Filler material for adsorbing smoke and its preparation method and cigarette

Abstract

The application provides a kind of filled material of adsorbing flue gas, including the following weight parts of components: modified plant fiber 10~80 parts, adsorption base material 1~50 parts, binder 0.1~5 parts;The plant fiber includes one or more of flax fiber, ramie fiber, mulberry fiber, coconut shell fiber or kapok fiber;The adsorption base material includes one or more of modified montmorillonite, diatomite, silica gel, activated carbon, macroporous adsorption resin, molecular sieve, zeolite, sepiolite, attapulgite.The application constructs three-dimensional network structure by modifying the inside of plant fiber, so that the adsorption base material can be embedded in the pore structure of different pore size of three-dimensional network structure, thereby playing a fixing role on the adsorption base material;The application adsorption base material is adsorbed by electrostatic force, hydrogen bond, π-π bond superposition interaction, and then realizes rapid adsorption of flue gas through multiple synergistic effects.

Description

Technical Field

[0001] This invention relates to the field of cigarette technology, and in particular to a filling material for absorbing smoke, its preparation method, and cigarettes. Background Technology

[0002] The smoke released during tobacco combustion contains approximately 7,000 known chemical substances, and nearly 10,000 compounds that have not been accurately identified, including carcinogens and suspected carcinogens present at approximately 0.2% (about 60 substances). To reduce the harm of tobacco products to consumers, attention has been focused on how to reduce the release of harmful components from tobacco smoke. Adsorption methods are characterized by low cost, simple operation, and low energy consumption. During the smoke adsorption process, the molecular weight, kinetic diameter, and physicochemical properties of the adsorbate molecules directly affect the adsorption process. Simultaneously, the adsorption process is also influenced by external adsorption conditions such as temperature and adsorbate concentration. The combination of these factors results in different affinities between the adsorbate and the adsorbent, thus affecting the adsorption rate and adsorption capacity.

[0003] Adsorption filtration is a widely studied technology both domestically and internationally. Commonly used adsorbents include activated carbon, carbon molecular sieves, carbonized polymers, polymer adsorbents, silica gel, activated alumina, clay, zeolite, and hemoglobin. While adsorption filtration has some effect, the effect is not very significant and cannot achieve highly efficient adsorption, thus failing to meet the requirement of reducing the content of harmful substances in cigarette smoke.

[0004] Therefore, in order to reduce the content of harmful substances in cigarette smoke, it is essential to provide filling materials that reduce harm to smokers without affecting the taste of cigarettes. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a filling material for adsorbing flue gas, and the filling material provided by the present invention has a good adsorption effect on flue gas.

[0006] This invention provides a filling material for adsorbing flue gas, comprising the following components in parts by weight:

[0007] 10-80 parts modified plant fiber, 1-50 parts adsorbent substrate, and 0.1-5 parts adhesive;

[0008] The plant fibers include one or more of flax fiber, ramie fiber, mulberry bark fiber, coconut shell fiber, or kapok fiber;

[0009] The adsorption substrate includes one or more of the following: modified montmorillonite, diatomaceous earth, silica gel, activated carbon, macroporous adsorption resin, molecular sieve, zeolite, sepiolite, and attapulgite.

[0010] Preferably, the filler material comprises the following components in parts by weight:

[0011] 20-60 parts modified plant fiber, 5-30 parts adsorbent substrate, and 0.5-3 parts adhesive;

[0012] The adhesive is selected from one or more of starch, dextrin, sucrose, gelatin, sodium alginate, polyvinylpyrrolidone, polyethylene glycol, sodium carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, or hydroxyethyl cellulose.

[0013] Preferably, the method for preparing the modified plant fiber is as follows:

[0014] a) Mix plant fiber with 3 wt% sodium hydroxide and stir at 800-1000 r / min for 24-30 h. Wash with deionized water until neutral and then add to a 70-80 wt% concentrated sulfuric acid aqueous solution. Continue stirring in a 50-60℃ water bath for 35-45 min and then wash repeatedly with ultrapure water until neutral to obtain hollow plant fiber.

[0015] b) Mix sodium oleate and 2wt%–3wt% calcium chloride aqueous solution and stir to obtain a suspension; then add 3wt%–4wt% sodium dihydrogen phosphate aqueous solution to obtain a reaction solution;

[0016] c) Add hollow plant fibers to the reaction solution, mix, heat to react, wash and dry after reaction to obtain modified plant fibers.

