Additive for reducing CO and tar release in cigars, and preparation method and application thereof

Abstract

The present invention relates to the technical field of cigars, and in particular to an additive for reducing the emission of CO and tar from cigars, as well as its preparation method and application. The additive has a core-shell structure comprising, from the inside out, an inner core, an intermediate layer, and an outer layer; the inner core comprises an organic acid, the intermediate layer comprises rosin glycerol ester, and the outer layer comprises chitosan-loaded metal oxide. The present application adopts a structure in which a rosin glycerol ester-coated organic acid is coated with chitosan-loaded metal oxide, and can apply an organic acid with a relatively low thermal decomposition temperature to cigars with a relatively low combustion temperature, thereby promoting thermal decomposition of the organic acid rather than combustion. The organic acid absorbs heat through thermal decomposition and conducts heat through the metal oxide, effectively reducing the combustion environment temperature of the cigar, thereby increasing the aerosol particle size to improve the tar filtration effect and reduce the amount of carbon monoxide generated, thereby achieving the effect of reducing the emission of CO and tar from the cigar.

Description

Technical Field

[0001] The present invention relates to the technical field of cigars, and in particular to an additive for reducing the release of CO and tar from cigars, and a preparation method and application thereof. Background Art

[0002] Cigars are a pure natural tobacco product made from raw tobacco leaves that have been air-dried, fermented, and aged. Traditional hand-made cigars are composed of three parts: the core, the binder, and the wrapper. When smoking, one end is lit and inhaled with the mouth at the other end to produce smoke.

[0003] Because the wrapper and binder of cigars have poor air permeability and are larger in size than cigarettes, and the tobacco core is wrapped with leaves and has a higher density, there is less air inside when smoking, and the combustion is more incomplete, resulting in higher tar release and CO content. Previous studies have shown that the tar release of cigars is as high as 201.2 mg / cigar, and the CO release of mainstream cigar smoke is as high as 497.4 mg / cigar.

[0004] To address the issue of CO and tar emissions in cigarettes, patent publication number CN101049184A discloses the use of a polyhydroxy organic acid salt in the preparation of cigarettes that reduce tar and carbon monoxide emissions. The polyhydroxy organic acid salt is used as an additive to the cigarette material, and its molecular formula contains three or more hydroxyl groups. The additive is added as a solution. This utilizes the polyhydroxy organic acid salt's ability to absorb heat and then undergo thermal decomposition, which lowers the temperature in the cigarette's combustion and decomposition zones. This increases the aerosol's particle size, causing it to settle and become more easily filtered by the filter, thereby reducing tar emissions. Furthermore, the reaction C + CO2 → CO is an endothermic equilibrium reaction, and the temperature drop facilitates the reverse reaction, thereby reducing carbon monoxide production.

[0005] However, compared to ordinary cigarettes, cigars burn at lower temperatures due to their thicker, denser tobacco leaves and less complete combustion. Generally speaking, the temperature at the center of a burning cigarette can reach 800-900°C, while the burning temperature of cigars is approximately 700-800°C. The technical effects achieved in existing technologies rely on the thermal decomposition of organic acid salts, which requires the organic acid salts to reach their thermal decomposition temperature. However, the thermal decomposition temperature of organic acid salts is relatively high, making them unsuitable for cigars, which burn at relatively low temperatures. Summary of the Invention

[0006] The present invention aims to solve the above problems and provides an additive suitable for cigars for reducing the amount of CO and tar released by cigars, as well as a preparation method and application thereof.

[0007] The technical solution to the problem solved by the present invention is as follows: first, an additive for reducing the CO and tar release of cigars is provided, wherein the additive has a core-shell structure comprising, from the inside to the outside, an inner core, an intermediate layer, and an outer layer; the inner core comprises an organic acid, the intermediate layer comprises rosin glycerol ester, and the outer layer comprises chitosan-loaded metal oxide.

[0008] In this application, organic acids are used in place of organic acid salts. Compared to organic acid salts, organic acids have lower thermal decomposition temperatures and can be used in cigars with lower combustion temperatures. Thermal decomposition absorbs heat, lowering the combustion temperature, thereby increasing aerosol particle size, improving tar filtration, and reducing carbon monoxide production, ultimately reducing CO and tar emissions. Furthermore, the acidic fragments produced by the decomposition of organic acids can adjust the ratio of protonated and free nicotine in the smoke, thereby improving the strength and flavor of the cigar and reducing the problem of aroma precursors not being able to decompose in time due to the decrease in combustion temperature, which reduces the aroma of the smoke.

