A paper stick filling material for effectively absorbing phenolic substances, a preparation method thereof, and an application thereof

Abstract

The application provides an adsorbing base material, which is a polycationic material loaded on a tobacco stem-based activated carbon after ZnCl2 activation, and the polycationic material is hydroxypropyl-beta-cyclodextrin and lauroyl arginine ethyl ester hydrochloride. The modified activated carbon has a common adsorption effect on basic substances and acidic substances in cigarette smoke. When the filling material in the application is applied to the preparation of a cigarette filter, the content of phenolic harmful substances in cigarette smoke can be selectively reduced.

Description

Technical Field

[0001] This invention belongs to the field of cigarette technology, specifically relating to a paper rod filling material for effectively absorbing phenolic substances, its preparation method, and its application. Background Technology

[0002] The smoke released when tobacco burns contains approximately 7,000 known chemicals, and nearly 10,000 compounds that have not been accurately identified, including carcinogens and suspected carcinogens present in approximately 0.2% (about 60 types).

[0003] Phenolic compounds are a major harmful substance in cigarette smoke. They can enter the body through the skin, mucous membranes, respiratory tract, and digestive tract, reacting chemically with proteins in the cytoplasm of cells, causing cumulative chronic poisoning or acute poisoning leading to coma and death. Phenol is the most toxic of these compounds, and therefore it is listed as one of the indicator compounds of harmful substances in cigarette smoke, requiring monitoring and control.

[0004] Adsorption filtration is a widely studied technique 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 results are not very significant and it cannot achieve the requirement of highly selectively reducing single harmful components in cigarette smoke.

[0005] In order to reduce the phenolic content in cigarette smoke, there is an urgent need to provide filling materials that can selectively reduce the phenolic content in cigarette smoke, thereby reducing harm to smokers without affecting the taste of cigarettes. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a paper rod filling material for effectively absorbing phenolic substances, a method for preparing the same, and its application. The paper rod filling material provided by the present invention can effectively adsorb phenolic substances.

[0007] The present invention provides an adsorption substrate, wherein the adsorption substrate is a polycationic material supported on ZnCl2-activated tobacco stem-based activated carbon, and the polycationic material is hydroxypropyl-β-cyclodextrin and lauroyl arginine ethyl ester hydrochloride.

[0008] The present invention also provides a method for preparing the above-mentioned adsorbent substrate, comprising the following steps:

[0009] A) Hydroxypropyl-β-cyclodextrin, lauroyl arginine ethyl ester hydrochloride were mixed with water and then dried to obtain hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride.

[0010] B) ZnCl2-activated tobacco stem-based activated carbon was mixed with sodium alginate aqueous solution and then dried to obtain a complex of sodium alginate and activated carbon.

[0011] C) Hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride was dissolved in water and then mixed with a complex of sodium alginate and activated carbon, and then dried to obtain the adsorption substrate.

[0012] Preferably, in step A), the mass ratio of hydroxypropyl-β-cyclodextrin to lauroyl arginine ethyl ester hydrochloride is 0.9–1.1:1;

[0013] The drying process is freeze drying, and the freeze drying temperature is -70℃ to -90℃.

[0014] Preferably, the preparation method of the ZnCl2-activated tobacco stem-based activated carbon includes the following steps:

[0015] 1) The tobacco stem powder was soaked in ZnCl2 aqueous solution and then filtered to activate it, thus obtaining activated tobacco stems;

[0016] 2) The activated tobacco stems were cooled under anaerobic conditions, ground, soaked in hydrochloric acid aqueous solution, and then ultrasonicated with ultrapure water. After filtration, washing and drying, ZnCl2-activated tobacco stem-based activated carbon was obtained.

[0017] Preferably, in step 1), the mass concentration of the ZnCl2 aqueous solution is 35% to 45%, the mass ratio of the tobacco stem powder to the ZnCl2 aqueous solution is 1:2.7 to 3.3, and the soaking time is 5 to 7 hours.

[0018] The activation is carried out under a nitrogen atmosphere at a temperature of 450–550°C for 1.5–2.5 h and a nitrogen flow rate of 225–275 mL / min.

[0019] In step 2), the mass fraction of the hydrochloric acid aqueous solution is 9-11%, the soaking time is 2-4 hours, the ultrasonic time is 0.5-1.5 hours, the washing is performed by rinsing with ultrapure water at 55-65°C until the pH is 7, and the drying temperature is 100-120°C for 10-14 hours.