[0017] Preferably, the modified plant fiber is ramie fiber and kapok fiber; the weight ratio of the ramie fiber to the kapok fiber is (0.1-1):1;

[0018] The heating reaction in step c) is carried out at a temperature of 200°C for 30 hours.

[0019] The mass-to-volume ratio of the hollow plant fiber to the reaction solution is 1g:18mL.

[0020] Preferably, the preparation method of the modified montmorillonite is as follows:

[0021] S1) Mix montmorillonite and sodium carbonate solution, stir, filter, wash, and dry to obtain sodium-based montmorillonite;

[0022] S2) Sodium-based montmorillonite and branched polyethyleneimine were mixed, stirred, washed, and dried to obtain a montmorillonite composite material.

[0023] S3) 4-Carboxyphenylboronic acid, acetone, anhydrous sodium sulfate, hydroxypropyl β-cyclodextrin, lauroyl arginine ethyl ester hydrochloride and N-hydroxysuccinimide are mixed and stirred, and then the montmorillonite composite material described in step S2) is added, heated and stirred, and then cooled, filtered, washed and dried to obtain modified montmorillonite.

[0024] Preferably, in step S1), the concentration of the sodium carbonate solution is 0.5 wt%; the stirring temperature is 50-60°C and the time is 4-5 h; the drying is specifically carried out at 60°C under reduced pressure for 12 h; and the weight ratio of montmorillonite to the sodium carbonate aqueous solution is (20-5):1.

[0025] In step S2), the concentration of branched polyethyleneimine is 50 wt%; the stirring time is 24 h; and the drying is performed at 40 °C under reduced pressure for 12 h.

[0026] Preferably, the weight ratio of the montmorillonite composite material in step S3) to the 4-carboxyphenylboronic acid, the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride, and the N-hydroxysuccinimide is 1:(1-3):(1-5):(3-10);

[0027] The specific method for preparing the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride is as follows:

[0028] Hydroxypropyl-β-cyclodextrin and lauroyl arginine ethyl ester hydrochloride were stirred and reacted, refrigerated overnight, and then freeze-dried to obtain solid hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride.

[0029] This invention provides a method for preparing the filling material for adsorbing flue gas as described in any one of the above technical solutions, comprising:

[0030] The modified plant fiber, adsorbent substrate, adhesive, and water are thoroughly mixed and granulated to obtain the final product.

[0031] The present invention provides a cigarette filter, comprising the filling material described in any one of the above technical solutions.

[0032] The present invention provides a cigarette, including the cigarette filter described in the above technical solution.

[0033] Compared with existing technologies, this invention provides a filling material for adsorbing flue gas, comprising the following components in parts by weight: 10-80 parts modified plant fiber, 1-50 parts adsorption substrate, and 0.1-5 parts binder; the plant fiber includes one or more of flax fiber, ramie fiber, mulberry bark fiber, coconut shell fiber, or kapok fiber; the adsorption substrate includes one or more of modified montmorillonite, diatomaceous earth, silica gel, activated carbon, macroporous adsorption resin, molecular sieve, zeolite, sepiolite, and attapulgite. This invention constructs a three-dimensional network structure within the modified plant fiber, allowing the adsorption substrate to be embedded in the pores of different sizes within the three-dimensional network structure, thereby fixing the adsorption substrate; the adsorption substrate of this invention adsorbs flue gas through the interaction of electrostatic forces, hydrogen bonds, and superimposed π-π bonds, thus achieving rapid adsorption through multiple synergistic effects. Detailed Implementation

[0034] This invention provides a filling material for absorbing smoke, its preparation method, and a cigarette. 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 protection 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] The filling material in this invention is used in the preparation of cigarette filters, which can reduce the content of harmful substances in cigarette smoke.

[0039] The hazardous substances described in this invention include, but are not limited to, CO, HCN, NNK, NH3, B[a]P, phenol, and crotonaldehyde.

[0040] This invention provides a filling material for adsorbing flue gas, comprising the following components in parts by weight:

[0041] 10-80 parts modified plant fiber, 1-50 parts adsorbent substrate, and 0.1-5 parts adhesive;

[0042] The plant fibers include one or more of flax fiber, ramie fiber, mulberry bark fiber, coconut shell fiber, or kapok fiber;

[0043] The adsorption substrate includes one or more of the following: modified montmorillonite, diatomaceous earth, silica gel, activated carbon, macroporous adsorption resin, molecular sieve, zeolite, sepiolite, and attapulgite.

