铬污染土壤特性表征与陶粒制备机制
摘要
随着城市化进程的加快，大量企业搬出主城区，其遗留下来的被污染的场地成为了阻碍城市建设的难题。在众多的重金属污染中，铬污染因具有致癌致畸效应而备受关注。目前我国尚处于铬渣治理的扫尾阶段，铬污染场地的治理与修复才刚刚起步。因此，对铬污染土壤处理或利用的研究将具有重要的意义。
文章成功结合陶粒焙烧和干法解毒工艺的特点，将铬污染土壤与解毒剂混合，高温下得到一种新颖的铬污染土壤资源化利用方法。文章完成了从土壤采样到产品利用的全过程研究，主要内容包括：场地调查与评价、典型铬污染土壤的特性表征分析、处理或利用方式筛选、解毒剂选择、陶粒烧制小试实验、烧制工艺优化过程、烧制机理分析、中试实验，陶粒产品检测与运用等。
以民丰化工原厂址区为研究对象，布点采样核实研究区的污染程度，运用潜在生态风险和健康风险评价方法评价场地的风险程度并确定修复限值。选取高浓度的铬污染土壤，通过XRF、FT-IR、XRD、激光粒径分析、表面积测试与孔径分析、TG-DSC综合热分析法等技术研究其理化性能及热力学特性；运用毒性浸出、分步提取、热灼烧等方法分析土壤重金属特性；据此筛选合适的铬污染土壤处理或利用方式。
选用粉煤灰、煤矸石和污泥等常见固废作为解毒剂混合土壤烧制陶粒，详细分析三种解毒剂性能；通过单因素实验分析烧成工艺对陶粒Cr(VI)浸出浓度、颗粒强度、表观密度和1h吸水率的影响；通过正交实验优化烧成工艺并用有约束的均匀设计方法对陶粒原料配比进行二次优化；开展陶粒生产的中试实验；全面分析了陶粒产品的建材特性品质和环境安全性指标；并对陶粒应用做了尝试。
根据烧成动力学理论分析陶粒烧成机理，根据胚料物质主要热反应特征建立热反应动力学模型并求解最概然机理函数。利用XEM和EDS观察陶粒产品表面、剖面的微观结构特征；利用FT-IR、XRD等技术手段研究陶粒形成和铬固化机理。
通过以上各方面的研究得到以下主要结论：
①研究区绝大部分为重度污染，土壤不能达到HJ305-2007中II级土壤要求；土壤潜在生态风险评价发现31.3%的土壤样品具有高生态风险；健康风险评价结果表明研究区土壤可能对敏感人群造成致癌和非致癌影响；研究区铬修复限值为：Cr(Ⅲ)8621.8mg/kg，Cr(VI)5.3mg/kg。
②供试土壤以中小颗粒为主，多孔结构不明显，吸附性不强；土壤富含SiO_2、Al_2O_3、Fe_2O_3等成分，主要晶体类型为α-石英相；土壤基本不具备热性能；总铬含量1726.3mg/kg，Cr(VI)浸出浓度60.25mg/L，是一种具备浸出毒性但不具备腐蚀性的危险废物；铬的结合形态排序为残渣态>弱酸提取态>可还原态>可氧化态；通过土壤处理方案筛选，确定干法解毒方案比淋洗和水泥固化更具有优越性。
③粉煤灰、煤矸石和污泥作为解毒剂富含SiO_2、Al_2O_3等成陶成分，含有残余碳粉或有机物成分，能在高温条件下产生CO等还原性气体使Cr(VI)还原并促使陶粒膨胀；三种添加剂的烧失量分别为5.97%、28.60%、33.24%；TG-DSC曲线表明三种材料均在空气氛围、不同升温速率下存在一个主要的热失重阶段。
④实验获得三种陶粒产品和相应的最佳工艺条件。实验表明温度为影响产品性能的主要条件，污泥添加量对陶粒产品性能有显著影响；铬污染土壤-煤矸石陶粒因易在空气中潮解，故被淘汰。运用有约束配方均匀混料法优化原料配方，得最佳原材料配比为：铬污染土壤75.1%，粉煤灰18.7%，污泥6.2%。
⑤胚料热反应过程依次经历了自由水挥发、有机物燃烧、碳酸盐受热分解、残留碳份氧化、金属氧化物熔融等过程。分析认为30K/min为烧制陶粒的最佳升温速率。整体而言，陶粒胚料在不同温度下衍射峰位置无明显差异，对比陶粒剖面和表面的微观形貌发现，烧制过程中仅有陶粒表面有新物相生成。陶粒胚料最终生成链状或骨架状结构的硅酸盐和硅铝酸盐，烧成过程中有大量玻璃化物质生成。球形对称相界反应R3机理函数为陶粒烧成反应的最概然机理函数。通过拟合计算，得该函数的动力学三因子Ea=214.37kJ/mol，A=4.80E+06(s~(-1))，G(a)=1-(1-a)~(1/3)。
⑥总结重金属铬的固化机理为：在超过800℃时Cr(VI)被C、CO等还原为Cr(Ⅲ)；热处理温度大于900℃时，Cr(Ⅲ)可能进入粘土Si-Al-O网状结构；高温下Cr(Ⅲ)氧化物与原料中的硅氧化物、铝氧化物充分接触生成NaCrSi_2O_6或CaCrAlSiO_6等稳定的固熔体；由于Fe(Ⅲ)、Cr(Ⅲ)与Al(Ⅲ)的半径相近，电荷相同，在高温条件下容易发生类质同相作用而形成一系列化合物；玻璃态物质对Cr(VI)起到有效的固定作用，也防止Cr(Ⅲ)物质被再次氧化。
