乳酸钾改善卷烟保润性能及烟气品质的研究
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摘要
卷烟保润性能对卷烟的物理特性（如烟丝的水分散失和造碎）、香气和吸食品质等有重要的影响。对于一些空气相对湿度较低的地区，烟丝水分将随烟草贮存时间的增加而逐渐散失，从而导致卷烟加工过程中的造碎以及抽吸过程中干燥感和刺激性的增强。随着人们生活水平的不断提高，人们对卷烟制品的要求也在发生一定的变化，从单纯追求生理上的满足感逐步向追求舒适感和享受感转移。因此，如何增强卷烟保润性能以及提高抽吸舒适度成为人们的首要关注问题。本课题针对我国卷烟低湿环境下水分散失较快、抽吸时烟气干燥的问题，采用添加新型保润剂的方法，在提高其物理保润性能的同时降低了烟气干燥感。主要研究内容及结果如下：
烟草物理保润性能的差异不仅表现在不同品种之间，还表现在相同品种不同等级和生长部位之间，但造成这种差异的原因尚未明确，缺乏关于烟草物理结构和化学成分对其物理保润性能影响的系统分析。实验首先建立烟草水分散失动力学方程，从动力学角度确定了烟草物理保润性能的评价指标。并通过分析不同烟草的物理结构和化学成份差异，考察烟草物理化学特性对其物理保润特性的影响。结果表明：有效水分扩散系数（Deff）可作为评价烟草物理保润性能的一个有力指标。烟草在解吸环境中的Deff值高于吸湿环境，且Deff值随环境湿度的增加（RH=33%，43%，75%，83%）呈现先增加后降低的趋势。简单相关性分析结果表明，比孔体积越大越有利于水分散失；果胶、水溶性总糖和水溶性还原糖的含量与有效水分扩散系数呈显著负相关。
通过添加保润剂的方法提高烟草的物理保润性能。对多糖类（透明质酸、裂褶菌多糖、壳聚糖和阿拉伯胶）、植物提取物（苹果皮、桔皮、山药、芦根和银耳提取物）以及有机盐（乳酸钾和乳酸钠）三类物质的保湿性分别进行比较，确定3类物质中透明质酸、芦根提取物和乳酸钾具有较高的保湿率。将透明质酸、芦根提取物和乳酸钾加入到烟草中，分析其对烟草物理保润性能的实际影响。结果表明：透明质酸、芦根提取物和乳酸钾均能提高烟草平衡水分，降低有效水分扩散系数，且有效水分扩散系数随其添加量的增加而降低。乳酸钾对烟草物理保润性能的提高最为明显。透明质酸、芦根提取物和乳酸钾对主流烟气中的总粒相物和焦油没有影响，但都不同程度的提高主流烟气中水分含量以及改善卷烟感官舒适度，乳酸钾对主流烟气水分的增加幅度最大，芦根提取物对感官舒适度的改善效果最为明显。
乳酸钾能够有效提高卷烟的物理保润性能，可作为新型保润剂应用到烟草中，但同时也对卷烟感官品质产生影响，降低抽吸时的干燥感。为分析乳酸钾对卷烟化学特性的具体影响，分别考察加入不同含量的乳酸钾后，卷烟主流烟气常规、挥发性和半挥发性成分组成以及燃烧行为的变化。结果表明，乳酸钾对卷烟主流烟气中总粒相物、烟碱、焦油、抽吸口数以及挥发性羰基化合物没有影响；但能显著提高水分含量和降低烟气pH。乳酸钾对主流烟气粒相物中不同种类的半挥发性成分表现出不同的作用。乳酸钾促进醇类、内酯、杂环氧化物和酰胺类物质的生成；对醛类、酸类、吡咯和吡嗪类物质的产生具有抑制作用；而对于酮类、酯类、酚类、烃类、吡啶、烟碱、含氮化合物以及半挥发性成分总量，乳酸钾仅在低剂量添加时（0.2%）表现出了抑制作用，当添加量>0.2%时，则对这些物质的生成没有影响。采用TG-FTIR联用技术和扫描电镜分别考察了乳酸钾对卷烟燃烧行为及烟灰形态的影响。结果表明，乳酸钾降低裂解和燃烧阶段的最大热失重速率，并促使燃烧阶段的峰值温度和终点温度向高温区移动。乳酸钾在卷烟燃烧过程中对烟灰形态的改变可能是影响卷烟燃烧的原因之一。
针对乳酸钾能显著提高卷烟主流烟气水分这一现象，为探讨乳酸钾影响烟气水分生成的原因，首先明确了卷烟烟气水分生成的影响因素。结果表明：烟草热失重过程主要有4个阶段，水分产生于600℃之前的三个热失重阶段。卷烟燃烧产生的水中，36%-38%是由于烟草自身吸附水在<140℃的低温区挥发；51-54%产生于第二失重阶段140-370℃；6%-12%在370-600℃温度范围内生成。热裂解过程中，烟草成分通过一级反应生成水。在低温区（<370℃）氧气呈现增强自由基效应，促进水分的生成；但在高温区，高浓度氧气（21%O2）则呈现出氧化破坏作用，抑制水分的形成。碳水化合物（葡萄糖、果糖、蔗糖和麦芽糖）、有机酸（苹果酸、草酸和柠檬酸）和木质素都能通过裂解或燃烧反应生成一定量的水分。其中单糖裂解生成水的产率最高，为烟气水分的主要前体物。
在了解卷烟烟气水分的形成机制后，分别考察乳酸钾对烟草在不同温度范围生成水分及烟气水分前体物的影响，并探讨了钾离子和乳酸根离子对卷烟燃烧过程中生成水分所表现的作用。结果显示：乳酸钾通过增加烟草的平衡水分含量、影响烟草的裂解和燃烧状态而提高主流烟气水分含量。乳酸钾提高烟丝平衡水分主要是由于乳酸根和钾离子共同作用；在烟支的燃烧阶段，乳酸根促进烟气水分的产生，而以有机盐形式存在的钾离子起到抑制作用。对于不同的烟气水分前体物，乳酸钾对其反应生成水分的影响作用不同。乳酸钾促进单糖、淀粉和纤维素裂解和燃烧产生水分，对二糖和果胶裂解生成水分没有影响，但能提高其燃烧产生的水分。有机酸在裂解和燃烧阶段生成的水分都不受乳酸钾的影响。乳酸钾能够提高木质素裂解产生的水分含量，但当氧气存在时，乳酸钾阻碍木质素燃烧生成水分。
