum drying oven at a drying pressure of ≤0.08 MPa and a temperature of 40-60 ℃ for 1-6 h.

[0046] The solid product, binder, and MOF material are mixed to obtain a mixture. The binder is at least one of sodium carboxymethyl cellulose, sodium alginate, or guar gum, and its addition amount is 3% to 5% of the mass of the dried solid product; specifically, it can be 3%, 4%, or 5%. The MOF material is added at 1% to 10% of the mass of the dried solid product; specifically, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%.

[0047] Add the extract from step A) to the mixture in batches, mix well, and stir to form a plastic wet material.

[0048] The resulting wet material is fed into a vibrating pellet mill or a high-speed mixing pellet mill for pelleting.

[0049] The granulation time described in this invention is 5 to 15 minutes; specifically, it can be 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, or 15 minutes.

[0050] The granulation is performed using a gyratory granulator with a gyratory frequency of 40 Hz to 60 Hz; specifically, it can be 40 Hz, 45 Hz, 50 Hz, 55 Hz, or 60 Hz.

[0051] The granulation process involves sieving and drying; then cooling to room temperature to obtain spice plant granules.

[0052] The sieving process involves passing through a sieve with a mesh size of 20 to 40; specifically, it can be 20 mesh, 25 mesh, 30 mesh, 35 mesh, or 40 mesh.

[0053] The drying process is carried out at 40–60 °C for 50–90 min.

[0054] The MOF material described in this invention is MIL-101-NH2(Fe); the specific method for synthesizing MIL-101-NH2(Fe) includes:

[0055] Dissolve FeCl3·6H2O and 2-aminoterephthalic acid in a solvent, heat to react, cool, wash and dry to obtain the product.

[0056] The molar ratio of FeCl3·6H2O to 2-aminoterephthalic acid is 2:1; the solvent is N,N-dimethylformamide; the reaction conditions are heating at 110~150 °C for 1~20 h. Specifically, the heating temperature can be 110 °C, 120 °C, 130 °C, 140 °C, or 150 °C, or any value within a range of two of these. The heating time can be 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h, 19 h, or 20 h.

[0057] This invention provides a MOF-based composite particle, prepared by any one of the preparation methods described in the above technical solutions.

[0058] The preparation method described above has been clearly described in this invention, and will not be repeated here.

[0059] This invention provides a flavor-enhancing and harm-reducing composite granule, including the MOF-based composite granules described in the above technical solution.

[0060] The composite particles of the present invention are composed of dried solid residue and MOF material to form a composite carrier, and the extract is loaded inside the carrier, which has the dual functions of slow-release aroma and adsorption of harmful gases.

[0061] This invention provides a cigarette in which the filter rod contains the aromatic plant composite particles based on MOF multi-stage sustained release as described in the above technical solution.

[0062] The composite particles are used as flavoring and aroma-enhancing additives in cigarette filter rods.

[0063] The amount of the MOF-based multi-stage sustained-release aromatic plant composite particles added to cigarettes according to this invention is 0.1wt%~3wt%; specifically, it can be 0.1wt%, 0.2wt%, 0.4wt%, 0.6wt%, 0.8wt%, 1.0wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2.0wt%, 2.2wt%, 2.4wt%, 2.6wt%, 2.8wt%, 3.0wt%; or any value within the range of the above two.

[0064] This method integrates MOF materials with aromatic plant extracts within the particles. The composite particles in cigarette filters can simultaneously achieve the slow release of aroma and the selective adsorption of harmful gases, solving the contradiction that traditional filter materials often weaken the aroma while adsorbing harmful substances, thus achieving a synergistic effect of "enhancing aroma and suppressing harm".

[0065] This invention utilizes the tunable pore structure and surface chemistry of MOF materials to selectively adsorb specific small molecule harmful substances, minimizing their impact on aroma molecules. Simultaneously, it achieves the "full-component, high-value" utilization of spice plant raw materials, with a green and efficient process.

[0066] It should be understood that the order of the steps or the order in which certain actions are performed is not important as long as the invention remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0067] The use of any and all instances or exemplary language such as “e.g.” or “including” in this document is merely intended to better illustrate the invention and is not intended to limit the scope of the invention unless the claims are made. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of the invention.