[0044] The filling material described above in this invention is preferably a paper tube filling material.

[0045] In some embodiments, the filler material comprises the following components in parts by weight:

[0046] 20-60 parts modified plant fiber, 5-30 parts adsorbent substrate, and 0.5-3 parts adhesive;

[0047] In some preferred embodiments of the present invention, the filler material comprises the following components in parts by weight:

[0048] 30-50 parts modified plant fiber, 15-30 parts adsorbent substrate, and 1-3 parts adhesive;

[0049] In some preferred embodiments of the present invention, the filler material comprises the following components in parts by weight:

[0050] 40-50 parts modified plant fiber, 20-30 parts adsorbent substrate, and 2-3 parts adhesive;

[0051] In one preferred embodiment of the present invention, the filler material comprises the following components in parts by weight:

[0052] 50 parts modified plant fiber, 20 parts absorbent substrate, and 2 parts adhesive.

[0053] As a preferred technical solution, the adhesive is selected from one or more of starch, dextrin, sucrose, gelatin, sodium alginate, polyvinylpyrrolidone, polyethylene glycol, sodium carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, or hydroxyethyl cellulose. More preferably, the adhesive is sodium alginate and hydroxyethyl cellulose. As a preferred technical solution, the weight ratio of sodium alginate to hydroxyethyl cellulose in the adhesive is 1:1.

[0054] As a preferred technical solution, the plant fiber is one or more of flax fiber, ramie fiber, mulberry bark fiber, coconut shell fiber, and kapok fiber.

[0055] The specific preparation method of the modified plant fiber according to the present invention is as follows:

[0056] a) Mix plant fiber with 3 wt% sodium hydroxide and stir at 800-1000 r / min for 24-30 h. Wash with deionized water until neutral and then add to a 70-80 wt% concentrated sulfuric acid aqueous solution. Continue stirring in a 50-60℃ water bath for 35-45 min and then wash repeatedly with ultrapure water until neutral to obtain hollow plant fiber.

[0057] In some embodiments, plant fibers and 3 wt% sodium hydroxide are mixed and stirred at 800-1000 r / min for 24-30 h. The mixture is washed with deionized water until neutral and then added to a 75 wt% concentrated sulfuric acid aqueous solution. The mixture is stirred for 40 min in a 55°C water bath and then washed repeatedly with ultrapure water until neutral to obtain hollow plant fibers.

[0058] b) Mix sodium oleate and 2wt%–3wt% calcium chloride aqueous solution and stir to obtain a suspension; then add 3wt%–4wt% sodium dihydrogen phosphate aqueous solution to obtain a reaction solution;

[0059] In some embodiments, sodium oleate and a 2.6 wt% calcium chloride aqueous solution are mixed and stirred to obtain a suspension; then a 3.6 wt% sodium dihydrogen phosphate aqueous solution is added to obtain a reaction solution.

[0060] c) Add hollow plant fibers to the reaction solution, mix, heat to react, wash and dry after reaction to obtain modified plant fibers.

[0061] In step c) of this invention, the heating reaction temperature is 200°C and the time is 30 hours; the mass-to-volume ratio of the hollow plant fiber and the reaction solution is 1 g: 18 mL.

[0062] Preferably, the modified plant fiber is ramie fiber and kapok fiber; the weight ratio of hollow ramie fiber to hollow kapok fiber is (0.1-1):1; more preferably, in the method of preparing the modified plant fiber, the weight ratio of hollow ramie fiber to hollow kapok fiber is (0.2-0.7):1; more preferably, in the method of preparing the modified plant fiber, the weight ratio of hollow ramie fiber to hollow kapok fiber is 0.6:1.

[0063] At this point, the specific method for preparing the modified plant fiber is as follows:

[0064] (1) Add ramie fiber to a 3 wt% sodium hydroxide aqueous solution and mechanically stir at 1000 r / min for 30 h. After washing repeatedly with deionized water until neutral, add it to a 75 wt% concentrated sulfuric acid aqueous solution and continue stirring in a 55℃ water bath for 40 min. Then wash repeatedly with ultrapure water until neutral to obtain hollow ramie fiber.

