油茶果壳中纳米纤维素的分离与成膜性能
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摘要
以茶籽油生产过程中的废弃物——油茶果壳为研究对象,首先采用亚硫酸盐预蒸煮实现纤维素、半纤维素和木素、茶皂素等组分的分离,然后经硫酸热水解得到油茶果壳纳米纤维素(CNC),最后压滤制得高强度透明薄膜。利用SEM、TEM、XRD、TG、UV-vis、电子万能试验机对纳米纤维素及其薄膜进行了结构表征与热学性能、光学性能、力学性能测试。结果表明,从油茶果壳中提取分离得到的纳米纤维素呈棒状,直径为6~10nm,长度为300~500 nm,属于纤维素Ⅰ型,结晶度为68%,热分解温度为230℃;压滤制备得到的纳米纤维素薄膜厚度为0.03 mm时,在600~800 nm波段处透光率为76%~81%,拉伸强度为75.6 MPa,可用于制备高强度的透明食品薄膜包装材料。
Cellulose, hemicellulose and lignin, tea saponin and other components were first separated from the waste in the production process of tea seed oil-shell of Camellia oleifera Abel(SCOA) by using sulfite predigesting. Then, the obtained cellulose was thermally hydrolyzed by sulfuric acid to produce cellulose nanocrystals(CNC). Finally, transparent films with high tensile strength were obtained by filter pressing. SEM, TEM, XRD, TG, UV-vis and universal strength testing machine were used to characterize the internal structure and thermal properties of CNC, the optical properties and mechanical properties of the films. The results showed that the derived CNC possessed a rod-like structure with a diameter in the range from 6 to 10 nm and a length from 300 to 500 nm. In addition, the CNC belonged to Ⅰ type cellulose, its crystallinity and decomposition temperature were about 68% and 230℃, respectively. The CNC film with 0.03 mm thickness exhibited transmittance between 76% and 81% at 600~800 nm wave-band with a tensile strength of 75.6 MPa. So, the CNC has a great potential for practical application in the field of food packaging.
Cellulose, hemicellulose and lignin, tea saponin and other components were first separated from the waste in the production process of tea seed oil-shell of Camellia oleifera Abel(SCOA) by using sulfite predigesting. Then, the obtained cellulose was thermally hydrolyzed by sulfuric acid to produce cellulose nanocrystals(CNC). Finally, transparent films with high tensile strength were obtained by filter pressing. SEM, TEM, XRD, TG, UV-vis and universal strength testing machine were used to characterize the internal structure and thermal properties of CNC, the optical properties and mechanical properties of the films. The results showed that the derived CNC possessed a rod-like structure with a diameter in the range from 6 to 10 nm and a length from 300 to 500 nm. In addition, the CNC belonged to Ⅰ type cellulose, its crystallinity and decomposition temperature were about 68% and 230℃, respectively. The CNC film with 0.03 mm thickness exhibited transmittance between 76% and 81% at 600~800 nm wave-band with a tensile strength of 75.6 MPa. So, the CNC has a great potential for practical application in the field of food packaging.
引文
[1]Panwar N L,Kaushik S C,Kothari S.Role of renewable energy sources in environmental protection:a review[J].Renew Sust Energ Rev,2011,15(3):1513-1524.
[2]J?rgensen H,Kristensen J B,Felby C.Enzymatic conversion of lignocellulose into fermentable sugars:challenges and opportunities[J].Biofuel Bioprod Bio,2007,1(2):119-134.
[3]Wang Linlin(王琳琳),Long Liujin(龙柳锦),Chen Xiaopeng(陈小鹏),et al.Characterization of mesoporous activated carbon from camellia oleifera shell and study on its porous structure[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2013,64(2):297-303.
[4]Song Yarui(宋亚蕊),Liu Juan(刘娟),Peng Shaofeng(彭邵锋),et al.Main nutritional components in selenium-riched oil-tea camellia seeds and antioxidant activity of selenium-riched oil-tea camellia seed oil[J].Chin Oils Fat(中国油脂),2014,39(10):39-44.
