CN1167364C - Combustion-supporting and harm-reducing additives for nanoporous cigarettes - Google Patents

Abstract

A cigarette additive capable of significantly reducing the content of nitrosamines in cigarette smoke and/or promoting the combustion of cigarettes and its use, which is suspended in uniform colloidal solution with particles of porous materials such as KA zeolite and the like. In particular, the porous material particle 3A zeolite with a particle diameter of 2-5 μm has a pore diameter of about 0.3 nm and contains alkali metal ions such as potassium ions. Spray the cigarette additive of the present invention on shredded tobacco, the amount of porous material particles added is 0.5-10.0% of the weight of shredded tobacco, and then make cigarettes after drying, the smoldering and burning time of cigarettes can be shortened by 5-12% and 5% respectively. 20-26%, the content of nitrosamines in the flue gas can be reduced by 23-33% and 43-63%, thereby greatly reducing the environmental pollution caused by smoking.

Description

Combustion-supporting and harm-reducing additives for nanoporous cigarettes

1. Technical field

The invention relates to a shredded tobacco additive for cigarettes and its application. In particular, additives and their applications that can significantly reduce the content of nitrosamines in cigarette smoke and promote the combustion of cigarettes

2. Background technology

Cigarette combustion produces mainstream and sidestream smoke. Mainstream smoke refers to the smoke inhaled by the smoker through the filter when the cigarette is inhaled and burned, while sidestream smoke refers to the smoke released directly into the air when the cigarette burns naturally, that is, smoldering. N-nitroso compounds (represented by nitrosamines) contained in cigarette smoke are highly carcinogenic. Nitrosamines in mainstream smoke directly endanger the health of smokers, while sidestream smoke from cigarettes spreads directly among the crowd, pollutes the environment and harms the health of passive smokers. Therefore, how to reduce the harm of cigarettes has become an urgent problem in ecological protection. The problem.

The foreign patent US19990166413P uses a carbonate solution to rinse the tobacco leaves, and after drying for four weeks, the nitrosamine content in the leaves can be reduced; however, the process of this method is complicated, which not only consumes a large amount of alkali and affects the taste of cigarettes, but also may cause secondary pollution to the environment. pollute. Patent EP0991329 uses microwave or high-frequency radiation to treat tobacco leaves to reduce NNK and NNN in cigarettes. Patent CN 1269992 uses microwave direct radiation to treat finished cigarettes. Tobacco-specific nitrosamines (TSNAs). These methods may cause tobacco shreds to smolder, and there are certain risks in industrial applications. It is difficult to selectively remove NOC by using filter rods, including filters doped with zeolite (such as patents CH-A-653200, UA-A-3703901, FR-A-2165174, WO9607335 and WO9704865), let alone solve the pollution of passive smoking question. Patent JP6214772 uses menthol, ascorbic acid, tyrosine, stearic acid, lecithin, benzoic acid, vanillin, etc. to make tobacco tar adsorbents, which can reduce nicotine, CO, Benzo[α]pyrene and nitrosamine content. This method not only has high cost, but also has insignificant effect because it only has adsorption effect.

In patent EP0740907, microporous zeolites such as Y, X, ZSM-5, M and β with a pore size of 0.5-0.7nm and gel (C-Gel) are mixed into LC-674 to form a suspension and then sprayed on the shredded tobacco to make a cigarette. Catalyzes the removal of harmful components in cigarette smoke, including nitrosamines, during combustion. However, the content of nitrosamines such as nitrosonornicotine (NNN) and nitrosoannicotine (NAB) decreased, while the content of dimethylnitrosamine (NDMA) increased. The patent does not clearly state whether the total amount of nitrosamines in the main and side stream smoke of cigarettes has been significantly reduced, and because the required amount of additives is too large, the cost has increased. Patent CN1228945 discloses a new method of using porous material particles such as 4A zeolite to make a suspension gel solution and spraying it on shredded tobacco to reduce the content of nitrosamines in cigarettes, but its pore size is limited to 0.4nm and has no combustion-supporting effect.

3. Contents of the invention

The object of the present invention is to provide a cigarette additive capable of supporting combustion and reducing the content of nitrosamines in cigarette smoke, as well as the use of the additive, that is, the cigarette containing the additive.

The technical scheme of the present invention is as follows: a cigarette additive for reducing the content of nitrosamines in cigarette smoke is selected from porous material particle 3A zeolite with a particle diameter of about 4 μm, a pore diameter of about 0.3 nm, and containing alkali metal ions such as potassium ions. The preferred porous material particle is potassium type A zeolite with a particle size of about 4 μm. It is used as a suspension in a solution of biological glue such as seaweed glue or cyclodextrin, or it can be solid mechanically mixed. The added amount of porous material particles is preferably 1-5% of the weight of shredded tobacco.

