琼脂-纳米SiO_2气凝胶的制备及在卷烟滤嘴中的应用
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摘要
为开发卷烟减害新材料,向琼脂基质中加入不同量的纳米SiO_2,采用溶胶-凝胶法制备了系列琼脂-纳米SiO_2气凝胶材料,对材料形貌和微结构进行了表征;采用模拟烟气吸附试验考察了材料对巴豆醛的吸附效果,并通过二元复合滤棒的形式考察了Agar-SiO_2-60%(气凝胶中纳米SiO_2的质量分数为60%)在卷烟滤嘴中的应用效果。结果表明:(1)该材料呈三维网络多孔结构,比表面积为73.62～424.75m~2/g,平均孔径为23.46～10.38 nm。(2)当气凝胶中纳米SiO_2的质量分数从0依次增加到20%、40%、60%、80%时,琼脂-纳米SiO_2气凝胶对巴豆醛的吸附量从1.65 mg/g依次增加到3.13、4.35、8.91、13.80 mg/g。(3)卷烟滤棒中Agar-SiO_2-60%添加量为30 mg/支时,试验卷烟主流烟气常规指标基本无变化,有害成分NNK、NH_3以及巴豆醛释放量较对照卷烟分别降低12.8%、11.3%和9.5%,烟气危害性指数降低0.6,且感官品质未下降。
In order to develop new materials for reducing harmful components in cigarette smoke, a series of agar-nano-SiO_2 aerogels was prepared by agar matrix and nano-SiO_2 powder through a sol-gel process. The morphology and microstructure of the aerogels were characterized, the adsorption property of the aerogels to crotonaldehyde in the simulated smoke was studied, and the application effect of the agar-SiO_2-60%(the mass fraction of nano-SiO_2 in aerogel was 60%) in the cigarette filter was investigated. The results showed that: 1)The agar-nano-SiO_2 aerogels presented three-dimensional network porous structure with a specific surface area of 73.62-424.75 m~2/g and the average pore size of 23.46-10.38 nm. 2) The amount of adsorbed crotonaldehyde increased from 1.65 mg/g to 3.13, 4.35, 8.91 and 13.80 mg/g when the mass fraction of nano-SiO_2 in aerogels increased from 0 to 20%, 40%, 60% and 80%, respectively. 3) When agar-SiO_2-60% was added to the dual-segment filtered cigarette at a rate of 30 mg/cig, the effects on the release of tar, nicotine and CO were negligible, and the release of NNK, NH_3 and crotonaldehyde was reduced by 12.8%, 11.3% and 9.5%,respectively. The overall hazard index of the test cigarette was decreased by 0.6, and the sensory quality of cigarette was unchanged.
In order to develop new materials for reducing harmful components in cigarette smoke, a series of agar-nano-SiO_2 aerogels was prepared by agar matrix and nano-SiO_2 powder through a sol-gel process. The morphology and microstructure of the aerogels were characterized, the adsorption property of the aerogels to crotonaldehyde in the simulated smoke was studied, and the application effect of the agar-SiO_2-60%(the mass fraction of nano-SiO_2 in aerogel was 60%) in the cigarette filter was investigated. The results showed that: 1)The agar-nano-SiO_2 aerogels presented three-dimensional network porous structure with a specific surface area of 73.62-424.75 m~2/g and the average pore size of 23.46-10.38 nm. 2) The amount of adsorbed crotonaldehyde increased from 1.65 mg/g to 3.13, 4.35, 8.91 and 13.80 mg/g when the mass fraction of nano-SiO_2 in aerogels increased from 0 to 20%, 40%, 60% and 80%, respectively. 3) When agar-SiO_2-60% was added to the dual-segment filtered cigarette at a rate of 30 mg/cig, the effects on the release of tar, nicotine and CO were negligible, and the release of NNK, NH_3 and crotonaldehyde was reduced by 12.8%, 11.3% and 9.5%,respectively. The overall hazard index of the test cigarette was decreased by 0.6, and the sensory quality of cigarette was unchanged.