The moisture content of tobacco can influence its physical properties, processingcharacteristics, combustion, flavor and sensory quality. When placed in a dry envrioment, themoisture content of tobacco decreased and “dry” cigarettes can yield harsher and moreirritating smoke. With the improvement of people’s life, the requirement for the cigarette wasundergoing some changes, shifted from physiological satiation to the sense of comfort andenjoyment. Therefore, enhancing the water-holding capacity and sensory quality of cigarettesbecame the primary cancern of people. In this research, a new humectant was applied toincrease the water holding capacity of tobacco. Meanwhile, the mouth dryness was improvedby the addition of humectant. The main research contents and results are as follows:
Differences in hygroscopicity may be observed not only between tobacco varieties butalso within different grades of the same variety. But the influence of physical structure andchemical composition of tobacco on the water holding capacity is still unclear. At first, thekinetic model of moisture migration was studied, and the evaluation index was established torepresent the water-holding capacity. The physical structure (specific surface area and porevolume) and chemical components (total nitrogen, protein, pectin, starch, water-soluble sugar,and total sugar) of tobacco were determined. Results showed that the effective diffusioncoefficient (Deff) could be a useful representation of water-holding capacity except forequilibrium moisture content (EMC).With the increasing of the relative humidity ofenvironment, the values of Deffincreased first, then decreased. Simple correlation analysisshowed that, the Deffwas significantly affected by the specific pore volume of tobacco atdesorption. Large specific pore volume was in favored of moisture diffusion. Besides, aremarkable negative correlation was found between the effective diffusion coefficient and thepectin, water-soluble sugar, and total sugar content.
