Preparation method of porous particles with effects of reducing tar and harm as well as product and application of porous particles

Abstract

The invention provides a preparation method of porous particles with effects of reducing tar and harm as well as a product and application of the porous particles. The preparation method comprises the following steps: (1) crushing and sieving plant raw materials to obtain plant particles; (2) mixing the plant particles and the inorganic filler, performing ball milling treatment, and drying to obtain mixed particles; (3) carrying out ultrafine treatment on the mixed particles, and sieving to obtain ultrafine particles; (4) mixing the ultrafine particles with a polyethylene glycol aqueous solution, carrying out suction filtration, and then carrying out drying treatment to obtain ultrafine porous particles; (5) acidizing the superfine porous particles to obtain acidized modified superfine porous particles; and (6) mixing and reacting the acidized and modified superfine porous particles with a metal ion aqueous solution, and drying to obtain the porous particles with the tar-reducing and harm-reducing effects. The porous particles prepared by the method disclosed by the invention have rich pore structures, and can better adsorb harmful ingredients in cigarette smoke.

Description

Technical Field

[0001] The invention belongs to the technical field of cigarette filter materials, and specifically relates to a preparation method of porous particles with tar-reducing and harm-reducing effects, and a product and application thereof. Background Art

[0002] Cigarettes are daily consumer goods that involve a large part of the consumer group. With the development of the times, people pay more and more attention to health issues, so cigarettes are gradually developing towards good taste and low harm. At present, in addition to reducing harmful substances in smoke by improving the quality of tobacco raw materials and reducing the amount of tobacco used, cigarette manufacturers mostly add granular materials to cigarettes to absorb harmful substances and adjust smoke.

[0003] CN102349698A discloses a method for preparing tobacco extract particles. The method comprises the following steps: firstly taking tobacco leaves and / or tobacco stems and chopping them, extracting them with water, ethanol or ether as solvent, obtaining tobacco extract liquid through sedimentation and filtration, and then concentrating the tobacco extract liquid to a relative density of 1.00-1.30 and controlling the temperature to be 20-40°C to obtain tobacco extract concentrate liquid or tobacco extract; then encapsulating tobacco flavor and β-cyclodextrin at a mass ratio of β-cyclodextrin: tobacco flavor of 1-3:1 for an inclusion time of 1 / 5-3 hours to obtain a flavor and β-cyclodextrin inclusion complex, and then spray-drying the flavor and β-cyclodextrin inclusion complex and tobacco extract concentrate liquid to obtain tobacco spray-dried powder; or directly spray-drying the tobacco extract to obtain tobacco spray-dried powder; and then granulating the tobacco spray-dried powder by adding excipient materials by dry or wet method to obtain tobacco extract particles. The granular tobacco extract prepared by the invention is applied to cigarettes, which can improve the tar-reducing and harm-reducing effects of cigarettes, perform aroma compensation, increase the utilization rate of waste tobacco leaf raw materials, and reduce cigarette costs.

[0004] CN106509988A discloses a kind of HEPA tobacco harm-reducing particles and its preparation method and application. The HEPA tobacco harm-reducing particles are made of HEPA fiber powder, propylene glycol, glycerol, honey and purified water as raw materials, and then stirred evenly to present agglomerated particles, which are then granulated by a granulator, and the prepared particles are dried, cooled and sieved to obtain 20-80 mesh HEPA particles. In the filter rod forming process, 5%-20% of the weight of the filter rod HEPA harm-reducing tobacco particles are evenly sprinkled on the filter rod tow to make a filter rod containing HEPA harm-reducing tobacco particles, and are compounded with conventional acetate fiber filter rods to make composite mouthpiece rods, and are made into cigarettes with tobacco rods, which have excellent harm-reducing performance and can reduce tar and nicotine in cigarettes. Moreover, it will not affect the smoking quality of cigarettes, but can make the aroma of cigarettes lighter, the taste milder, and the aftertaste more comfortable and clean.

[0005] Although more and more granular materials are used in cigarette products, there are still problems such as poor adsorption effect in actual application, which leads to the effect of reducing tar and reducing harm is not obvious. Therefore, it is of great significance to develop a tobacco granular product with better adsorption of harmful components in smoke. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide a method for preparing porous particles having the effects of reducing tar and harm, as well as a product and application thereof.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing porous particles having the effects of reducing tar and reducing harm, the preparation method comprising:

[0009] (1) crushing the plant raw material and sieving to obtain plant particles;

[0010] (2) mixing the plant particles and the inorganic filler, subjecting the mixture to ball milling, and drying the mixture to obtain mixed particles;

[0011] (3) subjecting the mixed particles to ultrafine processing and obtaining ultrafine particles after sieving;

[0012] (4) mixing the ultrafine particles with a polyethylene glycol aqueous solution, filtering and drying to obtain ultrafine porous particles;

[0013] (5) acidifying the ultrafine porous particles to obtain acid-modified ultrafine porous particles;

[0014] (6) The acid-modified ultrafine porous particles are mixed with a metal ion aqueous solution for reaction, and then dried to obtain the porous particles having the effect of reducing tar and reducing harm.