[0020] Preferably, the weight ratio of the hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride, the sodium alginate, and the ZnCl2-activated tobacco stem-based activated carbon is (0.1-1):(0.1-1):1.

[0021] The present invention also provides a paper rod filling material for effectively absorbing phenolic substances, comprising:

[0022] 10-80 parts modified plant fiber, 5-60 parts adsorbent substrate, and 1-10 parts auxiliary materials.

[0023] Preferably, the modified plant fiber is prepared according to the following method:

[0024] A suspension is obtained by mixing sodium oleate, calcium chloride and water;

[0025] The suspension was mixed with an aqueous solution of sodium dihydrogen phosphate and reacted to obtain a reaction solution.

[0026] The reaction solution was mixed with hollow plant fibers and heated under sealed conditions to obtain modified plant fibers.

[0027] The adsorption substrate is selected from one or more of the following: modified tobacco stem-based activated carbon, diatomaceous earth, silica gel, activated carbon, macroporous adsorption resin, molecular sieve, zeolite, and sepiolite; preferably, the adsorption substrate is the adsorption substrate according to claim 1.

[0028] The excipient is selected from one or more of sodium carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose ether, gum arabic, gum arabic, gum arabic, gum arabic, gum arabic, gum arabic, guar gum, xanthan gum, agar, agarose, or carrageenan; preferably, the excipient is hydroxyethyl cellulose.

[0029] The present invention also provides a method for preparing the above-mentioned paper rod filling material, comprising the following steps:

[0030] The modified plant fiber, adsorbent substrate, auxiliary materials and water are thoroughly mixed and granulated to obtain the paper rod filling material for effectively absorbing phenolic substances.

[0031] The present invention also provides a cigarette comprising the above-described adsorbent substrate or the above-described paper rod filling material.

[0032] Compared with the prior art, the present invention provides an adsorption substrate, wherein the adsorption substrate is a polycationic material supported on tobacco stem-based activated carbon after ZnCl2 activation, and the polycationic material is hydroxypropyl-β-cyclodextrin and lauroyl arginine ethyl ester hydrochloride. In the present invention, the Zn in the ZnCl2 solution... 2+ It has an 18-electron configuration, a strong effective charge, and contains empty orbitals 4S4P, while Cl... -ZnCl2 readily becomes an electron pair donor, thus possessing both excellent donor and acceptor centers. It can simultaneously remove hydrogen and oxygen from cellulose. The entire cellulose dissolution process is essentially a dehydration process. After dissolution, the cellulose undergoes high-temperature dehydration, adjusting the pore structure of the activated carbon. Cigarette smoke aerosols consist of three phases: gas, liquid, and solid. Harmful substances in the smoke are distributed across these three phases, with the same substance potentially distributed across aerosol particles of different sizes. The pore structure of activated carbon significantly impacts the filtration efficiency of the particulate phase and also affects its adsorption of harmful components in cigarette smoke. Therefore, activated carbon with a rich pore structure is more suitable for adsorbing phenolic substances in cigarette smoke. Furthermore, the porous adsorption capacity of the ZnCl2-activated tobacco stem-based activated carbon ensures adequate loading of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride. Hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride has abundant hydroxyl groups and also exhibits Lewis acid activity. Therefore, the modified activated carbon has a combined adsorption effect on alkaline and acidic substances in cigarette smoke. Applying the filling material of this invention to the preparation of cigarette filters can selectively reduce the content of harmful phenolic substances in cigarette smoke. Detailed Implementation

[0033] The present invention provides an adsorption substrate, wherein the adsorption substrate is a polycationic material supported on ZnCl2-activated tobacco stem-based activated carbon, and the polycationic material is hydroxypropyl-β-cyclodextrin and lauroyl arginine ethyl ester hydrochloride.

[0034] In this invention, the method for preparing the adsorption substrate includes the following steps:

[0035] A) Hydroxypropyl-β-cyclodextrin, lauroyl arginine ethyl ester hydrochloride were mixed with water and then dried to obtain hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride.

[0036] B) ZnCl2-activated tobacco stem-based activated carbon was mixed with sodium alginate aqueous solution and then dried to obtain a complex of sodium alginate and activated carbon.

[0037] C) Hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride was dissolved in water and then mixed with a complex of sodium alginate and activated carbon, and then dried to obtain the adsorption substrate.