The purposes and preparation method of cigarette additive in the present invention are: add seaweed gel into cold water at room temperature (ratio is 1: 75-1: 400, the present invention adopts 1: 200), first soak 0.1-1.0 hour (the present invention adopts more 0.25 hours), then heated to 30-100°C (40-50°C is often used in the present invention) and maintained for 0.1-1.0 hours (0.25 hours are mostly used in the present invention), and becomes a transparent viscous solution after cooling to room temperature. Add the calculated amount of porous material particles and stir to form a uniform suspension to obtain the cigarette additive of the present invention.

The method for making cigarettes with low nitrosamine content in the smoke of the present invention is to spray evenly on the shredded tobacco in the amount of 0.05-1.0% seaweed gel and 0.5-9.0% porous material particles by weight of shredded tobacco or tobacco leaves. or on the tobacco leaves, dried, and made into cigarettes, that is, a new type of cigarette with low nitrosamine content in the smoke is obtained.

The 3A nanoporous material, represented by KA zeolite, is added in the glue solution as the main additive component.

The A-type zeolite structure is a three-dimensional crystal structure in which β-cages are connected to each other by four-membered rings with four oxygen bridges. After 8 β-cages are connected to each other, an α-cage is formed among them; it is A-type zeolite The main crystal cavity contains exchangeable cations. When the cation is potassium ion K ⁺ , it is called KA zeolite, and because its effective pore size is 3 Å (0.3nm), it is also called 3A zeolite. Its ideal unit cell composition It is: K ₉₆ [Al ₉₆ Si ₉₆ O ₃₈₄ ]·216H ₂ O or K ₁₂ [Al ₁₂ Si ₁₂ O ₄₈ ]·27H ₂ O. The chemical formula can be written as K ₂ O·Al ₂ O ₃ ·2SiO ₂ ·4.5H ₂ O. The pore structure of KA zeolite is a three-dimensional straight channel, and contains the most exchangeable cations, which can be exchanged rapidly and in large quantities. Its specific surface is about 700m ² /g, and the particle size is about 4μm, generally 2-5μm. Cations may also contain other alkali metal ions, such as sodium, magnesium, calcium, and the like.

The characteristics of the present invention are as follows: (1) when the total addition amount (referring to biological glue such as seaweed glue or cyclodextrin and KA zeolite, excluding water) is about 3wt.%, it can obviously reduce the nitrous acid in cigarette smoke It can increase the amine content and improve the burning condition of cigarettes, that is, it has obvious combustion-supporting effect. (2) The solid particle in the additive adopts the zeolite molecular sieve material with a pore size of about 0.3nm, while the patent protection scope of EP0740907 for the zeolite pore size is 0.5-0.7nm, and CN1228945 is 0.4nm. (3) What is measured is the apparent total amount of nitrosamines in the smoke of cigarettes under smoking and smoldering conditions.

4. Specific implementation

Example: In order to detect the effect of the cigarette additive of the present invention on the removal of nitrosamine content in cigarette smoke, the semi-finished shredded tobacco to be rolled is taken out from the shredded tobacco storage cabinet on the shredded production line of a cigarette factory; the shredded tobacco is sprayed with the cigarette of the present invention Additives, let dry, and re-roll cigarettes with coil paper. The shredded tobacco that was not sprayed with the cigarette additive of the present invention was treated in the same way for comparison.

The present invention adopts the device and method that Caldwell reports in J.Assoc.Off.Anal.Chan., 73(5), 783,1990 to collect sidestream smoke, but changes its absorption liquid into 150mL citric acid with a pH value of 4.5 - Disodium hydrogen phosphate buffer solution. In order to observe the combustion-supporting effect more accurately, the sample smoke was kept smoldering in the cone burner, and the air was dried beforehand during the combustion process, and the flow rate was 1L/min. After lighting the cigarette in a self-made burner, pass the smoke through the absorption tube to absorb the smoke (four absorption tubes, each containing 15mL Na ₂ HPO ₄ -citric acid buffer solution), and ignite a total of 4 cigarettes (each burns about 20 minute). About 2 grams of sodium chloride was added to the obtained buffer, and then extracted with 240 mL of dichloromethane four times. The extract was filtered through a funnel equipped with anhydrous sodium sulfate, and the filtered extract was concentrated to 25 mL with a rotary evaporator (water bath temperature about 32° C., vacuum degree 0.03 MPa). Choose a ground-mouthed test tube with a branch, equipped with a ground-mouthed plug with an airway leading to the bottom of the tube. Put 10mL of nitrosamine solution in the test tube, then add 0.5mL of HBr/HOAc solution, and plug the ground stopper. Introduce high-purity N ₂ into the reaction solution through the air duct for 30 min, and the flow rate of N ₂ is 200 mL/min. The NO produced by the NN bond breakage of nitrosamines is blown out of the solution by N ₂ , then purified by three washing bottles containing 10 mL of NaOH solution with a concentration of 5 mol/L, and then oxidized into NO ₂ by the chromium trioxide oxidation tube. It is collected by the sulfonamide-naphthalene ethylenediamine hydrochloride absorption solution and converted into NO ₂ ^- and a color reaction occurs, and then the absorbance A is measured at 540nm. The content of nitrosamines was converted from the NaNO ₂ concentration-absorbance standard curve.