引文
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[7]冯守爱,黄泰松,邹克兴,等.疏水纳米SiO2选择性降低卷烟烟气有害成分含量[J].烟草科技,2011(10):49-53.FENG Shouai,HUANG Taisong,ZOU Kexing,et al.Selective reduction of harmful components in cigarette smoke with hydrophobic nanometer silicon dioxide[J].Tobacco Science&Technology,2011(10):49-53.
[8]Zhu Y,Hou H W,Tang G L,et al.Synthesis of three-quarter-sphere-likeγ-AlOOH superstructures with high adsorptive capacity[J].European Journal of Inorganic Chemistry,2010(6):872-878.
[9]刘志明,吴鹏.壳聚糖/纤维素气凝胶球的制备及其甲醛吸附性能[J].林产化学与工业,2017,37(1):27-35.LIU Zhiming,WU Peng.Preparation of chitosan/cellulose aerogel beads and its formaldehyde gas adsorption performance[J].Chemistry and Industry of Forest Products,2017,37(1):27-35.
[10]穆若郡,庞杰,王敏,等.魔芋葡甘聚糖气凝胶对海洋污染降解菌的吸附固定化[J].热带生物学报,2016,7(2):164-166.MU Ruojun,PANG Jie,WANG Ming,et al.Immobilization of marine pollutants degrading bacteria by Konjac glucomannan aerogel[J].Journal of Tropical Biology,2016,7(2):164-166.
[11]张艺钟,刘珊,刘志文,等.壳聚糖凝胶球对Cu(Ⅱ)和Cr(Ⅵ)吸附行为的对比[J].化工进展,2017,36(2):712-719.ZHANG Yizhong,LIU Shan,LIU Zhiwen,et al.Comparison for Cu(Ⅱ)and Cr(Ⅵ)adsorption behavior onto chitosan hydrogel beads[J].Chemical Industry and Engineering Progress,2017,36(2):712-719.
[12]权迪.纤维素气凝胶多孔材料的制备及改性应用[D].哈尔滨:东北林业大学,2016.QUAN Di.The preparation and modification of cellulose aerogel porous materials[D].Harbin:Northeast Forestry University,2016.
[13]李飞,邢丽,向军辉,等.疏水性纤维素-SiO2复合气凝胶的非超临界制备[J].稀有金属材料与工程,2015,44(增刊1):647-650.LI Fei,XING Li,XIANG Junhui,et al.Hydrophobic cellulose-SiO2composite aerogel prepared by a non-supercritical drying process[J].Rare Metal Materials and Engineering,2015,44(S1):647-650.
[14]李婧,刘志明.毛竹NFC/SiO2气凝胶的制备和疏水改性[J].纤维素科学与技术,2016,24(1):49-54.LI Jing,LIU Zhiming.Preparation and hydrophobic modification of Phyllostachys heterocycla cv.Pubescens NFC/SiO2aerogel[J].Journal of Cellulose Science and Technology,2016,24(1):49-54.
[15]刘昕昕,刘志明.疏水纤维素/SiO2复合气凝胶的制备和表征[J].生物质化学工程,2016,50(2):39-44.LIU Xinxin,LIU Zhiming.Preparation and characterization of hydrophobic cellulose/SiO2composite aerogel[J].Biomass Chemical Engineering,2016,50(2):39-44.
[16]马倩.壳聚糖-二氧化硅复合气凝胶的制备、改性及其性能研究[D].天津:天津大学,2014.MA Qian.Preparation,modification and properties of chitosan-silica composite aerogels[D].Tianjin:Tianjin University,2014.
[17]GB/T 19609-2004卷烟用常规分析用吸烟机测定总粒相物和焦油[S].GB/T 19609-2004 Cigarette-Determination of total and nicotine-free dry particulate matter using a routine analytical smoking machine[S].