[0038] Specifically, in this invention, hydroxypropyl-β-cyclodextrin is mixed with pure water and dissolved by stirring at room temperature. Then, lauroyl arginine ethyl hydrochloride is added, and the mixture is heated under stirring to obtain a hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride solution. The mass ratio of hydroxypropyl-β-cyclodextrin to lauroyl arginine ethyl hydrochloride is 0.9–1.1:1, which can be 0.9:1, 1:1, 1.1:1, or any value between 0.9 and 1.1:1, preferably 1:1. The heating reaction temperature is 55–65°C, preferably 60°C, and the time is 4–6 hours, preferably 5 hours.

[0039] Next, the obtained hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride solution is frozen at -20°C and then freeze-dried to obtain solid hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride. The freeze-drying temperature is -70°C to -90°C, preferably -80°C.

[0040] The present invention further describes the process of mixing ZnCl2-activated tobacco stem-based activated carbon with an aqueous solution of sodium alginate and then drying the mixture to obtain a complex of sodium alginate and activated carbon.

[0041] The preparation method of the ZnCl2-activated tobacco stem-based activated carbon includes the following steps:

[0042] 1) The tobacco stem powder was soaked in ZnCl2 aqueous solution and then filtered to activate it, thus obtaining activated tobacco stems;

[0043] 2) The activated tobacco stems were cooled under anaerobic conditions, ground, soaked in hydrochloric acid aqueous solution, and then ultrasonicated with ultrapure water. After filtration, washing and drying, ZnCl2-activated tobacco stem-based activated carbon was obtained.

[0044] Specifically, in step 1), the mass concentration of the ZnCl2 aqueous solution is 35% to 45%, which can be any value between 35%, 40%, 45%, or 35% to 45%, preferably 40%. The mass ratio of the tobacco stem powder to the ZnCl2 aqueous solution is 1:2.7 to 3.3, which can be any value between 1:2.7, 1:2.8, 1:2.9, 1:3, 1:3.2, 1:3.3, or 1:2.7 to 3.3, preferably 1:3. The soaking time is 5 to 7 hours, preferably 6 hours.

[0045] The activation is carried out under a nitrogen atmosphere. The activation temperature is 450-550℃, which can be 450, 500, 550, or any value between 450 and 550℃, preferably 500℃. The activation time is 1.5-2.5h, preferably 2h. The nitrogen flow rate is 225-275mL / min, preferably 250mL / min.

[0046] In step 2), the mass fraction of the hydrochloric acid aqueous solution is 9-11%, preferably 10%; the soaking time is 2-4 hours, preferably 3 hours; the ultrasonication time is 0.5-1.5 hours, preferably 1 hour; the washing is performed with ultrapure water at 55-65°C, preferably 60°C, until the pH reaches 7; the drying temperature is 100-120°C, preferably 110°C, and the drying time is 10-14 hours, preferably 12 hours.

[0047] After obtaining ZnCl2-activated tobacco stem-based activated carbon, the ZnCl2-activated tobacco stem-based activated carbon was mixed and stirred with sodium alginate aqueous solution, then allowed to stand at low temperature, filtered and dried to obtain a complex of sodium alginate and activated carbon.

[0048] The temperature for the low-temperature settling is 12-18°C, preferably 13-17°C, and more preferably 15°C, and the time is 1.5-2.5 hours, preferably 2 hours.

[0049] Finally, hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride was dissolved in water, then mixed and stirred with the sodium alginate and activated carbon complex, and dried to obtain the adsorption substrate.

[0050] Specifically, the stirring time is 24 hours, and after stirring, the mixture is left to stand at 14-16°C, preferably 15°C, for 1.5-2.5 hours, preferably 2 hours. After filtration, the mixture is dried to obtain the adsorbent substrate. The drying temperature is 55-65°C, preferably 60°C, and the drying time is 66-78 hours, preferably 72 hours.

[0051] The weight ratio of the hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride, the sodium alginate, and the ZnCl2-activated tobacco stem-based activated carbon is (0.1-1):(0.1-1):1. Preferably, the weight ratio of the hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride, the sodium alginate, and the ZnCl2-activated tobacco stem-based activated carbon in the modified tobacco stem-based activated carbon is (0.2-0.5):(0.2-0.5):1; more preferably, the weight ratio of the hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride, the sodium alginate, and the ZnCl2-activated tobacco stem-based activated carbon in the modified tobacco stem-based activated carbon is 0.3:0.2:1.

