固定化微生物技术在废水处理中的研究进展 6页

拟建中的阜阳市中国XXXX国际服装城依托中国XX国际服装城，拟建成为皖西北地区规格最高、规模最大、商务及功能最优的现代化、国际化服装专业市场，建设规模占地约128亩，建筑面积约25万平方米，项目总投资约5亿元人民币。经过1--2年的开发建设，能达到正常运营期的中国XX.XX国际服装城将吸纳全国和世界各地的经销商、代理商企业物流总部等500—1000家，预计年交易额实现68亿元人民币，每年实现税收8000—10000万元人民币，每年实现利润1.68亿元人民币，实现就业和创业人员约2万以上。固定化微生物技术在废水处理中的研究进展祝丽思（内蒙古建筑职业技术学院市政工程系）摘　要　固定化微生物技术是一种有效的废水生物处理技术,与普通生物处理法相比有许多优点。本文对固定化微生物技术、微生物的固定化方法、固定化载体及固定化技术在废水处理中的应用及研究进展状况进行了综述,并对其以后的发展作了探讨。关键词　固定化微生物　废水处理0引言固定化细胞技术是用化学或物理的手段将游离细胞定位于限定的空间区域，并使其保持活性，反复利用的方法，是六十年代发展起来的新技术。生物固定化技术以其独特的优点应用于城市废水的处理，近年来一直是国内外学者研究的热点之一。同时也获得了令人鼓舞的研究成果。研究和应用表明[1]，固定化微生物技术，具有微生物密度高、反应速度快、耐毒害能力强、微生物流失少、产物分离容易、处理设备小型化等优点。因此,该技术有着远大的应用潜力和发展前景。1固定化法国内外不同的研究工作者对固定化法采用不同的分类方法，目前较合理的固定法大致有吸附法、包埋法、共价结合法和交联法四大类，其中以包埋法最为常用[2]。1.1包埋法包埋法是用物理方法将微生物细胞包埋在凝胶的微小空格内或埋于半透膜聚合物的超滤膜内。根据载体材料和方法的不同，包埋法可分为凝胶包埋法和半透膜包埋法两种。凝胶包埋法是将细胞包埋在各种凝胶内部的微孔中而使细胞固定的方法；半透膜包埋法是将细胞包埋在由各种高分子聚合物制成的小球内而使细胞固定的方法。目前工业应用中以凝胶包埋法固定细胞最为广泛。1.2吸附法吸附法又叫载体结合法，是依据带电的微生物细胞和载体之间的静电、表面张力和粘附力的作用，而使微生物细胞固定在载体表面和内部形成生物膜的方法，可分为物理吸附法和离子吸附法两种。从本质上来看，吸附固定法是微生物自我固定，它在废水生物处理中已广泛应用，如生物塔滤池、生物接触氧化法、厌氧滤器、厌氧流化床等生物膜，以及上流式污泥床内厌氧颗粒污泥，都是依靠微生物吸附于载体（填料）表面或自聚凝而成，尽管成膜过程或颗粒化过程的机经济增长：在优化结构、提高效益和降低消耗的基础上，“十一五”期市GDP年均增长12%以上（现14%以上），2010年达到650亿元以上，人均GDP力争1000美元；财政收入达到80亿元；规模以上工业销售达到550亿以上；全社会固定资产投资年均长20%，五年累计1000亿元；社会消费品销售额260亿元，年均增长20%，外贸进口总额2.5亿美元，年均增长15%；五年累计招商引资突破500亿元，力争达到600亿元n拟建中的阜阳市中国XXXX国际服装城依托中国XX国际服装城，拟建成为皖西北地区规格最高、规模最大、商务及功能最优的现代化、国际化服装专业市场，建设规模占地约128亩，建筑面积约25万平方米，项目总投资约5亿元人民币。经过1--2年的开发建设，能达到正常运营期的中国XX.XX国际服装城将吸纳全国和世界各地的经销商、代理商企业物流总部等500—1000家，预计年交易额实现68亿元人民币，每年实现税收8000—10000万元人民币，每年实现利润1.68亿元人民币，实现就业和创业人员约2万以上。理不甚清楚，但技术工艺已非常成熟[3]。1.3共价结合法共价结合法是细胞表面上功能团（如α—，ε—氨基、α—，β—或γ—羧基或羟基咪唑基、酚基等）和固相支持物表面的反应基团之间形成化学共价键连接，从而成为固定化细胞。该法细胞与载体之间的连接键很牢固，使用过程中不会发生脱落，稳定性好，但反应条件激烈，操作复杂，控制条件苛刻。利用此法制备的固定化细胞，细胞大多死亡。有人用此法将卡尔酵母固定在已活化的多孔玻璃珠上[10]，虽然细胞已经死亡，但仍然保留生产尿酐酸的活性。1.4交联法交联法是利用双功能或多功能试剂，直接与细胞表面的反应基团（如氨基酸、羟基、硫基、咪唑基）发生反应，使其彼此交联形成网状结构的固定化细胞，其结合力是共价键。常用的交联剂有戊二醛、甲苯二异氰酸酯等。该法反应条件激烈，对细胞活性影响大。