[0009] However, organic acids differ from organic acid salts. If added directly to cigar tobacco, the burning process may cause the organic acids to combust, which consumes oxygen. As previously mentioned, the low air (oxygen) content in cigar tobacco contributes to its incomplete combustion, resulting in the production of more tar and CO. However, the oxygen consumption of organic acids may in turn result in a less pronounced reduction in tar and CO. Based on this, the present application considers encapsulating the organic acid in a shell to isolate the organic acid from the oxygen within the cigar tobacco, thereby promoting its decomposition rather than combustion. The shell should possess a certain degree of thermal stability and thermal conductivity. The thermal stability ensures that the organic acid remains stable and isolates it from oxygen at least until the organic acid reaches its thermal decomposition temperature. The thermal conductivity ensures that the organic acid effectively transfers the heat from the combustion of the cigar tobacco to the organic acid within the shell, thereby reducing its temperature. Therefore, the shell first comprises a chitosan-loaded metal oxide, with the metal oxide serving as a thermally stable and heat-conductive component and the chitosan serving as a film-forming coating. In addition, metal oxides can catalyze the conversion of CO into CO2, further reducing CO emissions, and can absorb tar. Chitosan also helps retain moisture in cigar tobacco leaves. However, because chitosan dissolves in acidic conditions, it is difficult to directly coat organic acids. Therefore, the shell also includes rosin glycerol ester. The rosin glycerol ester film is located between the organic acid and the chitosan-loaded metal oxide film. Hydrogen bonds are formed between the hydroxyl groups of the organic acid and the hydroxyl and amino groups of the chitosan, helping the chitosan-loaded metal oxide film to coat the organic acid. Rosin glycerol ester also protects the organic acid from being dissolved by water vapor generated during smoking, which would affect thermal cracking. It can also serve as a flavoring to reduce smoke irritation.

[0010] Based on the above content, the technical solution of this application is completed.

[0011] The choice of organic acid is not limited. Preferably, the pyrolysis product has no negative impact on cigar smoke, or even improves cigar smoke. Preferably, the organic acid is selected from at least one of citric acid, malic acid, and oxalic acid. The three organic acids can be used individually or as a mixture. When used as a mixture, the preferred mass ratio of citric acid, malic acid, and oxalic acid is (2-4):(1-3):1, more preferably 3:2:1.

[0012] The choice of metal oxide is not limited, and metal oxides having empty orbitals or having surface adsorption capacity are preferred. As a preferred embodiment of the present invention, the metal oxide is selected from at least one of iron oxide, copper oxide, aluminum oxide, zinc oxide, and cobalt oxide. Preferably, it is at least one of iron oxide and copper oxide.

[0013] Another object of the present invention is to provide a method for preparing an additive for reducing CO and tar emissions from cigars, comprising the following steps:

[0014] S1. Coating an organic acid with rosin glycerol ester to obtain product a;

[0015] S2. Using chitosan to load metal oxide to obtain product b;

[0016] S3. Add product a to the dispersion of product b, disperse, filter, and dry to obtain an additive.

[0017] In step S1 The coating method is not limited. As a preferred method of the present invention, an organic acid is added to a solution of rosin glycerol ester, dispersed, filtered, washed, and dried to obtain product a.

[0018] Preferably, the organic acid is dried organic acid solid particles, prepared by the following steps: freeze-drying the organic acid at -50 to -40°C in a vacuum for 1 to 4 hours, and then grinding the organic acid at 0 to 10°C and 300 to 400 r / min for 40 to 80 minutes to obtain the organic acid solid particles. The vacuum freeze-drying temperature can be -50°C, -48°C, -45°C, -42°C, or -40°C, preferably -45°C; the vacuum freeze-drying time can be 1 hour, 2 hours, 3 hours, or 4 hours, preferably 3 hours. The grinding temperature can be 0°C, 2°C, 4°C, 6°C, 8°C, or 10°C, preferably 2°C; the grinding speed can be 300 r / min, 320 r / min, 340 r / min, 360 r / min, 380 r / min, or 400 r / min, preferably 400 r / min; and the grinding time can be 40 min, 50 min, 60 min, 70 min, or 80 min, preferably 60 min.

[0019] Preferably, the rosin glycerol ester solution is a solution of rosin glycerol ester dissolved in dichloromethane, and the concentration of rosin glycerol ester in the solution is 10-40wt%, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, preferably 25wt%.

[0020] Preferably, the mass ratio of the organic acid to the rosin glycerol ester is 1:(1-4), such as 1:1, 1:2, 1:3, 1:4, preferably 1:2.