[0052] The present invention also provides a paper rod filling material for effectively absorbing phenolic substances, comprising:

[0053] 10-80 parts modified plant fiber, 5-60 parts adsorbent substrate, and 1-10 parts auxiliary materials.

[0054] The paper rod filling material for effectively absorbing phenolic substances provided by this invention comprises 10-80 parts of modified plant fiber, which can be any value between 10, 20, 30, 40, 50, 60, 70, 80, or 10-80 parts. The modified plant fiber is obtained by first treating plant fibers with acid and alkali, and then depositing ultralong nanowires on its surface using a solvothermal method.

[0055] As a preferred technical solution, the plant fiber is kapok fiber.

[0056] In this invention, the modified plant fiber is preferably prepared according to the following method:

[0057] A suspension is obtained by mixing sodium oleate, calcium chloride and water;

[0058] The suspension was mixed with an aqueous solution of sodium dihydrogen phosphate to obtain a reaction solution;

[0059] The reaction solution was mixed with hollow plant fibers and heated under sealed conditions to obtain modified plant fibers.

[0060] Specifically, under stirring conditions, sodium oleate is mixed with deionized water, and then an aqueous solution of calcium chloride is added to form a suspension. The mass-to-volume ratio of sodium oleate to deionized water is 35-50 g:500 ml, which can be any value between 35 g:500 ml, 40 g:500 ml, 50 g:500 ml, or 35-50 g:500 ml. The volume ratio of deionized water to the aqueous solution of calcium chloride is 500:130-170, which can be any value between 500:130, 500:140, 500:150, 500:160, 500:170, or 500:130-170. The concentration of the aqueous solution of calcium chloride is 2.4-2.8 wt%, which can be any value between 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, or 2.4-2.8 wt%.

[0061] Then, the suspension is mixed with an aqueous solution of sodium dihydrogen phosphate to obtain a reaction solution. The concentration of the sodium dihydrogen phosphate aqueous solution is 3.6 wt%, but can be any value between 3.2 wt% and 4.0 wt%, specifically 3.2 wt%, 3.4 wt%, 3.6 wt%, 3.8 wt%, 4.0 wt%, or any value between 3.2 wt% and 4.0 wt%. The volume ratio of the sodium dihydrogen phosphate aqueous solution to the calcium chloride aqueous solution is 150–170:150, and can be any value between 150:150, 160:150, 170:150, or any value between 150:170:150.

[0062] Next, the reaction solution is mixed with hollow plant fibers and heated under sealed conditions to obtain modified plant fibers.

[0063] The hollow plant fiber is prepared according to the following method:

[0064] Plant fibers are mixed and stirred with sodium hydroxide solution, then washed with deionized water until neutral, and then concentrated sulfuric acid with a concentration of 70-80 wt%, preferably 75 wt%, is added. The reaction is carried out under water bath conditions of 50-60°C, and then washed with ultrapure water until neutral to obtain hollow plant fibers.

[0065] The hollow plant fibers are heated to react with the reaction solution at a temperature of 180–220°C, preferably 200°C, for a time of 27–33 h, preferably 30 h. After the reaction is complete, the product is repeatedly washed with ethanol and deionized water, and then dried to obtain the modified plant fibers.

[0066] In this invention, plant fibers are treated with acid and alkali to remove impurities, resulting in hollow tubular plant fibers. Then, using the hollow plant fibers as a matrix, ultra-long nanowires are deposited on the hollow plant fibers using a calcium oleate precursor solvothermal method. Some of the deposited ultra-long nanowires enter the hollow tubes of the hollow plant fibers and overlap to form a network structure, thus constructing a three-dimensional network structure inside the hollow plant fibers. Modified tobacco stem-based activated carbon (adsorbent substrate) can be embedded in the large pores of the three-dimensional network structure, thereby fixing the modified tobacco stem-based activated carbon and forming a structurally stable filling material.

[0067] The paper rod filling material for effectively absorbing phenolic substances provided by this invention further includes 5-60 parts of an adsorption substrate, which can be any value between 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 5-60 parts. The adsorption substrate is selected from one or more of modified tobacco stem-based activated carbon, diatomaceous earth, silica gel, activated carbon, macroporous adsorption resin, molecular sieve, zeolite, and sepiolite; preferably, the adsorption substrate is one of the above-mentioned adsorption substrates, namely modified tobacco stem-based activated carbon.

