改性醋酸纤维丝束及其在烟气过滤中的应用研究
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摘要
卷烟烟气中的成份相当复杂，达五千多种，其中的有害物质，如烟草特有亚硝胺、苯并[a]芘、自由基等，对吸烟者造成一定的健康危害。为提高卷烟烟气的品质，降低其有害成份，国内外的研究人员做了大量长期的工作，主要方法是采用复合滤嘴取代普通滤嘴，增加卷烟滤嘴的截留能力。虽然改进的复合滤嘴和传统的滤嘴相比，在降焦减害及改善卷烟吸味方面具有一定的优势，但在工业化实际应用中存在均匀性差、加工复杂、污染严重、成本高等缺点，因此未能在卷烟行业中普遍推广。
为了有效解决和克服复合滤嘴使用降焦减害添加剂过程中存在的各类问题，本文拟在常规烟用醋酸纤维丝束制备工艺的基础上，以醋酸纤维素／丙酮浆液和纺丝油剂作为研究对象，利用纳米技术及丝束表面改性的途径研制具有减少卷烟烟气中有害成分的改性醋酸纤维Ⅰ、Ⅱ、Ⅲ、Ⅳ。本文研究的油剂添加复合技术及烟用二醋酸纤维生产过程中纳米复合技术的开发应用未见国内外任何公开报道。
在本论文中，研究了醋酸纤维滤材对烟气中粒相及气相物的过滤机制及过滤效率；建立了卷烟烟气中有害成份如焦油、烟碱、一氧化碳、亚硝胺、自由基等物质的测试方法。在此基础上探索烟用醋酸纤维改性的途径与方法，并研究了改性醋酸纤维对烟气中有害成份的作用机理。主要内容如下：
1降焦减害添加剂的筛选
多孔吸附剂、化学作用类、中草药类、生物类、纳米材料等各类添加剂在复合嘴棒中的研究报道较多，但其中能满足纺丝油剂添加要求及纺丝浆液添加要求的物质极少。其中，纺丝油剂添加剂要求无色、无味、食用安全级；易溶于水，不影响油剂体系的流动性能；pH值为6～8；热稳定性好，能耐120℃高温。浆液添加剂要求无色、无味、食用安全级；不溶于丙酮溶剂；粒度小于1微米，且在丙酮中的分散性能好，在高粘度浆液中不易聚集；热稳定性好，能耐120℃高温；有足够的机械强度。
在文献检索及大量前期工作的基础上，本文选择壳聚糖、聚乙烯醇、吡咯烷酮羧酸钠、山梨醇、改性淀粉作为纺丝油剂添加剂，在油剂乳化稳定性评价后确定了油剂体系的添加方式及添加量，并在试验装置上进行醋酸纤维改性实验。烟气分析结果表明，吡咯烷酮羧酸钠是一种适合于添加在纺丝油剂中的添加剂，该物质具有选择性清除烟气中焦油及亚硝胺的作用。
本文选择纳米二氧化硅、柠檬酸、纳米层状磷酸盐材料、分子筛微粉作为纺丝浆液的添加剂，将含有添加剂的母棒加工成复合嘴棒接成卷烟进行烟气预评价，以达到添加剂筛选的目的。结果表明，纳米二氧化硅(SiO_x)对焦油具有明显的清除作用。
2降焦减害添加剂的改性
在添加剂筛选的基础上，本文对医用级壳聚糖进行改性，研制了壳聚糖—g—β—环糊精作为纺丝油剂添加剂。实验结果表明，壳聚糖—g—β—环糊精兼具壳聚糖及β—环糊精的双重吸附效果，对烟气中焦油的吸附效果显著；采用壳聚糖—g—β—环糊精制备的改性醋酸纤维丝束Ⅱ对烟气中的稠环芳烃组份具有明显的去除作用。和常规醋酸纤维丝束空白样相比，卷烟烟气中稠环芳烃的总量同比下降48.1％。
此外，本文采用多孔淀粉为载体，通过交联—吸附的方式将生物活性酶固定在多孔淀粉上，研制成纺丝浆液添加剂。利用多孔淀粉的高吸附特性及固定的生物活性酶有效降低烟气中的焦油及自由基含量。结果表明，改性添加剂具备良好的酶活稳定性，且对自由基具有明显的抑制作用。
3改性醋酸纤维丝束的研制
本文利用醋酸纤维生产工艺流程的特点，提出通过油剂及纺丝浆液两种制备改性醋酸纤维的技术工艺。根据两种添加方式的要求，在分别进行多组添加剂的筛选后，选定吡咯烷酮羧酸钠、壳聚糖—g—β—环糊精作为油剂添加剂，纳米二氧化硅、改性多孔淀粉作为纺丝浆液添加剂。在突破烟用二醋酸纤维丝束生产过程中的添加点、添加量以及添加剂改性等一系列技术瓶颈难点后，在工业化设备上首次研制成功具有降焦油功能的纳米二氧化硅复合醋酸纤维丝束、及具有降焦油和降烟草特有亚硝胺功能的改性醋酸纤维丝束Ⅲ，初步实现了产品的工业化。
试验结果表明，采用吡咯烷酮羧酸钠改性的醋酸纤维丝束Ⅰ和普通醋酸纤维丝束相比，每支卷烟烟气中焦油含量下降2.55mg，同比下降16.4％；烟草特有亚硝胺总量下降25.7％，其中最具致癌性的N—亚硝基去甲基烟碱(NNN)含量下降67.6％。
通过对纳米二氧化硅的表面改性，使纳米二氧化硅颗粒在丙酮溶液中具有良好的分散性。并采用溶液共混法制备纺丝浆液，通过工业纺丝设备生产出含纳米二氧化硅的复合醋酸纤维Ⅲ。烟气分析结果表明，这种复合醋酸纤维Ⅲ对烟气中的焦油具有优良的截留能力，每支卷烟烟气中焦油含量下降4.94mg，同比下降31.7％。
通过对壳聚糖及多孔淀粉进行改性研究，发现壳聚糖—g—β—环糊精作为油剂添加剂对烟气中的焦油有明显的清除效果，采用壳聚糖—g—β—环糊精改性的醋酸纤维丝束Ⅱ对烟气中的稠环芳烃去除率达46.6％。同时，表明通过对添加剂的改性，能有效去除烟气中的稠环芳烃组份。
