Method for adsorbing tobacco-specific nitrosamines, tobacco absolute and atomizing matrix

Abstract

A method for adsorbing tobacco-specific nitrosamines from a tobacco absolute. The method comprises: 1) diluting a tobacco absolute with a solvent; 2) adding a zeolite to the diluted tobacco absolute for first stirring and adsorption; 3) subjecting the tobacco absolute, which has been adsorbed with zeolite, to first centrifugation and then first filtration to obtain a first filtrate; 4) adding a molecular sieve to the first filtrate for second stirring and adsorption; 5) subjecting the tobacco absolute, which has been adsorbed with a molecular system, to second centrifugation and then second filtration to obtain a second filtrate; and 6) concentrating the second filtrate under reduced pressure until the solid content thereof is the same as that of the tobacco absolute, so as to obtain a tobacco absolute that has been concentrated under reduced pressure, wherein the content of tobacco-specific nitrosamines in the tobacco absolute thta has been concentrated under reduced pressure is less than 18000 ng / g. In addition, a tobacco absolute obtained by the method and an atomizing matrix comprising the tobacco absolute are provided.

Description

Methods for adsorbing tobacco-specific nitrosamines, tobacco purified oil, and atomizing matrix

[0001] Cross-references to related applications

[0002] This application is based on and claims priority to Chinese Patent Application No. 202410982238.2, filed on July 19, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the field of electronic atomization, specifically to a method for adsorbing tobacco-specific nitrosamines in tobacco purified oil, tobacco purified oil, and atomization matrix. Background Technology

[0004] Tobacco-specific nitrosamines (TSNAs) are a class of N-nitrosamine compounds found only in tobacco and tobacco smoke. They are formed during the curing, fermentation, and combustion of tobacco through the nitrosation reaction of secondary and tertiary amine alkaloids with nitrates or nitrites. Four important TSNAs include nitrosonornicotinine (NNN), nitrosonechoic acid (NAT), nitrosopseudoestilineine (NAB), and 4-(methylnitrosamine)-1-(3-pyridyl)-1-butanone (NNK). TSNAs can induce various cancers in experimental animals. The carcinogenicity of NNN and NNK has been verified; therefore, it is generally believed that the content and composition of tobacco-specific nitrosamines directly affect the safety of tobacco products.

[0005] Therefore, it is necessary to remove tobacco-specific nitrosamines from tobacco purified oil. Summary of the Invention

[0006] In view of this, the main objective of this disclosure is to provide a method for effectively adsorbing tobacco-specific nitrosamines from tobacco purified oil. This method also saves costs and reduces environmental pollution, resulting in significant economic and social benefits. A further objective of this disclosure is to provide tobacco purified oil obtained by this method, and an atomizing matrix containing the tobacco purified oil.

[0007] To achieve the above objectives, the technical solution disclosed herein is implemented through the following means.

[0008] The first aspect of this disclosure provides a method for adsorbing tobacco-specific nitrosamines from tobacco purified oil, comprising:

[0009] 1) Dilute the tobacco puree with a solvent;

[0010] 2) Add zeolite to the diluted tobacco oil and perform a first stirring and adsorption process;

[0011] 3) The tobacco purified oil adsorbed by zeolite is subjected to a first centrifugation, followed by a first filtration to obtain the first filtrate;

[0012] 4) Add molecular sieves to the first filtrate for a second stirring adsorption;

[0013] 5) The tobacco oil adsorbed by the molecular sieve is subjected to a second centrifugation, followed by a second filtration to obtain a second filtrate; and

[0014] 6) The second filtrate is concentrated under reduced pressure until the solid content is the same as that of the tobacco purified oil to obtain tobacco purified oil concentrated under reduced pressure, wherein the content of tobacco-specific nitrosamines in the tobacco purified oil concentrated under reduced pressure is less than 18000 ng / g.

[0015] In some embodiments, the mass ratio of the zeolite to the molecular sieve to the tobacco purified oil is (5-10):(1-5):10.

[0016] In some embodiments, the zeolite has a particle size of 3 mm to 8 mm, preferably 4 mm to 6 mm, and more preferably 5 mm; and / or

[0017] The pore size of the zeolite is to Preferred

[0018] Preferably, the zeolite is selected from one or more of 3A zeolite, 4A zeolite, 5A zeolite and 13X zeolite, more preferably 5A zeolite.

[0019] In some embodiments, the pore size of the molecular sieve is to Preferred and / or

[0020] The silica-to-alumina ratio of the molecular sieve is from 12.5 to 25, preferably 25;

[0021] Preferably, the molecular sieve is selected from one or more of HZSM-5, NaZSM-5, NaA, and CaA, with HZSM-5 molecular sieve being the most preferred.

