海藻酸钠/纤维素复合微球的制备及性能表征
|
摘要
以短绒棉浆为原料,在NaOH/尿素溶剂体系中将纤维素与海藻酸钠按比例混合,采用溶胶凝胶转相法制备系列海藻酸钠/纤维素复合微球(SACCM),并探讨了SACCM对水相中磷酸根离子的吸附能力。采用扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)和激光粒度分析仪等对复合微球的结构和性能进行了分析。研究结果表明:系列复合微球均成球形,平均粒径约为360μm,微球均表现为具孔的三维网状结构,孔径2～5μm;通过FT-IR谱图可以看出,纤维素未与海藻酸钠发生化学反应,而是通过物理复合成球。吸附实验结果表明:复合微球对水相中磷酸根均具有较强的吸附性能,且吸附能力随着海藻酸钠质量分数的增加而变强,当海藻酸钠质量分数20%(SACCM20)时,对磷酸根的吸附性能最强,吸附效率可达到85.58%。
The cellulose solutions were prepared with the cotton linter pulp dissolved in NaOH/urea aqueous system at low temperature and mixed with sodium alginate for the preparation of sodium alginate/cellulose composite micropheres(SACCM) by sol-gel transition. Then a series of SACCM, which could be preserved in water phase, were prepared by turning the ratio of cellulose and sodium alginate. The structure and properties of the microspheres were characterized by scanning electron microscopy(SEM), Fourier transform infrared spectrometer(FT-IR) and laser particle size analyzer. And the adsorption ability of the sodium alginate/cellulose composite microspheres to phosphate in water phase were evaluated. The results showed that all the composite microspheres were spherical with the average diameter of about 360 μm, and the microspheres exhibited three-dimensional network porous structure. FT-IR spectra showed that cellulose and sodium alginate were physically combined through hydrogen bonding and intermolecular interaction. The results of adsorption experiments showed that these composite microspheres had a strong adsorption capacity for phosphate in aqueous phase, and the adsorption capacity of phosphate on the composite microspheres increased with the increase of sodium alginate content. Among them, SACCM20(mass fraction of sodium alginate 20%) had the strongest adsorption capacity for phosphate, and the adsorption efficiency could reach 85.58%.
The cellulose solutions were prepared with the cotton linter pulp dissolved in NaOH/urea aqueous system at low temperature and mixed with sodium alginate for the preparation of sodium alginate/cellulose composite micropheres(SACCM) by sol-gel transition. Then a series of SACCM, which could be preserved in water phase, were prepared by turning the ratio of cellulose and sodium alginate. The structure and properties of the microspheres were characterized by scanning electron microscopy(SEM), Fourier transform infrared spectrometer(FT-IR) and laser particle size analyzer. And the adsorption ability of the sodium alginate/cellulose composite microspheres to phosphate in water phase were evaluated. The results showed that all the composite microspheres were spherical with the average diameter of about 360 μm, and the microspheres exhibited three-dimensional network porous structure. FT-IR spectra showed that cellulose and sodium alginate were physically combined through hydrogen bonding and intermolecular interaction. The results of adsorption experiments showed that these composite microspheres had a strong adsorption capacity for phosphate in aqueous phase, and the adsorption capacity of phosphate on the composite microspheres increased with the increase of sodium alginate content. Among them, SACCM20(mass fraction of sodium alginate 20%) had the strongest adsorption capacity for phosphate, and the adsorption efficiency could reach 85.58%.
引文
[1]刘玲花,吴雷祥,刘来胜.农业废弃物去除水体中磷的研究综述[J].水利水电技术,2016,47(5):84-88.LIU L H,WU L X,LIU L S.Review on research of phosphorus removal from water body with agricultural residues[J].Water Resources and Hydropower Engineering,2016,47(5):84-88.
[2]杨平.水动力对藻类水华的影响及相关分析[D].南京:河海大学,2008.YANG P.Influence of hydrodynamics on algal blooms and related analysis[D].Nanjing:Hohai University,2008.