[0021] Preferably, the dispersion operation is as follows: adding the organic acid to the rosin glycerol ester solution at 30-40°C and stirring for 60-100 minutes. The temperature may be 30°C, 32°C, 34°C, 36°C, 38°C, or 40°C, preferably 30°C; and the stirring time may be 60 minutes, 70 minutes, 80 minutes, 90 minutes, or 100 minutes, preferably 90 minutes.

[0022] Preferably, the washing operation is: washing with ethanol and water alternately.

[0023] Preferably, the drying operation is: first vacuum drying at 45-60°C for 30-60 minutes, then vacuum freeze drying at -50--40°C for 1-4 hours. The vacuum drying temperature can be 45°C, 50°C, 55°C, or 60°C, preferably 55°C; the vacuum drying time can be 30 minutes, 40 minutes, 50 minutes, or 60 minutes, preferably 50 minutes. The vacuum freeze drying temperature can be -50°C, -48°C, -45°C, -42°C, or -40°C, preferably -45°C; the vacuum freeze drying time can be 1 hour, 2 hours, 3 hours, or 4 hours, preferably 3 hours.

[0024] In step S2 , the load mode is not restricted.

[0025] In some embodiments As a preferred embodiment of the present invention, the loading method is: dispersing the metal oxide in the chitosan solution, and then vacuum freeze-drying to obtain product b.

[0026] Preferably, the concentration of the chitosan solution is 1-3 wt%, such as 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, preferably 2 wt%.

[0027] Preferably, the mass ratio of metal oxide to chitosan is 1:(1-10), for example, it can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, and preferably 1:5.

[0028] Preferably, the dispersion operation is as follows: after adding the metal oxide to the chitosan solution, homogenizing at a speed of 400-600 r / min for 60-90 min. The speed may be 400 r / min, 450 r / min, 500 r / min, 550 r / min, 600 r / min, preferably 500 r / min; and the time may be 60 min, 70 min, 80 min, 90 min, preferably 90 min.

[0029] Preferably, the vacuum freeze-drying is performed at a temperature not exceeding -50°C for 24 to 36 hours. The vacuum freeze-drying temperature may be -50°C, -55°C, or -60°C, preferably -50°C; and the vacuum freeze-drying time may be 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, or 36 hours, preferably 30 hours.

[0030] In other embodiments As a preferred method of the present invention, the loading method is as follows: after mixing the metal precursor solution with the chitosan solution, heating to 60-90°C, then adding alkaline solution, reacting for 0.5-1.5 hours, centrifuging, washing, and drying to obtain product b. The heating temperature can be 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, or 90°C, preferably 75°C; the reaction time can be 0.5 hours, 1 hour, or 1.5 hours, preferably 1 hour.

[0031] Preferably, the metal precursor is selected from at least one of an organic acid salt of a metal and an inorganic acid salt of a metal. The organic acid salt of the metal is selected from at least one of metal acetate, metal succinate, metal tartrate, metal citrate, and metal fumarate. The inorganic acid salt of the metal is selected from at least one of metal nitric acid fumes, metal sulfate, and metal hydrochloride.

[0032] Preferably, the concentration of the chitosan solution is 1-3 wt%, such as 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, preferably 2 wt%.

[0033] Preferably, the chitosan is carboxymethyl chitosan.

[0034] Preferably, the mixing mass ratio of the metal precursor to chitosan is 1:(1-10), based on the mass of the metal oxide that can be obtained, such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, preferably 1:5.

[0035] Preferably, after mixing, homogenization is performed at a speed of 800-1000 r / min for 60-90 min. The speed may be 800 r / min, 850 r / min, 900 r / min, 950 / min, 1000 r / min, preferably 900 r / min; and the time may be 60 min, 70 min, 80 min, 90 min, preferably 80 min.

[0036] Preferably, the alkali solution is at least one of sodium hydroxide and potassium hydroxide.

[0037] Preferably, the concentration of the alkali solution is 0.1-0.3 wt%, such as 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, preferably 0.2 wt%.

[0038] Preferably, the washing operation is: washing with anhydrous ethanol at least three times.

[0039] Preferably, the drying operation is: vacuum drying at 70-80°C for 10-14 hours. The drying temperature can be 70°C, 72°C, 75°C, 78°C, 80°C, preferably 75°C; the drying time can be 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, preferably 12 hours.

[0040] In step S3 As a preferred embodiment of the present invention, the mass ratio of product a to product b is 1:(1~2), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, and preferably 1:1.5.

[0041] As a preferred embodiment of the present invention, the dispersion of product b is a dispersion of product b in deionized water. Preferably, the mass ratio of product b to deionized water is (0.5-1.5):1, for example, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, and preferably 1:1.