[0068] Furthermore, the numerical ranges and parameters used to define the present invention are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any value inevitably contains standard deviations due to individual test methods. Therefore, unless explicitly stated otherwise, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately". Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0069] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0070] The embodiments and comparative examples of this invention describe some examples, in which the embodiments illustrate certain implementations of the invention. However, this does not mean that the effects of the invention can only be achieved in these examples.

[0071] To further illustrate the present invention, the following describes in detail a composite coating process provided by the present invention with reference to embodiments.

[0072] Example 1: Preparation of cinnamon granules, the steps are as follows:

[0073] Cinnamon bark raw material was crushed and sieved to control the output particle size ≤1 mm. Cinnamon powder was mixed with 70% ethanol at a mass ratio of 1:8 and extracted in a vacuum internal boiling extraction device at 75℃ and 40kPa for 90 minutes. The extract and solid residue were obtained by vacuum filtration. The solid residue was placed in a vacuum drying oven and dried at 60℃ and 0.08MPa until the moisture content was ≤5%. 5% sodium carboxymethyl cellulose was added to the dried residue and mixed evenly. The extract was added in batches and stirred into a wet agglomerate. Granulation was carried out using a swing granulator with a 40-mesh sieve for 8 minutes. The wet granules were dried at 55℃ for 70 minutes and cooled to obtain cinnamon granules.

[0074] The resulting particles are added to the filter rod at a ratio of 1.5% of the total weight of the cigarette.

[0075] Example 2: Preparation of cinnamon-MIL-101-NH2 composite particles, the steps are as follows:

[0076] FeCl3·6H2O and 2-aminoterephthalic acid were ultrasonically dissolved in N,N-dimethylformamide (DMF) solution at a molar ratio of 2:1. The mixed solution was added to a stainless steel autoclave lined with polytetrafluoroethylene and heated at 110–150 °C for 1–20 h. After cooling to room temperature, the product was filtered out, washed with ethanol, and dried to obtain MIL-101-NH2(Fe) crystals. The SEM results of the crystals are shown below. Figure 1 As shown. Figure 1 SEM image of MIL-101-NH2 (Fe) crystal.

[0077] Cinnamon bark raw material was crushed and sieved to control the output particle size ≤1 mm. Cinnamon powder was mixed with 70% ethanol at a mass ratio of 1:8 and extracted in a vacuum internal boiling extraction device at 75℃ and 40kPa for 90 minutes. The extract and solid residue were obtained by vacuum filtration. The solid residue was placed in a vacuum drying oven and dried at 60℃ and 0.08MPa until the moisture content was ≤5%. 5% sodium carboxymethyl cellulose and 5% MIL-101-NH2 were added to the dried residue and mixed evenly. The extract was added in batches and stirred into a wet agglomerate. Granulation was carried out using a swing granulator with a 40-mesh sieve for 8 minutes. The wet granules were dried at 55℃ for 70 minutes and cooled to obtain cinnamon-MIL-101-NH2 composite granules.

[0078] The obtained cinnamon-MIL-101-NH2 composite particles were added to the filter rod at 1.5% of the total weight of the cigarette.

[0079] Cigarettes with different particulate filter rods obtained in Examples 1-2 were used as test cigarettes, and the following comparative examples were added, with cigarettes without any added functional particles serving as blank controls for sensory evaluation and smoke analysis. All cigarettes were equilibrated for 48 hours at a temperature of (22±1)℃ and a relative humidity of (60±2)% before the test.

[0080] Comparative Example 1: MIL-101 composite particles

[0081] The preparation method is the same as in Example 2, except that the MIL-101-NH2 MOF material is replaced with an equal mass of MIL-101 material (without functional group modification). This comparative example is used to compare the effect of functional group modification on the adsorption effect.

[0082] Comparative Example 2: UIO-66-NH2 composite particles

[0083] The preparation method is the same as in Example 2, except that the MIL-101-NH2 material is replaced with an equal mass of UIO-66-NH2 MOF material. This comparative example is used to compare the performance differences of MOF materials with different structures.

