摘要
随着现代工业的迅速发展,重金属污染日趋严重。如何消除重金属的危害并有效地回收重金属是当今环境保护工作面临的突出问题。生物吸附作为一种新兴的重金属去除回收方法,具有原料来源广泛、吸附效率高、环境友好、不产生二次污染等优点,展现了良好的应用前景。
本论文分别以常见农林废弃物橘子皮(OP)和杉树皮(Bark)为原料,通过化学改性的手段,分别制备改性橘子皮生物吸附剂和改性杉树皮生物吸附剂,详细研究了它们对水溶液中重金属离子的吸附行为。采用化学耗氧量、Zeta电位、扫描电镜、光电子能谱、红外光谱、化学成分分析等分析手段对生物吸附剂进行了表征；通过静态实验方法考察了溶液平衡pH值、温度、固液比、时间、金属离子浓度对吸附的影响；分析了各个元素的吸附动力学、吸附热力学及吸附等温线；对改性橘子皮生物吸附剂通过动态吸附实验探索了低pH下铅锌或铅镍溶液的分离；考察了生物吸附剂的循环使用性能及对多组分溶液的竞争吸附行为；并对吸附机理进行了探讨。
橘子皮和杉树皮的主要成分为果胶、纤维素、半纤维素和木质素,含有丰富的官能团,具备一定的吸附重金属离子的能力,但吸附效果不理想,因此通过化学改性的手段,分别制备了硫化改性橘子皮生物吸附剂——巯基乙酸改性橘子皮(MOP)、黄原酸化橘子皮(XOP);氯化盐改性橘子皮生物吸附剂——氯化镁改性橘子皮(MgOP)和氯化钾改性橘子皮(KOP),及三种改性杉树皮生物吸附剂——甲醛缩合改性杉树皮(FB)、稀硫酸改性杉树皮(AB)和浓硫酸缩合改性杉树皮(CB)。
系统研究了四种改性橘子皮生物吸附剂用于水溶液中Cu2+、Cd2+Pb2+、Zn2+和Ni2+的吸附行为,得到相似的吸附规律：最佳吸附平衡pH值为5.0～5.5；吸附过程为放热过程；吸附速度都很快,在20min内基本达到吸附平衡,吸附动力学均符合准二级动力学方程；计算得到MOP、XOP、MgOP和KOP对Cu2+、Cd2+、Pb2+、Zn2+和Ni2+的最大吸附量均高于原始橘子皮OP的吸附量,说明改性过程成功嫁接了有效官能团或使更多活性位点暴露在吸附剂表面；吸附了金属离子的改性橘子皮生物吸附剂可以用0.1mol/L HCl溶液解吸再生。动态吸附结果表明,MOP和XOP可以实现水溶液中Pb2+与Zn2+的分离；MgOP和KOP可以实现水溶液中Pb2+与Ni2+的分离。根据吸附前后溶液pH的变化和红外光谱中特征吸收峰的移动,说明在改性橘子皮生物吸附剂吸附过程中主要发生了重金属离子与活性官能团(羟基、羧基和含硫基团)的离子交换反应及少量的表面配合反应。
深入研究了氯化盐改性橘子皮生物吸附剂MgOP和KOP对两组分溶液的竞争吸附效应。常见K+、Na+、Ca2+和Mg2+的存在对MgOP和KOP吸附重金属离子Cu2+、Pb2+和Ni2+的影响较小,但高浓度的Ca2+和Mg2+会抑制目标离子的吸附。对两个二元系Cu/Pb和Ni/Pb的吸附行为表明Pb2+对Cu2+和Ni2+离子的吸附表现为抑制作用,而Cu2+或Ni2+的共存对Pb2+的吸附作用非常复杂,抑制作用和促进作用共同作用,与溶液中金属离子浓度有很大关系。
详细研究了三种改性杉树皮生物吸附剂对水溶液中Cr(Ⅵ)的吸附行为。低的溶液pH值有利于FB、AB和CB对Cr(Ⅵ)的去除,吸附过程伴随Cr(Ⅵ)还原为Cr(Ⅲ)的反应；初始pH越低,达到吸附平衡的时间越短,三种吸附剂达到吸附平衡的快慢顺序为CB>AB>FB;杉树皮生物吸附剂对Cr(Ⅵ)的吸附还原属于吸热反应；吸附动力学的研究结果表明,三种吸附剂在不同温度下的吸附动力学均更符合准二级动力学方程,颗粒内扩散模型拟合结果表明FB、AB和CB对Cr(Ⅵ)的吸附速率由膜扩散和内扩散共同控制；吸附等温线结果表明,FB、AB和CB在不同初始pH下对Cr(Ⅵ)的吸附均较符合Langmuir单分子层吸附模型,初始pH越低,吸附量越大,当初始pH为1时,CB、AB和FB对Cr(Ⅵ)的最大吸附量分别达到735、483和.444mg/g,远高于文献报道的一些农林废弃物生物吸附剂对Cr(Ⅵ)的最大吸附量。
三种杉树皮生物吸附剂对Cr(Ⅵ)的吸附机理为“吸附-还原”机理,在吸附过程中,Cr(Ⅵ)首先以阴离子形式吸附到吸附剂表面,随后主要被木质素及其衍生物分子结构上的给电子基团还原为Cr(Ⅲ),还原得到的Cr(Ⅲ)则以配合物的形式与吸附剂表面的羟基、羧基和甲氧基相结合。
本研究为高效利用废弃物质橘子皮、杉树皮及其用于含重金属废水处理提供了重要基础性数据。
