Preparation method of tar-reducing functional material for cigarettes as well as product and application of tar-reducing functional material

Abstract

The invention relates to a preparation method of a tar-reducing functional material for cigarettes as well as a product and application of the tar-reducing functional material. The preparation method comprises the following steps: drying caulis spatholobi, crushing, sieving and grinding; carrying out ultrafine treatment on the refined particles, and sieving; mixing the ultrafine particles with an alcohol-water solution, carrying out heat treatment, carrying out solid-liquid separation, and drying; carrying out amination modification on the superfine porous particles; and mixing and dipping the modified superfine porous particles and a metal ion solution, carrying out solid-liquid separation, and drying to obtain the tar-reducing functional material for cigarettes. The tar-reducing functional material for cigarettes prepared by the preparation method can remarkably reduce the release amount of harmful ingredients such as tar, hydrogen cyanide and crotonaldehyde in cigarette smoke, and can effectively improve the smoking safety of the cigarettes.

Description

Technical Field

[0001] The invention belongs to the technical field of tobacco materials, and relates to a preparation method of a tobacco tar-reducing functional material, a product and an application thereof. Background Art

[0002] Cigarette tar is a substance produced by incomplete combustion of organic components in an oxygen-deficient environment. It contains a variety of hydrocarbons and hydrocarbon derivatives containing oxygen, sulfur, and nitrogen. Although these substances are present in low levels, they pose health risks to the body. Therefore, studying how to reduce the release of tar and other harmful substances in cigarette smoke is of great significance to improving the safety of cigarette smoking and protecting the health of smokers.

[0003] There are many commonly used methods for reducing tar, such as optimization of breeding and cultivation, adjustment of formula, optimization of auxiliary material design, etc. Adding functional materials to filter rods is an important method for reducing harmful components in flue gas. For example, CN117244522A discloses a method for preparing diatomite particles that can reduce tar and CO in flue gas, including: mixing diatomite, adhesive and water to form wet powder, then placing the pellet core in a centrifugal shot blasting machine and spraying a wetting agent for granulation, using centrifugal force to coat the wet powder on the pellet core, and obtaining diatomite functional particles after drying. Diatomite particles with certain tar and CO adsorption functions are obtained by wrapping diatomite powder in the outer layer of the particle core. The preparation process is simple and the cost is low. The prepared diatomite particle filter rod has good tar and CO adsorption capacity. For example, CN103126073A discloses a filter rod fiber substrate additive and a compound additive and their application that can reduce the tar content in mainstream cigarette smoke. The additive contains one or more citric acid ester compounds as active ingredients; the filter rod made of a fiber substrate containing the additive can reduce the tar content in mainstream cigarette smoke by up to 10.3%.

[0004] The functional materials currently used in cigarette filter rods have a good interception effect on harmful components in smoke, but the tar reduction ability of such materials is limited. Therefore, it is very necessary to study more types of materials with good tar reduction ability. Summary of the invention

[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide a method for preparing a tar-reducing functional material for cigarettes, and a product and application thereof.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a method for preparing a tar-reducing functional material for tobacco, the method comprising the following steps:

[0008] (1) drying Millettia reticulata, crushing and sieving, and grinding the crushed product to obtain fine particles;

[0009] (2) subjecting the refined particles to ultrafine processing and sieving to obtain ultrafine particles;

[0010] (3) mixing the ultrafine particles with an alcohol aqueous solution, performing heat treatment, solid-liquid separation, and drying to obtain ultrafine porous particles;

[0011] (4) performing amination modification on the ultrafine porous particles to obtain modified ultrafine porous particles;

[0012] (5) The modified ultrafine porous particles are mixed with a metal ion solution and impregnated, the solid-liquid separation is performed, and the mixture is dried to obtain the tar-reducing functional material for tobacco.

[0013] The tar-reducing functional material for cigarettes involved in the present invention is made of the natural plant Millettia spatholobi as raw material, which is crushed, ground, and ultra-finely treated and then subjected to porous treatment to form uniformly connected holes inside the material, and its porous characteristics are more conducive to the adsorption of tar and other harmful components in cigarette smoke. When the smoke passes through the filter rod, the particles are intercepted by the material through diffusion deposition, direct interception and inertial collision, thereby reducing the content of tar and other harmful components in the cigarette smoke. Further, the ultrafine porous particles are subjected to amination modification and metal ion coordination treatment. After the amination modification introduces amino groups, the amino groups can react with crotonaldehyde to reduce its content. At the same time, the amino groups are more likely to load metal ions, and there is a complexation effect between the metal ions and hydrogen cyanide to reduce the content of hydrogen cyanide, which further improves the adsorption effect of harmful components in cigarette smoke.