[0022] In some embodiments, the solvent is selected from one or more of anhydrous ethanol, distilled water, glycerol, and propylene glycol; and the mass ratio of the solvent to the tobacco purifying oil is preferably 5:1 to 1:1, more preferably 3:1.

[0023] In some embodiments, the first stirring adsorption is carried out at room temperature for 1 hour to 8 hours; and / or

[0024] The second stirring adsorption is carried out at room temperature for 1 to 8 hours.

[0025] In some embodiments, the first and second centrifugations are performed at 4°C at 4000 rpm to 6000 rpm, preferably 5000 rpm, for 10 to 15 minutes; and / or

[0026] The first filtration is performed using a filter screen with a mesh size of 100 to 600; and / or

[0027] The second filtration is performed using a filter screen with a mesh size of 100 to 600; and / or

[0028] The vacuum concentration was carried out at 45°C to 65°C and 60 mbar to 120 mbar.

[0029] A second aspect of this disclosure provides a tobacco purified oil obtained according to the method of the first aspect of this disclosure, wherein the content of TSNAs in the tobacco purified oil is less than 18000 ng / g.

[0030] A third aspect of this disclosure provides an atomizing matrix comprising the tobacco purified oil of the second aspect of this disclosure.

[0031] In some embodiments, the tobacco purified oil contains 0.2% to 5% by mass relative to the total mass of the atomizing matrix, preferably 0.2% to 2%, and more preferably 0.5%.

[0032] In this disclosure, zeolite is used for initial adsorption, followed by molecular sieve adsorption. These two materials sequentially and stepwise effectively adsorb tobacco-specific nitrosamines (TSNAs) from tobacco purified oil, while simultaneously working together to minimize the loss of desired components. Therefore, the method of this disclosure can effectively and comprehensively remove TSNAs from tobacco purified oil, achieving a high removal rate without incurring a high loss rate. Furthermore, using low-cost zeolite and molecular sieve as adsorbents and employing liquid-phase adsorption for TSNA removal saves costs and reduces environmental pollution, resulting in significant economic and social benefits. Detailed Implementation

[0033] To provide a clear and consistent understanding of the terminology used in this disclosure, some definitions are provided below. Furthermore, unless otherwise specified, all technical and scientific terms used in this disclosure have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains.

[0034] Throughout this specification, unless otherwise specified, the terminology used herein should be understood as having the meaning as commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains.

[0035] It should be noted that, in the embodiments of this disclosure, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a method or apparatus that includes a list of elements includes not only the elements expressly described, but also other elements not expressly listed, or elements inherent to implementing the method or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other related elements in the method or apparatus that includes that element.

[0036] In this disclosure, the terms “aerosol for user inhalation”, “aerosol”, or “smoke” may include, but are not limited to, aerosols, suspensions, cryogenic vapors, and volatile gases.

[0037] TSNAs are not present in fresh tobacco leaves; they are produced during tobacco curing, processing, and smoking. The tobacco extraction and processing process enriches TSNAs, resulting in high TSNA content in the extract. Currently, methods for TSNA removal fall into two main categories: pretreatment and post-treatment. Pretreatment aims to reduce TSNAs by removing or controlling the content of TSNA precursors (nitrates, nitrites, alkaloids, etc.), primarily including removal at the tobacco source and improvements in tobacco curing methods. Post-treatment methods address TSNAs already present in the tobacco leaves, mainly through physical adsorption and microbial fermentation. For TSNAs already present in tobacco extracts, liquid-phase adsorption methods can be used, similar to those used for tobacco extracts. However, tobacco extracts have a more complex composition, containing more aroma compounds and having a higher density. Effectively removing TSNAs from these extracts is a major focus of research.

[0038] In view of this, the first aspect of this disclosure provides a method for adsorbing tobacco-specific nitrosamines (TSNAs) in tobacco purified oil. In the method of this disclosure, after initial adsorption using zeolite, secondary adsorption is performed using molecular sieves. Thus, the two materials effectively adsorb tobacco-specific nitrosamines (TSNAs) in tobacco purified oil in a stepwise manner, while the two materials can also cooperate with each other to minimize the loss of desired components in the tobacco purified oil.

[0039] Specifically, the methods disclosed herein include:

[0040] 1) Dilute the tobacco puree with a solvent;

[0041] 2) Add zeolite to the diluted tobacco oil for the first stirring and adsorption;

[0042] 3) The tobacco purified oil adsorbed by zeolite is subjected to a first centrifugation, followed by a first filtration to obtain the first filtrate;

[0043] 4) Add molecular sieves to the first filtrate for a second stirring adsorption;

[0044] 5) The tobacco oil adsorbed by the molecular sieve is subjected to a second centrifugation, followed by a second filtration to obtain a second filtrate; and

[0045] 6) The second filtrate is concentrated under reduced pressure until the solid content is the same as that of the tobacco purified oil to obtain tobacco purified oil concentrated under reduced pressure, wherein the content of tobacco-specific nitrosamines in the tobacco purified oil concentrated under reduced pressure is less than 18000 ng / g.