⑦利用回转窑进行中试实验，确定烧制陶粒的最优烧制条件为：铬污染土壤:粉煤灰:污泥=75.1:18.7:6.2，窑预热温度350℃，烧成温度1120℃，烧成温度保持时间2min。以此条件制得的陶粒，Cr(VI)浸出浓度0.065mg/L，颗粒强度540N，堆积密度530kg/m~3，1h吸水率7.2%，其他性能满足轻集料标准要求。陶粒的重金属浸出特性检测结果表明陶粒浸出液中各项重金属含量均远低于危险废物鉴别标准(GB/T5083.3-2007)、污水综合排放标准(GB8978-1996)、填埋标准(GB16889-2008)所规定的浓度限值，不会对环境造成二次污染，具有环境安全性。
With the rapid development of urbanization, a large number of companies movedout of the city, leaving the contaminated soil as a big problem for city construction.Among the heavy mental pollution, chromium pollution gained more attention becauseof its carcinogenic and teratogenic effects. To date, China is in the “mop-up stage” ofchromium disposal; and the remediation of chromium contaminated sites has just begun.Therefore, it would be of great significance to study the treatment or utilization ofchromium contaminated sites.
In this paper, the study centers on the collection of chromium contaminated soilsamples and their utilization. The main contents include: surveying and evaluatingselected sites, analyzing characteristics of typical chromium contaminated soil samples,screening disposal or treatment methods, selecting antidote, making ceramsite,optimizing the firing process, analyzing the firing mechanism, the mid-experiment ofsintering ceramsite, testing and applying the ceramsite products, and so forth.
The original site of Mingfeng Chemical Factory was chosen as the research area,and the pollution degree was assessed by verifying the samples collected from the studyarea. The potential ecological risk assessment and health risk assessment wereintroduced to determine the risk degree of the selected site as well as to obtain thelimited values for restoring. Afterwards, high concentrations of chromium contaminatedsoils was selected to delve into their physical and chemical properties and kineticcharacteristics of thermal reaction by way of X-ray diffraction analysis, Fourier infraredspectroscopy analysis, laser particle size analysis, static nitrogen absorption BET andpore size analysis, atomic absorption spectrophotometry, and TG-DSC method.Characteristics of heavy metals were analyzed by TCLP, step by step extraction, andthermal sintering method, thereby determining the appropriate disposal or treatmentmethods for chromium contaminated soils.