[0065] (2) Add the kapok fiber to a 3 wt% sodium hydroxide solution and mechanically stir at 1000 r / min for 30 h. After washing repeatedly with deionized water until neutral, add it to a 75 wt% concentrated sulfuric acid solution and continue stirring in a 55℃ water bath for 40 min. Then wash repeatedly with ultrapure water until neutral to obtain hollow kapok fiber.

[0066] (3) While stirring continuously at 100 r / min, 40 g of sodium oleate was dissolved in 500 mL of deionized water, and 150 mL of calcium chloride aqueous solution with a concentration of 2.6 wt% was added to form a suspension. Then, 160 mL of sodium dihydrogen phosphate aqueous solution with a concentration of 3.6 wt% was added and mixed to obtain a reaction solution. Hollow ramie fiber and hollow kapok fiber were added to the reaction solution according to a solid-liquid ratio of 1 g: 18 mL. After mixing, the solution was sealed and placed in a high-pressure reactor. The reaction was heated at 200 °C for 30 h. After the reaction was completed, the product was repeatedly washed with ethanol and deionized water and dried to obtain modified plant fiber.

[0067] In this invention, plant fibers are treated with acid and alkali to remove impurities, resulting in hollow tubular plant fibers (hollow ramie fibers, hollow kapok fibers). Then, using the hollow plant fibers as a matrix, ultra-long nanowires are deposited on the hollow plant fibers (hollow ramie fibers, hollow kapok fibers) using a calcium oleate precursor solvothermal method. Some of the deposited ultra-long nanowires enter the hollow tubes of the hollow plant fibers (hollow ramie fibers, hollow kapok fibers) and overlap to form multiple spatial network structures with different pore sizes. A multi-layer three-dimensional network structure is constructed inside the hollow plant fibers. The adsorbent substrate (e.g., modified montmorillonite) can be embedded in the pores of different pore sizes of the three-dimensional network structure, which plays a role in fixing the adsorbent substrate, thereby forming a structurally stable filling material.

[0068] As a preferred technical solution, the adsorption substrate is selected from one or more of the following: modified montmorillonite, diatomaceous earth, silica gel, activated carbon, macroporous adsorption resin, molecular sieve, zeolite, sepiolite, and attapulgite.

[0069] According to the present invention, the preparation method of the modified montmorillonite is specifically as follows:

[0070] S1) Mix montmorillonite and sodium carbonate solution, stir, filter, wash, and dry to obtain sodium-based montmorillonite;

[0071] S2) Sodium-based montmorillonite and branched polyethyleneimine were mixed, stirred, washed, and dried to obtain a montmorillonite composite material.

[0072] S3) 4-Carboxyphenylboronic acid, acetone, anhydrous sodium sulfate, hydroxypropyl β-cyclodextrin, lauroyl arginine ethyl ester hydrochloride and N-hydroxysuccinimide are mixed and stirred, and then the montmorillonite composite material described in step S2) is added, heated and stirred, and then cooled, filtered, washed and dried to obtain modified montmorillonite.

[0073] The method for preparing modified montmorillonite according to the present invention first involves mixing montmorillonite and sodium carbonate solution, stirring, filtering, washing, and drying to obtain sodium-based montmorillonite.

[0074] The montmorillonite used in this invention is preferably montmorillonite powder, which can be purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; preferably, it has passed through a 200-mesh sieve.

[0075] In step S1), the concentration of the sodium carbonate solution is 0.5 wt%; the stirring temperature is 50–60°C for 4–5 hours; preferably, the stirring temperature is 60°C for 5 hours; the drying is specifically performed at 60°C under reduced pressure for 12 hours; the weight ratio of montmorillonite to the sodium carbonate aqueous solution is (20–5):1. Preferably, the weight ratio of montmorillonite to the sodium carbonate aqueous solution is (15–7):1; more preferably, the weight ratio of montmorillonite to the sodium carbonate aqueous solution is 12:1.

[0076] The washing method described in this invention is preferably to wash five times with purified water and once with anhydrous ethanol.

[0077] Sodium-based montmorillonite and branched polyethyleneimine were mixed, stirred, washed, and dried to obtain a montmorillonite composite material.

[0078] The preferred concentration of branched polyethyleneimine in this invention is 50 wt%; it can be purchased from Shanghai Yuanye Biotechnology Co., Ltd. The mixture is stirred at room temperature for 24 hours; after stirring, it is filtered, the solid is collected, and washed three times with ultrapure water; the drying process is carried out at 40°C under reduced pressure for 12 hours.