[0046] It should be understood that in this disclosure, "tobacco purified oil" and "tobacco extract" are used interchangeably. In this disclosure, tobacco purified oil includes one or more of flue-cured tobacco extracts and burley tobacco extracts, such as flue-cured tobacco water extract, flue-cured tobacco alcohol extract, burley tobacco water extract, burley tobacco alcohol extract, etc.

[0047] In some embodiments, the dilution step is performed using one or more solvents selected from anhydrous ethanol, distilled water, glycerol, and propylene glycol. In some embodiments, ethanol is used as the solvent.

[0048] In some embodiments, the mass ratio of solvent to tobacco purified oil used in the above-mentioned dilution step can be 5:1 to 1:1, for example, 5:1, 4:1, 3:1, 2:1, or 1:1. In one specific embodiment, the mass ratio of solvent to tobacco purified oil used is 3:1. It is undesirable to be limited by theory; the solvent used during dilution needs to, on the one hand, control the concentration of the substances to be adsorbed in the tobacco purified oil within a certain range to facilitate the subsequent adsorption process, and on the other hand, avoid the loss of desired components in the tobacco purified oil caused by the solvent itself (such as precipitation). Within the mass ratio range limited by this disclosure, the time required for subsequent adsorption is shorter, and no precipitation loss of tobacco purified oil has been observed, resulting in good performance.

[0049] In some embodiments, the first stirring adsorption described above is carried out using zeolite. It should be understood that zeolite refers to a class of natural or synthetic minerals with a highly regular porous structure. The pore structure of zeolite can provide a large surface area, making it particularly effective in adsorption and separation processes. The pore size and shape of zeolite can be precisely controlled, which enables the selective adsorption of specific molecules.

[0050] In some embodiments, the particle size of the zeolite used is 3 mm to 8 mm, preferably 4 mm to 6 mm. Specifically, the particle size of the zeolite can be 3 mm, 3.5 mm, 4 mm, 4.5 mm, 5 mm, 5.5 mm, 6 mm, 6.5 mm, 7 mm, 7.5 mm, or 8 mm. In one specific embodiment, the particle size of the zeolite used is 5 mm.

[0051] In some embodiments, the pore size of the zeolite used is... to Preferred Specifically, the pore size of the zeolite used can be [missing information]. In one specific embodiment, the pore size of the zeolite used is...

[0052] In some embodiments, the zeolite used is selected from one or more of 3A zeolite, 4A zeolite, 5A zeolite, and 13X zeolite. In one specific embodiment, the zeolite used is 5A zeolite.

[0053] In some embodiments, the mass ratio of zeolite to tobacco oil is from 5:10 to 10:10. For example, the mass ratio of zeolite to tobacco oil can be 5:10, 6:10, 7:10, 8:10, 9:10, or 10:10. If the mass ratio of zeolite to tobacco oil is too low, the corresponding adsorption effect cannot be achieved, and the TSNA content in the tobacco oil remains relatively high. If the mass ratio of zeolite to tobacco oil is too high, it will cause a high loss rate. It has been verified that the mass ratio of zeolite to tobacco oil within the range of this disclosure results in a low TSNA content in the obtained tobacco oil after TSNA adsorption using the method of this disclosure, without causing a high loss rate.

[0054] In some embodiments, the first stirring adsorption is carried out at room temperature for 1 to 8 hours. In one specific embodiment, the first stirring adsorption is carried out at room temperature for 2 hours. Unless otherwise specified, room temperature refers to 20°C to 25°C.

[0055] In some embodiments, the first centrifugation is performed at 4°C and 4000 rpm to 6000 rpm, preferably 5000 rpm, for 10 to 15 minutes. In one specific embodiment, the first centrifugation is performed at 4°C and 5000 rpm for 10 minutes.

[0056] In some embodiments, the first filtration is performed using a filter screen with a mesh size of 100 to 600. There are no particular limitations on the filter screen, as long as it achieves the filtration effect. For example, gauze or nylon mesh can be used. In one specific embodiment, the first filtration is performed using 300-mesh gauze.

[0057] In some embodiments, the second stirring adsorption described above is carried out using molecular sieves. It should be understood that a molecular sieve is an inorganic material with a highly regular porous structure containing a large number of uniformly sized channels and pores. The size of these channels is typically at the nanometer scale, enabling the molecular sieve to selectively adsorb molecules based on their size, shape, or polarity. The framework of the molecular sieve is composed of oxides of silicon (Si) and aluminum (Al), and is charged and balanced by cations (such as sodium, potassium, etc.).