With the fast development of modern industry, heavy metal contaminant becomes more severe. How to elimnate the damage and effectively recover heavy metals is the outstanding problem of current environmental protection work. Biosorption as a novel heavy metal removal technology has many advantages, including abundant resource, low cost, high metal binding capacity, environmental friendly and without second pollution, which make biosorption have a wide application prospect.
In this paper, orange peel (OP) and spruce bark were chosen as the raw material to prepare modified orange peel biosorbents and modified spruce bark biosorbents through chemical modification. The adsorption behaviors for heavy metal ions by these biosorbents were investigated. The characterizations of biosorbents were determined by COD, Zeta potential, SEM, XPS, FTIR and so on. The effects of various parameters, including solution pH, temperature, solid/liquid ratio, adsorption time and metal ion concentration on the adsorption process were investigated by using batch adsorption techniques. The adsorption thermodynamic, adsorption kinetics and adsorption isotherms of each metal ion by each adsorbent were analyzed systematically and the values of adsorption heat, maximum adsorption capacity and average adsorption energy were calculated. The separation of lead/zinc and lead/nicole under low pH values was conducted by column adsorption experiments. Furthermore, the technology of desorption and reuse for the modified orange peel and competitive adsorption behavior of binary metal ion system were also tested. The adsorption mechanisms were discussed through instrumental identification.
The main components of orange peel and spruce bark are pectine, cellulose, hemi-cellulose and lignin, which have ability to bind heavy metal ions, but show lower adsorption capacity. By chemically modification, four kinds of orange peel biosorbents were prepared:MOP, XOP, MgOP and KOP which were modified by mercapto-acetic acid, carbon disulfide, magnesium chloride and potassium chloride, respectively and three kinds of spruce bark biosorbents were prepared: FB, AB and CB, which were modified by formaldehyde, dilute sulfuric acid and concentrated sulfuric acid, respectively.