[0068] The paper stick filling material for effectively absorbing phenolic substances provided by the present invention further includes 1-10 parts of excipients, which can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any value between 1 and 10 parts. The excipients are selected from one or more of sodium carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose ether, gum arabic, gum arabic, gum arabic, gum arabic, gum guaiac, gum guaiac, guar gum, xanthan gum, agar, agarose, or carrageenan; preferably, the excipient is hydroxyethyl cellulose.

[0069] As a preferred technical solution, the raw materials of the paper rod filling material include at least the following components: 20-50 parts of modified plant fiber, 10-40 parts of adsorbent substrate, and 1-5 parts of auxiliary materials.

[0070] As a preferred technical solution, the raw materials of the paper rod filling material include the following components: 45 parts of modified plant fiber, 23 parts of adsorbent substrate, and 3 parts of auxiliary materials.

[0071] The present invention also provides a method for preparing the above-mentioned paper rod filling material, comprising the following steps:

[0072] The modified plant fiber, adsorbent substrate, auxiliary materials and water are thoroughly mixed and granulated to obtain the paper rod filling material for effectively absorbing phenolic substances.

[0073] The present invention also provides a cigarette comprising the above-mentioned adsorbent substrate (modified tobacco stem-based activated carbon) or the above-mentioned paper rod filling material. The paper rod filling material, when used in the preparation of cigarette filters, can selectively reduce the content of harmful phenolic substances in cigarette smoke.

[0074] The modified plant fiber selected in this invention has an internal three-dimensional network structure, which allows the modified tobacco stem-based activated carbon to be embedded in the large pores of the three-dimensional network structure, thereby fixing the modified tobacco stem-based activated carbon.

[0075] ZnCl2 activation of tobacco stem-based activated carbon achieves pore structure adjustment, making the activated carbon with rich pore structure more suitable for adsorbing phenolic substances in cigarette smoke. At the same time, the porous adsorption capacity provides a guarantee for the loading of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride.

[0076] Hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride has abundant hydroxyl groups and also exhibits Lewis acid activity. Therefore, the modified activated carbon has a combined adsorption effect on alkaline and acidic substances in cigarette smoke.

[0077] The paper rod filling material provided by this invention can effectively adsorb phenolic substances.

[0078] To further understand the present invention, the following description, in conjunction with embodiments, illustrates the paper rod filling material for effectively absorbing phenolic substances provided by the present invention, its preparation method, and its application. The scope of protection of the present invention is not limited by the following embodiments.

[0079] Examples 1-5

[0080] Prepare all raw materials according to the formula, which is shown in Table 1.

[0081] The specific preparation method of the paper rod filling material for effectively absorbing phenolic substances is as follows:

[0082] Modified plant fiber, modified tobacco stem-based activated carbon, hydroxyethyl cellulose and water are thoroughly mixed according to the weight parts, and granulated to obtain the paper rod filling material for effectively absorbing phenolic substances.

[0083] The method for preparing the modified plant fiber is as follows:

[0084] (1) Add kapok fiber to a sodium hydroxide solution with a concentration of 3wt%, stir mechanically at 1000r / min for 30h, wash repeatedly with deionized water until neutral, then add it to concentrated sulfuric acid with a concentration of 75wt%, continue stirring in a water bath at 55℃ for 40min, and then wash repeatedly with ultrapure water until neutral to obtain hollow kapok fiber.

[0085] (2) Under continuous stirring 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 kapok fiber was added to the reaction solution according to a solid-liquid ratio of 1 g: 18 mL. After mixing, the mixture was sealed and placed in an autoclave. 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.

[0086] The modified tobacco stem-based activated carbon is prepared as follows:

[0087] (1) The clean tobacco stem raw material was crushed to 1-2 mm by a pulverizer and placed in an oven at 110℃ for 12 h. The tobacco stem powder was then soaked in a 40% ZnCl2 aqueous solution for 6 h with an impregnation ratio of 1:3 (the ratio of the mass of solid to the mass of liquid). The tobacco stem powder was filtered out and then placed in a tube furnace for activation at 500℃ in an N2 atmosphere with a N2 flow rate of 250 mL / min. The activated tobacco stem was cooled to room temperature under anaerobic conditions, ground, and then soaked in a 10% hydrochloric acid aqueous solution for 3 h. Ultrapure water was added and ultrasonicated for 1 h. Activated carbon was obtained by filtration and rinsed with 60℃ ultrapure water until the pH was about 7. The activated carbon was then placed in an oven at 110℃ for 12 h to obtain ZnCl2 activated tobacco stem-based activated carbon.

