摘要
卷烟燃烧时释放出的烟气中有很多危害人们身体健康的物质,如焦油、烟碱等物质,降焦减害提高卷烟吸食安全性一直是烟草行业的重点研究课题,也是国内外烟草行业所面临的难题和挑战。本文针对卷烟商品的特殊性,首次研制了一种含铁-活性炭的烟草薄片,在不改变卷烟吸味的前提下,能显著降低中低焦油卷烟中的焦油释放量。
首先比较了杏壳炭、椰壳炭和木质炭对卷烟燃烧的影响,发现添加活性炭可提高卷烟的燃烧温度,而且能降低卷烟焦油和烟碱的含量,其中以椰壳炭的降低效果最好,焦油和烟碱分别降低9.73%,23.76%。
基于催化燃烧的基本原理和卷烟食品的特殊要求,选择具有催化燃烧作用的铁活性组分,制备了一种含铁-活性炭的烟草薄片并应用于卷烟中,对于焦油含量为13.72%mg/支的中焦油卷烟,可使卷烟的焦油下降16.76%,烟碱下降32.04%。
研究发现,铁-活性炭的烟草薄片的降焦性能与其制备条件有关。在pH=12的碱性条件下制备的铁-活性炭比在pH=5的酸性条件下制备的铁-活性炭在卷烟中的降焦效果更好;以沉积沉淀法制备的铁-活性炭比简单地将铁的氢氧化物与活性炭混合效果更好。还考察了铁-活性炭烟草薄片中铁含量和原料来源的影响,随着活性炭中铁含量增加,降焦效果增加,当铁含量增加到26-2%时,降焦幅度基本不变;硫酸铁原料中杂质含量对铁-活性炭烟草薄片的降焦效果有负作用。
对在pH=5和pH=12两种pH条件下制备的铁的氢氧化物进行了XRD表征,
发现均为无定形状态或非晶态。把这两种铁的氢氧化物粉末灼烧后的产物进
行了XRD表征,结果表明在空气氛300℃样品处理条件下,pH=12条件下制
备的铁的氢氧化物己转化为Q一Fe203,而pH=5条件下制备的转化为Q一Fe00H;
对添加这两种条件下制备的铁的氢氧化物的卷烟燃吸后的烟灰进行XRD分
析,发现这两种铁的氢氧化物都可转化为Q一FeZO3。这种新生态的Q一FeZO3对
降低卷烟中焦油具有促进作用。
在不同pH条件下制备的铁的氢氧化物的TG分析表明,两者失重有明
显的差别。在pH=12的条件下制备的铁的氢氧化物只有60一300℃一个失重
阶段,残留率为85.56%;而在pH=5的条件下制备的铁的氢氧化物有两个
失重阶段,分别位于60一300℃和500一800℃,失重率分别是13.50%和8.57%,
残留率为74.72%。热分析表明在不同的pH的条件下,得到了不同的铁的氢
氧化物前驱体。
添加不同铁一活性炭烟草薄片的卷烟的TG分析表明,在130一380℃的
温度范围内,pH=12的条件下制备的铁一活性炭卷烟失重为46.8%,pH=5的
失重50.16%,对照卷烟失重52.49%。在卷烟中,焦油的形成主要集中在
130一380℃温度区域内,各样品的失重量基本可代表烟丝参与卷烟焦油形成
的物质量。pH=12的条件下制备的铁一活性炭卷烟中参与卷烟焦油形成的物
质最少,卷烟的焦油释放量也最低。
对卷烟主流烟气中半挥发性成分进行分析,结果表明铁一活性炭卷烟中
半挥发性物质的含量低于对照卷烟主流烟气中的量,分别为74.08 pg/支,
79.98 pg/支。
此外,还考察了铁一活性炭烟草薄片成型中,采用长纤维A:短纤维B=1:
2的纤维配比,670的纤维添加量能保证铁一活性炭烟草薄片的物理性能符合生
产要求,且成本较低。
Many compositions produced by smoking cigarette such as nicotine and tar are harmful to human health, There have been a lot of researches in tobacco industry to reduce the risk of smoking. Considering the speciality of cigarette, we have prepared a kind of Fe-active carbon (AC) reconstituted tobacco that can reduce the tar in the main-stream smoke of cigarette.
