污水污泥中重金属在热解过程中行为研究
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摘要
本文以污水污泥为原料,研究了污泥和不同热解温度下热解残渣中铜、锌、铅、镉的总量和形态,考察了热解温度对这些热解残渣中上述重金属形态和滤出性的影响。首先利用原子吸收分光光度法(AAS)分析了污泥和热解残渣中上述四种金属的总量。污泥中金属锌(2104.8mg/kg)超过了《农用污泥中污染物控制标准》污泥农用土壤标准；金属镉(5.2mg/kg)和铜(312.3mg/kg)的含量超过了该标准污泥农用的酸性土壤标准；铅(119.6mg/kg)低于该标准中污泥农用的酸性土壤标准。热解残渣中这四种金属含量的多少次序和污泥样品中的多少次序是一样的,但是当热解温度升高到700℃时,热解底物中的镉还原成镉单质从而挥发到热解气体当中去了,导致残渣中镉含量减少。
其次,使用现在通行的BCR (Community Bureau of Reference)法对污泥和热解残渣中这四种金属形态进行提取,然后利用AAS分析各个形态的含量。污泥中金属铜、镉、铅具有很大的潜在环境风险,因为每种金属的前三种形态分别占总量80%以上,其生物可利用性和环境毒性不可忽视。污泥中的锌的可交换态和可还原态的含量较高但部分可交换态的锌将会被土壤中的无机物晶格封闭而很稳定对环境无毒性,所以其生物有效性可能被高估。这四种金属的四种形态和热解温度的相关系数绝对值都没有超过0.8,有一半以上的相关系数都小于0.5,有些相关系数甚至小于0.3。所以,当热解温度不超过700℃时,能量还不足以打开上述四种金属形态的结合力,所以热解温度对残渣中的金属形态分布影响不大。
最后,污泥和热解残渣中的金属的滤出性通过优化的有毒物质滤出性检测方法(TCLP)进行测定。热解残渣中金属镉、铜、铅、锌的TCLP浓度分别在400℃,350℃,500℃,550℃的时候达到最大值0.74mg/L,15.69mg/L,10.25mg/L,85.63mg/L。分别达到这个极值以后,热解残渣中它们的TCLP浓度就会随着热解温度上升而迅速下降,这是因为其一,在污泥中金属大部分是以有机螯合物的形式存在的,当热解温度升高致使有机螯合物的链断裂,金属离子释放出来,所以随着热解温度的增加,金属的滤出性也随着增强。但是达到一定温度以后金属又被晶格化而固定在灰分品格中,所以金属的滤出性极大的降低了。其二,热解过程中pH值随着热解温度升高而升高,其对H+的缓冲性也极大提高,这个也是导致金属TCLP浓度变化的另一个原因。其三,除650℃外,热解残渣的比表面积随着热解温度的升高热解残渣的比表面积逐渐缓慢上升(热解温度是700℃的时候,其比表面积达到33m3/g)。热解残渣中比表面积升高,其对重金属离子吸附能力增强也是热解残渣中的金属TCLP浓度变化的一个重要原因。
The present study focuses on the total content and speciation of Cu, Zn, Pb, Cd in the sewage sludge and the in the pyrolysis residues obtained at different temperatures. The influence that the pyrolysis temperature exerts on the speciation distribution and the leachability of these metals in the residues was evaluated. At first, Atomic Adsorption Spectrometry was (AAS) was employed to analyze the total concentration of the heavy metals in the sludge and the residues. The concentration of Zn (2104.8mg/kg) in the sludge was beyond the permitted value which is stipulated in Control standards for pollutants in sludges from agricultural use. The concentration of Cd (5.2mg/kg) and Cu (312.3mg/kg) were beyond the permitted value when the sludge was applied to the soil with pH<6.5. The concentration of Zn in the sludge was lower than the permitted values. When it came to the residues, the same conclusion could be attained except Cd in the residue produced during the pyrolysis at the temperature of 700℃.
Secondly, BCR (Community Bureau of Reference) was used to extract the speciation of these metals and AAS was used to determine the concentration of these speciation. Cu, Cd, Pd in the sludge have great potential environment risk because the sum of the first three speciation accounts for 80%. Their bio-availability and toxicity can not be neglected. The sum of the first two speciation of Zn in the sludge is high. However some of exchangeable speciation can be fixed in the inorganic crystal lattice and pose no toxicity to the environment, so its bioavailability may be overestimated. All the absolute value of correlation coefficients between pyrolysis temperatures and the fractions of Cd, Cu, Pb, Zn in the residues are far less than 0.8 which is the minimum of high correlation. More than half of these correlation coefficients were below 0.5 and some were even below 0.3. The pyrolysis temperatures didn't effectively contribute to the distribution of metal speciation in the residues when the temperature was below 700℃, because the energy was not high enough to break the bonds.
At last, modified Toxicity Characteristic Leaching Procedure was applied to determine the leachability of these metals in the sludge and residues. TCLP concentrations of Cd, Cu, Pb, Zn maximized at 0.74mg/L,15.69mg/L,10.25mg/L, 85.63mg/L at 400℃,350℃,500℃,550℃respectively. When the temperatures exceeded those points, the TCLP concentrations declined sharply. There are three reasons:Firstly, the heavy metals exist in organic chelate, with the increase of the temperature, a lot of chelate bonds were easily to break, and the metal ions can be released in the test. However, when the temperature came to some points, these metals can be fixed in the ash crystal lattice and hardly to release in the test. Secondly, the pH rose in the residues with the increasing of the temperature. So the pH buffering capacity of the residues is the other reason for the change of TCLP concentration of the metals. Thirdly, the BET surface of the residues increased when the temperature increased except 650℃(it rose to 33m3/g when the temperature got to 700℃)。It means that the residue adsorption absorbability to these metals could be improved.