千烟一郎曾用此法制得具有天门冬氨酸活力的固定化大肠杆菌细胞[11]。2固定化细胞的载体开发筛选理想的固定化细胞载体是固定化细胞技术能否投入实用的关键。适用于废水处理的理想固定化细胞载体应具备以下特点：①对微生物无毒性；②传质性能好；③性质稳定，不易被生物分解；④强度高、寿命长；⑤细胞的固定化操作容易；⑥水不溶性；⑦价格低廉等。研制开发具有这些特性的载体是固定化微生物研究中最为重要的课题之一。各种常用载体性能见表2.1：表2.1常用载体性能的比较载体琼脂海藻酸钙角叉莱胶聚丙烯酰胺PVA—硼酸压缩强度（kg/cm2）0.50.80.81.42.75耐曝气强度差一般一般好好扩散系数（cm2/s）75685860/耐生物分解性差较差较差好好对生物毒性无无无较强一般固定的难易易易易难较易成本便宜较便宜贵贵便宜3固定化细胞在废水处理中的应用经济增长：在优化结构、提高效益和降低消耗的基础上，“十一五”期市GDP年均增长12%以上（现14%以上），2010年达到650亿元以上，人均GDP力争1000美元；财政收入达到80亿元；规模以上工业销售达到550亿以上；全社会固定资产投资年均长20%，五年累计1000亿元；社会消费品销售额260亿元，年均增长20%，外贸进口总额2.5亿美元，年均增长15%；五年累计招商引资突破500亿元，力争达到600亿元n拟建中的阜阳市中国XXXX国际服装城依托中国XX国际服装城，拟建成为皖西北地区规格最高、规模最大、商务及功能最优的现代化、国际化服装专业市场，建设规模占地约128亩，建筑面积约25万平方米，项目总投资约5亿元人民币。经过1--2年的开发建设，能达到正常运营期的中国XX.XX国际服装城将吸纳全国和世界各地的经销商、代理商企业物流总部等500—1000家，预计年交易额实现68亿元人民币，每年实现税收8000—10000万元人民币，每年实现利润1.68亿元人民币，实现就业和创业人员约2万以上。3.1在难降解有机污染物中的应用难降解有机物用在常规生物处理工艺时一般去除效率很低，这主要是因为分解和转化这些有机物的微生物的增殖速度极慢、世代时间很长，难以在常规生物处理装置内积累到足以使这些污染物产生明显降解的浓度。利用固定化微生物的特点，可选择性地筛选一些特殊优势菌种并加以固定化，增加其在生物处理装置内的生物浓度，以提高难降解有机物的处理效率。Yang[4]用三乙酸纤维素脂与海藻酸钙的复合载体包埋混合好氧菌处理含酚废水，并与采用同样载体的表面吸附生物膜法进行了比较。当容积负荷小于9.0kgCOD/m3·d时，包埋法固定的微生物的酚去除率达90%以上，其中三乙酸纤维单载体从固定化操作容易来看出复合载体有利；与采用同样载体的表面吸附生物膜法比较，当负荷小于1.3kgCOD/m3·d时，两种方法处理效果相差不大，但负荷较高时，包理法固定化微生物比生物膜法处理效果好，显示出优势。3.2固定化细胞技术处理氨氮废水在硝化、反硝化研究方面，最早是Nilsson[5]用海藻酸钙固定假单胞反硝化菌，采用填充柱对地下水中浓度为20mg／L的硝酸盐进行两个月的连续脱氮试验，脱氮效果良好，反硝化速度为66mg／（h·kg凝胶），容积负荷为3.6kg／（m3·d）。随后，Vanotti，Hunt等[6]用PVA冷冻法把硝化污泥固定在聚乙烯醇小球里，用来处理养猪废水。采用批量试验和连续试验进行好氧处理，研究结果表明：硝化污泥小球不受养猪废水高BOD浓度的影响，适用于快速和有效的去除厌氧养猪废水塘中的NH4+。3.3对废水中重金属离子的去除固定化微生物处理含金属离子废水研究也受到相应关注，这对于拓展固定化微生物处理废水领域而言意义重大。微生物固定化后，其稳定性增加，对毒性物质的承受能力和降解能力都明显增强，因此可被用于各种有机废水中各种重金属离子的去除。严国安、李益健[7]研究了固定化小球藻对含Hg2+废水净化及生理特征的影响，利用褐藻酸钙凝胶包埋固定化普通小球藻，并对人工配制的含汞废水进行静态净化试验。研究了不同Hg2+浓度对固定化小球藻净化废水过程中氨氮、正磷酸盐的处理效率以及小球藻的4个生理指标(叶绿素a、光和强度、生长和过氧化物酶)的影响，并与悬浮藻对照比较。结果表明：由于小球藻的固定化增加了对Hg2+毒性的抗性，0.2×10-6浓度的Hg2+对其净化效率无多大影响，而悬浮藻的净化效率明显下降；随着Hg2+浓度的增加，固定化小球藻对废水净化效率逐渐下降、但其净化效率仍高于不含Hg2+废水中悬浮藻的净化效率。同时固定化藻的生长、叶绿素a含量、光和强度和过氧化物酶活性与悬浮藻一样随Hg2+浓度的增加而降低，但悬浮藻降低幅度显著。