[0042] Finally, another object of the present invention is to provide a method for reducing the CO and tar emissions of cigars using an additive comprising the following steps:

[0043] (1) Before rolling the cigar, spray the above-mentioned additives on the surface of the cigar filler tobacco leaves;

[0044] (2) Wait until the moisture content of the cigar core tobacco leaves is balanced before rolling.

[0045] In the present application, the additive is applied to the cigar filler tobacco leaves so as to play the role of thermal decomposition and cooling of the additive during the cigar combustion process, thereby reducing the release of tar and CO.

[0046] In step (1), as a preferred embodiment of the present invention, the mass ratio of cigar filler tobacco leaves to additives is 1:(0.01-0.05), for example, it can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, and is preferably 1:0.03.

[0047] As a preferred embodiment of the present invention, the additive is dispersed in deionized water and then sprayed onto the cigar filler tobacco leaves.

[0048] In step (2), as preferred embodiments of the present invention, the temperature during moisture equilibrium is 23-27°C, for example, 23°C, 24°C, 25°C, 26°C, or 27°C, preferably 25°C; the relative humidity is 58%-62%, for example, 58%, 59%, 60%, 61%, or 62%, preferably 60%; and the moisture equilibrium time is 12-24 hours, for example, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, or 24 hours, preferably 18 hours. After moisture equilibrium, the moisture content of the cigar is 14%-17%, for example, 14%, 15%, 16%, or 17%, preferably 15%.

[0049] As preferred embodiment of the present invention, in some embodiments, the following steps are also included:

[0050] (3) After the cigar is rolled, a filter tip is attached to the cigar, wherein the filter tip is filled with a biochar adsorbent.

[0051] The release of CO and tar can be further reduced by using an external filter. The biochar adsorbent has a large specific surface area and can provide a large number of adsorption sites for CO and tar. Just like a sponge has many pores to absorb water, the numerous tiny pores of biochar can absorb CO and tar molecules in cigar smoke, intercepting and fixing them in the filter, thereby reducing the amount entering the human body.

[0052] Preferably, the biochar adsorbent is biochar modified with the additive. The additive, when used in the filter, absorbs heat and reduces the heat of smoke entering the oral cavity, thereby lowering the inhalation temperature. Furthermore, the metal oxides on the surface, together with the biochar, further reduce the amount of CO and tar entering the body.

[0053] Preferably, the additive-modified biochar is obtained by the following steps: adding biochar to a 1-5% additive suspension at a mass ratio of 1:(5-10), soaking at 40-60°C for 5-10 hours, filtering, washing, and drying. The mass ratio of biochar to additive can be 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, preferably 1:8; the soaking temperature can be 40°C, 45°C, 50°C, 55°C, or 60°C, preferably 50°C; and the soaking time can be 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, preferably 8 hours.

[0054] The preferred biochar adsorbent of the present invention is pyrolytically modified biochar. Modification of the pore size and distribution of biochar can enhance selectivity. Cigar smoke components vary in molecular size and properties. Pyrolytically modified biochar filters can adjust their pore structure to allow CO and tar molecules to more easily enter and be adsorbed, while other gas components are less readily adsorbed.

[0055] Preferably, the pyrolysis-modified biochar is obtained by pyrolyzing the biomass material at 400-800°C for 5-10 hours, followed by cooling, cleaning, grinding, screening, washing, and drying. The pyrolysis temperature can be 400°C, 500°C, 600°C, 700°C, or 800°C, preferably 600°C; the pyrolysis time can be 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, preferably 8 hours.

[0056] The preferred biochar adsorbent of the present invention is organic acid-modified biochar. Organic acid-modified biochar has abundant functional groups on its surface, such as carboxyl, hydroxyl, and amine groups. These functional groups can react with CO and tar molecules to form chemical bonds, thereby firmly fixing them to the filter material.

[0057] Preferably, the organic acid-modified biochar is obtained by the following steps: adding the biochar to a 0.1-1 mol / L organic acid solution at a mass ratio of 1:(5-10), soaking at 40-60°C for 5-10 hours, filtering, washing, and drying. The concentration of the organic acid solution can be 0.1 mol / L, 0.2 mol / L, 0.5 mol / L, 0.8 mol / L, or 1 mol / L, preferably 0.5 mol / L; the mass ratio of the biochar to the organic acid solution can be 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10, preferably 1:8; the soaking temperature can be 40°C, 45°C, 50°C, 55°C, or 60°C, preferably 50°C; and the soaking time can be 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, preferably 8 hours.

