改性介孔材料对贝类副产物中重金属离子的脱除性能
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摘要
为研究改性介孔材料对贝类副产物中重金属离子的脱除性能,对SBA-15介孔材料分别嫁接2-巯基噻唑啉、2-巯基苯并噻唑、吡咯烷二硫代氨基甲酸铵三种不同基团,得到三种材料分别记作MT-SBA-15、MBT-SBA-15、APDC-SBA-15,然后对材料孔结构进行表征,采用三种材料吸附铅(Pb)、铬(Cr)、镉(Cd)、铜(Cu)标准溶液,考察脱除pH、脱除时间、金属离子加标浓度对脱除能力的影响,最后用APDC-SBA-15脱除贝类副产物中重金属离子,考察重金属脱除率以及营养损失率。结果表明,三种材料都具有较大的比表面积和孔容。三种材料对重金属最优脱除pH为6.0,吸附平衡时间均为30 min;当金属离子浓度为1200 mg/L时,三种材料对金属离子吸附量最大,其中APDC-SBA-15的吸附量最高,对Pb、Cr、Cd、Cu吸附量分别为223.6、240.0、259.8、259.0 mg/g。APDC-SBA-15对菲律宾蛤仔蒸煮液中Pb的脱除率为100.00%,总糖损失率为7.32%;对菲律宾蛤仔蒸煮液多糖中Pb脱除率为84.50%,总糖损失率为2.57%;对牡蛎多肽中Pb、Cr的脱除率分别为62.20%和100.00%,对可溶性蛋白质的损失率为14.62%。综上,APDCSBA-15可以高效脱除贝类副产物中的重金属,对蛋白质、总糖等营养成分的损失率较低。
To investigate the removal of heavy metal ions from shellfish by-products by modified mesoporous materials,the silicon-based mesoporous material SBA-15 grafted with different groups( 2-mercaptothiazoline 2-mercaptobenzothiazole,and ammonium pyrrolidine dithiocarbamate) were prepared by post-grafted and characterized by mesopore pore size distribution,the standard solutions of four heavy metal ion lead,chromium,cadmium,and copper were used to investigate the adsorption capacity of the mesoporous materials.The optimal pH values,adsorption equilibrium time and adsorption quantities of different concentration of metal ions were studied.And the APDC-SBA-15 material was adopted to remove heavy metals in by-products of shellfish products. The removal rates of heavy metal ions and the loss rates of other nutrients were examined. The results showed that,three kinds of mesoporous materials( MT-SBA-15,MBT-SBA-15,APDC-SBA-15) were prepared successfully with optimal pore parameters.The optimal pH was 6.0,the adsorption equilibrium time was 30 min,and when the concentration of four standard metals was 1200 mg/L,the adsorption was largest for the three mesoporous materials.The adsorption capacity of APDC-SBA-15 for heavy metals was the largest among the three mesoporous materials,the maximum adsorption capacities for Pb,Cr,Cd,and Cu were 223.6,240.0,259.8 and 259.0 mg/g.The APDC-SBA-15 mesoporous material was adopted to remove heavy metals in cooking liquor of Ruditapes philippinarum,the removal rate of lead was 100.00%,and the loss rate of polysaccharide was 7.32%. The removal rates of lead was 84.50%,and the loss rate of polysaccharide was 2.57% when the APDC-SBA-15 mesoporous material was adopted in polysaccharide of Ruditapes philippinarum. When the APDC-SBA-15 mesoporous material was adopted in peptides of oysters,the removal rates of lead and chromium were 62.20% and 100.00%,respectively,and the loss rate of proteins was 14.62%.The APDC-SBA-15 mesoporous material could efficiently remove heavymetals and the loss rates of proteins and polysaccharides were low.
To investigate the removal of heavy metal ions from shellfish by-products by modified mesoporous materials,the silicon-based mesoporous material SBA-15 grafted with different groups( 2-mercaptothiazoline 2-mercaptobenzothiazole,and ammonium pyrrolidine dithiocarbamate) were prepared by post-grafted and characterized by mesopore pore size distribution,the standard solutions of four heavy metal ion lead,chromium,cadmium,and copper were used to investigate the adsorption capacity of the mesoporous materials.The optimal pH values,adsorption equilibrium time and adsorption quantities of different concentration of metal ions were studied.And the APDC-SBA-15 material was adopted to remove heavy metals in by-products of shellfish products. The removal rates of heavy metal ions and the loss rates of other nutrients were examined. The results showed that,three kinds of mesoporous materials( MT-SBA-15,MBT-SBA-15,APDC-SBA-15) were prepared successfully with optimal pore parameters.The optimal pH was 6.0,the adsorption equilibrium time was 30 min,and when the concentration of four standard metals was 1200 mg/L,the adsorption was largest for the three mesoporous materials.The adsorption capacity of APDC-SBA-15 for heavy metals was the largest among the three mesoporous materials,the maximum adsorption capacities for Pb,Cr,Cd,and Cu were 223.6,240.0,259.8 and 259.0 mg/g.The APDC-SBA-15 mesoporous material was adopted to remove heavy metals in cooking liquor of Ruditapes philippinarum,the removal rate of lead was 100.00%,and the loss rate of polysaccharide was 7.32%. The removal rates of lead was 84.50%,and the loss rate of polysaccharide was 2.57% when the APDC-SBA-15 mesoporous material was adopted in polysaccharide of Ruditapes philippinarum. When the APDC-SBA-15 mesoporous material was adopted in peptides of oysters,the removal rates of lead and chromium were 62.20% and 100.00%,respectively,and the loss rate of proteins was 14.62%.The APDC-SBA-15 mesoporous material could efficiently remove heavymetals and the loss rates of proteins and polysaccharides were low.