[0015] The invention uses natural plants as main raw materials, pre-crushes and screens the plants, mixes them with natural ores, and refines and separates the fibrous substances in the plant raw materials through ball mill treatment and ultra-fine treatment, thereby improving the surface properties of the fibers, increasing their roughness and active sites, and improving their surface reaction properties, which is beneficial to the physical and chemical modification of the materials.

[0016] At the same time, in order to more effectively adsorb harmful components in cigarette smoke, the material was further acidified and coordinated on the basis of the above treatment. After acidification, the plant structure is more likely to bind metal oxides, and there is a complexation effect between metal ions and hydrogen cyanide, which further improves the adsorption effect of harmful components in cigarette smoke.

[0017] Preferably, before the pulverization in step (1), the plant material is dried to a moisture content of ≤10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.

[0018] Preferably, the plant raw material includes any one of liquorice, platycodon, polygonatum, kudzu root, arisaema, magnolia or tangerine peel, or a combination of at least two thereof.

[0019] Preferably, the plant raw material is a combination of liquorice, polygonatum and kudzu root.

[0020] The plant raw materials selected in the present invention are liquorice, polygonatum and kudzu root, all of which are commonly used traditional Chinese medicines, have the effects of invigorating qi and harmonizing, moistening the lungs and relieving cough, and the combination of the three can also make the cigarette have herbal aroma, further improving the taste of the cigarette.

[0021] Preferably, the mass ratio of liquorice, polygonatum and kudzu root is (1-2):(0.1-1):(0.5-1.5).

[0022] Wherein "1-2" can be 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9, etc.;

[0023] “0.1-1” can be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, etc.;

[0024] “0.5-1.5” can mean 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3 or 1.4, etc.

[0025] Preferably, the mesh size of the sieving in step (1) is 40-80 mesh, for example, it can be 45 mesh, 50 mesh, 55 mesh, 60 mesh, 65 mesh, 70 mesh or 75 mesh, etc.

[0026] Preferably, the mass ratio of the plant particles to the inorganic filler in step (2) is 1:(2-5), for example, it can be 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5 or 1:3.8, etc.

[0027] Preferably, the inorganic filler includes any one of vermiculite, montmorillonite or kaolinite, or a combination of at least two of them.

[0028] Preferably, the inorganic filler is a combination of vermiculite, montmorillonite and kaolinite.

[0029] The inorganic filler in the present invention is a combination of vermiculite, montmorillonite and kaolinite. The combination of the three can refine the plant particles, make the particles have higher surface energy and reaction activity, and provide high-quality raw materials for subsequent physical or chemical modification processes.

[0030] Preferably, the mass ratio of the vermiculite, montmorillonite and kaolinite is (1-2):(3-5):(2-5).

[0031] Wherein "1-2" can be 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9, etc.;

[0032] "3-5" can be 3.1, 3.3, 3.5, 3.7, 3.9, 4, 4.1, 4.3, 4.5, 4.7 or 4.9, etc.;

[0033] “2-5” can mean 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5 or 4.8, etc.

[0034] Preferably, the ball milling treatment in step (2) is carried out in a ball mill.

[0035] Preferably, the rotation speed of the ball mill is 300-400 rpm, for example, 310 rpm, 330 rpm, 350 rpm, 370 rpm or 390 rpm.

[0036] Preferably, the ball milling treatment time is 0.5-2 h, for example, it can be 0.6 h, 0.8 h, 1 h, 1.2 h, 1.4 h, 1.6 h or 1.8 h.

[0037] Preferably, the drying in step (2) is performed to a moisture content of ≤3%, for example, 0.5%, 1%, 1.5%, 2% or 2.5%.

[0038] Preferably, the ultrafine treatment in step (3) is carried out in a jet mill.

[0039] Preferably, the mesh size of the sieving in step (3) is 200-400 mesh, for example, it can be 220 mesh, 250 mesh, 280 mesh, 300 mesh, 320 mesh, 350 mesh or 380 mesh.

[0040] Preferably, the liquid-to-material ratio of the ultrafine particles to the polyethylene glycol aqueous solution in step (4) is 0.05-0.15 g / mL, for example, 0.06 g / mL, 0.08 g / mL, 0.1 g / mL, 0.12 g / mL or 0.14 g / mL.

[0041] Preferably, the mass concentration of the polyethylene glycol aqueous solution is 10-25%, for example, 12%, 14%, 16%, 18%, 20%, 22% or 24%.