The present invention adopts the device and method reported by Miyake in J.Chromatogr.A, 1995, 693:376 to collect mainstream smoke: 150mL Na ₂ HPO ₄ -citric acid buffer is placed in a 1000mL separating funnel, and the liquid is separated by pumping. Vacuum the top of the funnel to 1.3kPa and stabilize for 10 minutes. Light the cigarette, make the smoke produced by smoking the cigarette absorbed by the Na ₂ HPO ₄ -citric acid buffer solution, and burn 30 cigarettes in total. Add about 2 grams of sodium chloride in the resulting buffer solution, then use 240mL dichloromethane to extract four times, the extract is filtered through a funnel equipped with anhydrous sodium sulfate, and the filtered extract is used with a rotary evaporator (water bath temperature about 32 °C, vacuum degree is 0.03MPa) and concentrated to 25mL. The processing method of the obtained solution is the same as above.

For the determination of the content of nitrosamines in the collected liquid of cigarette smoke, the inventors adopted the improved spectrophotometric method disclosed in CN1193741.

[Example 1] Dissolve 0.1051g of seaweed gel (produced by Jinzhuan Chemical Experimental Factory, the same below) into 20ml of water, heat to 40-50°C, dissolve, then add 6.0g KA zeolite (produced by Nanjing Inorganic Chemical Factory) after cooling to room temperature , the same below), stirred into a uniform suspension and sprayed on 200g of shredded tobacco A (the type of flue-cured tobacco produced in Yunnan Province, with a tar content of 15mg and a nicotine content of smoke of 1.2mg); the shredded tobacco has no change in color after drying. After being rolled into a cigarette and lit, the smoke was collected and analyzed for its nitrosamine content. In the mainstream smoke when inhaled, the content of nitrosamines decreased from 2.01nmol/cigarette to 0.67μg/cigarette, a decrease of 54.1%; the burning time decreased from 45 seconds/cigarette to 35 seconds/cigarette, a decrease of about 22%. The content of nitrosamines in cigarette smoldering smoke decreased from 29.25nmol/cigarette to 17.98μg/cigarette, a decrease of 27.5%; the smoldering time decreased from 20 minutes/cigarette to 19 minutes/cigarette, a decrease of 5%.

[Example 2] Dissolve 0.1056g of seaweed gel into 20ml of water, heat to 40-50°C, dissolve, then add 12.0g of KA zeolite after cooling to room temperature. Stir to form a uniform suspension and spray it on 200g of shredded tobacco A; the color of shredded tobacco remains unchanged after drying. After being rolled into a cigarette and lit, the smoke was collected and analyzed for its nitrosamine content. In the mainstream smoke when inhaled, the content of nitrosamines decreased from 2.01nmol/cigarette to 0.61nmol/cigarette, a reduction of 58.2%; the burning time was shortened from 45 seconds/cigarette to 35 seconds/cigarette, a decrease of about 22%. The content of nitrosamines in cigarette smoldering smoke decreased from 29.25nmol/stick to 12.77nmol/stick, a decrease of 29.0%. The smoldering time has been shortened from 20 minutes per stick to 19 minutes per stick, a reduction of 5%.

[Example 3] Dissolve 0.3009g of seaweed gel into 60ml of water, heat to 40-50°C, dissolve, then add 18.0g of KA zeolite after cooling to room temperature. Stir to form a uniform suspension and spray it on 200g of shredded tobacco A; the color of shredded tobacco remains unchanged after drying. After being rolled into a cigarette and lit, the smoke was collected and analyzed for its nitrosamine content. In the mainstream smoke during combustion, the content of nitrosamines decreased from 2.01nmol/cigarette to 0.56nmol/cigarette, a decrease of 61.6%. The burning time is shortened from 45 seconds per stick to 32 seconds per stick, a reduction of about 29%. The content of nitrosamines in cigarette smoldering smoke decreased from 29.25nmol/stick to 12.5nmol/stick, a decrease of 30.5%. The smoldering time has been shortened from 20 minutes per stick to 18 minutes per stick, a 10% reduction. When 2.0 g K and 3.0 g A zeolite were added under the above conditions, the reduction in burning time was slightly reduced by 1.