[3]王昶,吕晓翠,贾青竹,等.含磷废水处理技术研究进展[J].水处理技术,2009,35(12):16-21.WANG C,Lü X C,JIA Q Z,et al.Progress of phosphoru-containing wastewater treatment technology[J].Technology of Water Treatment,2009,35(12):16-21.
[4] 许醒.阳离子型生物质吸附剂的研制及其去除水中阴离子的效能及再生研究[D].济南:山东大学,2014.XU X.Preparation of biomass based cationic adsorbent and its adsorption,regeneration properties for different anions[D].Jinan:Shandong University,2014.
[5]张楠.天然纤维素和水滑石的改性及其对重金属和磷酸根的吸咐研究[D].合肥:中国科学技术大学,2016.ZHANG N.Modification of natural cellulose and hydrotalcite materials and their adsorption of heavy metal and phosphate[D].Hefei:University of Science and Technology of China,2016.
[6]KHALIL L B,ROPHAEL M W,MOURAD W E.The removal of the toxic Hg(II) salts from water by photocatalysis[J].Applied Catalysis B Environmental,2002,36(2):125-130.
[7]KAPOOR A,VIRARAGHAVAN T,CULLIMORE D R.Removal of heavy metals using the fungus Aspergillus niger[J].Bioresource Technology,1999,70(1):95-104.
[8]SAY R,DENIZLI A,ARICA M Y.Biosorption of cadmium(II),lead (II) and copper(II) with the filamentous fungus Phanerochaete chrysosporium[J].Bioresource Technology,2001,76(1):67-70.
[9]LI C C,ZHANG Y W,PENG J,et al.Adsorption of Cr(VI) using cellulose microsphere-based adsorbent prepared by radiation-induced grafting[J].Radiation Physics & Chemistry,2012,81(8):967-970.
[10]NGAH W S,AB G S,KAMARI A.Adsorption behaviour of Fe(II) and Fe(III) ions in aqueous solution on chitosan and cross-linked chitosan beads[J].Bioresource Technology,2005,96(4):443-450.
[11]GOTOH T,MATSUSHIMA K,KIKUCHI K.Adsorption of Cu and Mn on covalently cross-linked alginate gel beads[J].Chemosphere,2004,55(1):57-64.
[12] 隋欣恬.改性玉米秸秆去除水中硝酸根和磷酸根的特性和机理研究[D].广州:华南理工大学,2017.SUI X T.Study on the removal of nitrate and phosphate from water by modified corn straw:Characteristics and mechanism[D].Guangzhou:South China University of Technology,2017.
[13]吴鹏,刘志明.海藻酸钠/纤维素水凝胶球的制备与应用[J].功能材料,2015,46(10):10144-10147.WU P,LIU Z M.Preparation and application of sodium alginate/cellulose hydrogel beads[J].Journal of Functional Materials,2015,46(10):10144-10147.
[14]吕昂,张俐娜.纤维素溶剂研究进展[J].高分子学报,2007,1(10):937-944.Lü A,ZHANG L N.Advance in solvents of cellulose[J].Acta Polymerica Sinica,2007,1(10):937-944.
[15]LATEEF H,GRIMES S,KEWCHAROENWONG P,et al.Separation and recovery of cellulose and lignin using ionic liquids:A process for recovery from paper-based waste[J].Journal of Chemical Technology & Biotechnology,2010,84(12):1818-1827.
[16]MURAKAMI M,KANEKO Y,KADOKAWA J.Preparation of cellulose-polymerized ionic liquid composite by in-situ polymerization of polymerizable ionic liquid in cellulose-dissolving solution[J].Carbohydrate Polymers,2007,69(2):378-381.
[17]LEAL D,MATSUHIRO B,ROSSI M,et al.FT-IR spectra of alginic acid block fractions in three species of brown seaweeds[J].Carbohydrate Research,2008,343(2):308-316.