[0014] Among them, the grinding treatment can improve the surface properties of Millettia spatholobi fiber, increase its roughness and active sites, improve its surface reaction performance, and be more conducive to the subsequent porous treatment, amination modification and metal coordination treatment of the material. Among them, the ultrafine treatment can make Millettia spatholobi particles have higher surface energy and reaction activity, which is more conducive to the subsequent porous treatment, amination modification and metal coordination treatment of the material.

[0015] The tar-reducing functional material for cigarettes prepared by the above preparation method can significantly reduce the release of tar and harmful components such as hydrogen cyanide and crotonaldehyde in cigarette smoke, and can effectively improve the smoking safety of cigarettes.

[0016] Preferably, the drying in step (1) is performed to a content rate of less than 10%, for example, 10%, 9%, 8%, 7%, 6%, 5%, etc.

[0017] Preferably, the crushed material in step (1) is 30-80 mesh, for example, 30 mesh, 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, etc.

[0018] Preferably, the grinding treatment in step (1) includes disc grinding, ball grinding, roller grinding, cone grinding or knife grinding.

[0019] Preferably, the grinding treatment time in step (1) is 5-15 min, for example, 5 min, 6 min, 8 min, 9 min, 10 min, 12 min, 13 min, 14 min, 15 min, etc.

[0020] Grinding the crushed material using the above-mentioned specific process parameters has a better effect on improving the surface properties of Millettia spatholobi fiber, increasing its roughness and active sites, and improving its surface reaction performance.

[0021] Preferably, the ultrafine treatment in step (2) is carried out using a jet mill.

[0022] Preferably, the ultrafine particles in step (2) are 400-500 mesh, such as 400 mesh, 420 mesh, 430 mesh, 440 mesh, 450 mesh, 470 mesh, 500 mesh, etc.

[0023] Preferably, the solid-liquid ratio of the ultrafine particles to the alcohol aqueous solution in step (3) is 1:(15-25) g / mL, for example 15 g / mL, 18 g / mL, 20 g / mL, 22 g / mL, 24 g / mL, 25 g / mL, etc.

[0024] Preferably, the mass fraction of alcohol in the alcohol aqueous solution in step (3) is 70-95%, for example, 70%, 72%, 75%, 80%, 83%, 85%, 90%, 95%, etc.

[0025] Preferably, the alcohol in the alcohol aqueous solution in step (3) comprises any one of ethanol, isopropanol, methanol or a polyol, or a combination of at least two thereof.

[0026] Preferably, the alcohol in the alcohol aqueous solution in step (3) is ethanol or a combination of ethanol and isopropanol.

[0027] The effect of making the material porous by using the alcohol aqueous solution with the above-mentioned specific mass fraction, especially ethanol aqueous solution or ethanol and isopropanol mixed aqueous solution, is better, and its effect in reducing the release of harmful components such as tar and hydrogen cyanide and crotonaldehyde in cigarette smoke is more excellent.

[0028] Preferably, the temperature of the heat treatment in step (3) is 50-80°C, for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc.; the time is 1-3h, for example, 1h, 1.5h, 2h, 2.5h, 3h, etc.

[0029] Preferably, the amination modification in step (4) comprises first performing an epoxidation reaction on the ultrafine porous particles and then performing an amination reaction.

[0030] Preferably, the reagent used in the epoxidation reaction includes epichlorohydrin.

[0031] Preferably, the ratio of epichlorohydrin to ultrafine porous particles is (1-4) mL:1 g, for example, 1 mL:1 g, 1.5 mL:1 g, 2 mL:1 g, 2.5 mL:1 g, 3 mL:1 g, 3.5 mL:1 g, 4 mL:1 g, etc.

[0032] Preferably, the epoxidation reaction is carried out at 30-70°C (e.g., 30°C, 40°C, 45°C, 50°C, 55°C, 60°C, 70°C, etc.) for 4-8h (e.g., 4h, 4.5h, 5h, 5.5h, 6h, 7h, 8h, etc.).

[0033] Preferably, the amination agent used in the amination reaction includes any one of ethylenediamine, diethylenetriamine or triethylenetetramine, or a combination of at least two of them.

[0034] Preferably, the ratio of the amination reagent to the epoxidation-modified product is (0.5-3) mL:1 g, for example, 0.5 mL:1 g, 1 mL:1 g, 1.5 mL:1 g, 2 mL:1 g, 2.5 mL:1 g, 3 mL:1 g, etc.