[0042] After the ultrafine particles in the present invention are mixed with the polyethylene glycol aqueous solution, uniform and continuous pores can be formed inside the material. The porous characteristics of the material are conducive to the adsorption of tar and other harmful components in cigarette smoke. When the smoke passes through the filter rod, the smoke contacts the material in the filter rod, and the particles can be better retained by the material through diffusion deposition, direct interception and inertial collision.

[0043] Preferably, the mixing temperature in step (4) is 60-100°C (for example, 65°C, 70°C, 5°C, 80°C, 85°C, 90°C or 95°C, etc.), and the mixing time is 0.5-2h (for example, 0.6h, 0.8h, 1h, 1.2h, 1.4h, 1.6h or 1.8h, etc.).

[0044] Preferably, the drying method in step (4) is freeze-drying;

[0045] Preferably, the freeze-drying temperature is -10 to 0°C, for example, -1°C, -3°C, -5°C, -7°C or -9°C.

[0046] Preferably, the acid used for the acidification treatment in step (5) is any one of oxalic acid, citric acid, terephthalic acid or acetic acid, or a combination of at least two thereof.

[0047] Preferably, the acid is terephthalic acid.

[0048] The acid used in the acidification treatment of the present invention contains carboxyl groups. After the acidification treatment, carboxyl groups are introduced into the particles. The carboxyl groups can react with ammonia. Moreover, carboxyl groups are introduced into the particle structure after carboxylation modification, which makes it easier to subsequently combine with metal ions to form metal organic framework materials (MOFs).

[0049] Preferably, the concentration of the acid is 0.05-0.15 mol / L, for example, 0.06 mol / L, 0.08 mol / L, 0.1 mol / L, 0.12 mol / L or 0.14 mol / L.

[0050] Preferably, the temperature during the acidification treatment is 30-60°C (for example, it can be 32°C, 35°C, 38°C, 40°C, 42°C, 45°C, 48°C, 50°C, 52°C, 55°C or 58°C, etc.), and the time is 2-4h (for example, it can be 2.1h, 2.3h, 2.5h, 2.7h, 2.9h, 3.1h, 3.3h, 3.5h, 3.7h or 3.9h, etc.).

[0051] Preferably, the liquid ratio of the acid-modified ultrafine porous particles to the metal ion aqueous solution in step (6) is 0.1-0.2 g / mL, for example, 0.11 g / mL, 0.13 g / mL, 0.15 g / mL, 0.17 g / mL or 0.19 g / mL.

[0052] Preferably, the concentration of the metal ion aqueous solution is 0.5-2.5 mol / L, for example, it can be 0.6 mol / L, 0.8 mol / L, 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.6 mol / L, 1.8 mol / L, 2 mol / L, 2.2 mol / L or 2.4 mol / L, etc.

[0053] Preferably, the metal ions include any one of aluminum ions, iron ions or titanium ions, or a combination of at least two of them.

[0054] Preferably, the mixing reaction in step (6) is carried out in a polytetrafluoroethylene reactor.

[0055] Preferably, the reaction temperature is 90-120°C (for example, 92°C, 95°C, 98°C, 100°C, 102°C, 105°C, 108°C, 110°C, 112°C, 115°C or 118°C, etc.), and the reaction time is 6-9h (for example, 6.2h, 6.5h, 6.8h, 7h, 7.2h, 7.5h, 7.8h, 8h, 8.2h, 8.5h or 8.8h, etc.).

[0056] Preferably, the porous particles are centrifuged after the reaction;

[0057] Preferably, the centrifugal rotation speed is 4000-600 rpm (for example, it can be 4200 rpm, 4500 rpm, 4800 rpm, 5000 rpm, 5200 rpm, 5500 rpm or 5800 rpm, etc.), and the time is 5-15 min (for example, it can be 6 min, 8 min, 10 min, 12 min or 14 min, etc.).

[0058] Preferably, the porous particles are washed after the centrifugation.

[0059] Preferably, the washing solvent is DMF and / or anhydrous ethanol.

[0060] Preferably, the drying temperature in step (6) is 100-120°C (for example, 102°C, 105°C, 108°C, 110°C, 112°C, 115°C or 118°C, etc.), and the drying time is 8-12h (for example, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h or 11.5h, etc.).

[0061] Any specific point value within the above numerical range can be selected, and will not be described in detail here.

[0062] In a second aspect, the present invention provides a porous particle with tar-reducing and harm-reducing efficacy, wherein the porous particle with tar-reducing and harm-reducing efficacy is prepared by the method described in the first aspect.

[0063] In a third aspect, the present invention provides a use of the porous particles having tar-reducing and harm-reducing effects as described in the second aspect in cigarette filter materials.

[0064] Compared with the prior art, the present invention has the following beneficial effects:

[0065] The invention uses natural plants as main raw materials, pre-crushes and screens the plants, mixes them with natural ores, and refines and separates the fibrous substances in the plant raw materials through ball mill treatment and ultra-fine treatment, thereby improving the surface properties of the fibers, increasing their roughness and active sites, and improving their surface reaction properties, which is beneficial to the physical and chemical modification of the materials.