[2]杨平.水动力对藻类水华的影响及相关分析[D].南京:河海大学,2008.YANG P.Influence of hydrodynamics on algal blooms and related analysis[D].Nanjing:Hohai University,2008.
[3]王昶,吕晓翠,贾青竹,等.含磷废水处理技术研究进展[J].水处理技术,2009,35(12):16-21.WANG C,Lü X C,JIA Q Z,et al.Progress of phosphoru-containing wastewater treatment technology[J].Technology of Water Treatment,2009,35(12):16-21.
[4] 许醒.阳离子型生物质吸附剂的研制及其去除水中阴离子的效能及再生研究[D].济南:山东大学,2014.XU X.Preparation of biomass based cationic adsorbent and its adsorption,regeneration properties for different anions[D].Jinan:Shandong University,2014.
[5]张楠.天然纤维素和水滑石的改性及其对重金属和磷酸根的吸咐研究[D].合肥:中国科学技术大学,2016.ZHANG N.Modification of natural cellulose and hydrotalcite materials and their adsorption of heavy metal and phosphate[D].Hefei:University of Science and Technology of China,2016.
[6]KHALIL L B,ROPHAEL M W,MOURAD W E.The removal of the toxic Hg(II) salts from water by photocatalysis[J].Applied Catalysis B Environmental,2002,36(2):125-130.
[7]KAPOOR A,VIRARAGHAVAN T,CULLIMORE D R.Removal of heavy metals using the fungus Aspergillus niger[J].Bioresource Technology,1999,70(1):95-104.
[8]SAY R,DENIZLI A,ARICA M Y.Biosorption of cadmium(II),lead (II) and copper(II) with the filamentous fungus Phanerochaete chrysosporium[J].Bioresource Technology,2001,76(1):67-70.
[9]LI C C,ZHANG Y W,PENG J,et al.Adsorption of Cr(VI) using cellulose microsphere-based adsorbent prepared by radiation-induced grafting[J].Radiation Physics & Chemistry,2012,81(8):967-970.
[10]NGAH W S,AB G S,KAMARI A.Adsorption behaviour of Fe(II) and Fe(III) ions in aqueous solution on chitosan and cross-linked chitosan beads[J].Bioresource Technology,2005,96(4):443-450.
[11]GOTOH T,MATSUSHIMA K,KIKUCHI K.Adsorption of Cu and Mn on covalently cross-linked alginate gel beads[J].Chemosphere,2004,55(1):57-64.
[12] 隋欣恬.改性玉米秸秆去除水中硝酸根和磷酸根的特性和机理研究[D].广州:华南理工大学,2017.SUI X T.Study on the removal of nitrate and phosphate from water by modified corn straw:Characteristics and mechanism[D].Guangzhou:South China University of Technology,2017.
[13]吴鹏,刘志明.海藻酸钠/纤维素水凝胶球的制备与应用[J].功能材料,2015,46(10):10144-10147.WU P,LIU Z M.Preparation and application of sodium alginate/cellulose hydrogel beads[J].Journal of Functional Materials,2015,46(10):10144-10147.
[14]吕昂,张俐娜.纤维素溶剂研究进展[J].高分子学报,2007,1(10):937-944.Lü A,ZHANG L N.Advance in solvents of cellulose[J].Acta Polymerica Sinica,2007,1(10):937-944.
[15]LATEEF H,GRIMES S,KEWCHAROENWONG P,et al.Separation and recovery of cellulose and lignin using ionic liquids:A process for recovery from paper-based waste[J].Journal of Chemical Technology & Biotechnology,2010,84(12):1818-1827.
[16]MURAKAMI M,KANEKO Y,KADOKAWA J.Preparation of cellulose-polymerized ionic liquid composite by in-situ polymerization of polymerizable ionic liquid in cellulose-dissolving solution[J].Carbohydrate Polymers,2007,69(2):378-381.
[17]LEAL D,MATSUHIRO B,ROSSI M,et al.FT-IR spectra of alginic acid block fractions in three species of brown seaweeds[J].Carbohydrate Research,2008,343(2):308-316.