鸡毛交联纤维素多功能锌肥制备与性能研究
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摘要
以鸡毛(CF)和纤维素(Cell)为原料,氢氧化钾/水/尿素(KOH/H2O/CO(NH2)2)体系为复合溶剂,碱解鸡毛得到鸡毛碱解液,然后向鸡毛碱解液加入纤维素形成凝胶化的混合物,为发挥凝胶基质中官能团的保肥作用向其内部加入微量元素Zn,经过干燥并造粒,最后得到含N(150.6 mg/g)、K(136.7 mg/g)、Zn(13.9 mg/g)并同时含有硫、多肽和氨基酸等营养成分的鸡毛交联纤维素凝胶肥料(Cell-CF)。利用红外光谱(FTIR)、X射线衍射(XRD)、X射线光电子能谱(XPS)、荧光显微镜对Cell-CF水凝胶的交联结构及形成机理进行分析与表征。结果表明:经复合溶剂处理后鸡毛和纤维素原料的结晶结构破坏较完全,Cell-CF中的多肽和纤维素进行了分子间的穿插折叠并形成了较强的分子间作用力,Cell-CF中的官能团与锌离子进行了络合反应。另外,土壤培养实验和玉米盆栽实验结果表明,Cell-CF中锌的生物有效性高、肥效期长,可作为一种长效锌肥。
The development of new fertilizers from agricultural and industrial wastes could be both environmentally-friendly and low-cost. High-value utilization of chicken feather( CF) and cellulose( Cell) has always been a challenging endeavor. A multi-functional zinc-rich fertilizer was developed by cross-linking CF and Cell with KOH/H2 O/CO( NH2)2( KOH,1. 5 mol/L; CO( NH2)2,0. 12 g/m L)being a composite solvent,which was named Cell-CF. The main procedures were: the CF was firstly gone through alkaline hydrolysis in the composite solvent with ratio of solid to water of 1∶ 10 at temperature of75℃ for 2 h,then the polypeptide solution was obtained and cooled at-12℃; secondly,the Cell( 0. 06 g/m L) was immersed into the polypeptide solution and the Cell-CF hydrogel was obtained after highintensity stirring for 30 min; thirdly,dilute H2 SO4 solution was used to adjust the p H value of Cell-CF gel to 6. 5; fourthly,Zn SO4·7 H2 O was added to the gel followed by constant stirring of 1 h; finally,the above gel was prilled with a 1 cm × 1 cm × 1 cm cubic mould and dried at 60℃ in oven. Chemical analyses of the granulated Cell-CF fertilizer showed that it contained nitrogen of 150. 6 mg/g,potassium of 136. 7 mg/g and zinc of 13. 9 mg/g. Water sorption measurement indicated that Cell-CF had good swelling capacity in water. Hydrostatic nutrients release experiment revealed that Cell-CF could slow down the release of potassium and zinc into water. The formation mechanism of cross-linking structure of Cell-CF was investigated by FTIR and X-ray. It was demonstrated that the crystal structures of CF and Cell were destroyed after being treated with the composite solvent, and there was hydrogen bond interaction between the polypeptide and Cell. After the Cell-CF was immersed into water for 8 h,strong fluorescence signal was detected from the crossed Cell-CF while there was no fluorescence around CellCF,meaning that the polypeptide was not dissolved in water and the molecular interactions between Celland CF were strong. Photoelectron spectroscopy results showed that zinc was chelated with the functional groups of Cell-CF. Soil incubation experiment and pot experiment showed that Cell-CF could release high bio-available zinc in a long term.