[0058] Beneficial effects of the present invention:

[0059] The present application provides an additive, a preparation method thereof, and its application to cigar filler tobacco leaves. The additive adopts a structure in which chitosan-loaded metal oxides are coated with rosin glycerol esters and organic acids are coated. This structure enables the application of organic acids with relatively low thermal cracking temperatures in cigars with relatively low combustion temperatures, thereby promoting thermal cracking of the organic acids rather than combustion. The organic acid thermal cracking absorbs heat, which is then conducted by the metal oxides, effectively lowering the combustion temperature of the cigars. This increases the aerosol particle size, thereby improving the tar filtration effect and reducing the amount of carbon monoxide generated, thereby achieving the effect of reducing the amount of CO and tar released from the cigars. DETAILED DESCRIPTION

[0060] The following are specific embodiments of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.

[0061] Example 1

[0062] The invention discloses an additive for reducing the CO and tar release of cigars. The additive comprises citric acid as a core, rosin glycerol ester as a middle layer, and chitosan-loaded copper oxide as an outer layer.

[0063] This additive is prepared by the following steps:

[0064] S1. Coating an organic acid with rosin glycerol ester: Citric acid was freeze-dried at 45°C for 3 hours and then ground at 2°C and 400 rpm for 60 minutes to obtain citric acid solid particles. Rosin glycerol ester was dissolved in dichloromethane to prepare a membrane-forming solution with a rosin glycerol ester concentration of 25 wt%. One part of citric acid solid particles was added to eight parts of the membrane-forming solution (containing two parts of rosin glycerol ester) by weight and stirred at 30°C for 90 minutes. The solid was then filtered and washed alternately with ethanol and water. It was then vacuum-dried at 55°C for 30 minutes and then freeze-dried at -45°C for 3 hours to obtain product a.

[0065] S2. Loading metal oxides with chitosan: Dissolve carboxymethyl chitosan in deionized water to prepare a 2 wt% carboxymethyl chitosan solution. Add 2.5 parts of copper acetate monohydrate (approximately equivalent to 1 part of copper oxide) to 250 parts of the carboxymethyl chitosan solution (containing 5 parts of carboxymethyl chitosan) in a 30°C water bath and stir at 1500 r / min for 1 hour. The mixture was heated to 75°C and a 0.2 wt% sodium hydroxide solution was added dropwise at 1000 r / min. After reacting for 1 hour, the solid was filtered and washed three times with anhydrous ethanol by centrifugation. The solid was then vacuum-dried at 75°C for 12 hours to obtain product b.

[0066] S3. Add 1 part of product b to 1 part of deionized water, dispersing at 300 r / min for 10 minutes to obtain a dispersion. Add 1 part of product a to the dispersion, ultrasonically disperse for 45 minutes, filter out the solid, and vacuum dry the solid at 55°C for 30 minutes to obtain an additive.

[0067] The application of this additive includes the following steps:

[0068] (1) Add 3 parts of additives to 60 parts of deionized water according to mass, disperse evenly to obtain a suspension, and then spray it onto 100 parts of cigar filler tobacco leaves.

[0069] (2) Place the sprayed cigar core tobacco leaves at a temperature of 25°C and a humidity of 60% for 18 hours to achieve moisture balance, and then roll them into cigar products.

[0070] Example 2

[0071] This embodiment is basically the same as Embodiment 1, and the only difference is that step S2 is different.

[0072] Specifically: S2. Chitosan-loaded metal oxides: Prepare a 2 wt% chitosan solution, adding an appropriate amount of acetic acid to promote chitosan dissolution. Add 1 part copper oxide (by weight) to 250 parts chitosan solution (containing 5 parts chitosan). Homogenize at 500 rpm for 90 minutes at room temperature, then freeze-dry at -50°C for 30 hours to obtain product b.

[0073] Example 3

[0074] This embodiment is basically the same as embodiment 1, with the only difference being that the additives are citric acid and malic acid in a mass ratio of 3:1 as the core.

[0075] Specifically, only S1 is different: S1. Organic acid is coated with rosin glycerol ester: Citric acid is freeze-dried at 45°C for 3 hours and then ground at 2°C and 400 r / min for 60 minutes to obtain citric acid solid particles. Malic acid is freeze-dried at 45°C for 3 hours and then ground at 2°C and 400 r / min for 60 minutes to obtain malic acid solid particles. Rosin glycerol ester is dissolved in dichloromethane to prepare a membrane-forming solution with a rosin glycerol ester concentration of 25wt%. 0.75 parts of citric acid solid particles and 0.25 parts of malic acid solid particles are added to 8 parts of the membrane-forming solution, stirred at 30°C for 90 minutes, and then the solid is filtered and washed alternately with ethanol and water. The solid is first vacuum-dried at 55°C for 30 minutes and then vacuum-freeze-dried at -45°C for 3 hours to obtain product a.