[0066] At the same time, in order to more effectively adsorb harmful components in cigarette smoke, the material was further acidified and coordinated on the basis of the above treatment. After acidification, the plant structure and metal ions form a stable metal organic framework material with a highly ordered distribution of high specific surface area, and there is a complexation effect between metal ions and hydrogen cyanide, which further improves the adsorption effect of harmful components in cigarette smoke. DETAILED DESCRIPTION

[0067] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0068] The raw materials used in the following embodiments can be used as long as they are purchased from regular dealers.

[0069] Example 1

[0070] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm, and the preparation method comprises:

[0071] (1) First, 100 g of plant raw materials (licorice, polygonatum and kudzu root in a mass ratio of 3:1:2) were dried to a moisture content of 8%, then crushed, and passed through a 60-mesh sieve to obtain plant particles;

[0072] (2) ball milling the plant particles described in step (1) and 400 g of inorganic filler (vermiculite, montmorillonite and kaolinite in a mass ratio of 3:8:6) in a ball mill for 1.5 h, controlling the speed of the ball mill to 350 rpm, and drying the milled material to a moisture content of 2% to obtain mixed particles;

[0073] (3) The mixed particles are subjected to ultrafine treatment using a jet mill, and ultrafine particles are obtained after being sieved through a 300-mesh sieve;

[0074] (4) mixing the ultrafine particles with a 20% polyethylene glycol aqueous solution (solid-liquid ratio of 0.1 g / mL) at 80° C. for 1.5 h, filtering, and freeze-drying at −5° C. for 30 min to obtain ultrafine porous particles;

[0075] (5) subjecting the ultrafine porous particles to an acidification reaction with 0.1 mol / L terephthalic acid at 50° C. for 3 h to obtain acid-modified ultrafine porous particles;

[0076] (6) The acid-modified ultrafine porous particles were mixed with a 2 mol / L iron ion aqueous solution (solid-liquid ratio of 0.15 g / mL) in a polytetrafluoroethylene reactor, and then reacted at 100°C for 8 h. After cooling, the particles were taken out and centrifuged at 5000 rpm for 10 min. The particles were then washed alternately with DMF and anhydrous ethanol for 3 times each, and finally activated in an oven at 110°C for 10 h to obtain porous particles with tar reduction and harm reduction effects.

[0077] Example 2

[0078] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm, and the preparation method comprises:

[0079] (1) First, 100 g of plant raw materials (Glycyrrhiza uralensis, Polygonatum sibiricum and Pueraria lobata in a mass ratio of 2:0.4:0.5) were dried to a moisture content of 5%, then crushed, and passed through a 40-mesh sieve to obtain plant particles;

[0080] (2) ball milling the plant particles described in step (1) and 500 g of inorganic filler (vermiculite, montmorillonite and kaolinite in a mass ratio of 2:3:2) in a ball mill for 1 h, controlling the speed of the ball mill to 400 rpm, and drying the milled material to a moisture content of 3% to obtain mixed particles;

[0081] (3) The mixed particles are subjected to ultrafine treatment using a jet mill, and ultrafine particles are obtained after being sieved through a 400-mesh sieve;

[0082] (4) mixing the ultrafine particles with a 10% polyethylene glycol aqueous solution (solid-liquid ratio of 0.08 g / mL) at 90° C. for 1 h, filtering, and freeze-drying at −10° C. for 20 min to obtain ultrafine porous particles;

[0083] (5) subjecting the ultrafine porous particles to an acidification reaction with 0.08 mol / L terephthalic acid at 60° C. for 2 h to obtain acid-modified ultrafine porous particles;

[0084] (6) The acid-modified ultrafine porous particles were mixed with a 1 mol / L titanium ion aqueous solution (solid-liquid ratio of 0.1 g / mL) in a polytetrafluoroethylene reactor, and then reacted at 90°C for 9 h. After cooling, the particles were taken out and centrifuged at 6000 rpm for 8 min. The particles were then washed alternately with DMF and anhydrous ethanol twice each, and finally activated in an oven at 100°C for 12 h to obtain porous particles with tar reduction and harm reduction effects.