The development of new fertilizers from agricultural and industrial wastes could be both environmentally-friendly and low-cost. High-value utilization of chicken feather( CF) and cellulose( Cell) has always been a challenging endeavor. A multi-functional zinc-rich fertilizer was developed by cross-linking CF and Cell with KOH/H2 O/CO( NH2)2( KOH,1. 5 mol/L; CO( NH2)2,0. 12 g/m L)being a composite solvent,which was named Cell-CF. The main procedures were: the CF was firstly gone through alkaline hydrolysis in the composite solvent with ratio of solid to water of 1∶ 10 at temperature of75℃ for 2 h,then the polypeptide solution was obtained and cooled at-12℃; secondly,the Cell( 0. 06 g/m L) was immersed into the polypeptide solution and the Cell-CF hydrogel was obtained after highintensity stirring for 30 min; thirdly,dilute H2 SO4 solution was used to adjust the p H value of Cell-CF gel to 6. 5; fourthly,Zn SO4·7 H2 O was added to the gel followed by constant stirring of 1 h; finally,the above gel was prilled with a 1 cm × 1 cm × 1 cm cubic mould and dried at 60℃ in oven. Chemical analyses of the granulated Cell-CF fertilizer showed that it contained nitrogen of 150. 6 mg/g,potassium of 136. 7 mg/g and zinc of 13. 9 mg/g. Water sorption measurement indicated that Cell-CF had good swelling capacity in water. Hydrostatic nutrients release experiment revealed that Cell-CF could slow down the release of potassium and zinc into water. The formation mechanism of cross-linking structure of Cell-CF was investigated by FTIR and X-ray. It was demonstrated that the crystal structures of CF and Cell were destroyed after being treated with the composite solvent, and there was hydrogen bond interaction between the polypeptide and Cell. After the Cell-CF was immersed into water for 8 h,strong fluorescence signal was detected from the crossed Cell-CF while there was no fluorescence around CellCF,meaning that the polypeptide was not dissolved in water and the molecular interactions between Celland CF were strong. Photoelectron spectroscopy results showed that zinc was chelated with the functional groups of Cell-CF. Soil incubation experiment and pot experiment showed that Cell-CF could release high bio-available zinc in a long term.
引文
1宋孝周,吴清林,傅峰,等.农作物与其剩余物制备纳米纤维素研究进展[J].农业机械学报,2011,42(11):106-112.SONG Xiaozhou,WU Qinglin,FU Feng,et al.Research progress of nanocrystalline cellulose prepared from crops and agricultural residues[J].Transactions of the Chinese Society for Agricultural Machinery,2011,42(11):106-112.(in Chinese)
2 何明,窦瑶,陈智鹏,等.角蛋白膜材料的制备及改性研究进展[J].化工进展,2016,35(9):2839-2844.HE Ming,DOU Yao,CHEN Zhipeng,et al.Research progress in preparation and modification of keratin films[J].Chemical Industry and Engineering Progress,2016,35(9):2839-2844.(in Chinese)
3 田龙,马晓建.丙酸预处理小麦秸秆的纤维素水解动力学[J/OL].农业机械学报,2012,43(9):111-115.http:∥www.jcsam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20120921&flag=1.DOI:10.6041/j.issn.1000.1298.2012.09.021.TIAN Long,MA Xiaojian.Kinetics hydrolysis of cellulose of wheat straw pretreated with propionic acid[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2012,43(9):111-115.(in Chinese)
4 HOLKAR C R,JADHAV A J,BHAVSAR P S,et al.Acoustic cavitation assisted alkaline hydrolysis of wool based keratins to produce organic amendment fertilizers[J].ACS Sustainable Chemistry&Engineering,2016,4(5):2789-2796.
5 CAI J,ZHANG L,ZHOU J,et al.Multifilament fibers based on dissolution of cellulose in Na OH/urea aqueous solution:structure and properties[J].Advanced Materials,2007,19(6):821-825.
6 CAI J,ZHANG L.Unique gelation behavior of cellulose in Na OH/urea aqueous solution[J].Biomacromolecules,2006,7(1):183-189.
7 AGUAYO-VILLARREAL I A,BONILLA-PETRICIOLET A,HERNNDEZ-MONTOYA V,et al.Batch and column studies of Zn2+removal from aqueous solution using chicken feathers as sorbents[J].Chemical Engineering Journal,2011,167(1):67-76.
8 SCOTT E E,ROTHSTEIN D E.Amino acid uptake by temperate tree species characteristic of low-and high-fertility habitats[J].Oecologia,2011,167(2):547-557.
9 RAI S K,MUKHERJEE A K.Optimization for production of liquid nitrogen fertilizer from the degradation of chicken feather by iron-oxide(Fe3O4)magnetic nanoparticles coupledβ-keratinase[J].Biocatalysis and Agricultural Biotechnology,2015,4(4):632-644.
10 SNCHEZ-RODRGUEZ A,CANASVERAS J,del CAMPILLO M C,et al.Iron chlorosis in field grown olive as affected by phosphorus fertilization[J].European Journal of Agronomy,2013,51:101-107.
11 NADAL P,GARCA-DELGADO C,HERNNDEZ D,et al.Evaluation of Fe-N,N'-Bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetate(HBED/Fe3+)as Fe carrier for soybean(Glycine max)plants grown in calcareous soil[J].Plant and Soil,2012,360(1-2):349-362.