[5]Chen Yaqi(陈亚琪),Kang Haiquan(康海权),Chen Qiuping(陈秋平),et al.Antioxidant of extracts from the fruit shell of camellia oleifera[J].Scientia Silvae Sinicae(林业科学),2011,47(3):20-24.
[6]Zhou Qin(周琴),Qiu Huihua(邱会华),Shen Jian(沈健),et al.Preparation of activated carbons from oiltea shell promoted by zinc chloride in vacuum[J].Fine Chemicals(精细化工),2015,32(5):500-504.
[7]Sun F F,Tang S,Liu R,et al.Biorefining fractionation of the Camellia oleifera Abel hull into diverse bioproducts with a two-stage organosolv extraction[J].Ind Crop Prod,2016,94:790-799.
[8]Trache D,Hussin M H,Haafiz M K M,et al.Recent progress in cellulose nanocrystals:sources and production[J].Nanoscale,2017,9(5):1763-1786.
[9]Gümü?kaya E,Usta M.Dependence of chemical and crystalline structure of alkali sulfite pulp on cooking temperature and time[J].Carbohydr Polym,2006,65(4):461-468.
[10]Li Z,Zhang M,Cheng D,et al.Preparation of silver nano-particles immobilized onto chitin nano-crystals and their application to cellulose paper for imparting antimicrobial activity[J].Carbohydr Polym,2016,151:834-840.
[11]Hua K,Carlsson D O,?lander E,et al.Translational study between structure and biological response of nanocellulose from wood and green algae[J].Rsc Adv,2013,4(6):2892-2903.
[12]Lou Jiangtao(娄江涛).Study on the plant fiber materials chemical compositions quantitative analysis[D].Qingdao:Qingdao University(青岛大学),2010.
[13]An X,Wen Y,Cheng D,et al.Preparation of cellulose nano-crystals through a sequential process of cellulase pretreatment and acid hydrolysis[J].Cellulose,2016,23(4):2409-2420.
[14]Zhou Aijing(周爱静),Fu Shiyu(付时雨),Meng Qijun(蒙启骏).Preparation of nanocelluloses from three non-wood fiber resources and the properties of their membranes[J].Transactions of China Pulp and Paper(中国造纸学报),2016,31(4):18-24.
[15]Xu X,Liu F,Jiang L,et al.Cellulose nanocrystals vs.cellulose nanofibrils:a comparative study on their microstructures and effects as polymer reinforcing agents[J].Acs Appl Mater Inter,2013,5(8):2999-3009.
[16]French A D.Idealized powder diffraction patterns for cellulose polymorphs[J].Cellulose,2014,21(2):885-896.
[17]Qian W,Li X Z,Wu Z P,et al.Formulation of intumescent flame retardant coatings containing natural-based tea saponin[J].J Agr Food Chem,2015,63(10):2782-2788.
[18]Wang Q,Zhu J Y,Considine J M.Strong and optically transparent films prepared using cellulosic solid residue recovered from cellulose nanocrystals production waste stream[J].Acs Appl Mater Inter,2013,5(7):2527-2534.
[19]Huang J,Zhu H,Chen Y,et al.Highly transparent and flexible nanopaper transistors[J].Acs Nano,2013,7(3):2106-2113.
[20]Zhu H,Fang Z,Preston C,et al.Transparent paper:fabrications,properties and device applications[J].Energ Environ Sci,2014,7(1):269-287.
[2]J?rgensen H,Kristensen J B,Felby C.Enzymatic conversion of lignocellulose into fermentable sugars:challenges and opportunities[J].Biofuel Bioprod Bio,2007,1(2):119-134.