[0088] (2) 3% w / v hydroxypropyl-β-cyclodextrin (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) powder 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 (purchased from Beijing Huawi Ruike Chemical Co., Ltd.) powder was added (the molar ratio of hydroxypropyl-β-cyclodextrin / 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.

[0089] (3) Hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride was dissolved in water to prepare an aqueous solution of 0.2 mg / mL. ZnCl2-activated tobacco stem-based activated carbon was stirred with an aqueous solution of 10 mg / mL sodium alginate at room temperature for 1 h, allowed to stand at 15 °C for 2 h, filtered, and dried at 60 °C for 72 h. Then it was stirred with the aqueous solution of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride for 24 h, allowed to stand at 15 °C for 2 h, filtered, and dried at 60 °C for 72 h to obtain modified tobacco stem-based activated carbon.

[0090] Table 1. Specific formulations and dosages for Examples 1-5 (unit: g)

[0091] Example 1 Example 2 Example 3 Example 4 Example 5 Modified plant fibers 45 20 50 45 45 Adsorption substrate 23 48 18 23 23 auxiliary materials 3 3 3 3 3 water 60 60 60 60 60

[0092] In Examples 1-3, the weight ratio of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride to sodium alginate and ZnCl2-activated tobacco stem-based activated carbon in the modified tobacco stem-based activated carbon is 0.3:0.2:1; in Example 4, the weight ratio of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride to sodium alginate and ZnCl2-activated tobacco stem-based activated carbon in the modified tobacco stem-based activated carbon is 0.5:0.2:1; and in Example 5, the weight ratio of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl hydrochloride to sodium alginate and ZnCl2-activated tobacco stem-based activated carbon in the modified tobacco stem-based activated carbon is 0.2:0.5:1.

[0093] Comparative Example 1

[0094] Referring to Example 1, kapok fiber was used to replace the modified plant fiber.

[0095] Comparative Example 2

[0096] Referring to Example 1, the adsorption substrate was activated carbon based on tobacco stems after ZnCl2 activation.

[0097] Comparative Example 3

[0098] Referring to Example 1, the adsorption substrate is tobacco stem-based activated carbon.

[0099] Comparative Example 4

[0100] Referring to Example 1, kapok fiber was used to replace the modified plant fiber, and the adsorption substrate was ZnCl2-activated tobacco stem-based activated carbon.

[0101] Comparative Example 5

[0102] Referring to Example 1, kapok fiber was used to replace the modified plant fiber, and the adsorption substrate was tobacco stem-based activated carbon.

[0103] Comparative Example 6

[0104] Referring to Example 1, the polycationic material in the modified tobacco stem-based activated carbon is lauroyl arginine ethyl ester hydrochloride instead of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride.

[0105] Comparative Example 7

[0106] Referring to Example 1, the polycationic material in the modified tobacco stem-based activated carbon is hydroxypropyl-β-cyclodextrin instead of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride.

[0107] Comparative Example 8

[0108] Referring to Example 1, the polycationic material in the modified tobacco stem-based activated carbon is β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride instead of hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride. The β-cyclodextrin was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0109] Performance testing

[0110] The performance of the filler materials obtained in Examples 1-5 and Comparative Examples 1-8 was tested using the following methods:

[0111] The phenolic compounds in the sample cigarette smoke were determined and compared with those in commercially available cigarettes made from the same type of tobacco (using ordinary cellulose acetate filter rods of the same specifications). The phenolic compound content in the cigarette smoke was determined using a Cerulean SM450 smoking machine (Cerulean, UK) according to ISO 3308. The results are shown in Table 2.

[0112] Table 2. Performance test results of the filler materials obtained in Examples 1-5 and Comparative Examples 1-8

[0113]

[0114]

[0115] As shown in Table 2, the modified plant fiber in this invention has a three-dimensional network structure, which allows the modified tobacco stem-based activated carbon to be embedded in the large pores of the three-dimensional network structure, thus selectively reducing the content of harmful phenolic substances in cigarette smoke. The modified tobacco stem-based activated carbon has abundant hydroxyl groups, Lewis acid activity, and a rich pore structure, making it suitable for the efficient adsorption of phenolic substances in cigarette smoke.