[Example 4] Dissolve 1.0g of β-CD (β-cyclodextrin) into 20ml of water, heat to 40-50°C, dissolve until clear, then add 6.0g of KA zeolite after cooling to room temperature. Stir to form a uniform suspension and spray it on 200g of shredded tobacco A; the color of shredded tobacco remains unchanged after drying. After being rolled into a cigarette and lit, the smoke was collected and analyzed for its nitrosamine content. In the mainstream smoke during combustion, the content of nitrosamines decreased from 2.01nmol/cigarette to 0.53nmol/cigarette, a decrease of 63.7%. The burning time is shortened from 45 seconds per stick to 35 seconds per stick, a reduction of about 22%. The content of nitrosamines in cigarette smoldering smoke decreased from 29.25nmol/stick to 12.04nmol/stick, a decrease of 33.0%. The smoldering time has been shortened from 20 minutes per stick to 19 minutes per stick, a reduction of 5%.

[Example 5] Mechanically mix 3.0g KA zeolite on 100g shredded tobacco A, roll it into a cigarette and light it, collect the smoke and analyze its nitrosamine content; the nitrosamine content in the smoldering smoke increases from 29.25nmol/cigarette It was reduced to 26.59nmol/branch, which was reduced by 9.1%. The addition of 1.0 g and 5 g of KA zeolite had similar effects.

[Example 6] Dissolve 0.1021g seaweed gel into 20ml water, heat to 40-50°C to dissolve, then add 12.0g KA zeolite after cooling to room temperature. Stir to form a uniform suspension and spray it on 200g of shredded tobacco B (the type of flue-cured tobacco produced in Yunnan Province, with a tar content of 15mg and a smoke nicotine content of 1.2mg); the color of the shredded tobacco remains unchanged after drying. After being rolled into a cigarette and lit, the smoke was collected and analyzed for its nitrosamine content. In the mainstream smoke during combustion, the content of nitrosamines decreased from 1.88nmol/cigarette to 0.83nmol/cigarette, a reduction of 55.9%. The burning time is shortened from 45 seconds per stick to 35 seconds per stick, a reduction of about 22%. The content of nitrosamines in cigarette smoldering smoke decreased from 22.66nmol/stick to 14.82nmol/stick, a decrease of 32.5%. The smoldering time was shortened from 20 minutes per stick to 16.5 minutes per stick, a reduction of 12.5%.

[Example 7] Dissolve 0.046g of seaweed gel into 9.2ml of water, heat to 40-50°C, dissolve, then add 2.76g of KA zeolite after cooling to room temperature. Stir to form a uniform suspension and spray it on 92g of shredded tobacco C (Korea, Burley tobacco); the color of the shredded tobacco remains unchanged after drying. After being rolled into a cigarette and lit, the smoke was collected and its nitrosamine content was analyzed; the nitrosamine content in the smoldering smoke decreased from 50.9nmol/cigarette to 39.1nmol/cigarette, a decrease of 23.2%.

[Example 8] Dissolve 0.037g of seaweed gel into 7.4ml of water, heat to 40-50°C, dissolve, then add 2.22g of KA zeolite after cooling to room temperature, stir into a uniform suspension and spray it on 74g of tobacco flakes D (( Korea) above; dry at room temperature. Rolled into a cigarette and lit it, collected the smoke and analyzed its nitrosamine content; the nitrosamine content in the smoldering smoke was reduced from 25.23nmol/branch to 19.29nmol/branch, reducing 23.5%.

The cigarette additive for combustion-supporting/removing nitrosamines in flue gas of the present invention is easy to manufacture and low in cost. The content of nitrosamines in the smoldering and smoking smoke of the cigarette made by using the additive of the present invention is reduced by 23-33% and 43-63%, and the burning speed is obviously accelerated, which can greatly reduce the pollution of smoking to the environment, reduce the Cigarettes are harmful to the health of smokers and passive smokers, which can promote cigarette sales and bring benefits to enterprises.

Claims (4)

1, a kind of additive that can significantly reduce content of nitrosamines in the cigarette smoke and promote cigarette burning, it is characterized in that selecting for use particle diameter is the porous particulate material potassium type 3A zeolite of 2-5 μ m, about the 0.3nm of its aperture, described cigarette additive is the particulate that porous material is arranged that suspends in even colloidal solution.

2, the purposes of the described cigarette additive of a kind of claim 1 is characterized in that spraying the described additive of claim 1 on the pipe tobacco of cigarette, and the addition of porous particulate material is the 0.5-10.0% of pipe tobacco weight.

3,, it is characterized in that the addition of the porous particulate material that adds is the 0.02-1.0% of pipe tobacco weight in pipe tobacco according to the purposes of the described cigarette additive of claim 3.

4, according to the purposes of the described cigarette additive of claim 3, the addition that it is characterized in that porous particulate material is the 1-5% of pipe tobacco weight.