[0085] Example 3

[0086] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm, and the preparation method comprises:

[0087] (1) First, 100 g of plant raw materials (Glycyrrhiza uralensis, Polygonatum sibiricum and Pueraria lobata in a mass ratio of 1:1:1.5) were dried to a moisture content of 4%, then crushed, and passed through an 80-mesh sieve to obtain plant particles;

[0088] (2) ball milling the plant particles described in step (1) and 300 g of inorganic filler (vermiculite, montmorillonite and kaolinite in a mass ratio of 1:5:5) in a ball mill for 1 h, controlling the speed of the ball mill to 300 rpm, and drying the milled material to a moisture content of 2.5% to obtain mixed particles;

[0089] (3) The mixed particles are subjected to ultrafine treatment using a jet mill, and ultrafine particles are obtained after being sieved through a 200-mesh sieve;

[0090] (4) mixing the ultrafine particles with a 25% polyethylene glycol aqueous solution (solid-liquid ratio of 0.15 g / mL) at 60° C. for 2 h, filtering, and freeze-drying at −1° C. for 40 min to obtain ultrafine porous particles;

[0091] (5) subjecting the ultrafine porous particles to an acidification reaction with 0.15 mol / L terephthalic acid at 30° C. for 4 h to obtain acid-modified ultrafine porous particles;

[0092] (6) The acid-modified ultrafine porous particles were mixed with a 2.5 mol / L zinc ion aqueous solution (solid-liquid ratio of 0.2 g / mL) in a polytetrafluoroethylene reactor, and then reacted at 120°C for 6 h. After cooling, the particles were taken out and centrifuged at 4000 rpm for 15 min. The particles were then washed alternately with DMF and anhydrous ethanol once each, and finally activated in an oven at 120°C for 8 h to obtain porous particles with tar reduction and harm reduction effects.

[0093] Example 4

[0094] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm. The only difference between this method and embodiment 1 is that the plant raw materials in step (1) are only liquorice and polygonatum in a mass ratio of 3:1, and the amount of plant raw materials is kept unchanged. The remaining steps are consistent with embodiment 1.

[0095] Example 5

[0096] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm. The only difference between this method and embodiment 1 is that the plant raw materials in step (1) are only licorice and kudzu root in a mass ratio of 3:2, and the amount of plant raw materials is kept unchanged. The remaining steps are consistent with embodiment 1.

[0097] Example 6

[0098] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm. The only difference between this method and embodiment 1 is that the plant raw materials in step (1) are only Polygonatum sibiricum and Pueraria lobata in a mass ratio of 1:2, and the amount of plant raw materials is kept unchanged. The remaining steps are consistent with embodiment 1.

[0099] Example 7

[0100] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm. The only difference between the method and the embodiment 1 is that in step (2), the inorganic filler is vermiculite and montmorillonite in a mass ratio of 3:8, and the amount of the inorganic filler is kept unchanged. The remaining steps are consistent with the embodiment 1.

[0101] Example 8

[0102] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm. The only difference between the method and the embodiment 1 is that in step (2), the inorganic filler is vermiculite and kaolinite in a mass ratio of 1:2, and the amount of the inorganic filler is kept unchanged. The remaining steps are consistent with the embodiment 1.

[0103] Example 9

[0104] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm. The only difference between this method and Embodiment 1 is that in step (2), the inorganic filler is montmorillonite and kaolinite in a mass ratio of 4:3, and the amount of inorganic filler is kept unchanged. The remaining steps are consistent with Embodiment 1.

[0105] Example 10

[0106] This embodiment provides a method for preparing porous particles with the effect of reducing tar and reducing harm. The only difference between this method and Example 1 is that the acid used in step (5) is hydrochloric acid with a concentration of 0.1 mol / L, and the remaining steps are consistent with Example 1.

[0107] Comparative Example 1

[0108] This comparative example provides a method for preparing porous particles with tar reduction and harm reduction effects, the preparation method comprising:

[0109] (1) Pre-crushing: First, 100 g of plant raw materials (licorice, polygonatum and kudzu root in a mass ratio of 3:1:2) were dried to a moisture content of 8%, then crushed, and passed through a 60-mesh sieve to obtain plant particles;

[0110] (2) Ultrafine treatment: The plant particles are ultrafinely treated using a jet mill and passed through a 300-mesh sieve to obtain ultrafine particles;

[0111] (3) Porosification treatment: The ultrafine particles were mixed with a 20% polyethylene glycol aqueous solution (solid-liquid ratio of 0.1 g / mL) at 80°C for 1.5 h, filtered, and freeze-dried at -5°C for 30 min to obtain ultrafine porous particles;

[0112] (4) Acid modification: The ultrafine porous particles are subjected to an acidification reaction with 0.1 mol / L terephthalic acid at 50° C. for 3 h to obtain acid-modified ultrafine porous particles;

[0113] (5) Coordination treatment: The acid-modified ultrafine porous particles were mixed with a 2 mol / L iron ion aqueous solution (solid-liquid ratio of 0.15 g / mL) in a polytetrafluoroethylene reactor, and then reacted at 100°C for 8 h. After drying, porous particles with the effect of reducing tar and reducing harm were obtained.