[0058] Molecular sieves can adsorb TSNAs because of their porous structure and high specific surface area. Cations within the molecular sieve channels attract the negatively charged O atoms on the N-NO functional groups of TSNAs via electrostatic attraction, causing the N-NO functional groups to insert into the molecular sieve channels, thus adsorbing them wholly or partially. This disclosure utilizes molecular sieves with pore sizes similar to those of tobacco-specific nitrosamines such as NNK to selectively adsorb tobacco-specific nitrosamines.

[0059] In some embodiments, the pore size of the molecular sieve used is to For example, it can be... In one specific embodiment, the pore size of the molecular sieve used is...

[0060] In some embodiments, the silica-to-alumina ratio of the molecular sieve used is from 12.5 to 25, for example, 12.5, 15, 17.5, 20, 22.5, or 25. In one specific embodiment, the silica-to-alumina ratio of the molecular sieve used is 25. It should be understood that the silica-to-alumina ratio refers to the molar or mass ratio of silicon dioxide (SiO2) to aluminum oxide (Al2O3) in the material.

[0061] In some embodiments, the molecules used are screened from one or more of HZSM-5, NaZSM-5, NaA, and CaA, with HZSM-5 being preferred.

[0062] In some embodiments, the mass ratio of molecular sieve to tobacco oil is from 1:10 to 5:10, for example, 1:10, 2:10, 3:10, 4:10, or 5:10. If the mass ratio of molecular sieve to tobacco oil is too low, the corresponding adsorption effect cannot be achieved, and the TSNA content in the tobacco oil remains relatively high; if the mass ratio is too high, it will cause a high loss rate. It has been verified that the mass ratio of molecular sieve to tobacco oil within the range of this disclosure results in a low TSNA content in the obtained tobacco oil after TSNA adsorption using the method of this disclosure, without causing a high loss rate.

[0063] In some embodiments, the mass ratio of zeolite to molecular sieve to tobacco purified oil is (5-10):(1-5):10. Therefore, by controlling the mass ratio of the three components within the above range, on the one hand, more thorough and comprehensive adsorption of TSNAs in the tobacco purified oil can be achieved, resulting in a higher TSNA removal rate; on the other hand, using zeolite and molecular sieve within the above range can control the loss rate caused by adsorption within a certain range, avoiding excessive loss of desired components in the tobacco purified oil due to excessive use of adsorbent materials. In some embodiments, the mass ratio of zeolite to molecular sieve to tobacco purified oil is 5:1:10, 5:2:10, 5:3:10, 5:4:10, 5:5:10, 6:1:10, 6:2:10, 6:3:10, 6:4:10, 6:5:10, 7:1:10, 7:2:10, 7:3:10, 7:4:10, 7:5:10, 8:1:10, 8:2:10, 8:3:10, 8:4:10, 8:5:10, 9:1:10, 9:2:10, 9:3:10, 9:4:10, 9:5:10, 10:1:10, 10:2:10, 10:3:10, 10:4:10, or 10:5:10.

[0064] In some embodiments, the second stirring adsorption is carried out at room temperature for 1 to 8 hours. In one specific embodiment, the second stirring adsorption is carried out at room temperature for 2 hours.

[0065] In some embodiments, the second centrifugation is performed at 4°C and 4000 rpm to 6000 rpm, preferably 5000 rpm, for 10 to 15 minutes. In one specific embodiment, the second centrifugation is performed at 4°C and 5000 rpm for 10 minutes.

[0066] In some embodiments, the second filtration is performed using a filter screen with a mesh size of 100 to 600. There are no particular limitations on the filter screen, as long as it achieves the filtration effect. For example, gauze or nylon mesh can be used. In one specific embodiment, the second filtration is performed using 600-mesh gauze.

[0067] In some embodiments, the vacuum concentration is carried out at 45°C to 65°C and 60 mbar to 120 mbar. In one specific embodiment, the vacuum concentration is carried out at 60°C and 60 mbar. There is no particular limitation on the method of vacuum concentration; for example, a rotary evaporator can be used to perform the vacuum concentration, such as concentrating to the original concentration of the tobacco puree.

[0068] In some embodiments, the above-described vacuum concentration concentrates the second filtrate to a solid content similar to that of tobacco puree.