12 井大炜,邢尚军,刘方春,等.保水剂施用方式对侧柏根际微生态环境的影响[J/OL].农业机械学报,2016,47(5):146-154 .http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20160520&flag=1.DOI:10.6041/j.issn.1000-1298.2016.05.020.JING Dawei,XING Shangjun,LIU Fangchun,et al.Effect of application methods of super absorbent polymers on microecological environment in rhizosphere soil of playcladus orientalis[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2016,47(5):146-154.(in Chinese)
13 DAVIDSON D W,VERMA M S,GU F X.Controlled root targeted delivery of fertilizer using an ionically crosslinked carboxymethyl cellulose hydrogel matrix[J].Springer Plus,2013,2(1):Article 318.
14 HG/T 3997—2008硫包衣尿素[S].2008.
15 GB/T 8572—2010复混肥料中总氮含量的测定蒸馏后滴定法[S].2010.
16 PUGA A,ABREU C,MELO L,et al.Biochar application to a contaminated soil reduces the availability and plant uptake of zinc,lead and cadmium[J].Journal of Environmental Management,2015,159:86-93.
17 STEINER F,LANA M do Carmo,ZOZ T,et al.Extraction methods and potassium availability for soybean in the parana state’s soils,Brazil[J].Revista de Agricultura Neotropical,2015,1(2):83-92.
18 SHEPHERD M,GHANI A,RAJENDRAM G,et al.Soil total nitrogen concentration explains variation in pasture response to spring nitrogen fertiliser across a single farm[J].Nutrient Cycling in Agroecosystems,2015,101(3):377-390.
19 ISOGAI A,ATALLA R.Dissolution of cellulose in aqueous Na OH solutions[J].Cellulose,1998,5(4):309-319.
20 WANG J,LIU Z,WANG Y,et al.Production of a water-soluble fertilizer containing amino acids by solid-state fermentation of soybean meal and evaluation of its efficacy on the rapeseed growth[J].Journal of Biotechnology,2014,187:34-42.
21 曹胜磊,耿增超,王月玲,等.化学改性提高木质素的水溶性及其对Zn2+的络合能力[J].农业环境科学学报,2016,35(11):2216-2223.CAO Shenglei,GENG Zengchao,WANG Yueling,et al.Modification of lignin for improvement it’s water-soluble property and ability to complex with Zn2+[J].Journal of Agro-Environment Science,2016,35(11):2216-2223.(in Chinese)
22 王越,王宇欣,时光营.纤维素保水剂对基质特性和黄瓜幼苗生长的影响[J/OL].农业机械学报,2016,47(1):162-169.http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20160121&flag=1.DOI:10.6041/j.issn.1000-1298.2016.01.021.WANG Yue,WANG Yuxin,SHI Guangying.Effects of cellulose aquasorb on properties of substrate and growth of cucumber seedling[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2016,47(1):162-169.(in Chinese)
23 SMIDT E,MEISSL K.The applicability of Fourier transform infrared(FT-IR)spectroscopy in waste management[J].Waste Management,2007,27(2):268-276.
24 SUN P,LIU Z T,LIU Z W.Particles from bird feather:a novel application of an ionic liquid and waste resource[J].Journal of Hazardous Materials,2009,170(2):786-790.
25 CAI J,ZHANG L,CHANG C,et al.Hydrogen-bond-induced inclusion complex in aqueous cellulose/Li OH/urea solution at low temperature[J].Chem Phys Chem,2007,8(10):1572-1579.
26 PARK S,BAKER J O,HIMMEL M E,et al.Cellulose crystallinity index:measurement techniques and their impact on interpreting cellulase performance[J].Biotechnology for Biofuels,2010,3(1):1-10.
27 ZHANG Q,BENOIT M,De OLIVEIRA VIGIER K,et al.Green and inexpensive choline-derived solvents for cellulose decrystallization[J].Chemistry-A European Journal,2012,18(4):1043-1046.
28 OH S Y,YOO D I,SHIN Y,et al.Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy[J].Carbohydrate Research,2005,340(15):2376-2391.
29 XIE H,LI S,ZHANG S.Ionic liquids as novel solvents for the dissolution and blending of wool keratin fibers[J].Green Chemistry,2005,7(8):606-608.
30 ALUIGI A,ZOCCOLA M,VINEIS C,et al.Study on the structure and properties of wool keratin regenerated from formic acid[J].International Journal of Biological Macromolecules,2007,41(3):266-273.