[0114] Comparative Example 2

[0115] This comparative example provides a method for preparing porous particles with tar reduction and harm reduction effects, the preparation method comprising:

[0116] (1) Pre-crushing: First, 100 g of plant raw materials (licorice, polygonatum and kudzu root in a mass ratio of 3:1:2) were dried to a moisture content of 8%, then crushed, and passed through a 60-mesh sieve to obtain plant particles;

[0117] (2) solid phase mechanical treatment: the plant particles described in step (1) and 400 g of inorganic filler (vermiculite, montmorillonite and kaolinite in a mass ratio of 3:8:6) were ball milled in a ball mill for 1.5 h, the speed of the ball mill was controlled to 350 rpm, and the milled material was dried to a moisture content of 2% to obtain mixed particles;

[0118] (3) Porosification treatment: The mixed particles were mixed with a 20% polyethylene glycol aqueous solution (solid-liquid ratio of 0.1 g / mL) at 80°C for 1.5 h, filtered, and freeze-dried at -5°C for 30 min to obtain ultrafine porous particles;

[0119] (4) Acid modification: The ultrafine porous particles are subjected to an acidification reaction with 0.1 mol / L terephthalic acid at 50° C. for 3 h to obtain acid-modified ultrafine porous particles;

[0120] (5) Coordination treatment: The acid-modified ultrafine porous particles were mixed with a 2 mol / L iron ion aqueous solution (solid-liquid ratio of 0.15 g / mL) in a polytetrafluoroethylene reactor, and then reacted at 100°C for 8 h. After drying, porous particles with tar reduction and harm reduction effects were obtained.

[0121] Comparative Example 3

[0122] This comparative example provides a method for preparing porous particles with tar reduction and harm reduction effects, the preparation method comprising:

[0123] (1) Pre-crushing: First, 100 g of plant raw materials (licorice, polygonatum and kudzu root in a mass ratio of 3:1:2) were dried to a moisture content of 8%, then crushed, and passed through a 60-mesh sieve to obtain plant particles;

[0124] (2) solid phase mechanical treatment: the plant particles described in step (1) and 400 g of inorganic filler (vermiculite, montmorillonite and kaolinite in a mass ratio of 3:8:6) were ball milled in a ball mill for 1.5 h, the speed of the ball mill was controlled to 350 rpm, and the milled material was dried to a moisture content of 2% to obtain mixed particles;

[0125] (3) Ultrafine treatment: The mixed particles are ultrafinely treated using a jet mill and passed through a 300-mesh sieve to obtain ultrafine particles;

[0126] (4) Acidification modification: The ultrafine particles were subjected to an acidification reaction with 0.1 mol / L terephthalic acid at 50° C. for 3 h to obtain acid-modified ultrafine porous particles;

[0127] (5) Coordination treatment: The acid-modified ultrafine porous particles were mixed with a 2 mol / L copper ion aqueous solution (solid-liquid ratio of 0.15 g / mL) in a polytetrafluoroethylene reactor, and then reacted at 80°C for 2 h. After drying, porous particles with tar reduction and harm reduction effects were obtained.

[0128] Comparative Example 4

[0129] This comparative example provides a method for preparing porous particles with tar reduction and harm reduction effects, the preparation method comprising:

[0130] (1) Pre-crushing: First, 100 g of plant raw materials (licorice, polygonatum and kudzu root in a mass ratio of 3:1:2) were dried to a moisture content of 8%, then crushed, and passed through a 60-mesh sieve to obtain plant particles;

[0131] (2) solid phase mechanical treatment: the plant particles described in step (1) and 400 g of inorganic filler (vermiculite, montmorillonite and kaolinite in a mass ratio of 3:8:6) were ball milled in a ball mill for 1.5 h, the speed of the ball mill was controlled to 350 rpm, and the milled material was dried to a moisture content of 2% to obtain mixed particles;

[0132] (3) Ultrafine treatment: The mixed particles are ultrafinely treated using a jet mill and passed through a 300-mesh sieve to obtain ultrafine particles;

[0133] (4) Porosification treatment: The ultrafine particles were mixed with a 20% polyethylene glycol aqueous solution (solid-liquid ratio of 0.1 g / mL) at 80°C for 1.5 h, filtered, and freeze-dried at -5°C for 30 min to obtain ultrafine porous particles;

[0134] (5) Coordination treatment: The ultrafine porous particles were mixed with a 2 mol / L copper ion aqueous solution (solid-liquid ratio of 0.15 g / mL) in a polytetrafluoroethylene reactor, and then reacted at 80°C for 2 h. After drying, porous particles with tar reduction and harm reduction effects were obtained.