[0079] According to the present invention, the preferred mass ratio of sodium montmorillonite and branched polyethyleneimine is 5g:0.5mL.

[0080] 4-Carboxyphenylboronic acid, acetone, anhydrous sodium sulfate, hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride and N-hydroxysuccinimide are mixed and stirred, and then the montmorillonite composite material described in step S2) is added and heated and stirred. After cooling, filtering, washing and drying, modified montmorillonite is obtained.

[0081] In one preferred embodiment of the present invention, after 4-carboxyphenylboronic acid and acetone are dissolved by stirring, anhydrous sodium sulfate is added and stirred for 0.5 h, then hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride and N-hydroxysuccinimide are added, stirred at room temperature for 2 h, then montmorillonite composite material is added, heated and stirred at 60°C for 5 h, then cooled to room temperature, filtered, washed 1 to 3 times with anhydrous ethanol, and dried under reduced pressure at 40°C for 24 h to obtain modified montmorillonite.

[0082] As a preferred technical solution, in the preparation method of the modified montmorillonite, the weight ratio of the montmorillonite powder to the sodium carbonate aqueous solution is (20-5):1; preferably, the weight ratio of the montmorillonite to the sodium carbonate aqueous solution is (15-7):1; more preferably, the weight ratio of the montmorillonite to the sodium carbonate aqueous solution is 12:1.

[0083] As a preferred technical solution, in the preparation method of the modified montmorillonite, the weight ratio of the montmorillonite composite material to the 4-carboxyphenylboronic acid, the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl hydrochloride, and the N-hydroxysuccinimide is 1:(1-3):(1-5):(3-10); preferably, the weight ratio of the montmorillonite composite material to the 4-carboxyphenylboronic acid, the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl hydrochloride, and the N-hydroxysuccinimide is 1:(1-2):(2-4):(4-7); more preferably, the weight ratio of the montmorillonite composite material to the 4-carboxyphenylboronic acid, the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl hydrochloride, and the N-hydroxysuccinimide is 1:1.5:3:6.

[0084] According to the present invention, the preparation method of the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride is as follows:

[0085] Hydroxypropyl-β-cyclodextrin and lauroyl arginine ethyl ester hydrochloride were stirred and reacted, refrigerated overnight, and then freeze-dried to obtain solid hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride.

[0086] In some preferred embodiments, the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride can be prepared by the following method:

[0087] 3% w / v hydroxypropyl-β-cyclodextrin powder (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) was added to pure water and magnetically stirred at 700 rpm at room temperature until completely dissolved. Then, 1% w / v lauroyl arginine ethyl hydrochloride powder (purchased from Beijing Huawi Ruike Chemical Co., Ltd.) was added (the molar ratio of hydroxypropyl-β-cyclodextrin to lauroyl arginine ethyl hydrochloride was 1:1). The reaction was carried out by magnetic stirring at 60℃ and 700 rpm for 5 h to obtain a hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride solution. After being refrigerated at -20℃ overnight, it was freeze-dried at -80℃ for 48 h to obtain solid hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride.

[0088] The montmorillonite composite material (phenylboronic acid functionalized polyethyleneimine intercalated montmorillonite) of the present invention not only retains the original layered structure of montmorillonite, but also expands the interlayer space of montmorillonite after intercalation and amidation reactions, which is beneficial to the diffusion of flue gas.

[0089] Compared with montmorillonite, modified montmorillonite has thickened and curled fault edges, reduced specific surface area, increased average pore size, and abundant hydroxyl and carboxyl groups. Therefore, it can be adsorbed through the superposition of electrostatic forces, hydrogen bonds, and π-π bonds, and thus achieve rapid adsorption of flue gas through multiple synergistic effects.

[0090] The porous nature of modified montmorillonite ensures adequate adsorption capacity for hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride. Hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride possesses abundant hydroxyl groups and exhibits Lewis acid activity; therefore, modified montmorillonite exhibits a combined adsorption capacity for alkaline and acidic substances in cigarette smoke.

[0091] This invention provides a method for preparing the filling material for adsorbing flue gas as described in any one of the above technical solutions, comprising:

[0092] The modified plant fiber, adsorbent substrate, adhesive, and water are thoroughly mixed and granulated to obtain the final product.

[0093] The present invention does not limit the specific operation of the mixing and granulation, which is well known to those skilled in the art.