[3]Wang Linlin(王琳琳),Long Liujin(龙柳锦),Chen Xiaopeng(陈小鹏),et al.Characterization of mesoporous activated carbon from camellia oleifera shell and study on its porous structure[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2013,64(2):297-303.
[4]Song Yarui(宋亚蕊),Liu Juan(刘娟),Peng Shaofeng(彭邵锋),et al.Main nutritional components in selenium-riched oil-tea camellia seeds and antioxidant activity of selenium-riched oil-tea camellia seed oil[J].Chin Oils Fat(中国油脂),2014,39(10):39-44.
[5]Chen Yaqi(陈亚琪),Kang Haiquan(康海权),Chen Qiuping(陈秋平),et al.Antioxidant of extracts from the fruit shell of camellia oleifera[J].Scientia Silvae Sinicae(林业科学),2011,47(3):20-24.
[6]Zhou Qin(周琴),Qiu Huihua(邱会华),Shen Jian(沈健),et al.Preparation of activated carbons from oiltea shell promoted by zinc chloride in vacuum[J].Fine Chemicals(精细化工),2015,32(5):500-504.
[7]Sun F F,Tang S,Liu R,et al.Biorefining fractionation of the Camellia oleifera Abel hull into diverse bioproducts with a two-stage organosolv extraction[J].Ind Crop Prod,2016,94:790-799.
[8]Trache D,Hussin M H,Haafiz M K M,et al.Recent progress in cellulose nanocrystals:sources and production[J].Nanoscale,2017,9(5):1763-1786.
[9]Gümü?kaya E,Usta M.Dependence of chemical and crystalline structure of alkali sulfite pulp on cooking temperature and time[J].Carbohydr Polym,2006,65(4):461-468.
[10]Li Z,Zhang M,Cheng D,et al.Preparation of silver nano-particles immobilized onto chitin nano-crystals and their application to cellulose paper for imparting antimicrobial activity[J].Carbohydr Polym,2016,151:834-840.
[11]Hua K,Carlsson D O,?lander E,et al.Translational study between structure and biological response of nanocellulose from wood and green algae[J].Rsc Adv,2013,4(6):2892-2903.
[12]Lou Jiangtao(娄江涛).Study on the plant fiber materials chemical compositions quantitative analysis[D].Qingdao:Qingdao University(青岛大学),2010.
[13]An X,Wen Y,Cheng D,et al.Preparation of cellulose nano-crystals through a sequential process of cellulase pretreatment and acid hydrolysis[J].Cellulose,2016,23(4):2409-2420.
[14]Zhou Aijing(周爱静),Fu Shiyu(付时雨),Meng Qijun(蒙启骏).Preparation of nanocelluloses from three non-wood fiber resources and the properties of their membranes[J].Transactions of China Pulp and Paper(中国造纸学报),2016,31(4):18-24.
[15]Xu X,Liu F,Jiang L,et al.Cellulose nanocrystals vs.cellulose nanofibrils:a comparative study on their microstructures and effects as polymer reinforcing agents[J].Acs Appl Mater Inter,2013,5(8):2999-3009.
[16]French A D.Idealized powder diffraction patterns for cellulose polymorphs[J].Cellulose,2014,21(2):885-896.
[17]Qian W,Li X Z,Wu Z P,et al.Formulation of intumescent flame retardant coatings containing natural-based tea saponin[J].J Agr Food Chem,2015,63(10):2782-2788.
[18]Wang Q,Zhu J Y,Considine J M.Strong and optically transparent films prepared using cellulosic solid residue recovered from cellulose nanocrystals production waste stream[J].Acs Appl Mater Inter,2013,5(7):2527-2534.
[19]Huang J,Zhu H,Chen Y,et al.Highly transparent and flexible nanopaper transistors[J].Acs Nano,2013,7(3):2106-2113.
[20]Zhu H,Fang Z,Preston C,et al.Transparent paper:fabrications,properties and device applications[J].Energ Environ Sci,2014,7(1):269-287.