Adding humectants to the tobacco was used to improve its water holding capacity in thestudy. At first, the moisturizing efficiency of polysaccharide, plant extracts and organic saltswere determined at RH=40%and70%. They were polysaccharide: hyaluronic acid (HA),Schizophyllum, chitosan and arabic gum; plant extracts: extracts of apple peel, orange peel,Chinese yam, reed rhizome and tremella; organic salts: potassium lactate (PL) and sodiumlactate, respectively. The results showed that the HA, extract of reed rhizome and PLexhibited better moisture keeping performance. After added to the tobacco, HA, extract ofreed rhizome and PL could increase the EMC of tobacco, decrease the drying rate constantand Deff. The drying rate constant and Deffdecreased with the increasing of the adding amountof humectants. The effects of the three kinds of humectants on the mainstream chemisty andsensory quality of tobacco were investigated. The results demonstrated that HA, extract ofreed rhizome and PL had no effect on the total particulat matter and tar in the mainstreamsmoke, but increased the moisture content and sensory quality. The effect of PL on themoisture content in the mainstream smoke was the most obvious. The cigarettes treated withextract of reed rhizome exhibited the best sensory quality.
PL could be a new humectant due to its perfect performance to enhance the water holding capacity of tobacco. At first, the effects of different added amounts of PL on mainstreamsmoke chemistry, components distribution were determined. The mainstream smokechemistry detection of the cigarettes presented that PL had no effect on the content of TPM,NFDPM, puff number, nicotine and volatile carbonyl compounds, while increased themoisture content and decreased the CO content and the pH of smoke. Adding PL in thetobacco could increase the yield of alcohols, lactons, miscellaneous oxygenated compoundsand amides, but decrease the yield of aldehydes, acids, pyrroles and pyrazines. A small addedamount (0.2%) could lead to the reduction of the content of semi-volatile substancescompared with the control. However, when the added amount was beyond0.2%, the totalcontent of semi-volatile substances was not affected by the presence of PL. The same resultswere also achieved during the generation of ketones, esters, phenols, hydrocarbons, pyridines,tobacco alkaloids, and nitrogenous compound. Finally, the effect of potassium latate on thecombustion behavior and ash morphologies from tobacco were elucidated by TG–FTIR andSEM analysis. The results revealed that the maximum weight loss rate was decreased by theaddition of PL. The peak and end-point temperature of the combustion stage slightly movedtowards higher temperature. PL altered the ash morphology in a way that bonded the ashstronger and restricted the air flow. The alteration of ash morphology may be one of thereasons for the change of combustion behavior.
The moisture formation mechanism during the combustion of tobacco was firstlyresearched. DTG analysis revealed that tobacco thermal degradation occurred in four stepsand the H2O evolution was found to have three major peaks for the combustion of bothflue-cured and burley tobacco. About36%-38%of the H2O genterated at first step (from25℃to140℃) due to the evaporation of absorbed water;51-54%generated at140-370℃and6%-12%formed at370-600℃. The yield of moisture was not affected by the flow rateindicating that gas phase secondary reactions did not contribute to the yield of moisture at thethree stages.The radical enhancement effect caused by oxygen was dominant in the lowertemperature range（<370℃）and the oxygen promoted the generation of H2O. While theoxygen played the oxidative destruction effect in the higher temperature range and inhibitedthe formation of H2O. The H2O formed during the pyrolysis or combustion of carbohydrate,organic acid and lignin. The yield of H2O from monosaccharides was the highest, indicatingthe monosaccharide was the main potential precursor.