[0035] Preferably, the amination reaction is carried out at 55-85°C (e.g., 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, etc.) for 4-8h (e.g., 4h, 4.5h, 5h, 5.5h, 6h, 7h, 8h, etc.).

[0036] Preferably, the metal ions in step (5) include any one of iron ions, zinc ions, magnesium ions, copper ions or nickel ions, or a combination of at least two of them, preferably nickel ions.

[0037] Compared with other types of metal ions, materials modified with nickel ions are more effective in reducing the release of harmful components such as tar and hydrogen cyanide and crotonaldehyde in cigarette smoke.

[0038] Preferably, the concentration of the metal ion solution in step (5) is 0.2-1.5M, for example, 0.2M, 0.4M, 0.5M, 0.8M, 1.0M, 1.2M, 1.4M, 1.5M, etc.; the ratio of the metal ion solution to the modified ultrafine porous particles is (5-20)mL:1g, for example, 5mL:1g, 8mL:1g, 10mL:1g, 12mL:1g, 15mL:1g, 18mL:1g, 20mL:1g, etc.

[0039] Preferably, the impregnation in step (5) is carried out at 35-55°C (e.g., 35°C, 38°C, 40°C, 45°C, 50°C, 55°C, etc.) for 2-6h (e.g., 2h, 3h, 4h, 5h, 6h, etc.).

[0040] Preferably, after the drying in step (5), the product is further granulated by a fluidized bed granulation method.

[0041] Preferably, a binder is used in the granulation process, and the binder includes a carboxymethyl cellulose aqueous solution, and the dry matter of the binder accounts for 3-7% of the mass of the tobacco tar-reducing functional material.

[0042] In order to further improve the practicality of the tar-reducing functional material for cigarettes prepared by the present invention, the material is further granulated using a fluidized bed granulation method. Through the granulation treatment, granular materials with different particle sizes can be prepared, thereby better meeting the needs of various application scenarios.

[0043] In a second aspect, the present invention provides a tar-reducing functional material for tobacco prepared according to the preparation method described in the first aspect.

[0044] In a third aspect, the present invention provides use of the tobacco tar-reducing functional material according to the second aspect in the preparation of cigarette filter materials.

[0045] In a fourth aspect, the present invention provides a reduced-tar cigarette, wherein the tar-reducing functional material for cigarettes according to the second aspect is added to the filter of the reduced-tar cigarette.

[0046] Preferably, the loading amount of the tar-reducing functional material for cigarettes is 20-60 mg / cigarette, for example, 20 mg / cigarette, 25 mg / cigarette, 30 mg / cigarette, 40 mg / cigarette, 50 mg / cigarette, 60 mg / cigarette, etc.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] The tar-reducing functional material for cigarettes involved in the present invention uses the natural plant Millettia spatholobi as raw material, which is crushed, ground, ultra-finely processed and then porous to form uniform through holes inside the material. Its porous characteristics are more conducive to the adsorption of tar and other harmful components in cigarette smoke. When the smoke passes through the filter rod, the particles are retained by the material through diffusion deposition, direct interception and inertial collision, thereby reducing the content of tar and other harmful components in the cigarette smoke.

[0049] Furthermore, the ultrafine porous particles were subjected to amination modification and metal ion coordination treatment. After the amination modification introduced the amino group, the amino group could react with crotonaldehyde to reduce its content. At the same time, the amino group was easier to load metal ions, and there was a complexation effect between the metal ions and hydrogen cyanide, thereby reducing the content of hydrogen cyanide, which further improved the adsorption effect of harmful components in cigarette smoke.

[0050] Among them, the grinding treatment can improve the surface properties of Millettia spatholobi fiber, increase its roughness and active sites, improve its surface reaction performance, and be more conducive to the subsequent porous treatment, amination modification and metal coordination treatment of the material. Among them, the ultrafine treatment can make Millettia spatholobi particles have higher surface energy and reaction activity, which is more conducive to the subsequent porous treatment, amination modification and metal coordination treatment of the material.