[0116] 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 paper rod filling material for effectively absorbing phenolic substances, characterized in that, include: 10-80 parts modified plant fiber, 5-60 parts adsorbent substrate, and 1-10 parts auxiliary materials; The adsorption substrate is a polycationic material supported on tobacco stem-based activated carbon after ZnCl2 activation. The polycationic material is hydroxypropyl-β-cyclodextrin and lauroyl arginine ethyl ester hydrochloride, and the mass ratio of hydroxypropyl-β-cyclodextrin to lauroyl arginine ethyl ester hydrochloride is 0.9~1.1:

1. The method for preparing the adsorption substrate includes the following steps: A) Hydroxypropyl-β-cyclodextrin, lauroyl arginine ethyl ester hydrochloride were mixed with water and then dried to obtain hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride. B) ZnCl2-activated tobacco stem-based activated carbon was mixed with sodium alginate aqueous solution and then dried to obtain a complex of sodium alginate and activated carbon. C) Hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride was dissolved in water and then mixed with a complex of sodium alginate and activated carbon, stirred and dried to obtain an adsorption substrate; The weight ratio of the hydroxypropyl-β-cyclodextrin / lauroyl arginine ethyl ester hydrochloride, the sodium alginate, and the ZnCl2-activated tobacco stem-based activated carbon is (0.2-0.5):(0.2-0.5):

1. The modified plant fiber is prepared according to the following method: A suspension is obtained by mixing sodium oleate, calcium chloride and water; The suspension was mixed with an aqueous solution of sodium dihydrogen phosphate and reacted to obtain a reaction solution. The reaction solution was mixed with hollow plant fibers and heated under sealed conditions to obtain modified plant fibers. The phenolic substances include phenol, m-cresol, p-cresol, and o-cresol.

2. The paper rod filling material according to claim 1, characterized in that, In step A), the mass ratio of hydroxypropyl-β-cyclodextrin to lauroyl arginine ethyl ester hydrochloride is 0.9~1.1:1; The drying process is freeze drying, and the freeze drying temperature is -70℃ to -90℃.

3. The paper rod filling material according to claim 1, characterized in that, The preparation method of the ZnCl2-activated tobacco stem-based activated carbon includes the following steps: 1) The tobacco stem powder was soaked in ZnCl2 aqueous solution and then filtered to activate it, thus obtaining activated tobacco stems; 2) The activated tobacco stems were cooled under anaerobic conditions, ground, soaked in hydrochloric acid aqueous solution, and then ultrasonicated with ultrapure water. After filtration, washing and drying, ZnCl2-activated tobacco stem-based activated carbon was obtained.

4. The paper rod filling material according to claim 3, characterized in that, In step 1), the mass concentration of the ZnCl2 aqueous solution is 35%~45%, the mass ratio of the tobacco stem powder to the ZnCl2 aqueous solution is 1:2.7~3.3, and the soaking time is 5~7 hours; The activation is carried out under a nitrogen atmosphere at a temperature of 450-550°C for 1.5-2.5 hours and a nitrogen flow rate of 225-275 mL / min. In step 2), the mass fraction of the hydrochloric acid aqueous solution is 9-11%, the soaking time is 2-4 hours, the ultrasonic time is 0.5-1.5 hours, the washing is performed by rinsing with ultrapure water at 55-65°C until the pH is 7, and the drying temperature is 100-120°C for 10-14 hours.

5. The paper rod filling material according to claim 1, characterized in that, The excipients are selected from one or more of sodium carboxymethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose ether, gum arabic, gum arabic, gum arabic, gum arabic, gum arabic, gum arabic, guar gum, xanthan gum, agar, agarose, or carrageenan gum.

6. The paper rod filling material according to claim 1, characterized in that, The excipient is hydroxyethyl cellulose.

7. A method for preparing a paper rod filling material as described in any one of claims 1 to 6, characterized in that, Includes the following steps: The modified plant fiber, adsorbent substrate, auxiliary materials and water are thoroughly mixed and granulated to obtain the paper rod filling material for effectively absorbing phenolic substances.

8. A cigarette, characterized in that, Includes the paper stick filling material as described in any one of claims 1 to 6.

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