The effects of PL on the generation of H2O at different temperature ranges andprecursors were studied. The results showed that PL increased the moisture content inmainstream smoke by increasing EMC and affecting the combustion behavior of tobacco. Theincrease of EMC was due to the potassium ion and lactate group. During the process ofcombustion, the lactate group promoted the generation of H2O, while the potassium ionpresented in organic salts hindered the formation of H2O. PL increased the yield of H2O fromthe pyrolysis and combustion of monosaccharide, starch and cellulose, showed no effect onthe formation of H2O from the pyrolysis of disaccharide and pectin, but promoted thegeneration in the process of combustion. The yield of H2O from organic acids was notaffected by PL. PL increased the yield of H2O from the pyrolysis of lignin, but prevented thegeneration of H2O from the combustion of lignin.
烟草物理保润性能的差异不仅表现在不同品种之间，还表现在相同品种不同等级和生长部位之间，但造成这种差异的原因尚未明确，缺乏关于烟草物理结构和化学成分对其物理保润性能影响的系统分析。实验首先建立烟草水分散失动力学方程，从动力学角度确定了烟草物理保润性能的评价指标。并通过分析不同烟草的物理结构和化学成份差异，考察烟草物理化学特性对其物理保润特性的影响。结果表明：有效水分扩散系数（Deff）可作为评价烟草物理保润性能的一个有力指标。烟草在解吸环境中的Deff值高于吸湿环境，且Deff值随环境湿度的增加（RH=33%，43%，75%，83%）呈现先增加后降低的趋势。简单相关性分析结果表明，比孔体积越大越有利于水分散失；果胶、水溶性总糖和水溶性还原糖的含量与有效水分扩散系数呈显著负相关。
通过添加保润剂的方法提高烟草的物理保润性能。对多糖类（透明质酸、裂褶菌多糖、壳聚糖和阿拉伯胶）、植物提取物（苹果皮、桔皮、山药、芦根和银耳提取物）以及有机盐（乳酸钾和乳酸钠）三类物质的保湿性分别进行比较，确定3类物质中透明质酸、芦根提取物和乳酸钾具有较高的保湿率。将透明质酸、芦根提取物和乳酸钾加入到烟草中，分析其对烟草物理保润性能的实际影响。结果表明：透明质酸、芦根提取物和乳酸钾均能提高烟草平衡水分，降低有效水分扩散系数，且有效水分扩散系数随其添加量的增加而降低。乳酸钾对烟草物理保润性能的提高最为明显。透明质酸、芦根提取物和乳酸钾对主流烟气中的总粒相物和焦油没有影响，但都不同程度的提高主流烟气中水分含量以及改善卷烟感官舒适度，乳酸钾对主流烟气水分的增加幅度最大，芦根提取物对感官舒适度的改善效果最为明显。
乳酸钾能够有效提高卷烟的物理保润性能，可作为新型保润剂应用到烟草中，但同时也对卷烟感官品质产生影响，降低抽吸时的干燥感。为分析乳酸钾对卷烟化学特性的具体影响，分别考察加入不同含量的乳酸钾后，卷烟主流烟气常规、挥发性和半挥发性成分组成以及燃烧行为的变化。结果表明，乳酸钾对卷烟主流烟气中总粒相物、烟碱、焦油、抽吸口数以及挥发性羰基化合物没有影响；但能显著提高水分含量和降低烟气pH。乳酸钾对主流烟气粒相物中不同种类的半挥发性成分表现出不同的作用。乳酸钾促进醇类、内酯、杂环氧化物和酰胺类物质的生成；对醛类、酸类、吡咯和吡嗪类物质的产生具有抑制作用；而对于酮类、酯类、酚类、烃类、吡啶、烟碱、含氮化合物以及半挥发性成分总量，乳酸钾仅在低剂量添加时（0.2%）表现出了抑制作用，当添加量>0.2%时，则对这些物质的生成没有影响。采用TG-FTIR联用技术和扫描电镜分别考察了乳酸钾对卷烟燃烧行为及烟灰形态的影响。结果表明，乳酸钾降低裂解和燃烧阶段的最大热失重速率，并促使燃烧阶段的峰值温度和终点温度向高温区移动。乳酸钾在卷烟燃烧过程中对烟灰形态的改变可能是影响卷烟燃烧的原因之一。
针对乳酸钾能显著提高卷烟主流烟气水分这一现象，为探讨乳酸钾影响烟气水分生成的原因，首先明确了卷烟烟气水分生成的影响因素。结果表明：烟草热失重过程主要有4个阶段，水分产生于600℃之前的三个热失重阶段。卷烟燃烧产生的水中，36%-38%是由于烟草自身吸附水在<140℃的低温区挥发；51-54%产生于第二失重阶段140-370℃；6%-12%在370-600℃温度范围内生成。热裂解过程中，烟草成分通过一级反应生成水。在低温区（<370℃）氧气呈现增强自由基效应，促进水分的生成；但在高温区，高浓度氧气（21%O2）则呈现出氧化破坏作用，抑制水分的形成。碳水化合物（葡萄糖、果糖、蔗糖和麦芽糖）、有机酸（苹果酸、草酸和柠檬酸）和木质素都能通过裂解或燃烧反应生成一定量的水分。其中单糖裂解生成水的产率最高，为烟气水分的主要前体物。