In this paper, it is proved that adding 5 wt % of coconuts carbon in cigarette can raise the burning temperature of cigarette and reduce 9.73% and 23.76% of tar and nicotine respectively.
Based on the researches of coconuts carbon, another additive Fe-AC reconstituted tobacco was prepared and used to reduce the cigarette tar. It can reduce 16.76% and 32.04% of tar and nicotine respectively.
The effects of Fe-AC reconstituted tobacco on reducing cigarette tar and nicotine are depend on the conditions, such as preparing method of Fe and AC, pH value and the purity of the raw materials. In reducing cigarette tar, the Fe-AC prepared by the method of deposition-precipitation performs better than the Fe-AC prepared by the method of mixing. The Fe-AC prepared at pH=12 has a better effect than the Fe-AC prepared at pH=5. Impurities of Fe2(SO4)3 reagent have negative influence in reducing cigarette tar. The effect of reducing tar is also related to the content of Fe in the Fe-AC. Increasing the content of Fe in the Fe-AC, the efficiency of reducing cigarette tar increases until the content of Fe
increases up to 26.2%.
The obtained hydroxides of Fe prepared at pH=12 and pH=5 are characterized by XRD patterns, which indicate that both of them are non-crystal phase or amorphous phase. Treated them at 300C in air, the hydroxide of Fe prepared at pH=12 is easily transformed to a -Fe2O3, and the hydroxide of Fe at pH=5 is transformed to a -FeO(OH). XRD analysis were carried on the cigarette ashes, which showed that both the two different hydroxides transformed to a -Fe2O3. The new formed a -Fe2O3 in cigarette suggests they can promote the burning of cigarette and reducing the tar.
Thermal gravity analysis (TG) of the above two different hydroxides indicate that the difference is obvious, in the weight-loss. The hydroxide of Fe prepared at pH=12 loses less than that at pH=5. Weight loss of the former mainly occurs in the zone of 60-300C and the residual mass is 85.86%. Weight loss of the latter occurs in the zone of 60-300C and 500-800C, and the residual mass is 74.72%. The results show that their decomposition process are different.
The results of XRD analysis and TG analysis indicate that the precursors of Fe hydroxides prepared at different pH value are different.
TG analysis of the cigarette has showed the weight loss occurring in the zone of 130-380 C of cigarette is different. TG analysis indicate that the cigarette with Fe-AC reconstituted tobacco prepared at pH=12 loses 46.8% and that at pH=5 loses 50.16%, but the common cigarette loses 52.49%. Because the
forming of cigarette tar is mainly in the zone of 130-380C, the weight loss occurring in this zone is related to forming tar. The more weight loses, the more tar produces.
Analysis on semi-volatility compositions in cigarette tar has been found that the quantity of compositions in the cigarette with Fe-AC reconstituted tobacco is less than that of the cigarette without Fe-AC reconstituted tobacco. The amount of the cigarette with additive of Fe-AC is 74.08 ug/cig, and the common cigarette is 79.98 ug/cig.
In order to the Fe-AC reconstituted tobacco is suitable for producing, the fiber used in the traditional reconstituted tobacco was replaced by the mixture of long wood fiber and short wood fiber. The ratio of long wood fiber to short wood fiber in the mixture is 1:2 .The content of the mixture in the reconstituted tobacco is 6 wt%.
引文
1. Guerin, Measuring environmental emissions from tobacco combustion: sidestream cigarette smoke literature review, Atmosphere Envi., 1987, 21(2): 291-297。
2.Davis L D等编著,国家烟草专卖局组织翻译,烟草-生产、化学和技术,化学工业出版社,2003,251
3. Weeks,W.W, Chemistry of tobacco constituents influencing flavor and aroma. Rec. Adv. Tob.Sci.,1985, (11): 175-200
4. Baker, R.R, Temperature variation within a cigarette combustion coal during the smoking cycle. High Temp. Sci.,1975, 7: 236-47
5. Robinson, Tobacco combustion-the last ten years. Rec.Adv.Tob.Sci., 1990,16,3-71
6. Baker, R.R, Combustion and thermal decomposition region inside a burning cigarette .Combust Flame,1977, 30:21-32
7. Johnson W R, Hale R W, The distribution of products between mainstream and sidestream smoke, Tob. Sci., 1973, 17:141-144