[0076] Example 4

[0077] This embodiment is basically the same as embodiment 1, with the only difference being that the additives are citric acid, malic acid and oxalic acid in a mass ratio of 3:2:1 as the core.

[0078] Specifically, only S1 is different: S1. Organic acid coated with rosin glycerol ester: Citric acid was freeze-dried at 45°C for 3 hours in a vacuum atmosphere, and then ground at 2°C and 400 r / min for 60 minutes to obtain citric acid solid particles. Malic acid was freeze-dried at 45°C for 3 hours in a vacuum atmosphere, and then ground at 2°C and 400 r / min for 60 minutes to obtain malic acid solid particles. Oxalic acid was freeze-dried at 45°C for 3 hours in a vacuum atmosphere, and then ground at 2°C and 400 r / min for 60 minutes to obtain oxalic acid solid particles. Rosin glycerol ester was dissolved in dichloromethane to prepare a membrane-forming solution with a rosin glycerol ester concentration of 25 wt%. According to parts by mass, 0.5 parts of citric acid solid particles, 0.33 parts of malic acid solid particles, and 0.17 parts of oxalic acid solid particles were added to 8 parts of membrane-forming liquid and stirred at 30°C for 90 minutes. The solid matter was then filtered and washed alternately with ethanol and water. The solid matter was first vacuum-dried at 55°C for 30 minutes and then vacuum-freeze-dried at -45°C for 3 hours to obtain product a.

[0079] Example 5

[0080] This embodiment is basically the same as embodiment 1, with the only difference being that the additive uses chitosan loaded with iron oxide as the outer layer.

[0081] Specifically, only S2 differs: S2. Metal oxide loading with chitosan: Carboxymethyl chitosan was dissolved in deionized water to prepare a 2 wt% carboxymethyl chitosan solution. In a 30°C water bath, 1.8 parts of ferric acetate tetrahydrate (approximately equivalent to 1 part of iron oxide) were added to 250 parts of the carboxymethyl chitosan solution (containing 5 parts of carboxymethyl chitosan) and stirred at 1500 r / min for 1 hour. The mixture was heated to 75°C and a 0.2 wt% sodium hydroxide solution was added dropwise to the mixture at a stirring speed of 1000 r / min. After reacting for 1 hour, the solid was filtered and washed three times with anhydrous ethanol by centrifugation. The solid was then vacuum dried at 75°C for 12 hours to obtain product b.

[0082] Example 6

[0083] This embodiment is basically the same as embodiment 1, except that the mass ratio of the organic acid to the rosin glycerol ester is 1:1.

[0084] Specifically, only S1 is different: S1. Organic acid coated with rosin glycerol ester: Citric acid was freeze-dried at 45°C for 3 hours and then ground at 2°C and 400 rpm for 60 minutes to obtain citric acid solid particles. Rosin glycerol ester was dissolved in dichloromethane to prepare a film-forming solution with a rosin glycerol ester concentration of 25wt%. One part of citric acid solid particles was added to four parts of the film-forming solution (containing one part of rosin glycerol ester) by weight and stirred at 30°C for 90 minutes. The solid was then filtered and washed alternately with ethanol and water. It was then vacuum-dried at 55°C for 30 minutes and then freeze-dried at -45°C for 3 hours to obtain product a.

[0085] Example 7

[0086] This embodiment is substantially the same as embodiment 1, except that the mass ratio of the organic acid to the rosin glycerol ester is 1:4.

[0087] Specifically, only S1 is different: S1. Organic acid coated with rosin glycerol ester: Citric acid was freeze-dried at 45°C for 3 hours and then ground at 2°C and 400 rpm for 60 minutes to obtain citric acid solid particles. Rosin glycerol ester was dissolved in dichloromethane to prepare a membrane-forming solution with a rosin glycerol ester concentration of 25 wt%. One part of citric acid solid particles was added to 16 parts of the membrane-forming solution (containing 4 parts of rosin glycerol ester) by weight and stirred at 30°C for 90 minutes. The solid was then filtered and washed alternately with ethanol and water. It was then vacuum-dried at 55°C for 30 minutes and then freeze-dried at -45°C for 3 hours to obtain product a.

[0088] Example 8

[0089] This embodiment is basically the same as embodiment 1, except that the mass ratio of metal oxide to chitosan is 1:1.