[0051] The tar-reducing functional material for cigarettes prepared by the above preparation method can significantly reduce the release of tar and harmful components such as hydrogen cyanide and crotonaldehyde in cigarette smoke, and can effectively improve the smoking safety of cigarettes. DETAILED DESCRIPTION

[0052] In order to further explain the technical means and effects adopted by the present invention, the technical solution of the present invention is further described below in conjunction with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

[0053] Example 1

[0054] This embodiment provides a tar-reducing functional material for cigarettes, and the preparation method thereof is as follows:

[0055] (1) drying Millettia spatholobi to a moisture content of 8%, adding the mixture into a grinder for grinding, and screening the particles within a range of 30-80 meshes;

[0056] (2) adding the crushed Millettia spatholobi to a ZGM refiner for grinding, controlling the slurry concentration to 15%, the refiner speed to 600 r / min, and grinding for 10 min; collecting the ground material and drying it to a moisture content of 3% to obtain refined particles;

[0057] (3) taking the refined particles and adding them into a jet mill for ultrafine treatment, and screening ultrafine particles in the range of 400-500 mesh;

[0058] (4) 100 g of ultrafine particles were added to 2000 mL of 80% ethanol aqueous solution, and the mixture was kept in a water bath at 70° C. for 2 h. The product was filtered and freeze-dried to obtain ultrafine porous particles.

[0059] (5) 40 g of ultrafine porous particles were added to 1000 mL of a 0.1 mol / L NaOH solution, and then 69 mL of epichlorohydrin was added, and the reaction was shaken at 50° C. for 6 h. After the reaction was completed, the product was filtered, washed with deionized water until neutral, and dried at 50° C. for 12 h to obtain epoxidized ultrafine porous particles.

[0060] 30 g of epoxidized ultrafine porous particles were soaked in 1000 mL of deionized water for 30 min, and then 15 mL of triethylenetetramine and 0.5 g of sodium bicarbonate were added, and the mixture was shaken and reacted at 75 °C for 6 h. After the reaction, the product was filtered, washed, and dried to obtain aminated ultrafine porous particles.

[0061] (6) adding 20 g of aminated ultrafine porous particles into 200 mL of 0.25 mol / L nickel sulfate solution, stirring at 45° C. for 4 h, filtering, washing, and drying;

[0062] (7) The dried product is granulated. The specific process is based on the method disclosed in the prior art (Liu Luan, Wu Di, Sha Luping, et al. Study on the process of preparing rumen-passing methionine micropellets in fluidized bed [J]. Applied Chemical Industry, 2022, 51(S1): 128-132.), wherein a 2.5wt% carboxymethyl cellulose aqueous solution is used as a binder, and the dry binder used accounts for 5% of the mass of the product of step (6); the sieved particle size is 30-80 mesh. The tar-reducing functional material for tobacco is obtained.

[0063] Example 2

[0064] This embodiment provides a tar-reducing functional material for cigarettes, and the preparation method thereof is as follows:

[0065] (1) drying Millettia spatholobi to a moisture content of 7%, adding the mixture into a grinder for grinding, and screening the particles within a range of 30-80 meshes;

[0066] (2) adding the crushed Millettia spatholobi to a ZGM refiner for grinding, controlling the slurry concentration to 15%, the refiner speed to 600 r / min, and grinding for 15 min; collecting the ground material and drying it to a moisture content of 4% to obtain refined particles;

[0067] (3) taking the refined particles and adding them into a jet mill for ultrafine treatment, and screening ultrafine particles in the range of 400-500 mesh;

[0068] (4) 100 g of ultrafine particles were added to 2500 mL of 95% ethanol aqueous solution, and the mixture was kept in a water bath at 80° C. for 1 h. The product was filtered and freeze-dried to obtain ultrafine porous particles.

[0069] (5) 40 g of ultrafine porous particles were added to 1000 mL of a 0.1 mol / L NaOH solution, and then 80 mL of epichlorohydrin was added, and the reaction was shaken at 70° C. for 4 h. After the reaction, the product was filtered, washed with deionized water until neutral, and dried at 50° C. for 12 h to obtain epoxidized ultrafine porous particles.

[0070] 30 g of epoxidized ultrafine porous particles were soaked in 1000 mL of deionized water for 30 min, and then 30 mL of diethylenetriamine and 0.5 g of sodium bicarbonate were added, and the mixture was shaken and reacted at 85 °C for 4 h. After the reaction, the product was filtered, washed, and dried to obtain aminated ultrafine porous particles.

[0071] (6) adding 20 g of aminated ultrafine porous particles into 300 mL of 0.5 mol / L nickel sulfate solution, stirring at 55° C. for 2 h, filtering, washing, and drying;

[0072] (7) The dried product is granulated. The specific process is based on the method disclosed in the prior art (Liu Luan, Wu Di, Sha Luping, et al. Study on the process of preparing rumen-passing methionine micropellets in fluidized bed [J]. Applied Chemical Industry, 2022, 51(S1): 128-132.), wherein a 2.5wt% carboxymethyl cellulose aqueous solution is used as a binder, and the dry binder used accounts for 5% of the mass of the product of step (6); the sieved particle size is 30-80 mesh. The tar-reducing functional material for tobacco is obtained.