本文采用交联—吸附的方法将过氧化氢酶固定在多孔淀粉材料中制得改性浆液添加剂，经改性后的添加剂不仅对烟气中的焦油具有明显的吸附效果，而且具备生物活性，对自由基有明显的抑制效果。采用该改性醋酸纤维丝束Ⅳ加工的滤嘴经抽吸后，每支卷烟烟气中的焦油自由基含量同比下降21.34％，气相自由基含量同比下降25.07％。
4改性醋酸纤维的作用机理
本文通过研究认为，改性醋酸纤维对烟气中的粒相物的过滤机理有：直接拦截过滤、惯性碰撞过滤、扩散沉积过滤。此外，由于吡咯烷酮羧酸钠等富电性物质的加入，对烟气中的带电粒子还存在电荷吸附机理；由于纳米二氧化硅、壳聚糖—g—β—环糊精表面存在大量羟基和不饱和残键，对烟气组分形成分子间的氢键缔合机理。
本文首次采用BET方法测定醋酸纤维的比表面积及表征改性醋酸纤维的物理吸附能力。研究结果表明，由于纳米材料的表面效应，改性醋酸纤维的比表面积比普通醋酸纤维增加了104％。改性醋酸纤维表面存在2～3nm的纳米孔洞，及由于部分纳米颗粒在丝束表面团聚产生的20～100nm大小的孔洞。这种改性醋酸纤维表面状态与常规醋酸纤维相比所发生的很大改变，使改性纤维对烟气中的焦油等粒相物起到了明显的截留作用。
本文研究了改性醋酸纤维对亚硝胺的作用机理。富电子的吡咯烷酮羧酸钠与氨基N~+相结合，增加了亚硝胺在改性醋酸纤维表面的吸附量。此外，本文提出吡咯烷酮羧酸钠与氨基N~+形成共轭体系的作用机理：
吸附机理表明吡咯烷酮羧酸钠对具有平面结构的亚硝胺具有很强的作用，但由于烟碱既具有立体结构，又带有与吡咯烷酮羧酸钠相同的电性，所以改性醋酸纤维对烟碱不产生吸附作用，使得能够在保证烟气口味及劲头的前提下，实现了对烟气中有害物质的选择性吸附。
本文还研究了改性醋酸纤维对自由基的清除作用，提出了主流烟气中烷基自由基、烷氧基自由基和半醌自由基的催化衰变机理：
5本文研究课题的创新点及推广前景
本文主要创新点如下：
(1)本论文采用纺丝油剂添加方式及纺丝浆液添加方式对常规烟用醋酸纤维进行改性。本文采用的改性途径及改性烟用二醋酸纤维研制过程中纳米技术的开发应用未见国内外任何公开报道。
(2)本论文的系列研究突出“选择性降焦减害”，即在保留烟碱及抽吸口感的基础上，选择性清除焦油、苯并[a]芘、烟草特有亚硝胺、自由基等有害成份，并成功研制出具有上述功能的系列化醋酸纤维丝束Ⅰ、Ⅱ、Ⅲ、Ⅳ。
(3)本文研制的改性醋酸纤维丝束保证了单根纤维添加剂含量的均匀性，解决了复合滤嘴直接添加粉体均匀性较差的问题。
(4)本文研究的改性醋酸纤维丝束的成本比常规丝束仅增加2％左右，和复合嘴棒的成本增加30％相比具有明显的成本优势，具有行业内推广的广阔前景。
(5)本文深入研究了改性醋酸纤维对烟气的作用机理。首次采用BET方法有效表征了改性醋酸纤维的吸附能力。
通过对改性醋酸纤维丝束所制卷烟的烟气评吸，分析结果表明，采用改性醋酸纤维制备的卷烟在降低卷烟烟气中相关有害物质的同时能够较好地保留烟气的余味，并使烟气的刺激性降低，卷烟烟气口感变柔和，对香气的质和量无任何不良影响，，符合卷烟消费者的生理需求及中式卷烟发展的趋势。目前我国市售卷烟的焦油含量明显高于发达国家，卷烟行业“降焦减害”的压力日益增加，本文研究的改性醋酸纤维丝束清除烟气中焦油和亚硝胺含量等方面的性能突出，使得改性烟用二醋酸纤维丝束在替代普通烟用二醋酸纤维丝束上具有推广的应用前景。
Carcinogens of many kinds in the cigarette smoke, such as TSNAs,PAHs and free radical, can be harmful to health. Lots of domestic and foreign researchers have accomplished much long-term work, among which adopting multiple cigarette filters instead of conventional filters is the main method. The multiple cigarette filters can dramatically improve the filtration ability and taste of the smoke, but they also have many disadvantages. The uniformity of additive in multiple filters may be poor. The process of manufacturing multiple cigarette filters is complex. The pollution of the air during the manufacturing process is grievous. And the cost of multiple cigarette filters is much higher. The disadvantages have limited the popularization of multiple filters.