Fly coal ash, coal gangue, and sludge were chosen as the antidote; and theirphysical and chemical characteristics were analyzed. The single factor experiment wasconducted to analyze raw material ratios, sintering temperature, sintering time, Cr (VI)leaching concentration, particle strength, surface particle density and one-hour waterabsorption, and so on. Sintering process of ceramsite was optimized by orthogonalexperimental design. Thereafter, the second optimization of ceramsite raw material ratio was conducted by uniform design method based on the advantages and disadvantages ofceramsite. The evolution of ceramsite was simulated by a quadratic polynomialnonlinear fitting, according to the most probable mechanism function. The mechanismof ceramsite formation and chromium solidification were studied by observing thesurface and the microscopic structural characteristics with X-ray micro-spectroscopyscanning electron microscope.
The results are shown as follows：
Most of the research areas were heavily polluted. The soil quality cannot meet theHJ305-2007and also cannot used as stadium land, green land, commercial land, andpublic municipal land. In potential ecological risk assessment,31.3%of soil sampleshad high ecological risks. In health risk assessment, all HQ and CR values exceeded thethreshold, posing a great threat to human health. The repair limit values of Cr (III) andCr (VI) were8621.8and5.3mg/kg, respectively.
Most soil in study area was small or mid-sized. The pore was large and had nostrong absorption, and its structure was inconspicuous. Soil was rich in SiO_2, Al_2O_3, andFe_2O_3. The main crystal type was quartz, and did not have thermal properties. The totalchromium content was1726.3mg/kg, and the leaching concentration of Cr (VI) was60.25mg/l, indicating that it is not a hazardous waste. Chromium migrated easily in thesoil, with residual> weak acid extractable> reducible> oxidisable. The dryingdetoxification programs had more advantages than leaching and cement solidificationby comparing the disposal method of soil.
Additives of fly coal ash, coal gangue and sludge were rich in SiO_2, Al_2O_3, tonerresidual and organic ingredients, generated CO under high temperature to deoxygenizeCr (VI), and eventually promote the expansion of ceramsite. The losses of threeadditives were5.97%,28.60%, and33.24%, respectively. TG-DSC curves evinced thatthere was a major phase of thermal loss at atmospheric conditions or different heatingrates.
The optimal process conditions for sintering ceramsite of chromium contaminatedsoils and fly coal ash were25%of fly coal ash addition, the temperature of1120℃, andsintering time of10min. The characteristics of ceramsite were as follows: the leachingconcentration of Cr (VI) was0.042mg/l; the strength of particle was600N; the densityof particle was1.19g/cm3; one-hour water absorption was15.2%. Similarly, the optimalprocess conditions for sintering ceramsite of chromium contaminated soils and sludgewere12%of sludge addition, the temperature of1030℃, and sintering time of10min, with0.067mg/l leaching concentration,440N particle strength,1.08g/cm3particledensity, and20.2%one-hour water absorption. Temperature was the main factor forsintering ceramsite of chromium contaminated soils and fly coal ash, while both thecontent of sludge addition and sintering temperature were important for sinteringceramsite of chromium contaminated soils and sludge. Furthermore, ceramsite ofchromium contaminated soils and coal gangue was abandoned for its deliquescent.
The constraint mixing method was introduced to optimize the raw material ratios.The results indicated that75.1%of chromium contaminated soil,18.7%of fly ash, and6.2%sludge; the total heat loss rate of ceramsite billet decreased with the heating rateincreased, while the peak temperature of DSC curves increased as the heating rateincreased. The thermal reaction of the billet involved water volatilization, combustionof organic compounds, thermal decomposition of carbonate, oxidation of residualcarbon, and melting process of metal oxides. The increase of heating rate was conduciveto reducing the ceramsite quality. More intense reaction between the components of thebillet was good for firing ceramsite.30K/min was generally considered as the optimalheating rate for sintering ceramisite.