在了解卷烟烟气水分的形成机制后，分别考察乳酸钾对烟草在不同温度范围生成水分及烟气水分前体物的影响，并探讨了钾离子和乳酸根离子对卷烟燃烧过程中生成水分所表现的作用。结果显示：乳酸钾通过增加烟草的平衡水分含量、影响烟草的裂解和燃烧状态而提高主流烟气水分含量。乳酸钾提高烟丝平衡水分主要是由于乳酸根和钾离子共同作用；在烟支的燃烧阶段，乳酸根促进烟气水分的产生，而以有机盐形式存在的钾离子起到抑制作用。对于不同的烟气水分前体物，乳酸钾对其反应生成水分的影响作用不同。乳酸钾促进单糖、淀粉和纤维素裂解和燃烧产生水分，对二糖和果胶裂解生成水分没有影响，但能提高其燃烧产生的水分。有机酸在裂解和燃烧阶段生成的水分都不受乳酸钾的影响。乳酸钾能够提高木质素裂解产生的水分含量，但当氧气存在时，乳酸钾阻碍木质素燃烧生成水分。
The moisture content of tobacco can influence its physical properties, processingcharacteristics, combustion, flavor and sensory quality. When placed in a dry envrioment, themoisture content of tobacco decreased and “dry” cigarettes can yield harsher and moreirritating smoke. With the improvement of people’s life, the requirement for the cigarette wasundergoing some changes, shifted from physiological satiation to the sense of comfort andenjoyment. Therefore, enhancing the water-holding capacity and sensory quality of cigarettesbecame the primary cancern of people. In this research, a new humectant was applied toincrease the water holding capacity of tobacco. Meanwhile, the mouth dryness was improvedby the addition of humectant. The main research contents and results are as follows:
Differences in hygroscopicity may be observed not only between tobacco varieties butalso within different grades of the same variety. But the influence of physical structure andchemical composition of tobacco on the water holding capacity is still unclear. At first, thekinetic model of moisture migration was studied, and the evaluation index was established torepresent the water-holding capacity. The physical structure (specific surface area and porevolume) and chemical components (total nitrogen, protein, pectin, starch, water-soluble sugar,and total sugar) of tobacco were determined. Results showed that the effective diffusioncoefficient (Deff) could be a useful representation of water-holding capacity except forequilibrium moisture content (EMC).With the increasing of the relative humidity ofenvironment, the values of Deffincreased first, then decreased. Simple correlation analysisshowed that, the Deffwas significantly affected by the specific pore volume of tobacco atdesorption. Large specific pore volume was in favored of moisture diffusion. Besides, aremarkable negative correlation was found between the effective diffusion coefficient and thepectin, water-soluble sugar, and total sugar content.