In order to solve the disadvantages of multiple filters, we plan to prepare modified cellulose acetate tow based on conventional process of cellulose acetate tow. The methods by using nanotechnology in spinning dope and surface modification of conventional cellulose acetate fibers haven't been reported in public.
In this paper, the mechanism of filtration of particulate materials and vapour materials through cigarette filter and the filtration efficiency have been investigated. The test methods of tar,nicotine,carbon monoxide, TSNAs and free radicals have been established. The modifying process and filtration mechanism of harmful materials in the smoke have been investigated. The main contents are as following:
1 Selection of additives
Porous materials, chemical materials, Chinese traditional medicine, biological materials and nano particles used in multiple filters have been reported. But there are few materials can be used in this paper. The additives used in spinning oil should be achromatous and flavourless, and be soluble in water.The pH value of additive solution should be 6～8. The additives used in spinning dope should be achromatous and flavourless, and be insoluble in acetone. The particle size of additives should be less than 1 um and easy to be dispersed in acetone. All of the additives selected in this paper can be heated to 120°C.
Chitosan, polyvinyl alcohol, sodium pyroglutamic acid, zinc gluconate, sorbitol and starch were used as additives in spinning oil. The modified cellulose acetate fibers were prepared when we confirmed the adding sequence and quantity of additives.The results showed that sodium pyroglutamic acid was suitable to be added in spinning oil, and the modified cellulose acetate fibers could selectively eliminate tar and TSNAs in the smoke.
Nano-silica, citric acid, nano-phosphate and zeolite particles were used as additives in spinning dope. The results showed that nano-silica had notable effection on tar in the smoke.