[0094] The present invention provides a cigarette filter, comprising the filling material described in any one of the above technical solutions.

[0095] The filling amount of the above-mentioned filling material is 10-15 wt% of the total mass of the filter rod.

[0096] Applying the filling material of this invention to the preparation of cigarette filters can effectively adsorb cigarette smoke and reduce the content of harmful substances in cigarette smoke.

[0097] The present invention provides a cigarette, including the cigarette filter described in the above technical solution.

[0098] The present invention modifies the internal structure of plant fibers to construct a three-dimensional network structure, which allows modified montmorillonite to be embedded in the pores of different sizes in the three-dimensional network structure, thereby fixing the modified montmorillonite.

[0099] A montmorillonite composite material (phenylboronic acid functionalized polyethyleneimine intercalated montmorillonite) was successfully synthesized through intercalation and amidation. This material retains the original layered structure of montmorillonite while expanding the interlayer space, which is beneficial for flue gas diffusion.

[0100] Modified montmorillonite adsorbs flue gas through the superposition of electrostatic forces, hydrogen bonds, and π-π bonds, thereby achieving rapid adsorption through multiple synergistic effects.

[0101] Hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride has abundant hydroxyl groups and Lewis acid activity. Therefore, modified montmorillonite has a combined adsorption effect on alkaline and acidic substances in cigarette smoke.

[0102] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a filling material for absorbing smoke, its preparation method, and a cigarette provided by the present invention.

[0103] Examples 1-5

[0104] Prepare all raw materials according to the formula, which is shown in Table 1.

[0105] A method for preparing a filling material for effectively adsorbing flue gas includes the following steps:

[0106] The modified plant fiber, adsorbent substrate, binder and water are thoroughly mixed according to the weight parts, and granulated to obtain the filling material for effectively adsorbing flue gas.

[0107] The method for preparing the modified plant fiber is as follows:

[0108] (1) Add ramie fiber to a 3 wt% sodium hydroxide aqueous solution and mechanically stir at 1000 r / min for 30 h. After washing repeatedly with deionized water until neutral, add it to a 75 wt% concentrated sulfuric acid aqueous solution and continue stirring in a 55℃ water bath for 40 min. Then wash repeatedly with ultrapure water until neutral to obtain hollow ramie fiber.

[0109] (2) Add the kapok fiber to a 3 wt% sodium hydroxide solution and mechanically stir at 1000 r / min for 30 h. After washing repeatedly with deionized water until neutral, add it to a 75 wt% concentrated sulfuric acid solution and continue stirring in a 55℃ water bath for 40 min. Then wash repeatedly with ultrapure water until neutral to obtain hollow kapok fiber.

[0110] (3) While stirring continuously at 100 r / min, 40 g of sodium oleate was dissolved in 500 mL of deionized water, and 150 mL of calcium chloride aqueous solution with a concentration of 2.6 wt% was added to form a suspension. Then, 160 mL of sodium dihydrogen phosphate aqueous solution with a concentration of 3.6 wt% was added and mixed to obtain a reaction solution. Hollow ramie fiber and hollow kapok fiber were added to the reaction solution according to a solid-liquid ratio of 1 g: 18 mL. After mixing, the solution was sealed and placed in a high-pressure reactor. The reaction was heated at 200 °C for 30 h. After the reaction was completed, the product was repeatedly washed with ethanol and deionized water and dried to obtain modified plant fiber.

[0111] The modified montmorillonite is prepared as follows:

[0112] (1) Montmorillonite powder (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) was passed through a 200-mesh sieve, and sodium carbonate aqueous solution (concentration 0.5wt%) was added. The mixture was stirred at 60℃ for 5 hours, cooled to room temperature, filtered, washed 5 times with purified water, washed once with anhydrous ethanol, and dried under reduced pressure at 60℃ for 12 hours to obtain sodium-based montmorillonite. The weight ratio of montmorillonite to sodium carbonate aqueous solution was 12:1.

[0113] (2) Add 5.0g of sodium montmorillonite to a reaction flask, add 50mL of purified water, add 0.5mL of branched polyethyleneimine (concentration 50wt%, purchased from Shanghai Yuanye Biotechnology Co., Ltd.), stir at room temperature for 24h, filter, collect the solid, wash 3 times with ultrapure water, and dry under reduced pressure at 40℃ for 12h to obtain montmorillonite composite material.