[18]GB/T 23355-2009卷烟总粒相物中烟碱的测定气相色谱法[S].GB/T 23355-2009 Cigarettes-Determination of nicotine in smoke condensates-Gas-chromatographic method[S].
[19]GB/T 21130-2007卷烟烟气总粒相物中苯并[a]芘的测定[S].GB/T 21130-2007 Cigarettes-Determination of benzo[a]pyrene in total particulate matter[S].
[20]YC/T 253-2008卷烟主流烟气中氰化氢的测定连续流动法[S].YC/T 253-2008 Cigarettes-Determination of hydrogen cyanide in cigarette mainstream smokeContinuous flow method[S].
[21]YC/T 254-2008卷烟主流烟气中主要羰基化合物的测定高效液相色谱法[S].YC/T 254-2008 Cigarettes-Determination of major carbonyls in mainstream cigarette smoke-High performance liquid chromatographic method[S].
[22]YC/T 255-2008卷烟主流烟气中主要酚类化合物的测定高效液相色谱法[S].YC/T 255-2008 Cigarettes-Determination of major phenolic compounds in mainstream cigarette smokeHigh performance liquid chromatographic method[S].
[23]GB/T 23228-2008卷烟主流烟气总粒相物中烟草特有N-亚硝胺的测定气相色谱-热能分析联用法[S].GB/T 23228-2008 Cigarette-Determination of tobacco specific N-nitrosamines in total particulate matter of mainstream cigarette smoke-GC-TEA method[S].
[24]GB/T 23356-2009卷烟烟气气相中一氧化碳的测定非散射红外法[S].GB/T 23356-2009 Cigarettes-Determination of carbon monoxide in the vapour phase of cigarette smoke-NDIR method[S].
[25]YC/T 377-2010卷烟主流烟气中氨的测定离子色谱法[S].YC/T 377-2010 Cigarettes-Determination of ammonia in mainstream cigarette smoke-Ion chromatography method[S].
[26]谢剑平,刘惠民,朱茂祥,等.卷烟烟气危害性指数研究[J].烟草科技,2009(2):5-15.XIE Jianping,LIU Huimin,ZHU Maoxiang,et al.Development of a novel hazard index of mainstream cigarette smoke and its application on risk evaluation of cigarette products[J].Tobacco Science&Technology,2009(2):5-15.
[27]GB 5606.4-2005卷烟第4部分:感官技术要求[S].GB 5606.4-2005 Cigarettes-Part 4:technical requirements for sense evaluation[S].
[28]庄森炀.生物质基多孔超轻质复合材料的研究[D].福州:福建农林大学,2016.ZHUANG Senyang.Study of bio-based porous and lightweight composites materials[D].Fuzhou:Fujian Agriculture and Forestry University,2016.
[29]乐垚.二氧化硅的形貌调控及其吸附性能研究[D].武汉:武汉理工大学,2013.LE Yao.Morphological control of silica and its adsorption performance[D].Wuhan:Wuhan University of Technology,2013.
[2]谢兰英,钟科军,刘琦,等.纤维素纸沟槽滤嘴选择性降低卷烟烟气中有害成分[J].烟草科技,2017,50(5):45-52.XIE Lanying,ZHONG Kejun,LIU Qi,et al.Selectively reducing harmful components in mainstream cigarette smoke with grooved cellulose paper filter[J].Tobacco Science&Technology,2017,50(5):45-52.
[3]孙学辉,杨松,孙培健,等.基于卷烟降焦减害的滤嘴添加剂研究与应用进展[J].烟草科技,2017,50(2):86-96.SUN Xuehui,YANG Song,SUN Peijian,et al.Progress in research and application of filter additives to reducing tar and harmful components in cigarette smoke[J].Tobacco Science&Technology,2017,50(2):86-96.