2 Modification of additives
Based on selection of additives, chitosan was modifed in order to get better performance. We prepared chitosan-g-β- dextrine as additive in spinning dope. The results show that chitosan-g-β- dextrine has notable effection on tar and PAHs in the smoke. Compared with conventional cellulose acetate fibers, the modified ones containing chitosan-g-β- dextrine had better effection, and the reduction in PAHs in the smoke after filtration with the modified fibers was 48.1%.
Besides, porous starch was used as carrier for biological enzyme by interconnection and adsorption. The porous starch with enzyme was used as additive in spinning dope. The results showed that the porous starch with enzyme had good and stable biological activity.
3 Preparation of modified cellulose fibers tow
Two methods of preparing modified cellulose fibers tow by spinning oil and dope were studied in this paper. We chose sodium pyroglutamic acid and chitosan-g- β- dextrine as additives in spinning oil, nano-silica and porous starch with enzyme as additives in spinning dope. We prepared cellulose acetate/nano-silica composite fibers and other modified cellulose acetate fibers on the industrial equipment successfully.
The results showed that reduction in tar and TSNA in the smoke after filtration with the modified fibers containing sodium pyroglutamic acid was 16.4% and 25.7%. Among TSNA in the smoke , the reduction of the content of NNN was 67.6%.
Nano-silica particles were easy to be dispersed in acetone after the surface modification with silane. Cellulose acetate/nano-SiO2 composites were prepared and spun into fibers. The results showed that the composite fibers had an optimal filtration effect on the tar in cigarette smoke. Compared with conventional cellulose acetate fibers, the composite ones had greater specific surface area, and the reduction in tar in the smoke after filtration with the composite fibers was 31.7%.
Chitosan-g-β- dextrine had evident effection on tar and PAHs in the smoke. The reduction of PAHs was 46.6% which meaned that the modification of chitosan was effective.
Porous starch was used as carrier for biological enzyme by interconnection and adsorption. The porous starch with enzyme was used as additive in spinning dope. The results showed that the reduction of free radicals in particulate phase and vapor phase were 21.34% and 25.07% by using the modified cellulose fibers.
4 Mechanisms of effections on harmful components
The mechanisms of filtration of cellulose fibers in cigarette filters contain direct interception, inertial impaction,and diffusional deposition. A new mechanism was proposed in this paper was electric charge adsoption. Besides, much hydroxy and unsaturated bond exist on the surface of nano-silica and chitosan-g-β- dextrine. Thus many components in the smoke are easy to form hydrogen bond with the additives.
BET method was used to characterize the adsorption ability of modified cellulose fibers. It is apparent that composite fibers have a greater specific surface area than pure CA fibers because of the gigantic specific area of the nano-silica particles on the surface. The increase of specific surface area was 104% ,and there existed lots of pores of 20～100nm on the surface of modified cellulose fibers. The filtration of harmful components in particulate phase was improved dramatically because of the change of surface morphology.
The effection mechanism of filtration of TSNA is showed as following:
The mechanism shows that sodium pyroglutamic acid has strong effection on TSNA with plane structure. But sodium pyroglutamic acid has the same electric charge with nicotine in the smoke, the modified cellulose fibers don't adsorpt nicotine. Thus the modified cellulose fibers can hold the taste of cigarette smoke. They eliminate harmful components such as tar and TSNA selectively.
The effection mechanism of elimination of free radiclas is showed as following:
5 Innovation points in the paper
Innovation points in this paper are listed as following:
(1) Modified cellulose acetate tow based on conventional process of cellulose acetate tow were prepared successfully. The methods by using nanotechnology in spinning dope and surface modification of conventional cellulose acetate fibers haven't been reported in public .
(2) A series of modified cellulose fibers with different function have been prepared successfully. They can eliminate harmful components such as tar, TSNA, free radicals and PAHs selectively. Such products haven't been reported yet in the world.
(3) Very single filament among the modified cellulose fibers contains additives. Thus modified cellulose fibers solve the disadvantage of poor uniformity of additive in multiple filters
(4) Compared with conventioanl cellulose fibers, the cost of modified cellulose fibers only increases about 2%, and the cost of multiple filters will increase about 30%. The modified cellulose fibers have obvious cost advantage.