8. Plimmer, J.R. The chemical constituents of tobacca and tobacco smoke. Chem.Rev.,1959, 7, 885-936.
9. Dube,M.F.& Greene, Method of collection of smoke for analytical purpose. Rec. Adv. Tob.Sci.,1985, (8): 42-102
10. Halter, H.M, Effect of tobacco reconstitution and expansion process on smoke composition. Rec. Adv. Tob.Sci. 1986,(4), 113-132
11.沈德和,金闻博,刘祥春等,被动吸烟,中国轻工业出版社,1996
12. T.Yamamoto, Effect of exogenous potassium on reduction in reliveries of tar nicotine and carbon monoxide in the mainstream smoke of cigarette, Central research institue, Japan tobacco Inc.
13.王建民,几种钾盐的降焦效果分析,郑州轻工业学院学报,2001,(12):62-64
14.戴亚等,外加钾盐对卷烟焦油释放量的影响,烟草科技,1998,(1):11-12
15.许萍,微量元素在卷烟中的应用研究,埠阳师范学院学报,1998, (2):27-31
16.宁敏,添加有机酸钾对卷烟焦油量的影响,合肥工业大学学报,1999,(6):88-93
17. Doolittle. Tar prellctor simplifies cig. design. Tobacco Rep. 1990, (10): 34-36
18. Beggett, Slective. removal of semi-volatile components of cigarette smoke by various filter Tobacco Rep. 1985, (7): 39-46
19.魏信波,安全香烟,中国专利,87101312,1987
20.安惠,烟用降焦、滤毒复合材料及其制备工艺,中国专利,94113133,1994
21. Morie, Parameters affecting the selective filtration of
certain tobacco smoke components, Tabakforch, 1975, (8),145-49
22. Tokida, Selective removal of semivolatile compinents of cigarette smoke by activated carbon in vented filters. Sene Gakkaishi, 1985,41,539-41
23.高志明,CuO_2/活性炭和Fe_2O_3/活性炭催化还原NO,应用化学,1996,(4),77-79
24.谢有畅,第四届全国催化学术报告会论文集。
25.陈仰光,铁/活性炭催化剂的穆斯堡尔谱研究,催化学报,1992(5):325-331
26.宋昭峥,铁系催化剂组分间的作用,西安石油学院学报,2001,(1),36-40
27.侯斌等,生物质热解产物中焦油的催化裂解,燃料化学学报,2001.,(2):70-75
28.王铁军等,生物质焦油裂解催化剂的制备及其催化裂解性能,煤炭转化,2003(1):89-93
29.刘艳华,几种含铁化合物对煤燃烧特性的影响,西安交通大学学报,2000,(9):20-24
30. Zhu. Z.P, Gu.Y.D. 8th International Conferenceon Coal Science. Oviedo. Spain, 1995, vol. 1.695
31.朱珍平等,燃料化学学报,1996,24(1):48
32.崔洪,铁催化聚丙烯腈脱氮的研究,环境化学,1996,(7):301-306
33.季伟捷,单层型氧化铁的制备及其前体的表征,催化化学,1994,(11):339-433
34.陈白珍,硫酸盐湿法铁红晶种生成过程研究,无机盐工业,2002,(5):1-3
35.朱建育,纳米α-FeOOH颗粒的形态和结构,功能材料,2002,(2):225-227
36.赵建路,Fe(OH)_3凝胶两步法水解制备均分散针行铁红胶粒,无机材料学报,1998.(12):813-817
37.魏雨,无机添加剂的浓度及pH值对纺锤行形Fe_2O_3粒子晶貌的影响,功能材料,1996(6):506-508
38.马红钦等,铁基高温变换催化剂制备的穆斯堡尔谱研究,催化学报,1995,(5):365-370
39.张伟达,氢氧化铁凝胶的制备及其热转变过程,陶瓷研究,1992,(3):145-148
40. H. R.Burtion, Thermal decomposition of tobacco, purchased by agriculture research serve U.S. department of agriculture for official use.
41.胡源等,热分析技术在阻燃材料研究中的应用,火灾科学,1999.(1):74-78