[0069] In this disclosure, zeolite is used for initial adsorption, followed by molecular sieve for secondary adsorption. The two materials sequentially adsorb tobacco-specific nitrosamines (TSNAs) in tobacco purified oil, avoiding excessive loss of desired components in tobacco purified oil due to overuse of a single component. The method of this disclosure can effectively and comprehensively adsorb TSNAs in tobacco purified oil, achieving a high removal rate of TSNAs. At the same time, using low-cost zeolite and molecular sieve as adsorbent materials and employing liquid-phase adsorption for TSNA removal can save costs and reduce environmental pollution, resulting in significant economic and social benefits.

[0070] This disclosure also provides a tobacco purified oil obtained by the method of this disclosure. In this tobacco purified oil, the TSNA content is less than 18000 ng / g.

[0071] This disclosure also provides an atomizing matrix comprising the tobacco purified oil of this disclosure. In some embodiments, the mass percentage of the tobacco purified oil relative to the total mass of the atomizing matrix is ​​0.2% to 5%, preferably 0.2% to 2%, and more preferably 0.5%.

[0072] In addition to the tobacco puree disclosed herein, the atomizing matrix may include other additional components, such as solvents and additives.

[0073] The solvent in the atomizing matrix is ​​used to dissolve various components and generate an aerosol during atomization, giving consumers the sensation of exhaling mist. For example, the solvent is selected from at least one of water, ethanol, ethylene glycol, propanol, propylene glycol, glycerol, butanol, butanediol, benzyl alcohol, triethyl citrate, triacetin, and caprylic / capric triglycerides. This disclosure does not impose any particular limitation on the amount and proportion of solvent added; any amount and proportion of solvent conventionally used in atomizing matrices can be used in the atomizing matrix of this disclosure.

[0074] The additives in the atomizing matrix may include at least one of sweeteners, cooling agents, and organic acids. Cooling agents and sweeteners can further provide different flavor profiles. Organic acids can further reduce throat irritation and enhance satisfaction to some extent. This disclosure does not impose any particular limitation on the types of sweeteners, cooling agents, and organic acids; those commonly used can be used in the atomizing matrix. Examples of cooling agents include WS-3, WS-5, WS-12, WS-14, WS-23, WS-25, WS-27, menthol, menthol, and menthyl esters, but are not limited to these. Examples of organic acids include acetic acid, butyric acid, 2-methylbutyric acid, lactic acid, levulinic acid, malic acid, tartaric acid, benzoic acid, and citric acid, but are not limited to these. Examples of sweeteners include neotame, adventitia, sucralose, acesulfame potassium, glucosylstevioside, aspartame, hesperidin dihydrochalcone, neohesperidin diaminochalcone, and naringin dihydrochalcone, but are not limited to these. This disclosure does not impose any particular restrictions on the amount of sweeteners, cooling agents, or organic acids added.

[0075] It should be understood that this disclosure does not particularly limit the preparation method of the atomizing matrix, which generally includes the step of mixing the components evenly. According to some embodiments, the components can be heated and mixed, for example, heated at about 30°C-50°C for 10-20 minutes.

[0076] The present disclosure is illustrated in more detail below through embodiments. It should be understood that the embodiments described below are exemplary and are only used to explain the present disclosure, and should not be construed as limiting the present disclosure. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in the art or in accordance with the product manual.

[0077] Example

[0078] Test methods

[0079] Detection of TSNAs in tobacco purified oil: Weigh 0.1 g of tobacco purified oil sample into a centrifuge tube and add 2 mL of 0.1 mol / L ammonium acetate solution containing internal standards (internal standards are 40.0 ng / mL of NNK-d4, NNN-d4, NAB-d4 and NAT-d4). Extract thoroughly by sonication for 30 min. Then, take an appropriate amount of extract and filter it through a 0.22 μm aqueous filter membrane, and transfer it to a chromatographic analysis bottle for HPLC-MS / MS analysis.

[0080] Preparation of the atomizing matrix containing tobacco puree: 0.5% tobacco puree was added, and 99.5% propylene glycol and glycerol mixed solution (6:4 to 1:1, w / w) was added.

[0081] Determination of TSNAs in the smoke from the atomized matrix containing tobacco oil: The raw material sample was prepared into a tobacco cartridge, and the smoke was drawn according to the standard of GB-41770. The drawing parameters were: 55 mL, 30 s, 3 s, 100 puffs. The smoke was then collected using two 44 mm glass fiber filters and placed in an Erlenmeyer flask. 15 mL of 0.1 mol / L ammonium acetate solution containing internal standards (internal standards were 40.0 ng / mL of NNK-d4, NNN-d4, NAB-d4, and NAT-d4) was added. The mixture was shaken on a shaker for 30 min for complete extraction. An appropriate amount of the extract was then filtered through a 0.22 μm aqueous phase filter membrane and transferred to a chromatographic analysis bottle for HPLC-MS / MS analysis.