31 鲍文毅,徐晨,宋飞,等.纤维素/壳聚糖共混透明膜的制备及阻隔抗菌性能研究[J].高分子学报,2015(1):49-56.BAO Wenyi,XU Chen,SONG Fei,et al.Preparation and properties of cellulose/chitosan transparent films[J].Acta Polymerica Sinica,2015(1):49-56.(in Chinese)
32 张晶晶,容建华,李文迪,等.细菌纤维素/聚丙烯酰胺水凝胶的制备及性能表征[J].高分子学报,2011(6):602-607.ZHANG Jingjing,RONG Jianhua,LI Wendi,et al.Preparation and characterization of bacterial cellulose/polyacrylamide hydrogel[J].Acta Polymerica Sinica,2011(6):602-607.(in Chinese)
33 MOULDER J,STIKLE W,SOBOL P,et al.Handbook of X-ray photoelectron spectroscopy[M].Minnesota:Perkin-Elmer,1995:213-242.
34 GEISSELER D,SCOW K M.Long-term effects of mineral fertilizers on soil microorganisms—a review[J].Soil Biology and Biochemistry,2014,75:54-63.
2 何明,窦瑶,陈智鹏,等.角蛋白膜材料的制备及改性研究进展[J].化工进展,2016,35(9):2839-2844.HE Ming,DOU Yao,CHEN Zhipeng,et al.Research progress in preparation and modification of keratin films[J].Chemical Industry and Engineering Progress,2016,35(9):2839-2844.(in Chinese)
3 田龙,马晓建.丙酸预处理小麦秸秆的纤维素水解动力学[J/OL].农业机械学报,2012,43(9):111-115.http:∥www.jcsam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20120921&flag=1.DOI:10.6041/j.issn.1000.1298.2012.09.021.TIAN Long,MA Xiaojian.Kinetics hydrolysis of cellulose of wheat straw pretreated with propionic acid[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2012,43(9):111-115.(in Chinese)
4 HOLKAR C R,JADHAV A J,BHAVSAR P S,et al.Acoustic cavitation assisted alkaline hydrolysis of wool based keratins to produce organic amendment fertilizers[J].ACS Sustainable Chemistry&Engineering,2016,4(5):2789-2796.
5 CAI J,ZHANG L,ZHOU J,et al.Multifilament fibers based on dissolution of cellulose in Na OH/urea aqueous solution:structure and properties[J].Advanced Materials,2007,19(6):821-825.
6 CAI J,ZHANG L.Unique gelation behavior of cellulose in Na OH/urea aqueous solution[J].Biomacromolecules,2006,7(1):183-189.
7 AGUAYO-VILLARREAL I A,BONILLA-PETRICIOLET A,HERNNDEZ-MONTOYA V,et al.Batch and column studies of Zn2+removal from aqueous solution using chicken feathers as sorbents[J].Chemical Engineering Journal,2011,167(1):67-76.
8 SCOTT E E,ROTHSTEIN D E.Amino acid uptake by temperate tree species characteristic of low-and high-fertility habitats[J].Oecologia,2011,167(2):547-557.
9 RAI S K,MUKHERJEE A K.Optimization for production of liquid nitrogen fertilizer from the degradation of chicken feather by iron-oxide(Fe3O4)magnetic nanoparticles coupledβ-keratinase[J].Biocatalysis and Agricultural Biotechnology,2015,4(4):632-644.
10 SNCHEZ-RODRGUEZ A,CANASVERAS J,del CAMPILLO M C,et al.Iron chlorosis in field grown olive as affected by phosphorus fertilization[J].European Journal of Agronomy,2013,51:101-107.
11 NADAL P,GARCA-DELGADO C,HERNNDEZ D,et al.Evaluation of Fe-N,N'-Bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetate(HBED/Fe3+)as Fe carrier for soybean(Glycine max)plants grown in calcareous soil[J].Plant and Soil,2012,360(1-2):349-362.
12 井大炜,邢尚军,刘方春,等.保水剂施用方式对侧柏根际微生态环境的影响[J/OL].农业机械学报,2016,47(5):146-154 .http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20160520&flag=1.DOI:10.6041/j.issn.1000-1298.2016.05.020.JING Dawei,XING Shangjun,LIU Fangchun,et al.Effect of application methods of super absorbent polymers on microecological environment in rhizosphere soil of playcladus orientalis[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2016,47(5):146-154.(in Chinese)
13 DAVIDSON D W,VERMA M S,GU F X.Controlled root targeted delivery of fertilizer using an ionically crosslinked carboxymethyl cellulose hydrogel matrix[J].Springer Plus,2013,2(1):Article 318.
14 HG/T 3997—2008硫包衣尿素[S].2008.
15 GB/T 8572—2010复混肥料中总氮含量的测定蒸馏后滴定法[S].2010.
16 PUGA A,ABREU C,MELO L,et al.Biochar application to a contaminated soil reduces the availability and plant uptake of zinc,lead and cadmium[J].Journal of Environmental Management,2015,159:86-93.