[0135] Comparative Example 5

[0136] This comparative example provides a method for preparing porous particles with tar reduction and harm reduction effects, the preparation method comprising:

[0137] (1) Pre-crushing: First, 100 g of plant raw materials (licorice, polygonatum and kudzu root in a mass ratio of 3:1:2) were dried to a moisture content of 8%, then crushed, and passed through a 60-mesh sieve to obtain plant particles;

[0138] (2) solid phase mechanical treatment: the plant particles described in step (1) and 400 g of inorganic filler (vermiculite, montmorillonite and kaolinite in a mass ratio of 3:8:6) were ball milled in a ball mill for 1.5 h, the speed of the ball mill was controlled to 350 rpm, and the milled material was dried to a moisture content of 2% to obtain mixed particles;

[0139] (3) Ultrafine treatment: The mixed particles are ultrafinely treated using a jet mill and passed through a 300-mesh sieve to obtain ultrafine particles;

[0140] (4) Porosification treatment: The ultrafine particles were mixed with a 20% polyethylene glycol aqueous solution (solid-liquid ratio of 0.1 g / mL) at 80°C for 1.5 h, filtered, and freeze-dried at -5°C for 30 min to obtain ultrafine porous particles;

[0141] (5) Acidification modification: The ultrafine porous particles are subjected to an acidification reaction with terephthalic acid at a concentration of 50°C for 3 hours to obtain porous particles with the effect of reducing tar and reducing harm.

[0142] Test Example 1

[0143] The porous particles obtained in Examples 1-10 and Comparative Examples 1-5 were added to the cigarette filter at an amount of 40 mg / cigarette. 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) to pick out the test cigarettes that meet the standards. The cigarette smoking test was carried out on a smoking machine according to standard smoking conditions, and the tar, ammonia and crotonaldehyde in the cigarette smoke were detected according to standards GB / T19609-2004, YC / T377-2019 and YC / T254-2008, respectively. The cigarettes without any particles were used as control cigarettes.

[0144] The results are shown in Table 1.

[0145] Table 1

[0146] sample <![CDATA[Tar (mg·cig -1 )]]> <![CDATA[Ammonia (μg·cig -1 )]]> <![CDATA[Crotonaldehyde (μg·cig -1 )]]> Example 1 5.4 3.2 6.2 Example 2 5.5 3.1 6.5 Example 3 5.7 3.4 6.3 Example 4 5.9 3.6 6.8 Example 5 5.8 3.7 6.7 Example 6 6.1 3.6 6.6 Example 7 6.8 3.5 7.1 Example 8 6.9 3.8 6.8 Example 9 7.1 3.7 6.9 Example 10 6.8 3.8 6.8 Comparative Example 1 7.6 5.8 11.1 Comparative Example 2 7.5 5.7 11.6 Comparative Example 3 7.6 6.2 10.9 Comparative Example 4 7.4 6.1 10.8 Comparative Example 5 7.7 6.0 11.2 Control cigarettes 8.8 9.2 14.1

[0147] It can be seen from the data in Table 1 that the porous particles with tar-reducing and harm-reducing effects obtained by the present invention have lower contents of harmful chemical components in cigarette smoke after being used in cigarettes.

[0148] In Examples 7-9, when the inorganic filler in the preparation process is not the combination specified in the present invention, the modification effect of the plant particles is poor, and thus the adsorption performance thereof is also reduced;

[0149] In Example 10, only when the acid used in the acidification reaction is a carboxylic acid as defined in the present invention can the effect of reducing harmful components in flue gas be better.

[0150] In Comparative Examples 1-5, when any step in the method is missing during the preparation process, the adsorption effect of the porous particles will be affected.

[0151] Test Example 2 Sensory Evaluation

[0152] The particles of Examples 1-6 were prepared into test cigarettes according to the method of Test Example 1, and cigarettes without any other ingredients were used as control cigarettes for sensory evaluation.

[0153] Organize 7 tasters to evaluate and score the food according to the evaluation contents and criteria in Table 2-3. The sensory quality indicators are scored on a 100-point scale.

[0154] The sensory quality evaluation indicators are: smoke volume (referring to smoke concentration and consistency), aroma, strength, harmony, irritation and taste (aftertaste); the specific definitions of the six sensory quality evaluation indicators are shown in Table 3, and the evaluation criteria of the six sensory quality evaluation indicators are shown in Table 3.

[0155] Table 2

[0156]

[0157] Table 3

[0158]

[0159]

[0160] The specific results are shown in Table 4:

[0161] Table 4

[0162] sample Smoke volume aroma Momentum coordination Irritant Taste Total score Example 1 8.8 28.9 9.2 9.1 14.5 23.8 94.3 Example 2 9.2 28.6 9.4 9.2 14.2 24.1 94.7 Example 3 8.6 28.4 9.2 8.9 14.1 23.9 93.1 Example 4 7.2 25.6 7.6 6.9 11.5 20.5 79.3 Example 5 7.8 24.9 7.2 6.8 12.1 21.2 80 Example 6 7.5 25.1 7.3 6.7 12.2 21.3 80.1 Control cigarettes 6.5 23.1 7.1 6.2 10.5 18.6 72

[0163] It can be seen from the data in Table 4 that after adding the porous particles with tar-reducing and harm-reducing effects of the present invention, the tobacco aroma of the cigarette is stronger, fuller and softer, and can effectively reduce throat irritation and improve the aftertaste in the mouth.