[0082] Method for determining TSNAs content in samples: TSNAs were determined on HPLC-MS / MS (Thermo Fisher Orbitrap Exploris 120) with the following parameters: Hypersil GOLD™ aQ 18 column (1.9 μm, 2.1 mm × 100 mm); mobile phase A was 0.1% formic acid, and mobile phase B was 100 mmol ammonium acetate solution; flow rate was 0.2 mL / min; column temperature was 35 ℃; injection volume was 2 μL per sample; electrospray ionization (ESI) was used as the ion source with an electrospray voltage of 5000 V; positive ion scanning was used, and multiple reaction detection (MRM) was used for detection. The final solution was quantified using the internal standard method. NNN, NNK, NAT, and NAB standards (purity ≥98%) were prepared into a series of standard working solutions (the concentration gradients of NNN, NNK, NAT, and NAB were 1.0, 2.0, 8.0, 20.0, 40.0, 80.0, 200, and 400 ng / mL, and the concentration of the four internal standards was 40.0 ng / mL). The solutions were injected sequentially, and a standard working curve was plotted. The correlation coefficient was greater than or equal to 0.99. The result calculated from the working curve was used as the quantitative result.

[0083] Example 1

[0084] 1) Dilute 100g of tobacco pure oil (purchased from Yunnan Maishi Biotechnology Co., Ltd., solid content 65%) with 300g of anhydrous ethanol;

[0085] 2) Weigh 50g of zeolite (purchased from Taizhou Mingrui Teaching Equipment Co., Ltd., zeolite type 5A3, particle size 5mm, pore size...). Add the tobacco oil to the diluted solution and stir for 2 hours at room temperature to allow it to absorb.

[0086] 3) Centrifuge the tobacco oil adsorbed by zeolite at 4℃ and 5000rpm for 10min, and then filter it through 300-mesh gauze to obtain the first filtrate.

[0087] 4) Add 10g of molecular sieve (purchased from Shanghai Titan Technology Co., Ltd., molecular sieve model HZSM-5, pore size) to the first filtrate. (Silicon-to-aluminum ratio of 25), adsorption was carried out by stirring at room temperature for 2 hours.

[0088] 5) Centrifuge the tobacco oil adsorbed by molecular sieve at 4℃ and 5000rpm for 10min, and then filter it a second time using 600-mesh gauze to obtain the second filtrate.

[0089] 6) At 60°C and 60 mbar, the second filtrate is concentrated to a solid content of 65% using a rotary evaporator to obtain tobacco pure oil concentrated under reduced pressure.

[0090] Subsequently, the obtained tobacco purified oil was tested using the TSNAs content determination method described above. The test results are shown in Table 1 below. The removal rate (%) = (TSNAs before treatment - TSNAs after treatment) / TSNAs before treatment × 100%; the loss rate (%) = (1 - m sample after treatment / m sample before treatment) × 100%.

[0091] Example 2

[0092] In addition to weighing out 100g of zeolite (purchased from Taizhou Mingrui Teaching Equipment Co., Ltd., zeolite model 5A3, particle size 5mm, pore size...), Except for adding it to the tobacco puree diluent, this example is carried out in the same manner as Example 1.

[0093] The TSNA content was determined using the same method as in Example 1.

[0094] Example 3

[0095] In addition to adding 20g of molecular sieve (purchased from Shanghai Titan Technology Co., Ltd., molecular sieve model HZSM-5, pore size) to the first filtrate Except for the silicon-to-aluminum ratio of 25, this embodiment is carried out in the same manner as in Example 2.

[0096] The TSNA content was determined using the same method as in Example 1.

[0097] Example 4

[0098] In addition to adding 20g of molecular sieve (purchased from Shanghai Titan Technology Co., Ltd., molecular sieve model HZSM-5, pore size) to the first filtrate Except for the silicon-to-aluminum ratio of 25, this embodiment is carried out in the same manner as in Example 1.

[0099] The TSNA content was determined using the same method as in Example 1.

[0100] Example 5

[0101] In addition to adding 50g of molecular sieve (purchased from Shanghai Titan Technology Co., Ltd., molecular sieve model HZSM-5, pore size) to the first filtrate Except for the silicon-to-aluminum ratio of 25, this embodiment is carried out in the same manner as in Example 2.

[0102] The TSNA content was determined using the same method as in Example 1.

[0103] Example 6

[0104] In addition to adding 50g of molecular sieve (purchased from Shanghai Titan Technology Co., Ltd., molecular sieve model HZSM-5, pore size) to the first filtrate Except for the silicon-to-aluminum ratio of 25, this embodiment is carried out in the same manner as in Example 1.

[0105] The TSNA content was determined using the same method as in Example 1.