[0084] Seven evaluators conducted sensory evaluations according to the YC / T 415-2011 sensory evaluation method for tobacco products. Table 1 provides a quantitative description of each sensory evaluation indicator using a 9-point scoring system. Specific results are shown in Table 2 below. The cigarettes from Example 2 (cinnamon-MIL-101-NH2 composite granules) showed higher scores in all indicators compared to the control group. They exhibited a fuller aroma, significantly improved texture, pronounced spicy characteristics, a delicate and smooth smoke, good penetration and impurity removal, and a significant reduction in irritation. Oral dryness, cleanliness, and sweetness were also significantly improved.

[0085] Table 1. Quantitative description of individual sensory evaluation indicators using a 9-point scoring system.

[0086]

[0087] Table 2 Sensory evaluation scores for different samples

[0088]

[0089] The release amounts of CO, total particulate matter, and tar in cigarette smoke were determined according to the methods in GB / T 23356-2009 and YC / T 253-2008, with formaldehyde release also tested. The results are as follows: Figure 2 As shown. Figure 2 Emission levels of mainstream flue gas components in different samples; by Figure 2It can be seen that among the samples, the release of tar and CO was lowest in Example 2. Compared with the pure cinnamon plant particles in Example 1, the release of harmful components such as tar and CO in Example 2 was significantly reduced due to the introduction of MOF material. Compared with the MOF material without amino functional groups in Comparative Example 1, the MIL-101-NH2 material of this invention has a stronger adsorption capacity for specific harmful components. Compared with Comparative Example 2 (UIO-66-NH2), Example 2 also has a strong adsorption capacity for harmful components such as tar and CO, indicating that MIL-101-NH2 has a strong binding force on these components in terms of pore structure or surface chemistry.

[0090] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing MOF-based composite particles, characterized in that, Includes the following steps: A) The aromatic plant raw materials are crushed, extracted with solvent, and separated into solid and liquid components to obtain an extract and a solid product; B) The solid product is dried and then mixed with a binder and MOF material to obtain a mixture; the MOF material is MIL-101-NH2 (Fe); C) Add the extract to the mixture to obtain a wet material; granulate the wet material to obtain composite particles.

2. The preparation method according to claim 1, characterized in that, The specific method for synthesizing MIL-101-NH2 (Fe) includes: Dissolve FeCl3·6H2O and 2-aminoterephthalic acid in a solvent, heat to react, cool, wash and dry to obtain the product; The molar ratio of FeCl3·6H2O to 2-aminoterephthalic acid is 2:1; the solvent is N,N-dimethylformamide; and the reaction conditions are heating at 110~150 °C for 1~20 h.

3. The preparation method according to claim 2, characterized in that, The extraction temperature in step A) is 40 ℃~80 ℃, the extraction time is 30 min~90 min, and the extraction pressure is 20 kPa~50 kPa.

4. The preparation method according to claim 1, characterized in that, The aromatic plant ingredients include one or more of star anise, cinnamon, cloves, dried plum, fennel, nutmeg, or lemongrass; The pulverization is performed to a mesh size of 100-150; the extraction solvent is an ethanol-water mixture with an ethanol content of 40%-60%; and the mass ratio of the pungent plant material to the extraction solvent is 1:5-1:

10.

5. The preparation method according to claim 1, characterized in that, Step B) The solid product is dried to a moisture content of ≤5%; the drying equipment for the solid product is a vacuum drying oven, with a drying pressure of ≤0.08 MPa and a temperature of 40~60 ℃ for 1~6 h. The binder is at least one of sodium carboxymethyl cellulose, sodium alginate, or guar gum, and its addition amount is 3% to 5% of the mass of the dried solid product; the MOF material is added at 1% to 10% of the mass of the dried solid product.

6. The preparation method according to claim 1, characterized in that, The granulation time is 5 to 15 minutes; the granulation is carried out using a gyratory granulator with a gyratory frequency of 40 Hz to 60 Hz. The granulation process is followed by sieving and drying; the sieving process involves passing the material through a 20-40 mesh sieve; the drying process is carried out at 40-60°C for 50-90 minutes.

7. A MOF-based composite particle, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 6.

8. A flavor-enhancing and harm-reducing composite granule, characterized in that, Including the MOF-based composite particles as described in claim 7.

9. A cigarette, characterized in that, The cigarette filter rod contains the MOF-based composite particles as described in claim 7.

10. The cigarette according to claim 9, characterized in that, The amount of MOF-based composite particles added to cigarettes is 0.1wt%~3wt%.

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