The diffraction peaks of ceramsite billet had no significant difference at differenttemperatures, signifying that very few new substances were generated during thesintering process. However, the contents of each phase were quite different as thetemperature increased, and a large number of amorphous materials were produced at1150℃. After sintering, SiO_2, metal or nonmetal oxide, silicon oxide in themontmorillonite clay, and aluminum oxide in ceramsite billet reacted to generate a chainor skeleton-like structure of silicate. Meanwhile, other chemical groups have all beendestroyed. R3mechanism function was the most probable mechanism function forsintering ceramsite. Three kinetic factors of fitting equation were Ea=214.37kJ/mol,A=4.80E+06(s~(-1)), and G (a)=1-(1-a)~(1/3).
The mechanism of chromium solidification was as follows. Cr (VI) wasdeoxygenize by C and CO at the temperature of more than800℃. Cr (Ⅲ) may enterSi-Al-O structure of clay when temperature was greater than900℃. Cr (Ⅲ) oxide andsilicon and aluminum oxide in raw material would generate NaCrSi_2O_6or CaCrAlSiO_6.Fe (Ⅲ), Cr (Ⅲ), and Al (Ⅲ) have similar radius and same charge. Glassy substances ofCr (VI) can not only play a fixed role, but also prevent re-oxidation of Cr (Ⅲ)substances.
Rotary kiln experiment was conducted to determine the optimum sintering conditions for sintering ceramsite. The optimum conditions were as follows:Temperature of kiln preheating is350℃, the sintering temperature was1120℃, and thehold time was2min. The characteristics of ceramsite were0.065mg/l Cr (VI) leachingconcentration,540N particle strength,530kg/m~3particle density,7.2%one-hour waterabsorption, meeting the standards of lightweight aggregate. Results of leaching heavymetals shown that heavy metals in ceramsite leaching solution were much lower thanthe hazardous waste identification standards (GB/T5083.3-2007), wastewater dischargestandard (GB8978-1996), and landfill standards (GB16889-2008), revealing theirenvironmental safety.
文章成功结合陶粒焙烧和干法解毒工艺的特点，将铬污染土壤与解毒剂混合，高温下得到一种新颖的铬污染土壤资源化利用方法。文章完成了从土壤采样到产品利用的全过程研究，主要内容包括：场地调查与评价、典型铬污染土壤的特性表征分析、处理或利用方式筛选、解毒剂选择、陶粒烧制小试实验、烧制工艺优化过程、烧制机理分析、中试实验，陶粒产品检测与运用等。
以民丰化工原厂址区为研究对象，布点采样核实研究区的污染程度，运用潜在生态风险和健康风险评价方法评价场地的风险程度并确定修复限值。选取高浓度的铬污染土壤，通过XRF、FT-IR、XRD、激光粒径分析、表面积测试与孔径分析、TG-DSC综合热分析法等技术研究其理化性能及热力学特性；运用毒性浸出、分步提取、热灼烧等方法分析土壤重金属特性；据此筛选合适的铬污染土壤处理或利用方式。