Adding humectants to the tobacco was used to improve its water holding capacity in thestudy. At first, the moisturizing efficiency of polysaccharide, plant extracts and organic saltswere determined at RH=40%and70%. They were polysaccharide: hyaluronic acid (HA),Schizophyllum, chitosan and arabic gum; plant extracts: extracts of apple peel, orange peel,Chinese yam, reed rhizome and tremella; organic salts: potassium lactate (PL) and sodiumlactate, respectively. The results showed that the HA, extract of reed rhizome and PLexhibited better moisture keeping performance. After added to the tobacco, HA, extract ofreed rhizome and PL could increase the EMC of tobacco, decrease the drying rate constantand Deff. The drying rate constant and Deffdecreased with the increasing of the adding amountof humectants. The effects of the three kinds of humectants on the mainstream chemisty andsensory quality of tobacco were investigated. The results demonstrated that HA, extract ofreed rhizome and PL had no effect on the total particulat matter and tar in the mainstreamsmoke, but increased the moisture content and sensory quality. The effect of PL on themoisture content in the mainstream smoke was the most obvious. The cigarettes treated withextract of reed rhizome exhibited the best sensory quality.
PL could be a new humectant due to its perfect performance to enhance the water holding capacity of tobacco. At first, the effects of different added amounts of PL on mainstreamsmoke chemistry, components distribution were determined. The mainstream smokechemistry detection of the cigarettes presented that PL had no effect on the content of TPM,NFDPM, puff number, nicotine and volatile carbonyl compounds, while increased themoisture content and decreased the CO content and the pH of smoke. Adding PL in thetobacco could increase the yield of alcohols, lactons, miscellaneous oxygenated compoundsand amides, but decrease the yield of aldehydes, acids, pyrroles and pyrazines. A small addedamount (0.2%) could lead to the reduction of the content of semi-volatile substancescompared with the control. However, when the added amount was beyond0.2%, the totalcontent of semi-volatile substances was not affected by the presence of PL. The same resultswere also achieved during the generation of ketones, esters, phenols, hydrocarbons, pyridines,tobacco alkaloids, and nitrogenous compound. Finally, the effect of potassium latate on thecombustion behavior and ash morphologies from tobacco were elucidated by TG–FTIR andSEM analysis. The results revealed that the maximum weight loss rate was decreased by theaddition of PL. The peak and end-point temperature of the combustion stage slightly movedtowards higher temperature. PL altered the ash morphology in a way that bonded the ashstronger and restricted the air flow. The alteration of ash morphology may be one of thereasons for the change of combustion behavior.
The moisture formation mechanism during the combustion of tobacco was firstlyresearched. DTG analysis revealed that tobacco thermal degradation occurred in four stepsand the H2O evolution was found to have three major peaks for the combustion of bothflue-cured and burley tobacco. About36%-38%of the H2O genterated at first step (from25℃to140℃) due to the evaporation of absorbed water;51-54%generated at140-370℃and6%-12%formed at370-600℃. The yield of moisture was not affected by the flow rateindicating that gas phase secondary reactions did not contribute to the yield of moisture at thethree stages.The radical enhancement effect caused by oxygen was dominant in the lowertemperature range（<370℃）and the oxygen promoted the generation of H2O. While theoxygen played the oxidative destruction effect in the higher temperature range and inhibitedthe formation of H2O. The H2O formed during the pyrolysis or combustion of carbohydrate,organic acid and lignin. The yield of H2O from monosaccharides was the highest, indicatingthe monosaccharide was the main potential precursor.
The effects of PL on the generation of H2O at different temperature ranges andprecursors were studied. The results showed that PL increased the moisture content inmainstream smoke by increasing EMC and affecting the combustion behavior of tobacco. Theincrease of EMC was due to the potassium ion and lactate group. During the process ofcombustion, the lactate group promoted the generation of H2O, while the potassium ionpresented in organic salts hindered the formation of H2O. PL increased the yield of H2O fromthe pyrolysis and combustion of monosaccharide, starch and cellulose, showed no effect onthe formation of H2O from the pyrolysis of disaccharide and pectin, but promoted thegeneration in the process of combustion. The yield of H2O from organic acids was notaffected by PL. PL increased the yield of H2O from the pyrolysis of lignin, but prevented thegeneration of H2O from the combustion of lignin.
引文
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