经济增长：在优化结构、提高效益和降低消耗的基础上，“十一五”期市GDP年均增长12%以上（现14%以上），2010年达到650亿元以上，人均GDP力争1000美元；财政收入达到80亿元；规模以上工业销售达到550亿以上；全社会固定资产投资年均长20%，五年累计1000亿元；社会消费品销售额260亿元，年均增长20%，外贸进口总额2.5亿美元，年均增长15%；五年累计招商引资突破500亿元，力争达到600亿元n拟建中的阜阳市中国XXXX国际服装城依托中国XX国际服装城，拟建成为皖西北地区规格最高、规模最大、商务及功能最优的现代化、国际化服装专业市场，建设规模占地约128亩，建筑面积约25万平方米，项目总投资约5亿元人民币。经过1--2年的开发建设，能达到正常运营期的中国XX.XX国际服装城将吸纳全国和世界各地的经销商、代理商企业物流总部等500—1000家，预计年交易额实现68亿元人民币，每年实现税收8000—10000万元人民币，每年实现利润1.68亿元人民币，实现就业和创业人员约2万以上。3.4固定化细胞处理农药、杀虫剂废水的研究陈敏，罗启芳[8]利用聚乙烯醇包埋活性炭和微生物的固定化技术对有机磷农药水胺硫磷的降解进行了试验研究，结果表明，经固定的微生物对温度、pH值和水样水胺硫磷浓度的适应范围扩大，在三个月的连续试验中，水样初始CODcr浓度为1300~2500mg/L，水样pH为7,停留时间24小时，在恒温摇床（30℃，150r/min）内降解，其去除率为55%~70%。3.5固定化细胞处理印染废水废水的研究采用固定化微生物处理印染废水亦有不少报道。牛志卿，吴国庆，张琳等[9]采用聚集—交联法固定化紫色非硫光合细菌用于处理活性艳红X-3B染液，比较游离微生物和固定化微生物的某些性质时发现，两种微生物的反应最适合温度均为30-40℃，固定化微生物的反应适宜pH值范围较宽，热稳定性较好，但Cu2+对两种微生物酶活力均有抑制作用。比较所得固定化微生物和由海藻酸钠包埋固定化微生物的脱色能力时，前者比后者脱色活力较高、成本低、操作方法简单，易于工业化应用。4细胞固定化技术的发展前景　　细胞固定化技术以其特有的优点在废水处理领域中引起了普遍的关注,但目前尚处于实验研究阶段,要实现其实用化或工业化,还有许多问题需要进一步研究解决,主要的研究方向如下:(1)寻找高效、廉价、抗毒性强的生物;(2)寻找性能稳定、传质好、强度高、寿命长、价格低的固定化载体;(3)发展多种生物共生的固定化体系;(4)开发高效的固定化反应器;(5)研究对生物无破坏性、高效率的解吸剂;(6)大力发展生物再生技术。　相信通过不断的研究和改进,细胞固定化技术必将成为一项高效而实用的废水处理技术,在废水处理中获得广泛的应用。经济增长：在优化结构、提高效益和降低消耗的基础上，“十一五”期市GDP年均增长12%以上（现14%以上），2010年达到650亿元以上，人均GDP力争1000美元；财政收入达到80亿元；规模以上工业销售达到550亿以上；全社会固定资产投资年均长20%，五年累计1000亿元；社会消费品销售额260亿元，年均增长20%，外贸进口总额2.5亿美元，年均增长15%；五年累计招商引资突破500亿元，力争达到600亿元n拟建中的阜阳市中国XXXX国际服装城依托中国XX国际服装城，拟建成为皖西北地区规格最高、规模最大、商务及功能最优的现代化、国际化服装专业市场，建设规模占地约128亩，建筑面积约25万平方米，项目总投资约5亿元人民币。经过1--2年的开发建设，能达到正常运营期的中国XX.XX国际服装城将吸纳全国和世界各地的经销商、代理商企业物流总部等500—1000家，预计年交易额实现68亿元人民币，每年实现税收8000—10000万元人民币，每年实现利润1.68亿元人民币，实现就业和创业人员约2万以上。参考文献[1]闫志明，普红平，阳立平.生物固定化技术研究及应用评述.四川化工，2004，7(1)：12~15.[2]李峰，吕锡武等.聚乙烯醇作为固定化细胞包埋剂的研究［J］.中国给排水，2000，16（12）：14～17.[3]徐向阳.固定化细胞技术在废水处理中的应用［J］.中国给水排水，1992，8（2）：39～43.[4]YangPY.Packed-entrapped-mixedmicrobialcellsforsmallwastewatertreatment.WaterScienceandTechnology.1990,22(3/4):343.