选用粉煤灰、煤矸石和污泥等常见固废作为解毒剂混合土壤烧制陶粒，详细分析三种解毒剂性能；通过单因素实验分析烧成工艺对陶粒Cr(VI)浸出浓度、颗粒强度、表观密度和1h吸水率的影响；通过正交实验优化烧成工艺并用有约束的均匀设计方法对陶粒原料配比进行二次优化；开展陶粒生产的中试实验；全面分析了陶粒产品的建材特性品质和环境安全性指标；并对陶粒应用做了尝试。
根据烧成动力学理论分析陶粒烧成机理，根据胚料物质主要热反应特征建立热反应动力学模型并求解最概然机理函数。利用XEM和EDS观察陶粒产品表面、剖面的微观结构特征；利用FT-IR、XRD等技术手段研究陶粒形成和铬固化机理。
通过以上各方面的研究得到以下主要结论：
①研究区绝大部分为重度污染，土壤不能达到HJ305-2007中II级土壤要求；土壤潜在生态风险评价发现31.3%的土壤样品具有高生态风险；健康风险评价结果表明研究区土壤可能对敏感人群造成致癌和非致癌影响；研究区铬修复限值为：Cr(Ⅲ)8621.8mg/kg，Cr(VI)5.3mg/kg。
②供试土壤以中小颗粒为主，多孔结构不明显，吸附性不强；土壤富含SiO_2、Al_2O_3、Fe_2O_3等成分，主要晶体类型为α-石英相；土壤基本不具备热性能；总铬含量1726.3mg/kg，Cr(VI)浸出浓度60.25mg/L，是一种具备浸出毒性但不具备腐蚀性的危险废物；铬的结合形态排序为残渣态>弱酸提取态>可还原态>可氧化态；通过土壤处理方案筛选，确定干法解毒方案比淋洗和水泥固化更具有优越性。
③粉煤灰、煤矸石和污泥作为解毒剂富含SiO_2、Al_2O_3等成陶成分，含有残余碳粉或有机物成分，能在高温条件下产生CO等还原性气体使Cr(VI)还原并促使陶粒膨胀；三种添加剂的烧失量分别为5.97%、28.60%、33.24%；TG-DSC曲线表明三种材料均在空气氛围、不同升温速率下存在一个主要的热失重阶段。
④实验获得三种陶粒产品和相应的最佳工艺条件。实验表明温度为影响产品性能的主要条件，污泥添加量对陶粒产品性能有显著影响；铬污染土壤-煤矸石陶粒因易在空气中潮解，故被淘汰。运用有约束配方均匀混料法优化原料配方，得最佳原材料配比为：铬污染土壤75.1%，粉煤灰18.7%，污泥6.2%。
⑤胚料热反应过程依次经历了自由水挥发、有机物燃烧、碳酸盐受热分解、残留碳份氧化、金属氧化物熔融等过程。分析认为30K/min为烧制陶粒的最佳升温速率。整体而言，陶粒胚料在不同温度下衍射峰位置无明显差异，对比陶粒剖面和表面的微观形貌发现，烧制过程中仅有陶粒表面有新物相生成。陶粒胚料最终生成链状或骨架状结构的硅酸盐和硅铝酸盐，烧成过程中有大量玻璃化物质生成。球形对称相界反应R3机理函数为陶粒烧成反应的最概然机理函数。通过拟合计算，得该函数的动力学三因子Ea=214.37kJ/mol，A=4.80E+06(s~(-1))，G(a)=1-(1-a)~(1/3)。
⑥总结重金属铬的固化机理为：在超过800℃时Cr(VI)被C、CO等还原为Cr(Ⅲ)；热处理温度大于900℃时，Cr(Ⅲ)可能进入粘土Si-Al-O网状结构；高温下Cr(Ⅲ)氧化物与原料中的硅氧化物、铝氧化物充分接触生成NaCrSi_2O_6或CaCrAlSiO_6等稳定的固熔体；由于Fe(Ⅲ)、Cr(Ⅲ)与Al(Ⅲ)的半径相近，电荷相同，在高温条件下容易发生类质同相作用而形成一系列化合物；玻璃态物质对Cr(VI)起到有效的固定作用，也防止Cr(Ⅲ)物质被再次氧化。
⑦利用回转窑进行中试实验，确定烧制陶粒的最优烧制条件为：铬污染土壤:粉煤灰:污泥=75.1:18.7:6.2，窑预热温度350℃，烧成温度1120℃，烧成温度保持时间2min。以此条件制得的陶粒，Cr(VI)浸出浓度0.065mg/L，颗粒强度540N，堆积密度530kg/m~3，1h吸水率7.2%，其他性能满足轻集料标准要求。陶粒的重金属浸出特性检测结果表明陶粒浸出液中各项重金属含量均远低于危险废物鉴别标准(GB/T5083.3-2007)、污水综合排放标准(GB8978-1996)、填埋标准(GB16889-2008)所规定的浓度限值，不会对环境造成二次污染，具有环境安全性。
With the rapid development of urbanization, a large number of companies movedout of the city, leaving the contaminated soil as a big problem for city construction.Among the heavy mental pollution, chromium pollution gained more attention becauseof its carcinogenic and teratogenic effects. To date, China is in the “mop-up stage” ofchromium disposal; and the remediation of chromium contaminated sites has just begun.Therefore, it would be of great significance to study the treatment or utilization ofchromium contaminated sites.