[0090] Specifically, only S2 differs: S2. Chitosan-loaded metal oxide: Carboxymethyl chitosan was dissolved in deionized water to prepare a 2 wt% carboxymethyl chitosan solution. In a 30°C water bath, 2.5 parts of copper acetate monohydrate (approximately equivalent to 1 part of copper oxide) were added to 50 parts of the carboxymethyl chitosan solution (containing 1 part of carboxymethyl chitosan) and stirred at 1500 r / min for 1 hour. The mixture was heated to 75°C and a 0.2 wt% sodium hydroxide solution was added dropwise to the mixture at a stirring speed of 1000 r / min. After reacting for 1 hour, the solid was filtered and washed three times with anhydrous ethanol by centrifugation. The solid was then vacuum-dried at 75°C for 12 hours to obtain product b.

[0091] Example 9

[0092] This embodiment is substantially the same as embodiment 1, except that the mass ratio of the metal oxide to the chitosan is 1:10.

[0093] Specifically, only S2 differs: S2. Chitosan-loaded metal oxide: Carboxymethyl chitosan was dissolved in deionized water to prepare a 2 wt% carboxymethyl chitosan solution. In a 30°C water bath, 2.5 parts of copper acetate monohydrate (approximately equivalent to 1 part of copper oxide) were added to 500 parts of the carboxymethyl chitosan solution (containing 10 parts of carboxymethyl chitosan) and stirred at 1500 r / min for 1 hour. The mixture was heated to 75°C and a 0.2 wt% sodium hydroxide solution was added dropwise to the mixture at a stirring speed of 1000 r / min. After reacting for 1 hour, the solid was filtered and washed three times with anhydrous ethanol by centrifugation. The solid was then vacuum-dried at 75°C for 12 hours to obtain product b.

[0094] Example 10

[0095] This embodiment is substantially the same as embodiment 1, except that the mass ratio of product a to product b is 1:1.5.

[0096] Specifically, only S3 was different: S3. 1.5 parts of product b were added to 1.5 parts of deionized water, dispersed at 300 r / min for 10 minutes to obtain a dispersion. 1 part of product a was added to the dispersion, ultrasonically dispersed for 45 minutes, and the solid was filtered and vacuum dried at 55°C for 30 minutes to obtain an additive.

[0097] Example 11

[0098] This embodiment is substantially the same as embodiment 1, except that the mass ratio of product a to product b is 1:2.

[0099] Specifically, only S3 is different: S3. 2 parts of product b were added to 2 parts of deionized water, dispersed at 300 r / min for 10 minutes to obtain a dispersion. 1 part of product a was added to the dispersion, ultrasonically dispersed for 45 minutes, and the solid was filtered and vacuum dried at 55°C for 30 minutes to obtain an additive.

[0100] Blank example

[0101] (1) Spray 60 parts of deionized water onto 100 parts of cigar filler tobacco leaves.

[0102] (2) Place the sprayed cigar core tobacco leaves at a temperature of 25°C and a humidity of 60% for 18 hours to allow moisture to equilibrate, and then roll them into cigar products.

[0103] Comparative Example 1

[0104] Citric acid is used as an additive.

[0105] (1) Add 3 parts of citric acid to 60 parts of deionized water, disperse evenly to obtain a citric acid solution, and then spray it onto 100 parts of cigar filler tobacco leaves.

[0106] (2) Place the sprayed cigar core tobacco leaves at a temperature of 25°C and a humidity of 60% for 18 hours to achieve moisture balance, and then roll them into cigar products.

[0107] Comparative Example 2

[0108] This comparative example is basically the same as Example 1, except that only product a is used as an additive.

[0109] (1) Add 3 parts of product a to 60 parts of deionized water, disperse uniformly to obtain a suspension, and then spray it onto 100 parts of cigar filler tobacco leaves.

[0110] (2) Place the sprayed cigar core tobacco leaves at a temperature of 25°C and a humidity of 60% for 18 hours to achieve moisture balance, and then roll them into cigar products.

[0111] Comparative Example 3

[0112] This comparative example is basically the same as Example 1, except that only product b is used as the additive.

[0113] (1) Add 3 parts of product b to 60 parts of deionized water, disperse evenly to obtain a suspension, and then spray it onto 100 parts of cigar filler tobacco leaves.

[0114] (2) Place the sprayed cigar core tobacco leaves at a temperature of 25°C and a humidity of 60% for 18 hours to achieve moisture balance, and then roll them into cigar products.

[0115] Comparative Example 4

[0116] This comparative example is basically the same as Example 1, except that the additives include sodium citrate as the core, rosin glycerol ester as the middle layer, and chitosan-loaded copper oxide as the outer layer.