[0073] Example 3

[0074] This embodiment provides a tar-reducing functional material for cigarettes, and the preparation method thereof is as follows:

[0075] (1) drying Millettia spatholobi to a moisture content of 6%, adding the mixture into a grinder for grinding, and screening the particles within a range of 30-80 meshes;

[0076] (2) adding the crushed Millettia spatholobi to a ZGM refiner for grinding, controlling the slurry concentration to 15%, the refiner speed to 600 r / min, and grinding for 5 min; collecting the ground material and drying it to a moisture content of 5% to obtain refined particles;

[0077] (3) taking the refined particles and adding them into a jet mill for ultrafine treatment, and screening ultrafine particles in the range of 400-500 mesh;

[0078] (4) 100 g of ultrafine particles were added to 1500 mL of a 70% methanol aqueous solution, and the mixture was kept in a water bath at 60° C. for 3 h. The product was filtered and freeze-dried to obtain ultrafine porous particles.

[0079] (5) 40 g of ultrafine porous particles were added to 1000 mL of a 0.1 mol / L NaOH solution, and then 87 mL of epichlorohydrin was added, and the reaction was shaken at 40° C. for 8 h. After the reaction was completed, the product was filtered, washed with deionized water until neutral, and dried at 50° C. for 12 h to obtain epoxidized ultrafine porous particles.

[0080] 30 g of epoxidized ultrafine porous particles were soaked in 1000 mL of deionized water for 30 min, and then 60 mL of triethylenetetramine and 0.5 g of sodium bicarbonate were added, and the mixture was shaken and reacted at 55 °C for 8 h. After the reaction, the product was filtered, washed, and dried to obtain aminated ultrafine porous particles.

[0081] (6) adding 20 g of aminated ultrafine porous particles into 300 mL of 1 mol / L nickel sulfate solution, stirring at 40° C. for 6 h, filtering, washing, and drying;

[0082] (7) The dried product is granulated. The specific process is based on the method disclosed in the prior art (Liu Luan, Wu Di, Sha Luping, et al. Study on the process of preparing rumen-passing methionine micropellets in fluidized bed [J]. Applied Chemical Industry, 2022, 51(S1): 128-132.), wherein a 2.5wt% carboxymethyl cellulose aqueous solution is used as a binder, and the dry binder used accounts for 5% of the mass of the product of step (6); the sieved particle size is 30-80 mesh. The tar-reducing functional material for tobacco is obtained.

[0083] Example 4

[0084] This embodiment provides a tar-reducing functional material for cigarettes, and the preparation method thereof is as follows:

[0085] (1) drying Millettia spatholobi to a moisture content of 6%, adding the mixture into a grinder for grinding, and screening the particles within a range of 30-80 meshes;

[0086] (2) adding the crushed Millettia spatholobi to a ZGM refiner for grinding, controlling the slurry concentration to 15%, the refiner speed to 600 r / min, and grinding for 12 min; collecting the ground material and drying it to a moisture content of 2% to obtain refined particles;

[0087] (3) taking the refined particles and adding them into a jet mill for ultrafine treatment, and screening ultrafine particles in the range of 400-500 mesh;

[0088] (4) 100 g of ultrafine particles were added to 2000 mL of 75% ethanol aqueous solution, and the mixture was kept in a water bath at 70° C. for 2 h. The product was filtered and freeze-dried to obtain ultrafine porous particles.

[0089] (5) 40 g of ultrafine porous particles were added to 1000 mL of a 0.1 mol / L NaOH solution, and then 100 mL of epichlorohydrin was added, and the reaction was shaken at 50° C. for 7 h. After the reaction was completed, the product was filtered, washed with deionized water until neutral, and dried at 50° C. for 12 h to obtain epoxidized ultrafine porous particles;

[0090] 30 g of epoxidized ultrafine porous particles were soaked in 1000 mL of deionized water for 30 min, and then 45 mL of triethylenetetramine and 0.5 g of sodium bicarbonate were added, and the mixture was shaken and reacted at 75 °C for 6 h. After the reaction, the product was filtered, washed, and dried to obtain aminated ultrafine porous particles.