In this paper, the study centers on the collection of chromium contaminated soilsamples and their utilization. The main contents include: surveying and evaluatingselected sites, analyzing characteristics of typical chromium contaminated soil samples,screening disposal or treatment methods, selecting antidote, making ceramsite,optimizing the firing process, analyzing the firing mechanism, the mid-experiment ofsintering ceramsite, testing and applying the ceramsite products, and so forth.
The original site of Mingfeng Chemical Factory was chosen as the research area,and the pollution degree was assessed by verifying the samples collected from the studyarea. The potential ecological risk assessment and health risk assessment wereintroduced to determine the risk degree of the selected site as well as to obtain thelimited values for restoring. Afterwards, high concentrations of chromium contaminatedsoils was selected to delve into their physical and chemical properties and kineticcharacteristics of thermal reaction by way of X-ray diffraction analysis, Fourier infraredspectroscopy analysis, laser particle size analysis, static nitrogen absorption BET andpore size analysis, atomic absorption spectrophotometry, and TG-DSC method.Characteristics of heavy metals were analyzed by TCLP, step by step extraction, andthermal sintering method, thereby determining the appropriate disposal or treatmentmethods for chromium contaminated soils.
Fly coal ash, coal gangue, and sludge were chosen as the antidote; and theirphysical and chemical characteristics were analyzed. The single factor experiment wasconducted to analyze raw material ratios, sintering temperature, sintering time, Cr (VI)leaching concentration, particle strength, surface particle density and one-hour waterabsorption, and so on. Sintering process of ceramsite was optimized by orthogonalexperimental design. Thereafter, the second optimization of ceramsite raw material ratio was conducted by uniform design method based on the advantages and disadvantages ofceramsite. The evolution of ceramsite was simulated by a quadratic polynomialnonlinear fitting, according to the most probable mechanism function. The mechanismof ceramsite formation and chromium solidification were studied by observing thesurface and the microscopic structural characteristics with X-ray micro-spectroscopyscanning electron microscope.
The results are shown as follows：
Most of the research areas were heavily polluted. The soil quality cannot meet theHJ305-2007and also cannot used as stadium land, green land, commercial land, andpublic municipal land. In potential ecological risk assessment,31.3%of soil sampleshad high ecological risks. In health risk assessment, all HQ and CR values exceeded thethreshold, posing a great threat to human health. The repair limit values of Cr (III) andCr (VI) were8621.8and5.3mg/kg, respectively.
Most soil in study area was small or mid-sized. The pore was large and had nostrong absorption, and its structure was inconspicuous. Soil was rich in SiO_2, Al_2O_3, andFe_2O_3. The main crystal type was quartz, and did not have thermal properties. The totalchromium content was1726.3mg/kg, and the leaching concentration of Cr (VI) was60.25mg/l, indicating that it is not a hazardous waste. Chromium migrated easily in thesoil, with residual> weak acid extractable> reducible> oxidisable. The dryingdetoxification programs had more advantages than leaching and cement solidificationby comparing the disposal method of soil.