[4]Deng Q X,Huang C Z,Xie W,et al.Significant reduction of harmful compounds in tobacco smoke by the use of titanate nanosheets and nanotubes[J].Chemical Communications,2011,47(21):6153-6155.
[5]张东海,岳勇,许锴霖,等.过渡金属修饰的碳纳米管降低烟气中氢氰酸[J].广州化工,2013,41(23):66-68.ZHANG Donghai,YUE Yong,XU Kailin,et al.Study the selective reduction of hydrogen cyanide in cigarette smoke by three transition metals modified carbon nanotubes[J].Guangzhou Chemical Industry,2013,41(23):66-68.
[6]童保云,陈开波,李村,等.金属掺杂多孔氧化物选择性降低卷烟烟气HCN和苯酚研究[J].中国烟草学报,2014,20(1):9-14.TONG Baoyun,CHEN Kaibo,LI Cun,et al.Selective reduction of HCN and phenol in mainstream cigarette smoke using metal-doped oxide material with porous structure[J].Acta Tabacaria Sinica,2014,20(1):9-14.
[7]冯守爱,黄泰松,邹克兴,等.疏水纳米SiO2选择性降低卷烟烟气有害成分含量[J].烟草科技,2011(10):49-53.FENG Shouai,HUANG Taisong,ZOU Kexing,et al.Selective reduction of harmful components in cigarette smoke with hydrophobic nanometer silicon dioxide[J].Tobacco Science&Technology,2011(10):49-53.
[8]Zhu Y,Hou H W,Tang G L,et al.Synthesis of three-quarter-sphere-likeγ-AlOOH superstructures with high adsorptive capacity[J].European Journal of Inorganic Chemistry,2010(6):872-878.
[9]刘志明,吴鹏.壳聚糖/纤维素气凝胶球的制备及其甲醛吸附性能[J].林产化学与工业,2017,37(1):27-35.LIU Zhiming,WU Peng.Preparation of chitosan/cellulose aerogel beads and its formaldehyde gas adsorption performance[J].Chemistry and Industry of Forest Products,2017,37(1):27-35.
[10]穆若郡,庞杰,王敏,等.魔芋葡甘聚糖气凝胶对海洋污染降解菌的吸附固定化[J].热带生物学报,2016,7(2):164-166.MU Ruojun,PANG Jie,WANG Ming,et al.Immobilization of marine pollutants degrading bacteria by Konjac glucomannan aerogel[J].Journal of Tropical Biology,2016,7(2):164-166.
[11]张艺钟,刘珊,刘志文,等.壳聚糖凝胶球对Cu(Ⅱ)和Cr(Ⅵ)吸附行为的对比[J].化工进展,2017,36(2):712-719.ZHANG Yizhong,LIU Shan,LIU Zhiwen,et al.Comparison for Cu(Ⅱ)and Cr(Ⅵ)adsorption behavior onto chitosan hydrogel beads[J].Chemical Industry and Engineering Progress,2017,36(2):712-719.
[12]权迪.纤维素气凝胶多孔材料的制备及改性应用[D].哈尔滨:东北林业大学,2016.QUAN Di.The preparation and modification of cellulose aerogel porous materials[D].Harbin:Northeast Forestry University,2016.
[13]李飞,邢丽,向军辉,等.疏水性纤维素-SiO2复合气凝胶的非超临界制备[J].稀有金属材料与工程,2015,44(增刊1):647-650.LI Fei,XING Li,XIANG Junhui,et al.Hydrophobic cellulose-SiO2composite aerogel prepared by a non-supercritical drying process[J].Rare Metal Materials and Engineering,2015,44(S1):647-650.
[14]李婧,刘志明.毛竹NFC/SiO2气凝胶的制备和疏水改性[J].纤维素科学与技术,2016,24(1):49-54.LI Jing,LIU Zhiming.Preparation and hydrophobic modification of Phyllostachys heterocycla cv.Pubescens NFC/SiO2aerogel[J].Journal of Cellulose Science and Technology,2016,24(1):49-54.