The adsorption behaviors of modified orange peel biosorbents for the removal of Cu2+, Cd2+, Pb2+, Zn2+and Ni2+were investigated, and similar results were obtained:best equilibrium adsorption pH range was5.0-5.5; adsorption process was exothermic; fast adsorption rate was noticed that adsorption equilibrium could be reached within20minutes. All the adsorption processes could be well described by the pseudo-second-order equation. The calculated maximum adsorption capacities for Cu2+, Cd2+,Pb2+, Zn2+and Ni2+by MOP, XOP, MgOP and KOP were higher than orinigal orange peel, which confirm the chemical modification processes successfully improve the adsorption ability of OP through adding functional groups or making more active sites exposure on the adsorbent surface. Metal loaded adsorbents could be regenerated using0.1mol/L HC1solution and repeatedly for ten times with little loss of adsorption capacity. The results of column adsorption experiments suggested that effective mutual separation of Pb2+away from Zn2+can be realized by MOP and XOP, and mutual separation of Pb2+away from Ni2+by MgOP and KOP could be satisfactorily achieved. Based on the analysis of the change of solution pH and movement of typical adsorption peaks in FTIR spectrum before and after heavy metal adsorption, the adsorption mechanism of modified orange peel biosorbents was mainly ion exchange and little complexation between heavy metal ions and functional groups (-OH,-COOH and sulfur bearing groups) on the surface of biosorbents.
The competitive adsorption behavior for binary metal ion solutions by MgOP and KOP were discussed. The effects of the existence of common cations including K+, Na+, Ca2+and Mg2+on the adsorption of Cu2+, Pb2+and Ni2+by MgOP and KOP were negligible, but high concentrations of Ca2+and Mg2+will interfere the adsorption of target metal ions. MgOP and KOP were used to test the competitive adsorption behavior of two binary systems:Pb/Cu and Pb/Ni. And the results showed that the effects of Pb2+ions on the uptake capacities of Cu2+and Ni2+ions were antagonistic, whereas the effect of the coexistence of Cu2+or Ni2+ions in the binary mixture on the adsorption of Pb2+was very complicated and could be considered to be a combination of antagonistic and synergistic depending on the metal ion concentration in the mixtures.
The adsorption behavior for the removal of Cr(Ⅵ) from aqueous solutions by modified spruce bark biosorbents were investigated. Spruce bark biosorbents has higher relative lignin content and more porous morphology, which plays a very important role in the adsorption of Cr(Ⅵ). The results of thr modified spruce bark biosorbents for the removal of Cr(VI) indicated that:lower pH was benefical for the adsorption of Cr(Ⅵ) by FB, AB and CB; adsorption process was accompanied by reduction reaction from Cr(Ⅵ) to Cr(Ⅲ); the lower the initial solution pH, the shorter the time to reach equilibrium, the speed order of the three spruce biosorbents was CB>AB>FB; the adsorption process was endothermic. Under different temperatures, all the adsorption processes could be well described by the pseudo-second-order equation. Fitting results of intra-particle diffusion model indicated that the adsorption process was controlled by both film and intraparticle diffusion. By analyzing the adsorption isotherms, the adsoprtion of Cr(Ⅵ) on FB, AB and CB fitted Langmuir model better. The lower the initial solution pH, the higher the adsorption capacity. When the initial pH was1, the maximum adsorption capacties of FB, AB and CB for the adsorption Cr(Ⅵ) were735,483and444mg/g, which were much higher than the reported adsorption capacities in literatures. The obtained results give a answer that there is no need to use traditional formaldehyde for modification method.
The Cr(Ⅵ) adsorption processes by three kinds of spruce bark biosorbents were supposed to be typical adsorption-coupled reduction mechanism. During adsorption, Cr(Ⅵ) was first be adsorbed as anoin ions onto the surface of bark biosorbents, then was reduced to Cr(Ⅲ) by electron donor groups on the lignin and lignin derivatives, after that, the Cr(Ⅲ) was adsorbed onto the biosorbent surface through surface complexation with hydroxy, carboxyl and methoxy.
This paper provides important foundmental date for the effective reuse of watste orange peel and spruce bark and their applications for heavy meatl ion wastewater treatment.
引文
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