其次,使用现在通行的BCR (Community Bureau of Reference)法对污泥和热解残渣中这四种金属形态进行提取,然后利用AAS分析各个形态的含量。污泥中金属铜、镉、铅具有很大的潜在环境风险,因为每种金属的前三种形态分别占总量80%以上,其生物可利用性和环境毒性不可忽视。污泥中的锌的可交换态和可还原态的含量较高但部分可交换态的锌将会被土壤中的无机物晶格封闭而很稳定对环境无毒性,所以其生物有效性可能被高估。这四种金属的四种形态和热解温度的相关系数绝对值都没有超过0.8,有一半以上的相关系数都小于0.5,有些相关系数甚至小于0.3。所以,当热解温度不超过700℃时,能量还不足以打开上述四种金属形态的结合力,所以热解温度对残渣中的金属形态分布影响不大。
最后,污泥和热解残渣中的金属的滤出性通过优化的有毒物质滤出性检测方法(TCLP)进行测定。热解残渣中金属镉、铜、铅、锌的TCLP浓度分别在400℃,350℃,500℃,550℃的时候达到最大值0.74mg/L,15.69mg/L,10.25mg/L,85.63mg/L。分别达到这个极值以后,热解残渣中它们的TCLP浓度就会随着热解温度上升而迅速下降,这是因为其一,在污泥中金属大部分是以有机螯合物的形式存在的,当热解温度升高致使有机螯合物的链断裂,金属离子释放出来,所以随着热解温度的增加,金属的滤出性也随着增强。但是达到一定温度以后金属又被晶格化而固定在灰分品格中,所以金属的滤出性极大的降低了。其二,热解过程中pH值随着热解温度升高而升高,其对H+的缓冲性也极大提高,这个也是导致金属TCLP浓度变化的另一个原因。其三,除650℃外,热解残渣的比表面积随着热解温度的升高热解残渣的比表面积逐渐缓慢上升(热解温度是700℃的时候,其比表面积达到33m3/g)。热解残渣中比表面积升高,其对重金属离子吸附能力增强也是热解残渣中的金属TCLP浓度变化的一个重要原因。
The present study focuses on the total content and speciation of Cu, Zn, Pb, Cd in the sewage sludge and the in the pyrolysis residues obtained at different temperatures. The influence that the pyrolysis temperature exerts on the speciation distribution and the leachability of these metals in the residues was evaluated. At first, Atomic Adsorption Spectrometry was (AAS) was employed to analyze the total concentration of the heavy metals in the sludge and the residues. The concentration of Zn (2104.8mg/kg) in the sludge was beyond the permitted value which is stipulated in Control standards for pollutants in sludges from agricultural use. The concentration of Cd (5.2mg/kg) and Cu (312.3mg/kg) were beyond the permitted value when the sludge was applied to the soil with pH<6.5. The concentration of Zn in the sludge was lower than the permitted values. When it came to the residues, the same conclusion could be attained except Cd in the residue produced during the pyrolysis at the temperature of 700℃.
Secondly, BCR (Community Bureau of Reference) was used to extract the speciation of these metals and AAS was used to determine the concentration of these speciation. Cu, Cd, Pd in the sludge have great potential environment risk because the sum of the first three speciation accounts for 80%. Their bio-availability and toxicity can not be neglected. The sum of the first two speciation of Zn in the sludge is high. However some of exchangeable speciation can be fixed in the inorganic crystal lattice and pose no toxicity to the environment, so its bioavailability may be overestimated. All the absolute value of correlation coefficients between pyrolysis temperatures and the fractions of Cd, Cu, Pb, Zn in the residues are far less than 0.8 which is the minimum of high correlation. More than half of these correlation coefficients were below 0.5 and some were even below 0.3. The pyrolysis temperatures didn't effectively contribute to the distribution of metal speciation in the residues when the temperature was below 700℃, because the energy was not high enough to break the bonds.
At last, modified Toxicity Characteristic Leaching Procedure was applied to determine the leachability of these metals in the sludge and residues. TCLP concentrations of Cd, Cu, Pb, Zn maximized at 0.74mg/L,15.69mg/L,10.25mg/L, 85.63mg/L at 400℃,350℃,500℃,550℃respectively. When the temperatures exceeded those points, the TCLP concentrations declined sharply. There are three reasons:Firstly, the heavy metals exist in organic chelate, with the increase of the temperature, a lot of chelate bonds were easily to break, and the metal ions can be released in the test. However, when the temperature came to some points, these metals can be fixed in the ash crystal lattice and hardly to release in the test. Secondly, the pH rose in the residues with the increasing of the temperature. So the pH buffering capacity of the residues is the other reason for the change of TCLP concentration of the metals. Thirdly, the BET surface of the residues increased when the temperature increased except 650℃(it rose to 33m3/g when the temperature got to 700℃)。It means that the residue adsorption absorbability to these metals could be improved.
引文
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