17 STEINER F,LANA M do Carmo,ZOZ T,et al.Extraction methods and potassium availability for soybean in the parana state’s soils,Brazil[J].Revista de Agricultura Neotropical,2015,1(2):83-92.
18 SHEPHERD M,GHANI A,RAJENDRAM G,et al.Soil total nitrogen concentration explains variation in pasture response to spring nitrogen fertiliser across a single farm[J].Nutrient Cycling in Agroecosystems,2015,101(3):377-390.
19 ISOGAI A,ATALLA R.Dissolution of cellulose in aqueous Na OH solutions[J].Cellulose,1998,5(4):309-319.
20 WANG J,LIU Z,WANG Y,et al.Production of a water-soluble fertilizer containing amino acids by solid-state fermentation of soybean meal and evaluation of its efficacy on the rapeseed growth[J].Journal of Biotechnology,2014,187:34-42.
21 曹胜磊,耿增超,王月玲,等.化学改性提高木质素的水溶性及其对Zn2+的络合能力[J].农业环境科学学报,2016,35(11):2216-2223.CAO Shenglei,GENG Zengchao,WANG Yueling,et al.Modification of lignin for improvement it’s water-soluble property and ability to complex with Zn2+[J].Journal of Agro-Environment Science,2016,35(11):2216-2223.(in Chinese)
22 王越,王宇欣,时光营.纤维素保水剂对基质特性和黄瓜幼苗生长的影响[J/OL].农业机械学报,2016,47(1):162-169.http:∥www.j-csam.org/jcsam/ch/reader/view_abstract.aspx?file_no=20160121&flag=1.DOI:10.6041/j.issn.1000-1298.2016.01.021.WANG Yue,WANG Yuxin,SHI Guangying.Effects of cellulose aquasorb on properties of substrate and growth of cucumber seedling[J/OL].Transactions of the Chinese Society for Agricultural Machinery,2016,47(1):162-169.(in Chinese)
23 SMIDT E,MEISSL K.The applicability of Fourier transform infrared(FT-IR)spectroscopy in waste management[J].Waste Management,2007,27(2):268-276.
24 SUN P,LIU Z T,LIU Z W.Particles from bird feather:a novel application of an ionic liquid and waste resource[J].Journal of Hazardous Materials,2009,170(2):786-790.
25 CAI J,ZHANG L,CHANG C,et al.Hydrogen-bond-induced inclusion complex in aqueous cellulose/Li OH/urea solution at low temperature[J].Chem Phys Chem,2007,8(10):1572-1579.
26 PARK S,BAKER J O,HIMMEL M E,et al.Cellulose crystallinity index:measurement techniques and their impact on interpreting cellulase performance[J].Biotechnology for Biofuels,2010,3(1):1-10.
27 ZHANG Q,BENOIT M,De OLIVEIRA VIGIER K,et al.Green and inexpensive choline-derived solvents for cellulose decrystallization[J].Chemistry-A European Journal,2012,18(4):1043-1046.
28 OH S Y,YOO D I,SHIN Y,et al.Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy[J].Carbohydrate Research,2005,340(15):2376-2391.
29 XIE H,LI S,ZHANG S.Ionic liquids as novel solvents for the dissolution and blending of wool keratin fibers[J].Green Chemistry,2005,7(8):606-608.
30 ALUIGI A,ZOCCOLA M,VINEIS C,et al.Study on the structure and properties of wool keratin regenerated from formic acid[J].International Journal of Biological Macromolecules,2007,41(3):266-273.
31 鲍文毅,徐晨,宋飞,等.纤维素/壳聚糖共混透明膜的制备及阻隔抗菌性能研究[J].高分子学报,2015(1):49-56.BAO Wenyi,XU Chen,SONG Fei,et al.Preparation and properties of cellulose/chitosan transparent films[J].Acta Polymerica Sinica,2015(1):49-56.(in Chinese)
32 张晶晶,容建华,李文迪,等.细菌纤维素/聚丙烯酰胺水凝胶的制备及性能表征[J].高分子学报,2011(6):602-607.ZHANG Jingjing,RONG Jianhua,LI Wendi,et al.Preparation and characterization of bacterial cellulose/polyacrylamide hydrogel[J].Acta Polymerica Sinica,2011(6):602-607.(in Chinese)
33 MOULDER J,STIKLE W,SOBOL P,et al.Handbook of X-ray photoelectron spectroscopy[M].Minnesota:Perkin-Elmer,1995:213-242.
34 GEISSELER D,SCOW K M.Long-term effects of mineral fertilizers on soil microorganisms—a review[J].Soil Biology and Biochemistry,2014,75:54-63.