[15]刘昕昕,刘志明.疏水纤维素/SiO2复合气凝胶的制备和表征[J].生物质化学工程,2016,50(2):39-44.LIU Xinxin,LIU Zhiming.Preparation and characterization of hydrophobic cellulose/SiO2composite aerogel[J].Biomass Chemical Engineering,2016,50(2):39-44.
[16]马倩.壳聚糖-二氧化硅复合气凝胶的制备、改性及其性能研究[D].天津:天津大学,2014.MA Qian.Preparation,modification and properties of chitosan-silica composite aerogels[D].Tianjin:Tianjin University,2014.
[17]GB/T 19609-2004卷烟用常规分析用吸烟机测定总粒相物和焦油[S].GB/T 19609-2004 Cigarette-Determination of total and nicotine-free dry particulate matter using a routine analytical smoking machine[S].
[18]GB/T 23355-2009卷烟总粒相物中烟碱的测定气相色谱法[S].GB/T 23355-2009 Cigarettes-Determination of nicotine in smoke condensates-Gas-chromatographic method[S].
[19]GB/T 21130-2007卷烟烟气总粒相物中苯并[a]芘的测定[S].GB/T 21130-2007 Cigarettes-Determination of benzo[a]pyrene in total particulate matter[S].
[20]YC/T 253-2008卷烟主流烟气中氰化氢的测定连续流动法[S].YC/T 253-2008 Cigarettes-Determination of hydrogen cyanide in cigarette mainstream smokeContinuous flow method[S].
[21]YC/T 254-2008卷烟主流烟气中主要羰基化合物的测定高效液相色谱法[S].YC/T 254-2008 Cigarettes-Determination of major carbonyls in mainstream cigarette smoke-High performance liquid chromatographic method[S].
[22]YC/T 255-2008卷烟主流烟气中主要酚类化合物的测定高效液相色谱法[S].YC/T 255-2008 Cigarettes-Determination of major phenolic compounds in mainstream cigarette smokeHigh performance liquid chromatographic method[S].
[23]GB/T 23228-2008卷烟主流烟气总粒相物中烟草特有N-亚硝胺的测定气相色谱-热能分析联用法[S].GB/T 23228-2008 Cigarette-Determination of tobacco specific N-nitrosamines in total particulate matter of mainstream cigarette smoke-GC-TEA method[S].
[24]GB/T 23356-2009卷烟烟气气相中一氧化碳的测定非散射红外法[S].GB/T 23356-2009 Cigarettes-Determination of carbon monoxide in the vapour phase of cigarette smoke-NDIR method[S].
[25]YC/T 377-2010卷烟主流烟气中氨的测定离子色谱法[S].YC/T 377-2010 Cigarettes-Determination of ammonia in mainstream cigarette smoke-Ion chromatography method[S].
[26]谢剑平,刘惠民,朱茂祥,等.卷烟烟气危害性指数研究[J].烟草科技,2009(2):5-15.XIE Jianping,LIU Huimin,ZHU Maoxiang,et al.Development of a novel hazard index of mainstream cigarette smoke and its application on risk evaluation of cigarette products[J].Tobacco Science&Technology,2009(2):5-15.
[27]GB 5606.4-2005卷烟第4部分:感官技术要求[S].GB 5606.4-2005 Cigarettes-Part 4:technical requirements for sense evaluation[S].
[28]庄森炀.生物质基多孔超轻质复合材料的研究[D].福州:福建农林大学,2016.ZHUANG Senyang.Study of bio-based porous and lightweight composites materials[D].Fuzhou:Fujian Agriculture and Forestry University,2016.
[29]乐垚.二氧化硅的形貌调控及其吸附性能研究[D].武汉:武汉理工大学,2013.LE Yao.Morphological control of silica and its adsorption performance[D].Wuhan:Wuhan University of Technology,2013.