[5]NilssonI，etal.EurJApplMicrobialBiotechnol，1980，10：261；NilssonI，etal.EurJApplMicrobialBiotechnol，1982，14：86.[6]VanottiMB.HuntPG.Nitrificationtreatmentofswinewastewaterwithacclimatednitrifyingsludgeimmobilizedinpolymerpellets[J].TansactionsoftheAsae,2000,43(2)::405~414.[7]严国安，李益健.Hg2+对固定化小球藻污水净化及生理特征的影响.环境科学，1994，14(5)：6~9.[8]陈敏，罗启芳.聚乙烯醇包埋活性炭与微生物的固定化技术及对水胺硫磷降解的研究［J］.环境科学，1993，15(3)：11~14.[9]牛志卿，吴国庆，张琳等.固定化紫色非硫光合细菌降解活性艳红X—3B的研究.环境科学，1994，15(5)：49~52.内部资料仅供参考9JWKffwvG#tYM*Jg&6a*CZ7H$dq8KqqfHVZFedswSyXTy#&QA9wkxFyeQ^!djs#XuyUP2kNXp6X4NGpP$vSTT#UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5ux^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmUE9aQ@Gn8xp$R#͑Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5ux^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z8vG#tYM*Jg&6a*CZ7H$dq8KqqfHVZFedswSyXTy#&QA9wkxFyeQ^!djs#XuyUP2kNXpRWXmA&UE9aQ@Gn8xp$R#͑Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5ux^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z8vG#tYM*Jg&6a*CZ7H$dq8KqqfHVZFedswSyXTy#&QA9wkxFyeQ^!djs#XuyUP2kNXpRWXmA&UE9aQ@Gn8xp$R#͑Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5ux^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmUE9aQ@Gn8xp$R#͑Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5ux^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNuGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5ux^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$U*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89Amv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5ux^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$U*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz84!z89Amv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5ux^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWpazadNu##KN&MuWFA5uxY7JnD6YWRrWwc^vR9CpbK!zn%Mz849Gx^Gjqv^$UE9wEwZ#Qc@UE%&qYp@Eh5pDx2zVkum&gTXRm6X4NGpP$vSTT#&ksv*3tnGK8!z89AmYWv*3tnGK8!z89A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