[0114] (3) Add 0.3g of 4-carboxyphenylboronic acid and 50mL of acetone to the reaction flask, stir to dissolve, add 3g of anhydrous sodium sulfate, stir for 0.5h, then add hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride and N-hydroxysuccinimide, stir at room temperature for 2h, add the montmorillonite composite material obtained in step (2), stir at 60℃ for 5h, cool to room temperature, filter, collect the solid, wash 3 times with anhydrous ethanol, dry under reduced pressure at 40℃ for 24h to obtain the modified montmorillonite. The weight ratio of the montmorillonite composite material to the 4-carboxyphenylboronic acid, the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride and the N-hydroxysuccinimide is 1:1.5:3:6.

[0115] Table 1. Specific formulations and dosages for Examples 1-5 (unit: g)

[0116] Example 1 Example 2 Example 3 Example 4 Example 5 Modified plant fibers 50 40 50 50 50 Adsorption substrate 20 30 20 20 20 adhesives 2 2 2 2 2 water 60 60 60 60 60

[0117] The adhesive is sodium alginate and hydroxyethyl cellulose; the weight ratio of sodium alginate to hydroxyethyl cellulose in the adhesive is 1:1.

[0118] The difference between Example 3 and Example 1 is that the weight ratio of hollow ramie fiber to hollow kapok fiber in the preparation method of the modified plant fiber is 0.2:1.

[0119] The difference between Example 4 and Example 1 is that the weight ratio of the montmorillonite composite material to the 4-carboxyphenylboronic acid, the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride, and the N-hydroxysuccinimide is 1:1:2:4.

[0120] The difference between Example 5 and Example 1 is that the weight ratio of the montmorillonite composite material to the 4-carboxyphenylboronic acid, the hydroxypropyl β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride, and the N-hydroxysuccinimide is 1:2:4:7.

[0121] The present invention also provides comparative examples.

[0122] Comparative Example 1

[0123] Referring to Example 1, kapok fiber was used to replace the modified plant fiber.

[0124] Comparative Example 2

[0125] Referring to Example 1, ramie fiber was used to replace the modified plant fiber.

[0126] Comparative Example 3

[0127] Referring to Example 1, the adsorption substrate was montmorillonite (passed through a 200-mesh sieve).

[0128] Comparative Example 4

[0129] Referring to Example 1, the adsorption substrate is montmorillonite composite material (prepared in step (2) of the preparation method of the modified montmorillonite);

[0130] Comparative Example 5

[0131] Referring to Example 1, kapok fiber was used instead of modified plant fiber, and montmorillonite (passed through a 200-mesh sieve) was used as the adsorption substrate.

[0132] Comparative Example 6

[0133] Referring to Example 1, the modified montmorillonite was modified by replacing hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride with hydroxypropyl-β-cyclodextrin / quaternary ammonium salt.

[0134] Performance testing

[0135] The filling materials obtained in Examples 1-5 and Comparative Examples 1-5 were placed on a smoking machine at a filling amount of 10% wt. Cigarette smoking experiments were conducted on the smoking machine under standard smoking conditions. Seven harmful components—CO, HCN, NNK, NH3, B[a]P, phenol, and crotonaldehyde—in the cigarette smoke samples were captured and measured according to relevant tobacco industry standard methods. The test methods are as follows:

[0136] GB / T23356-2009 Determination of Carbon Monoxide in Gas Phase of Cigarette Smoke - Non-scattering Infrared Method;

[0137] YC / T253-2019 Determination of Hydrogen Cyanide in Mainstream Cigarette Smoke - Continuous Flow Method

[0138] GB / T23228-2008 Determination of Tobacco-Specific N-Nitrosamines in Total Particulate Matter of Mainstream Cigarette Smoke - Gas Chromatography-Thermal Analysis

[0139] YC / T377-2019 Determination of Ammonia in Mainstream Cigarette Smoke - Impregnated Cambridge Filter Collection - Ion Chromatography

[0140] GB / T 21130-2007 Determination of Benzo[a]pyrene in Total Particulate Matter of Cigarette Smoke

[0141] YC / T255-2008 Determination of Major Phenolic Compounds in Mainstream Cigarette Smoke by High Performance Liquid Chromatography

[0142] YC / T254-2008 Determination of Major Carbonyl Compounds in Mainstream Cigarette Smoke by High Performance Liquid Chromatography

[0143] The results are shown in Table 2 below:

[0144] Table 2. Results of Sample Adsorption Test

[0145]

[0146]

[0147] 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 filler material for adsorbing flue gas, characterized by, Comprise the following components by weight: Modified plant fiber 10~80 parts, adsorption base material 1~50 parts, adhesive 0.1~5 parts; The plant fiber comprises one or more of flax fiber, ramie fiber, mulberry fiber, coconut shell fiber or kapok fiber; The adsorption base material is modified montmorillonite; The preparation method of the modified montmorillonite is specifically: S1) Mix montmorillonite and sodium carbonate solution, stir, filter, wash, dry, and obtain sodium-based montmorillonite; S2) Mix sodium-based montmorillonite and branched polyethyleneimine, stir, wash, and dry to obtain a montmorillonite composite material; S3) Mix 4-carboxyphenylboronic acid, acetone, anhydrous sodium sulfate, hydroxypropyl β-cyclodextrin, lauroyl arginine ethyl ester hydrochloride, and N-hydroxysuccinimide, and then add the montmorillonite composite material of step S2) to stir and heat, and then cool, filter, wash, and dry to obtain modified montmorillonite.

2. The material of claim 1, wherein, The filling material comprises the following components by weight: Modified plant fiber 20~60 parts, adsorption base material 5~30 parts, adhesive 0.5~3 parts; The adhesive is selected from one or more of starch, dextrin, sucrose, gelatin, sodium alginate, polyvinylpyrrolidone, polyethylene glycol, sodium carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, or hydroxyethyl cellulose.

3. The material of claim 1, wherein The preparation method of the modified plant fiber is specifically: a) Mix plant fiber and 3wt% sodium hydroxide, stir at a rotation speed of 800~1000r / min for 24~30h, wash with deionized water until neutral, then add a 70~80wt% concentrated sulfuric acid aqueous solution, continue to stir at 50~60℃ water bath for 35~45min, and then repeatedly wash with ultrapure water until neutral to obtain hollow plant fiber; b) Mix sodium oleate and 2wt%~3wt% calcium chloride aqueous solution to obtain a suspension; then add 3wt%~4wt% sodium dihydrogen phosphate aqueous solution to obtain a reaction solution; c) Add the hollow plant fiber to the reaction solution, mix, heat and react, wash after reaction, and dry to obtain the modified plant fiber.

4. The material of claim 3, wherein, The modified plant fiber is ramie fiber and kapok fiber; the weight ratio of the ramie fiber to the kapok fiber is (0.1~1):1; The temperature of the heating reaction in step c) is 200℃, and the time is 30h; The mass-volume ratio of the hollow plant fiber to the reaction solution is 1g:18mL.

5. The material of claim 1, wherein The concentration of the sodium carbonate solution in step S1) is 0.5wt%; the stirring temperature is 50~60℃, and the time is 4~5h; the drying is specifically 60℃ reduced pressure drying for 12h; and the weight ratio of montmorillonite to the sodium carbonate solution is (20~5):1; The concentration of the branched polyethyleneimine in step S2) is 50wt%; the stirring time is 24h; and the drying is 40℃ reduced pressure drying for 12h.

6. The material of claim 1, wherein The weight ratio of the montmorillonite composite material to the 4-carboxyphenylboronic acid, the hydroxypropyl β-cyclodextrin / lauromycin arginine ethyl ester hydrochloride, and the N-hydroxysuccinimide in step S3) is 1:(1~3):(1~5):(3~10). The preparation method of the hydroxypropyl beta-cyclodextrin / lauric arginine ethyl ester hydrochloride is specifically as follows: Hydroxypropyl beta-cyclodextrin and lauric arginine ethyl ester hydrochloride are stirred and reacted, refrigerated overnight, and freeze-dried to obtain solid hydroxypropyl-beta-cyclodextrin / lauric arginine ethyl ester hydrochloride.

7. A method of producing the filler material for adsorbing flue gas according to any one of claims 1 to 6, characterized by, The application relates to a modified plant fiber adsorption material and a preparation method thereof. The modified plant fiber, the adsorption substrate, the adhesive and water are sufficiently mixed and granulated to obtain the modified plant fiber adsorption material.

8. A cigarette filter, characterized by, The application relates to a filling material, and the filling material comprises the modified plant fiber adsorption material.

9. A cigarette, characterized by The application relates to a cigarette filter, and the cigarette filter comprises the filling material.

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