(5) The mechanism of effections on harmful components were investigated deeply in this paper. And BET method was used to characterize adsorption ability of modified cellulose fibers for the first time.
We invited experts to taste cigarette using modified cellulose acetate fibers. The results showed that the taste of cigarette using modified fibers became softer and lighter. And it matchs the demand of customers and the trend of "Chinese style cigarette". The modifed cellulose fibers in this paper has a great prospect of popularization in cigarette industry.
为了有效解决和克服复合滤嘴使用降焦减害添加剂过程中存在的各类问题，本文拟在常规烟用醋酸纤维丝束制备工艺的基础上，以醋酸纤维素／丙酮浆液和纺丝油剂作为研究对象，利用纳米技术及丝束表面改性的途径研制具有减少卷烟烟气中有害成分的改性醋酸纤维Ⅰ、Ⅱ、Ⅲ、Ⅳ。本文研究的油剂添加复合技术及烟用二醋酸纤维生产过程中纳米复合技术的开发应用未见国内外任何公开报道。
在本论文中，研究了醋酸纤维滤材对烟气中粒相及气相物的过滤机制及过滤效率；建立了卷烟烟气中有害成份如焦油、烟碱、一氧化碳、亚硝胺、自由基等物质的测试方法。在此基础上探索烟用醋酸纤维改性的途径与方法，并研究了改性醋酸纤维对烟气中有害成份的作用机理。主要内容如下：
1降焦减害添加剂的筛选
多孔吸附剂、化学作用类、中草药类、生物类、纳米材料等各类添加剂在复合嘴棒中的研究报道较多，但其中能满足纺丝油剂添加要求及纺丝浆液添加要求的物质极少。其中，纺丝油剂添加剂要求无色、无味、食用安全级；易溶于水，不影响油剂体系的流动性能；pH值为6～8；热稳定性好，能耐120℃高温。浆液添加剂要求无色、无味、食用安全级；不溶于丙酮溶剂；粒度小于1微米，且在丙酮中的分散性能好，在高粘度浆液中不易聚集；热稳定性好，能耐120℃高温；有足够的机械强度。
在文献检索及大量前期工作的基础上，本文选择壳聚糖、聚乙烯醇、吡咯烷酮羧酸钠、山梨醇、改性淀粉作为纺丝油剂添加剂，在油剂乳化稳定性评价后确定了油剂体系的添加方式及添加量，并在试验装置上进行醋酸纤维改性实验。烟气分析结果表明，吡咯烷酮羧酸钠是一种适合于添加在纺丝油剂中的添加剂，该物质具有选择性清除烟气中焦油及亚硝胺的作用。
本文选择纳米二氧化硅、柠檬酸、纳米层状磷酸盐材料、分子筛微粉作为纺丝浆液的添加剂，将含有添加剂的母棒加工成复合嘴棒接成卷烟进行烟气预评价，以达到添加剂筛选的目的。结果表明，纳米二氧化硅(SiO_x)对焦油具有明显的清除作用。
2降焦减害添加剂的改性
在添加剂筛选的基础上，本文对医用级壳聚糖进行改性，研制了壳聚糖—g—β—环糊精作为纺丝油剂添加剂。实验结果表明，壳聚糖—g—β—环糊精兼具壳聚糖及β—环糊精的双重吸附效果，对烟气中焦油的吸附效果显著；采用壳聚糖—g—β—环糊精制备的改性醋酸纤维丝束Ⅱ对烟气中的稠环芳烃组份具有明显的去除作用。和常规醋酸纤维丝束空白样相比，卷烟烟气中稠环芳烃的总量同比下降48.1％。
此外，本文采用多孔淀粉为载体，通过交联—吸附的方式将生物活性酶固定在多孔淀粉上，研制成纺丝浆液添加剂。利用多孔淀粉的高吸附特性及固定的生物活性酶有效降低烟气中的焦油及自由基含量。结果表明，改性添加剂具备良好的酶活稳定性，且对自由基具有明显的抑制作用。
3改性醋酸纤维丝束的研制
本文利用醋酸纤维生产工艺流程的特点，提出通过油剂及纺丝浆液两种制备改性醋酸纤维的技术工艺。根据两种添加方式的要求，在分别进行多组添加剂的筛选后，选定吡咯烷酮羧酸钠、壳聚糖—g—β—环糊精作为油剂添加剂，纳米二氧化硅、改性多孔淀粉作为纺丝浆液添加剂。在突破烟用二醋酸纤维丝束生产过程中的添加点、添加量以及添加剂改性等一系列技术瓶颈难点后，在工业化设备上首次研制成功具有降焦油功能的纳米二氧化硅复合醋酸纤维丝束、及具有降焦油和降烟草特有亚硝胺功能的改性醋酸纤维丝束Ⅲ，初步实现了产品的工业化。
试验结果表明，采用吡咯烷酮羧酸钠改性的醋酸纤维丝束Ⅰ和普通醋酸纤维丝束相比，每支卷烟烟气中焦油含量下降2.55mg，同比下降16.4％；烟草特有亚硝胺总量下降25.7％，其中最具致癌性的N—亚硝基去甲基烟碱(NNN)含量下降67.6％。
通过对纳米二氧化硅的表面改性，使纳米二氧化硅颗粒在丙酮溶液中具有良好的分散性。并采用溶液共混法制备纺丝浆液，通过工业纺丝设备生产出含纳米二氧化硅的复合醋酸纤维Ⅲ。烟气分析结果表明，这种复合醋酸纤维Ⅲ对烟气中的焦油具有优良的截留能力，每支卷烟烟气中焦油含量下降4.94mg，同比下降31.7％。
通过对壳聚糖及多孔淀粉进行改性研究，发现壳聚糖—g—β—环糊精作为油剂添加剂对烟气中的焦油有明显的清除效果，采用壳聚糖—g—β—环糊精改性的醋酸纤维丝束Ⅱ对烟气中的稠环芳烃去除率达46.6％。同时，表明通过对添加剂的改性，能有效去除烟气中的稠环芳烃组份。