[0106] Blank control group

[0107] Tobacco oil without any adsorption treatment was used as a blank control group. Extraction was performed using ammonium acetate solution containing an internal standard, and the TSNA content was determined by HPLC-MS / MS. Simultaneously, tobacco oil was prepared as a 0.5% additive e-liquid, filled into e-cigarette cartridges, and smoke was drawn according to GB-41770 standards. The smoke was captured using two 44mm glass fiber aluminum plates, extracted using ammonium acetate solution containing an internal standard, and the TSNA content in the smoke was determined by HPLC-MS / MS.

[0108] Comparative Example 1

[0109] 1) Dilute 100g of tobacco pure oil (purchased from Yunnan Maishi Biotechnology Co., Ltd., solid content 65%) with 300g of anhydrous ethanol;

[0110] 2) Weigh 100g of zeolite (purchased from Taizhou Mingrui Teaching Equipment Co., Ltd., zeolite type 5A3, particle size 5mm, pore size...). Add the tobacco oil to the diluted solution and stir for 2 hours at room temperature to allow it to absorb.

[0111] 3) Centrifuge the tobacco oil adsorbed by zeolite at 4℃ and 5000rpm for 10min, and then filter it through 300-mesh gauze to obtain the filtrate;

[0112] 4) At 60℃ and 60mbar, the filtrate was concentrated to a solid content of 65% using a rotary evaporator to obtain tobacco pure oil concentrated under reduced pressure.

[0113] The TSNA content was determined using the same method as in Example 1.

[0114] Comparative Example 2

[0115] 1) Dilute 100g of tobacco pure oil (purchased from Yunnan Maishi Biotechnology Co., Ltd., solid content 65%) with 300g of anhydrous ethanol;

[0116] 2) Weigh 100g of molecular sieve (purchased from Shanghai Titan Technology Co., Ltd., molecular sieve model HZSM-5, pore size: (Silicon-to-aluminum ratio of 25) was added to the diluted tobacco oil solution and stirred for 2 hours at room temperature for adsorption.

[0117] 3) Centrifuge the tobacco oil adsorbed by molecular sieve at 4℃ and 5000rpm for 10min, and then filter it with 600-mesh gauze to obtain the filtrate;

[0118] 3) At 60℃ and 60mbar, the filtrate was concentrated to a solid content of 65% using a rotary evaporator to obtain tobacco pure oil concentrated under reduced pressure.

[0119] The TSNA content was determined using the same method as in Example 1.

[0120] Comparative Example 3

[0121] 1) Dilute 100g of tobacco pure oil (purchased from Yunnan Maishi Biotechnology Co., Ltd., solid content 65%) with 300g of anhydrous ethanol;

[0122] 2) Weigh 50g of zeolite (purchased from Taizhou Mingrui Teaching Equipment Co., Ltd., zeolite type 5A3, particle size 5mm, pore size...). ) and 10g of molecular sieve (purchased from Shanghai Titan Technology Co., Ltd., molecular sieve model HZSM-5, pore size is The silica-aluminum ratio is 25), and the mixture is added to the diluted tobacco oil solution and stirred for 4 hours at room temperature for adsorption.

[0123] 3) Centrifuge the adsorbed tobacco oil at 4℃ and 5000rpm for 10min, then filter it through 600-mesh gauze to obtain the filtrate;

[0124] 4) At 60℃ and 60mbar, the filtrate was concentrated to a solid content of 65% using a rotary evaporator to obtain tobacco pure oil concentrated under reduced pressure.

[0125] The TSNA content was determined using the same method as in Example 1.

[0126] Comparative Example 4

[0127] 1) Dilute 100g of tobacco pure oil (purchased from Yunnan Maishi Biotechnology Co., Ltd., solid content 65%) with 300g of anhydrous ethanol;

[0128] 2) Weigh 10g of molecular sieve (purchased from Shanghai Titan Technology Co., Ltd., molecular sieve model HZSM-5, pore size: (Silicon-to-aluminum ratio of 25) was added to the diluted tobacco oil solution and stirred for 2 hours at room temperature for adsorption.

[0129] 3) Centrifuge the tobacco oil adsorbed by molecular sieve at 4℃ and 5000rpm for 10min, and then filter it through 600-mesh gauze to obtain the first filtrate.

[0130] 4) Add 50g of zeolite (purchased from Taizhou Mingrui Teaching Equipment Co., Ltd., zeolite type 5A3, particle size 5mm, pore size [not specified]) to the first filtrate. Adsorption was carried out by stirring at room temperature for 2 hours.

[0131] 5) Centrifuge the tobacco oil adsorbed by zeolite at 4℃ and 5000rpm for 10min, and then filter it a second time using 300-mesh gauze to obtain the second filtrate.