[0091] (6) adding 20 g of aminated ultrafine porous particles into 300 mL of 0.75 mol / L nickel sulfate solution, stirring at 45° C. for 4 h, filtering, washing, and drying;

[0092] (7) The dried product is granulated. The specific process is based on the method disclosed in the prior art (Liu Luan, Wu Di, Sha Luping, et al. Study on the process of preparing rumen-passing methionine micropellets in fluidized bed [J]. Applied Chemical Industry, 2022, 51(S1): 128-132.), wherein a 2.5wt% carboxymethyl cellulose aqueous solution is used as a binder, and the dry binder used accounts for 5% of the mass of the product of step (6); the sieved particle size is 30-80 mesh. The tar-reducing functional material for tobacco is obtained.

[0093] Example 5

[0094] This embodiment provides a tar-reducing functional material for cigarettes, and the preparation method thereof is as follows:

[0095] (1) Dry Millettia spatholobi to a moisture content of 5%, add the mixture into a grinder for grinding, and screen out particles within a range of 30-80 meshes;

[0096] (2) adding the crushed Millettia spatholobi to a ball mill for ball milling, controlling the slurry concentration to 15%, the grinding speed to 600 r / min, and grinding for 10 min; collecting the ground material, drying it to a moisture content of 2%, and obtaining fine particles;

[0097] (3) taking the refined particles and adding them into a jet mill for ultrafine treatment, and screening ultrafine particles in the range of 400-500 mesh;

[0098] (4) 100 g of ultrafine particles were added to 2000 mL of 90% ethanol aqueous solution, and the mixture was kept in a water bath at 70° C. for 2 h. The product was filtered and freeze-dried to obtain ultrafine porous particles.

[0099] (5) 40 g of ultrafine porous particles were added to 1000 mL of a 0.1 mol / L NaOH solution, and then 111 mL of epichlorohydrin was added, and the reaction was shaken at 50° C. for 8 h. After the reaction was completed, the product was filtered, washed with deionized water until neutral, and dried at 50° C. for 12 h to obtain epoxidized ultrafine porous particles;

[0100] 30 g of epoxidized ultrafine porous particles were soaked in 1000 mL of deionized water for 30 min, and then 78 mL of ethylenediamine and 0.5 g of sodium bicarbonate were added, and the mixture was shaken and reacted at 75 °C for 8 h. After the reaction, the product was filtered, washed, and dried to obtain aminated ultrafine porous particles.

[0101] (6) adding 20 g of aminated ultrafine porous particles into 300 mL of 1.3 mol / L nickel sulfate solution, stirring at 45° C. for 4 h, filtering, washing, and drying;

[0102] (7) The dried product is granulated. The specific process is based on the method disclosed in the prior art (Liu Luan, Wu Di, Sha Luping, et al. Study on the process of preparing rumen-passing methionine micropellets in fluidized bed [J]. Applied Chemical Industry, 2022, 51(S1): 128-132.), wherein a 2.5wt% carboxymethyl cellulose aqueous solution is used as a binder, and the dry binder used accounts for 5% of the mass of the product of step (6); the sieved particle size is 30-80 mesh. The tar-reducing functional material for tobacco is obtained.

[0103] Example 6

[0104] This embodiment provides a tar-reducing functional material for cigarettes, and the preparation method thereof is as follows:

[0105] (1) drying Millettia spatholobi to a moisture content of 7%, adding the mixture into a grinder for grinding, and screening the particles within a range of 30-80 meshes;

[0106] (2) adding the crushed Millettia spatholobi to a ball mill for ball milling, controlling the slurry concentration to 15%, the grinding speed to 600 r / min, and grinding for 10 min; collecting the ground material and drying it to a moisture content of 4% to obtain refined particles;

[0107] (3) taking the refined particles and adding them into a jet mill for ultrafine treatment, and screening ultrafine particles in the range of 400-500 mesh;

[0108] (4) 100 g of ultrafine particles were added to 2000 mL of 80% ethanol aqueous solution, and the mixture was kept in a water bath at 70° C. for 3 h. The product was filtered and freeze-dried to obtain ultrafine porous particles.

[0109] (5) 40 g of ultrafine porous particles were added to 1000 mL of a 0.1 mol / L NaOH solution, and then 133 mL of epichlorohydrin was added, and the reaction was shaken at 50° C. for 8 h. After the reaction was completed, the product was filtered, washed with deionized water until neutral, and dried at 50° C. for 12 h to obtain epoxidized ultrafine porous particles;

[0110] 30 g of epoxidized ultrafine porous particles were soaked in 1000 mL of deionized water for 30 min, and then 90 mL of triethylenetetramine and 0.5 g of sodium bicarbonate were added, and the mixture was shaken and reacted at 75 °C for 8 h. After the reaction, the product was filtered, washed, and dried to obtain aminated ultrafine porous particles.