本文采用交联—吸附的方法将过氧化氢酶固定在多孔淀粉材料中制得改性浆液添加剂，经改性后的添加剂不仅对烟气中的焦油具有明显的吸附效果，而且具备生物活性，对自由基有明显的抑制效果。采用该改性醋酸纤维丝束Ⅳ加工的滤嘴经抽吸后，每支卷烟烟气中的焦油自由基含量同比下降21.34％，气相自由基含量同比下降25.07％。
4改性醋酸纤维的作用机理
本文通过研究认为，改性醋酸纤维对烟气中的粒相物的过滤机理有：直接拦截过滤、惯性碰撞过滤、扩散沉积过滤。此外，由于吡咯烷酮羧酸钠等富电性物质的加入，对烟气中的带电粒子还存在电荷吸附机理；由于纳米二氧化硅、壳聚糖—g—β—环糊精表面存在大量羟基和不饱和残键，对烟气组分形成分子间的氢键缔合机理。
本文首次采用BET方法测定醋酸纤维的比表面积及表征改性醋酸纤维的物理吸附能力。研究结果表明，由于纳米材料的表面效应，改性醋酸纤维的比表面积比普通醋酸纤维增加了104％。改性醋酸纤维表面存在2～3nm的纳米孔洞，及由于部分纳米颗粒在丝束表面团聚产生的20～100nm大小的孔洞。这种改性醋酸纤维表面状态与常规醋酸纤维相比所发生的很大改变，使改性纤维对烟气中的焦油等粒相物起到了明显的截留作用。
本文研究了改性醋酸纤维对亚硝胺的作用机理。富电子的吡咯烷酮羧酸钠与氨基N~+相结合，增加了亚硝胺在改性醋酸纤维表面的吸附量。此外，本文提出吡咯烷酮羧酸钠与氨基N~+形成共轭体系的作用机理：
吸附机理表明吡咯烷酮羧酸钠对具有平面结构的亚硝胺具有很强的作用，但由于烟碱既具有立体结构，又带有与吡咯烷酮羧酸钠相同的电性，所以改性醋酸纤维对烟碱不产生吸附作用，使得能够在保证烟气口味及劲头的前提下，实现了对烟气中有害物质的选择性吸附。
本文还研究了改性醋酸纤维对自由基的清除作用，提出了主流烟气中烷基自由基、烷氧基自由基和半醌自由基的催化衰变机理：
5本文研究课题的创新点及推广前景
本文主要创新点如下：
(1)本论文采用纺丝油剂添加方式及纺丝浆液添加方式对常规烟用醋酸纤维进行改性。本文采用的改性途径及改性烟用二醋酸纤维研制过程中纳米技术的开发应用未见国内外任何公开报道。
(2)本论文的系列研究突出“选择性降焦减害”，即在保留烟碱及抽吸口感的基础上，选择性清除焦油、苯并[a]芘、烟草特有亚硝胺、自由基等有害成份，并成功研制出具有上述功能的系列化醋酸纤维丝束Ⅰ、Ⅱ、Ⅲ、Ⅳ。
(3)本文研制的改性醋酸纤维丝束保证了单根纤维添加剂含量的均匀性，解决了复合滤嘴直接添加粉体均匀性较差的问题。
(4)本文研究的改性醋酸纤维丝束的成本比常规丝束仅增加2％左右，和复合嘴棒的成本增加30％相比具有明显的成本优势，具有行业内推广的广阔前景。
(5)本文深入研究了改性醋酸纤维对烟气的作用机理。首次采用BET方法有效表征了改性醋酸纤维的吸附能力。
通过对改性醋酸纤维丝束所制卷烟的烟气评吸，分析结果表明，采用改性醋酸纤维制备的卷烟在降低卷烟烟气中相关有害物质的同时能够较好地保留烟气的余味，并使烟气的刺激性降低，卷烟烟气口感变柔和，对香气的质和量无任何不良影响，，符合卷烟消费者的生理需求及中式卷烟发展的趋势。目前我国市售卷烟的焦油含量明显高于发达国家，卷烟行业“降焦减害”的压力日益增加，本文研究的改性醋酸纤维丝束清除烟气中焦油和亚硝胺含量等方面的性能突出，使得改性烟用二醋酸纤维丝束在替代普通烟用二醋酸纤维丝束上具有推广的应用前景。
Carcinogens of many kinds in the cigarette smoke, such as TSNAs,PAHs and free radical, can be harmful to health. Lots of domestic and foreign researchers have accomplished much long-term work, among which adopting multiple cigarette filters instead of conventional filters is the main method. The multiple cigarette filters can dramatically improve the filtration ability and taste of the smoke, but they also have many disadvantages. The uniformity of additive in multiple filters may be poor. The process of manufacturing multiple cigarette filters is complex. The pollution of the air during the manufacturing process is grievous. And the cost of multiple cigarette filters is much higher. The disadvantages have limited the popularization of multiple filters.