引文
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[23]Bechtel P J,Oliveira A C,Demir N,et al.Chemical composition of the giant red sea cucumber,Parastichopus californicus,commercially harvested in Alaska[J].Food Science&Nutrition,2013,1(1):63-73.
[24]高岳,林研彤,侯淑敏,等.不同产地和养殖方式的刺参微量元素含量的比较[J].大连海洋大学学报,2014,29(5):498-501.
[25]孔庆龙,余汪平,郭冬梅,等.苯酚-硫酸法测定三七枸杞酒中多糖含量[J].食品安全质量检测学报,2017,8(6):2267-2271.
[26]刘芬,王联珠,朱文嘉,等.水产制品中总糖含量检测方法的研究[J].食品安全质量检测学报,2017,8(1):56-61.
[27]程涛,孙艳波,李健.双缩脲法测定乳中酪蛋白含量[J].中国乳品工业,2000,28(3):33-35.
[2]王宇,刘东红.贝类中重金属的研究进展[J].食品科学,2011,32(13):336-340.
[3]龚倩.海水滩涂贝类中重金属镉的检测及富集规律的研究[D].青岛:中国海洋大学,2011.
[4]童永彭,朱志鹏.近海海域海产品汞、铅和砷污染状况的研究进展[J].食品科学,2015,36(23):301-306.
[5]Jarup L.Hazards of heavy metal contamination[J].British Medical Bulletin,2003,68:167-182.
[6]王静凤,张学成,单宝田.环境因子对贝类累积溶解态重金属的影响[J].中国海洋大学学报:自然科学版,2005(3):382-386.
[7]李佰磊,任丹丹,汪秋宽,等.改性壳聚糖及其对贝类提取液重金属脱除的研究进展[J].食品工业科技,2014,35(14):370-373,380.
[8]Canli M,Furness R W.Toxicity of heavy-metals dissolved in sea-water and influences of sex and size on metal accumulation and tissue distribution in the norway lobster nephrops-norvegicus[J].Marine Environmental Research,1993,36(4):217-236.
[9]傅亚平,吴卫国.食品中重金属检测与脱除技术研究进展[J].食品与机械,2015,31(2):252-256.
[10]Nagajyoti P C,Lee K D,Sreekanth T V M.Heavy metals,occurrence and toxicity for plants:A review[J].Environmental Chemistry Letters,2010,8(3):199-216.
[11]程东伟.水产品中重金属污染现状及脱除研究进展[A].广东省食品学会.“食品工业新技术与新进展”学术研讨e会暨2014年广东省食品学会年会论文集[C].广东省食品学会,2014:5.
[12]林婵.水产品中重金属的检测和去除方法[J].现代食品,2018(2):101-104.
[13]Robens E,Staszczuk P,Dabrowski A,et al.The origin of nanopores[J].Journal of Thermal Analysis and Calorimetry,2005,79(3):499-507.
[14]李玲玲.SBA-15介孔材料的制备、改性及吸附性能研究[D].武汉:武汉理工大学,2012.
[15]徐彦芹,曹渊,魏红娟.介孔分子筛在废水处理中的应用[J].水处理技术,2010,36(2):9-14.
[16]贺旷驰,王蒙,赵斌,等.介孔二氧化硅纳米复合材料的研究进展[J].材料导报,2014(13):33-37.
[17]蒲秋梅,任凤莲,谭爱喜,等.新型功能介孔材料的合成及其对铅离子吸附性能研究[J].冶金分析,2012,32(10):45-49.
[18]倪瑞芳,胡骏,王开洋.水产品加工副产物的综合利用[J].河北渔业,2010(8):47-50.
[19]Olsen R L,Toppe J,Karunasagar L.Challenges and realistic opportunities in the use of by-products from processing of fish and shellfish[J].Trends in Food Science&Technology,2014,36(2):144-151.
[20]Zhao D Y,Feng J L,Huo Q S,et al.Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J].Science,1998,279(5350):548-552.
[21]Zhao D Y,Huo Q S,Feng J L,et al.Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered,hydrothermally stable,mesoporous silica structures[J].Journal of the American Chemical Society,1998,120(24):6024-6036.
[22]蒋菁莉,任发政,蔡华伟.牛乳酪蛋白降血压肽的超滤分离[J].食品科学,2006(7):124-128.
[23]Bechtel P J,Oliveira A C,Demir N,et al.Chemical composition of the giant red sea cucumber,Parastichopus californicus,commercially harvested in Alaska[J].Food Science&Nutrition,2013,1(1):63-73.
[24]高岳,林研彤,侯淑敏,等.不同产地和养殖方式的刺参微量元素含量的比较[J].大连海洋大学学报,2014,29(5):498-501.
[25]孔庆龙,余汪平,郭冬梅,等.苯酚-硫酸法测定三七枸杞酒中多糖含量[J].食品安全质量检测学报,2017,8(6):2267-2271.
[26]刘芬,王联珠,朱文嘉,等.水产制品中总糖含量检测方法的研究[J].食品安全质量检测学报,2017,8(1):56-61.
[27]程涛,孙艳波,李健.双缩脲法测定乳中酪蛋白含量[J].中国乳品工业,2000,28(3):33-35.