[0164] It can be seen from Examples 4-6 that liquorice, polygonatum and kudzu root have a synergistic effect in improving the aroma and taste of cigarettes.

[0165] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the preparation method of porous particles with tar reduction and harm reduction effects, its products and applications, 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.

[0166] 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.

[0167] 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 porous particles with tar reduction and harm reduction effects, characterized in that: The preparation method comprises: (1) crushing the plant raw material and sieving to obtain plant particles; (2) mixing the plant particles and the inorganic filler, subjecting the mixture to ball milling, and drying the mixture to obtain mixed particles; (3) subjecting the mixed particles to ultrafine processing and obtaining ultrafine particles after sieving; (4) mixing the ultrafine particles with a polyethylene glycol aqueous solution, filtering and drying to obtain ultrafine porous particles; (5) acidifying the ultrafine porous particles to obtain acid-modified ultrafine porous particles; (6) The acid-modified ultrafine porous particles are mixed with a metal ion aqueous solution for reaction, and then dried to obtain the porous particles having the effect of reducing tar and reducing harm.

2. The preparation method according to claim 1, characterized in that: Before the pulverization in step (1), the plant material is dried to a moisture content of ≤10%; Preferably, the plant raw material comprises any one of liquorice, platycodon, polygonatum, kudzu root, arisaema, magnolia or tangerine peel, or a combination of at least two thereof; Preferably, the plant raw material is a combination of liquorice, polygonatum and kudzu root; Preferably, the mass ratio of liquorice, polygonatum and kudzu root is (1-2):(0.1-1):(0.5-1.5); Preferably, the mesh size of the sieving in step (1) is 40-80 meshes.

3. The preparation method according to claim 1 or 2, characterized in that: The mass ratio of the plant particles to the inorganic filler in step (2) is 1:(2-5); Preferably, the inorganic filler comprises any one of vermiculite, montmorillonite or kaolinite or a combination of at least two thereof; Preferably, the inorganic filler is a combination of vermiculite, montmorillonite and kaolinite; Preferably, the mass ratio of the vermiculite, montmorillonite and kaolinite is (1-2):(3-5):(2-5).

4. The preparation method according to any one of claims 1 to 3, characterized in that The ball milling process in step (2) is carried out in a ball mill; Preferably, the rotation speed of the ball mill is 300-400 rpm; Preferably, the ball milling time is 0.5-2h; Preferably, the drying in step (2) is performed to a moisture content of ≤3%.

5. The preparation method according to any one of claims 1 to 4, characterized in that The ultrafine treatment in step (3) is carried out in a jet mill; Preferably, the mesh size of the sieving in step (3) is 200-400 mesh.

6. The preparation method according to any one of claims 1 to 5, characterized in that The solid-liquid ratio of the ultrafine particles to the polyethylene glycol aqueous solution in step (4) is 0.05-0.15 g / mL; Preferably, the mass concentration of the polyethylene glycol aqueous solution is 10-25%; Preferably, the mixing temperature in step (4) is 60-100° C. and the mixing time is 0.5-2 h; Preferably, the drying method in step (4) is freeze-drying; Preferably, the freeze-drying temperature is -10 to 0°C.

7. The preparation method according to any one of claims 1 to 6, characterized in that The acid used in the acidification treatment in step (5) is any one of oxalic acid, citric acid, terephthalic acid or acetic acid, or a combination of at least two thereof; Preferably, the acid is terephthalic acid; Preferably, the concentration of the acid is 0.05-0.15 mol / L; Preferably, the acidification treatment is carried out at a temperature of 30-60°C and for a time of 2-4 hours.

8. The preparation method according to any one of claims 1 to 7, characterized in that In step (6), the solid-liquid ratio of the acidified modified ultrafine porous particles to the metal ion aqueous solution is 0.1-0.2 g / mL; Preferably, the concentration of the metal ion aqueous solution is 0.5-2.5 mol / L; Preferably, the metal ions include any one or a combination of at least two of aluminum ions, iron ions or titanium ions; Preferably, the mixing reaction in step (6) is carried out in a polytetrafluoroethylene reactor; Preferably, the reaction temperature is 90-120°C and the reaction time is 6-9h; Preferably, the porous particles are centrifuged after the reaction; Preferably, the centrifugal speed is 4000-600 rpm and the time is 5-15 min; Preferably, the porous particles are washed after the centrifugation; Preferably, the washing solvent is DMF and / or anhydrous ethanol; Preferably, the drying temperature in step (6) is 100-120° C. and the drying time is 8-12 h.

9. A porous particle with the effect of reducing tar and harm, characterized in that: The porous particles with tar reduction and harm reduction effects are prepared by the method described in any one of claims 1 to 8.

10. Use of the porous particles with tar-reducing and harm-reducing effects as claimed in claim 9 in cigarette filter materials.

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