In order to solve the disadvantages of multiple filters, we plan to prepare modified cellulose acetate tow based on conventional process of cellulose acetate tow. The methods by using nanotechnology in spinning dope and surface modification of conventional cellulose acetate fibers haven't been reported in public.
In this paper, the mechanism of filtration of particulate materials and vapour materials through cigarette filter and the filtration efficiency have been investigated. The test methods of tar,nicotine,carbon monoxide, TSNAs and free radicals have been established. The modifying process and filtration mechanism of harmful materials in the smoke have been investigated. The main contents are as following:
1 Selection of additives
Porous materials, chemical materials, Chinese traditional medicine, biological materials and nano particles used in multiple filters have been reported. But there are few materials can be used in this paper. The additives used in spinning oil should be achromatous and flavourless, and be soluble in water.The pH value of additive solution should be 6～8. The additives used in spinning dope should be achromatous and flavourless, and be insoluble in acetone. The particle size of additives should be less than 1 um and easy to be dispersed in acetone. All of the additives selected in this paper can be heated to 120°C.
Chitosan, polyvinyl alcohol, sodium pyroglutamic acid, zinc gluconate, sorbitol and starch were used as additives in spinning oil. The modified cellulose acetate fibers were prepared when we confirmed the adding sequence and quantity of additives.The results showed that sodium pyroglutamic acid was suitable to be added in spinning oil, and the modified cellulose acetate fibers could selectively eliminate tar and TSNAs in the smoke.
Nano-silica, citric acid, nano-phosphate and zeolite particles were used as additives in spinning dope. The results showed that nano-silica had notable effection on tar in the smoke.
2 Modification of additives
Based on selection of additives, chitosan was modifed in order to get better performance. We prepared chitosan-g-β- dextrine as additive in spinning dope. The results show that chitosan-g-β- dextrine has notable effection on tar and PAHs in the smoke. Compared with conventional cellulose acetate fibers, the modified ones containing chitosan-g-β- dextrine had better effection, and the reduction in PAHs in the smoke after filtration with the modified fibers was 48.1%.