[0132] 6) At 60°C and 60 mbar, the second filtrate is concentrated to a solid content of 65% using a rotary evaporator to obtain tobacco pure oil concentrated under reduced pressure.

[0133] The TSNA content was determined using the same method as in Example 1.

[0134] Table 1. TSNA detection results of the blank control group, Examples 1 to 6, and Comparative Examples 1 to 4

[0135] ND indicates not detected.

[0136] Therefore, due to the complex composition and high solid content of tobacco purified oil, the adsorption effect of a single adsorbent material is limited, and excessive use will lead to the loss of the desired components in the tobacco purified oil. This disclosure uses two adsorbent materials in combination, first using 5A zeolite for preliminary adsorption, and then using HZSM-5 molecular sieve for secondary adsorption. This achieves optimal TSNA removal efficiency, with a TSNA removal rate of up to 99.3%. After formulation into e-cigarette e-liquid, the TSNA content in the vapor is reduced to undetectable levels, ensuring the safety of the e-cigarette e-liquid. Therefore, the method of this disclosure is low-cost, effective, and has good economic and social benefits.

[0137] The above description is merely a preferred embodiment of this disclosure and is not intended to limit the scope of protection of this disclosure.

[0138] Although this disclosure has been described with reference to specific exemplary embodiments thereof, many different variations, modifications, etc. will become apparent to those skilled in the art.

[0139] By studying the disclosure and the appended claims, those skilled in the art can understand and implement variations of the disclosed embodiments when practicing this disclosure.

Claims

1. A method for adsorbing tobacco-specific nitrosamines from tobacco purified oil, comprising: 1) Dilute the tobacco puree with a solvent; 2) Add zeolite to the diluted tobacco oil and perform a first stirring and adsorption process; 3) The tobacco purified oil adsorbed by zeolite is subjected to a first centrifugation, followed by a first filtration to obtain the first filtrate; 4) Add molecular sieves to the first filtrate for a second stirring adsorption; 5) The tobacco oil adsorbed by molecular sieve is subjected to a second centrifugation, followed by a second filtration to obtain a second filtrate; and 6) The second filtrate is concentrated under reduced pressure until the solid content is the same as that of the tobacco purified oil to obtain tobacco purified oil concentrated under reduced pressure, wherein the content of tobacco-specific nitrosamines in the tobacco purified oil concentrated under reduced pressure is less than 18000 ng / g.

2. The method of claim 1, wherein, The mass ratio of the zeolite to the molecular sieve to the tobacco purified oil is (5-10):(1-5):

10.

3. The method of claim 1 or 2, wherein, The zeolite has a particle size of 3 mm to 8 mm, preferably 4 mm to 6 mm, and more preferably 5 mm; and / or The pore size of the zeolite is To Preferably Preferably, the zeolite is selected from one or more of 3A zeolite, 4A zeolite, 5A zeolite and 13X zeolite, more preferably 5A zeolite.

4. The method of any one of claims 1 to 3, wherein, The pore size of the molecular sieve is from 4.0 to 5.0 A preferably from 4.2 to 4.8 A and / or from 4.0 to 5.0 A from 4.0 to 5. The silica-to-alumina ratio of the molecular sieve is from 12.5 to 25, preferably 25; Preferably, the molecular sieve is selected from one or more of HZSM-5, NaZSM-5, NaA, and CaA, with HZSM-5 molecular sieve being the most preferred.

5. The method of any one of claims 1 to 4, wherein, The solvent is selected from one or more of anhydrous ethanol, distilled water, glycerol, and propylene glycol; and the mass ratio of the solvent to the tobacco puree is preferably 5:1 to 1:1, more preferably 3:

1.

6. The method of any one of claims 1 to 5, wherein, The first stirring adsorption is carried out at room temperature for 1 to 8 hours; and / or The second stirring adsorption is carried out at room temperature for 1 to 8 hours.

7. The method according to any one of claims 1 to 6, wherein, The first and second centrifugations are performed at 4°C at 4000 rpm to 6000 rpm, preferably 5000 rpm, for 10 to 15 minutes; and / or The first filtration is performed using a filter screen with a mesh size of 100 to 600; and / or The second filtration is performed using a filter screen with a mesh size of 100 to 600; and / or The vacuum concentration was carried out at 45°C to 65°C and 60 mbar to 120 mbar.

8. A tobacco puree, obtained by the method according to any one of claims 1 to 7.

9. An atomizing matrix comprising the tobacco puree according to claim 8.

10. The aerosolizing substrate of claim 9 wherein, The tobacco purified oil has a mass percentage of 0.2% to 5% relative to the total mass of the atomizing matrix, preferably 0.2% to 2%, and more preferably 0.5%.

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