[0111] (6) adding 20 g of aminated ultrafine porous particles into 300 mL of 1.5 mol / L nickel sulfate solution, stirring at 45° C. for 4 h, filtering, washing, and drying;

[0112] (7) The dried product is granulated. The specific process is based on the method disclosed in the prior art (Liu Luan, Wu Di, Sha Luping, et al. Study on the process of preparing rumen-passing methionine micropellets in fluidized bed [J]. Applied Chemical Industry, 2022, 51(S1): 128-132.), wherein a 2.5wt% carboxymethyl cellulose aqueous solution is used as a binder, and the dry binder used accounts for 5% of the mass of the product of step (6); the sieved particle size is 30-80 mesh. The tar-reducing functional material for tobacco is obtained.

[0113] Example 7

[0114] This embodiment provides a tar-reducing functional material for cigarettes, and the preparation method thereof is different from that of Embodiment 1 only in that in step (4), an equal volume of 80% ethanol aqueous solution is replaced by 80% isopropanol aqueous solution, and other conditions remain unchanged.

[0115] Example 8

[0116] This embodiment provides a tar-reducing functional material for tobacco, and the preparation method thereof differs from that of Embodiment 1 only in that in step (4), an equal volume of the 80% ethanol aqueous solution is replaced by a mixed aqueous solution of ethanol and isopropanol with a total alcohol concentration of 80% (the volume ratio of ethanol to isopropanol is 1:1), and other conditions remain unchanged.

[0117] Example 9

[0118] This embodiment provides a tar-reducing functional material for tobacco, and the preparation method thereof is different from that of Embodiment 1 only in that in step (6), an equal volume of a 0.25 mol / L nickel sulfate solution is replaced by a 0.25 mol / L zinc sulfate solution, and other conditions remain unchanged.

[0119] Example 10

[0120] This embodiment provides a tar-reducing functional material for tobacco, and the preparation method thereof is different from that of Embodiment 1 only in that in step (6), an equal volume of a 0.25 mol / L nickel sulfate solution is replaced by a 0.25 mol / L magnesium sulfate solution, and other conditions remain unchanged.

[0121] Embodiment 11

[0122] This embodiment provides a tar-reducing functional material for tobacco, and the preparation method thereof is different from that of Embodiment 1 only in that in step (6), an equal volume of a 0.25 mol / L nickel sulfate solution is replaced by a 0.25 mol / L copper sulfate solution, and other conditions remain unchanged.

[0123] Comparative Example 1

[0124] This comparative example provides a functional material for reducing tar in tobacco, and the preparation method thereof is different from that of Example 1 only in that the Millettia reticulata raw material is replaced by Platycodon grandiflorum raw material, and other operations remain unchanged.

[0125] Comparative Example 2

[0126] This comparative example provides a tar-reducing functional material for tobacco, and the preparation method thereof is different from that of Example 1 only in that the Millettia reticulata raw material is replaced with corn stalk raw material, and other operations remain unchanged.

[0127] Comparative Example 3

[0128] This comparative example provides a functional material for reducing tar in cigarettes, and the steps (1) to (4) of the preparation method thereof are the same as the steps (1) to (4) of Example 1;

[0129] (5) The obtained ultrafine porous particles are granulated. The specific process refers to the method disclosed in the prior art (Liu Luan, Wu Di, Sha Luping, et al. Study on the process of preparing rumen-passing methionine micropellets in fluidized bed [J]. Applied Chemical Industry, 2022, 51(S1): 128-132.), wherein a 2.5wt% carboxymethyl cellulose aqueous solution is used as a binder, and the dry binder used accounts for 5% of the mass of the product of step (4); the sieved particle size is 30-80 mesh. The tar-reducing functional material for tobacco is obtained.

[0130] Test Case

[0131] The tar-reducing functional materials for cigarettes prepared in Examples 1-11 and Comparative Examples 1-3 were added to the filter tips of cigarettes using transparent tipping paper, respectively, with an addition amount of 40 mg / stick, recorded as test cigarettes 1-14, and cigarettes without the tar-reducing functional materials for cigarettes were used as the control group. The cigarettes used were balanced for 48 hours under the conditions of temperature (22±1)°C and relative humidity (60±2)% before the test, and then sorted by weight (average weight±0.02g) and draw resistance (average draw resistance±49Pa), and the test cigarettes that met the standards were selected. The cigarette smoking test was carried out on a smoking machine according to standard smoking conditions, and the release of tar, hydrogen cyanide and crotonaldehyde in the cigarette smoke was detected according to standards GB / T19609-2004, YC / T253-2008 and YC / T254-2008, respectively, and the results are shown in Table 1.