Besides, porous starch was used as carrier for biological enzyme by interconnection and adsorption. The porous starch with enzyme was used as additive in spinning dope. The results showed that the porous starch with enzyme had good and stable biological activity.
3 Preparation of modified cellulose fibers tow
Two methods of preparing modified cellulose fibers tow by spinning oil and dope were studied in this paper. We chose sodium pyroglutamic acid and chitosan-g- β- dextrine as additives in spinning oil, nano-silica and porous starch with enzyme as additives in spinning dope. We prepared cellulose acetate/nano-silica composite fibers and other modified cellulose acetate fibers on the industrial equipment successfully.
The results showed that reduction in tar and TSNA in the smoke after filtration with the modified fibers containing sodium pyroglutamic acid was 16.4% and 25.7%. Among TSNA in the smoke , the reduction of the content of NNN was 67.6%.
Nano-silica particles were easy to be dispersed in acetone after the surface modification with silane. Cellulose acetate/nano-SiO2 composites were prepared and spun into fibers. The results showed that the composite fibers had an optimal filtration effect on the tar in cigarette smoke. Compared with conventional cellulose acetate fibers, the composite ones had greater specific surface area, and the reduction in tar in the smoke after filtration with the composite fibers was 31.7%.
Chitosan-g-β- dextrine had evident effection on tar and PAHs in the smoke. The reduction of PAHs was 46.6% which meaned that the modification of chitosan was effective.
Porous starch was used as carrier for biological enzyme by interconnection and adsorption. The porous starch with enzyme was used as additive in spinning dope. The results showed that the reduction of free radicals in particulate phase and vapor phase were 21.34% and 25.07% by using the modified cellulose fibers.
4 Mechanisms of effections on harmful components
The mechanisms of filtration of cellulose fibers in cigarette filters contain direct interception, inertial impaction,and diffusional deposition. A new mechanism was proposed in this paper was electric charge adsoption. Besides, much hydroxy and unsaturated bond exist on the surface of nano-silica and chitosan-g-β- dextrine. Thus many components in the smoke are easy to form hydrogen bond with the additives.
BET method was used to characterize the adsorption ability of modified cellulose fibers. It is apparent that composite fibers have a greater specific surface area than pure CA fibers because of the gigantic specific area of the nano-silica particles on the surface. The increase of specific surface area was 104% ,and there existed lots of pores of 20～100nm on the surface of modified cellulose fibers. The filtration of harmful components in particulate phase was improved dramatically because of the change of surface morphology.
The effection mechanism of filtration of TSNA is showed as following:
The mechanism shows that sodium pyroglutamic acid has strong effection on TSNA with plane structure. But sodium pyroglutamic acid has the same electric charge with nicotine in the smoke, the modified cellulose fibers don't adsorpt nicotine. Thus the modified cellulose fibers can hold the taste of cigarette smoke. They eliminate harmful components such as tar and TSNA selectively.
The effection mechanism of elimination of free radiclas is showed as following:
5 Innovation points in the paper
Innovation points in this paper are listed as following:
(1) Modified cellulose acetate tow based on conventional process of cellulose acetate tow were prepared successfully. The methods by using nanotechnology in spinning dope and surface modification of conventional cellulose acetate fibers haven't been reported in public .
(2) A series of modified cellulose fibers with different function have been prepared successfully. They can eliminate harmful components such as tar, TSNA, free radicals and PAHs selectively. Such products haven't been reported yet in the world.
(3) Very single filament among the modified cellulose fibers contains additives. Thus modified cellulose fibers solve the disadvantage of poor uniformity of additive in multiple filters
(4) Compared with conventioanl cellulose fibers, the cost of modified cellulose fibers only increases about 2%, and the cost of multiple filters will increase about 30%. The modified cellulose fibers have obvious cost advantage.
(5) The mechanism of effections on harmful components were investigated deeply in this paper. And BET method was used to characterize adsorption ability of modified cellulose fibers for the first time.
We invited experts to taste cigarette using modified cellulose acetate fibers. The results showed that the taste of cigarette using modified fibers became softer and lighter. And it matchs the demand of customers and the trend of "Chinese style cigarette". The modifed cellulose fibers in this paper has a great prospect of popularization in cigarette industry.
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