Additives of fly coal ash, coal gangue and sludge were rich in SiO_2, Al_2O_3, tonerresidual and organic ingredients, generated CO under high temperature to deoxygenizeCr (VI), and eventually promote the expansion of ceramsite. The losses of threeadditives were5.97%,28.60%, and33.24%, respectively. TG-DSC curves evinced thatthere was a major phase of thermal loss at atmospheric conditions or different heatingrates.
The optimal process conditions for sintering ceramsite of chromium contaminatedsoils and fly coal ash were25%of fly coal ash addition, the temperature of1120℃, andsintering time of10min. The characteristics of ceramsite were as follows: the leachingconcentration of Cr (VI) was0.042mg/l; the strength of particle was600N; the densityof particle was1.19g/cm3; one-hour water absorption was15.2%. Similarly, the optimalprocess conditions for sintering ceramsite of chromium contaminated soils and sludgewere12%of sludge addition, the temperature of1030℃, and sintering time of10min, with0.067mg/l leaching concentration,440N particle strength,1.08g/cm3particledensity, and20.2%one-hour water absorption. Temperature was the main factor forsintering ceramsite of chromium contaminated soils and fly coal ash, while both thecontent of sludge addition and sintering temperature were important for sinteringceramsite of chromium contaminated soils and sludge. Furthermore, ceramsite ofchromium contaminated soils and coal gangue was abandoned for its deliquescent.
The constraint mixing method was introduced to optimize the raw material ratios.The results indicated that75.1%of chromium contaminated soil,18.7%of fly ash, and6.2%sludge; the total heat loss rate of ceramsite billet decreased with the heating rateincreased, while the peak temperature of DSC curves increased as the heating rateincreased. The thermal reaction of the billet involved water volatilization, combustionof organic compounds, thermal decomposition of carbonate, oxidation of residualcarbon, and melting process of metal oxides. The increase of heating rate was conduciveto reducing the ceramsite quality. More intense reaction between the components of thebillet was good for firing ceramsite.30K/min was generally considered as the optimalheating rate for sintering ceramisite.
The diffraction peaks of ceramsite billet had no significant difference at differenttemperatures, signifying that very few new substances were generated during thesintering process. However, the contents of each phase were quite different as thetemperature increased, and a large number of amorphous materials were produced at1150℃. After sintering, SiO_2, metal or nonmetal oxide, silicon oxide in themontmorillonite clay, and aluminum oxide in ceramsite billet reacted to generate a chainor skeleton-like structure of silicate. Meanwhile, other chemical groups have all beendestroyed. R3mechanism function was the most probable mechanism function forsintering ceramsite. Three kinetic factors of fitting equation were Ea=214.37kJ/mol,A=4.80E+06(s~(-1)), and G (a)=1-(1-a)~(1/3).
The mechanism of chromium solidification was as follows. Cr (VI) wasdeoxygenize by C and CO at the temperature of more than800℃. Cr (Ⅲ) may enterSi-Al-O structure of clay when temperature was greater than900℃. Cr (Ⅲ) oxide andsilicon and aluminum oxide in raw material would generate NaCrSi_2O_6or CaCrAlSiO_6.Fe (Ⅲ), Cr (Ⅲ), and Al (Ⅲ) have similar radius and same charge. Glassy substances ofCr (VI) can not only play a fixed role, but also prevent re-oxidation of Cr (Ⅲ)substances.
Rotary kiln experiment was conducted to determine the optimum sintering conditions for sintering ceramsite. The optimum conditions were as follows:Temperature of kiln preheating is350℃, the sintering temperature was1120℃, and thehold time was2min. The characteristics of ceramsite were0.065mg/l Cr (VI) leachingconcentration,540N particle strength,530kg/m~3particle density,7.2%one-hour waterabsorption, meeting the standards of lightweight aggregate. Results of leaching heavymetals shown that heavy metals in ceramsite leaching solution were much lower thanthe hazardous waste identification standards (GB/T5083.3-2007), wastewater dischargestandard (GB8978-1996), and landfill standards (GB16889-2008), revealing theirenvironmental safety.
引文
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