[0117] Specifically, only S1 differs: S1. Coating an organic acid salt with rosin glycerol ester: Sodium citrate was freeze-dried in a vacuum at 45°C for 3 hours and then ground at 2°C and 400 rpm for 60 minutes to obtain sodium citrate solid particles. Rosin glycerol ester was dissolved in dichloromethane to prepare a membrane-forming solution with a rosin glycerol ester concentration of 25 wt%. One part of sodium citrate solid particles was added to eight parts of the membrane-forming solution (containing two parts of rosin glycerol ester) by weight and stirred at 30°C for 90 minutes. The solid was then filtered and washed alternately with ethanol and water. It was then vacuum-dried at 55°C for 30 minutes and then freeze-dried at -45°C for 3 hours to obtain product a.

[0118] Detection of CO and tar (nicotine-free dry particulate matter) content in mainstream cigar smoke

[0119] The cigar products obtained in Examples 1-11, the blank examples, and Comparative Examples 1-4 were tested for CO and tar emissions according to the methods specified in "YC / T 466-2013 Determination of Carbon Monoxide in Mainstream Cigar Smoke - Non-scattering Infrared Method" and "YC / T 463-2013 Cigars - Determination of Total Particulate Matter and Tar Using a Conventional Analytical Cigar Smoking Machine." The test results are shown in Table 1 below.

[0120] Table 1.

[0121]

[0122] As shown in Table 1, compared with the blank example, the amount of CO in Example 1 was reduced by 30.09% and the amount of tar was reduced by 33.86%, indicating that the additive of the present application can effectively reduce the CO and tar release of cigars. Comparing Example 1 with Comparative Example 1, it can be seen that when the organic acid is used alone, the rate of reduction in the CO and tar release of cigars is low, which may be due to the consumption of oxygen by the combustion of the organic acid. Comparing Example 1 with Comparative Examples 2 and 3, it can be seen that after the product a is coated with product b in the present application, the rate of reduction in the CO and tar release of cigars is increased compared to when products a and b are used separately. This may be due to the further protection of the organic acid by the metal oxide loaded on the chitosan of product b during coating and the thermal conductivity. Comparing Example 1 with Comparative Example 4, it can be seen that in cigar smoke, organic acids have a better effect of reducing CO and tar release than organic acid salts.

[0123] The specific embodiments described herein are merely illustrative of the spirit of the present invention. Persons skilled in the art may make various modifications, additions, or substitutions to the described specific embodiments without departing from the spirit of the present invention or exceeding the scope of the appended claims.

Claims

1. An additive for reducing CO and tar emissions from cigars, characterized by: The additive is a core-shell structure including a core, a middle layer, and an outer layer from the inside to the outside; The inner core is organic acid, the middle layer is rosin glycerol ester, and the outer layer is chitosan loaded metal oxide; The organic acid is selected from at least one of citric acid, malic acid, and oxalic acid; The metal oxide is selected from at least one of iron oxide, aluminum oxide and zinc oxide.

2. A method for preparing the additive for reducing CO and tar emissions from cigars as claimed in claim 1, characterized in that: The following steps are involved: S1. Coating an organic acid with rosin glycerol ester to obtain product a; S2. Using chitosan to load metal oxide to obtain product b; S3. Add product a to the dispersion of product b, disperse, filter, and dry to obtain an additive.

3. The method for preparing an additive for reducing CO and tar emissions from cigars according to claim 2, characterized in that: In step S1, an organic acid is added to a dichloromethane solution of rosin glycerol ester, dispersed, filtered, washed, and dried to obtain product a; the mass ratio of the organic acid to the rosin glycerol ester is 1:(1-4).

4. The method for preparing an additive for reducing CO and tar emissions from cigars according to claim 2, characterized in that: In step S2, the metal oxide is dispersed in the chitosan solution, and then vacuum freeze-dried to obtain product b.

5. The method for preparing an additive for reducing CO and tar emissions from cigars according to claim 2, characterized in that: In step S2, the metal precursor solution and the chitosan solution are mixed, heated to 60-90° C., and then an alkali solution is added and reacted for 0.5-1.5 h. The mixture is then centrifuged, washed, and dried to obtain product b.

6. The method for preparing an additive for reducing CO and tar emissions from cigars according to claim 2, characterized in that: The mass ratio of the metal oxide to chitosan is 1:(1-10).

7. The method for preparing an additive for reducing CO and tar emissions from cigars according to claim 2, characterized in that: In step S3, the mass ratio of the product a to the product b is 1:(1~2).

8. Use of the additive for reducing CO and tar emissions from cigars as claimed in claim 1, characterized in that: The following steps are involved: Before rolling the cigar, the additive is sprayed on the surface of the cigar filler tobacco leaves, and the mass ratio of the cigar filler tobacco leaves to the additive is 1: (0.01-0.05); The cigar core tobacco leaves are rolled after the moisture content is balanced.

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