[0132] Table 1

[0133]

[0134]

[0135] It can be seen from the data results in Table 1 that, compared with the comparative example materials, the tar-reducing functional material for cigarettes prepared by the preparation method of the present invention can further reduce the release of tar, hydrogen cyanide and crotonaldehyde in cigarette smoke, and can effectively improve the smoking safety of cigarettes.

[0136] The applicant declares that the present invention illustrates the technical solution of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0137] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0138] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A method for preparing a tar-reducing functional material for cigarettes, characterized in that: The preparation method of the tobacco tar-reducing functional material comprises the following steps: (1) drying Millettia spatholobi, crushing and sieving, and grinding the crushed product to obtain fine particles; (2) subjecting the refined particles to ultrafine processing and sieving to obtain ultrafine particles; (3) mixing the ultrafine particles with an alcohol aqueous solution, performing heat treatment, solid-liquid separation, and drying to obtain ultrafine porous particles; (4) performing amination modification on the ultrafine porous particles to obtain modified ultrafine porous particles; (5) The modified ultrafine porous particles are mixed with a metal ion solution and impregnated, the solid-liquid separation is performed, and the mixture is dried to obtain the tar-reducing functional material for tobacco.

2. The method for preparing the tobacco tar-reducing functional material according to claim 1, characterized in that: Step (1) drying to a content rate of less than 10%; Preferably, the pulverized material in step (1) is 30-80 mesh; Preferably, the grinding treatment in step (1) includes disc grinding, ball grinding, roller grinding, cone grinding or knife grinding; Preferably, the grinding time in step (1) is 5-15 min.

3. The method for preparing the tobacco tar-reducing functional material according to claim 1 or 2, characterized in that: The ultrafine treatment in step (2) is carried out using a jet mill; Preferably, the ultrafine particles in step (2) are 400-500 mesh.

4. The method for preparing the tobacco tar-reducing functional material according to any one of claims 1 to 3, characterized in that: In step (3), the liquid ratio of the ultrafine particles to the alcohol aqueous solution is 1:(15-25) g / mL; Preferably, the mass fraction of alcohol in the alcohol aqueous solution in step (3) is 70-95%; Preferably, the alcohol in the alcohol aqueous solution in step (3) comprises any one of ethanol, isopropanol, methanol or a polyol or a combination of at least two thereof; Preferably, the alcohol in the alcohol aqueous solution in step (3) is ethanol or a combination of ethanol and isopropanol.

5. The method for preparing the tobacco tar-reducing functional material according to any one of claims 1 to 4, characterized in that: The heat treatment temperature in step (3) is 50-80°C and the time is 1-3h.

6. The method for preparing the tobacco tar-reducing functional material according to any one of claims 1 to 5, characterized in that: The amination modification in step (4) comprises firstly performing an epoxidation reaction on the ultrafine porous particles and then performing an amination reaction; Preferably, the reagent used in the epoxidation reaction includes epichlorohydrin; Preferably, the ratio of epichlorohydrin to ultrafine porous particles is (1-4) mL:1 g; Preferably, the epoxidation reaction is carried out at 30-70° C. for 4-8 h; Preferably, the amination agent used in the amination reaction includes any one of ethylenediamine, diethylenetriamine or triethylenetetramine, or a combination of at least two thereof; Preferably, the ratio of the amination reagent to the epoxidation-modified product is (0.5-3) mL:1 g; Preferably, the amination reaction is carried out at 55-85° C. for 4-8 h.

7. The method for preparing the tobacco tar-reducing functional material according to any one of claims 1 to 6, characterized in that: The metal ions in step (5) include any one of iron ions, zinc ions, magnesium ions, copper ions or nickel ions, or a combination of at least two of them, preferably nickel ions; Preferably, the concentration of the metal ion solution in step (5) is 0.2-1.5M; the ratio of the metal ion solution to the modified ultrafine porous particles is (5-20) mL:1 g; Preferably, the immersion in step (5) is carried out at 35-55° C. for 2-6 hours; Preferably, after the drying in step (5), the product is further granulated by a fluidized bed granulation method.

8. The tar-reducing functional material for tobacco obtained by the preparation method according to any one of claims 1 to 7.

9. Use of the tobacco tar-reducing functional material according to claim 8 in the preparation of cigarette filter materials.

10. A reduced-tar cigarette, characterized in that: The filter of the reduced-tar cigarette contains the tar-reducing functional material for cigarettes as claimed in claim 8; Preferably, the loading amount of the tar-reducing functional material for cigarettes is 20-60 mg / cigarette.

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