铬渣的热解无害化处理

采用热解工艺无害化处理铬渣,探讨了稻秆在铬渣无害化处理中的作用.研究了热解温度、稻秆与铬渣质量比、铬渣粒径及保温时间对铬渣热解无害化处理的影响,并分析了热解前后热解产物中铬元素形态的变化.结果表明,热解工艺能有效地将铬渣中Cr(Ⅵ)还原,稻秆热解过程中产生的气相挥发分对Cr(Ⅵ)的还原起核心作用.较为适宜的热解条件:热解温度为400 ℃,稻秆与铬渣质量比为0.10,铬渣粒径<2 000 μm,保温时间为10 min.在该热解条件处理下,热解产物中的Cr(Ⅵ)质量浓度为121 mg/kg,低于热解前铬渣中的Cr(Ⅵ)(3 400 mg/kg).热解后,可交换态及碳酸盐结合态铬含量降低,大部分铬转化成了稳定的有机结合态和残渣态,极大地降低了铬渣的危害.第一作者:张大磊,男,1982生,博士研究生,研究方向为固体废弃物热处理.     

Effect of pyrolysis and oxidation characteristics on lauric acid and stearic acid dust explosion hazards

The effect of pyrolysis and oxidation characteristics on the explosion sensitivity and severity parameters, including the minimum ignition energy MIE, minimum ignition temperature MIT, minimum explosion concentration MEC, maximum explosion pressure P_max, maximum rate of pressure rise (dP/dt)_max and deflagration index K_st, of lauric acid and stearic acid dust clouds was experimentally investigated. A synchronous thermal analyser was used to test the particle thermal characteristics. The functional test apparatuses including the 1.2 L Hartmann-tube apparatus, modified Godbert-Greenwald furnace, and 20 L explosion apparatus were used to test the explosion parameters. The results indicated that the rapid and slow weight loss processes of lauric acid dust followed a one-dimensional diffusion model (D1 model) and a 1.5 order chemical reaction model (F1.5 model), respectively. In addition, the rapid and slow weight loss processes of stearic acid followed a 1.5 order chemical reaction model (F1.5 model) and a three-dimensional diffusion model (D3 model), respectively, and the corresponding average apparent activation energy E and pre-exponential factor A were larger than those of lauric acid. The stearic acid dust explosion had higher values of MIE and MIT, which were mainly dependent on the higher pyrolysis and oxidation temperatures and the larger apparent activation energy E determining the slower rate of chemical bond breakage during pyrolysis and oxidation. In contrast, the lauric acid dust explosion had a higher MEC related to a smaller pre-exponential factor A with a lower amount of released reaction heat and a lower heat release rate during pyrolysis and oxidation. Additionally, due to the competition regime of the higher oxidation reaction heat release and greater consumption of oxygen during explosion, the explosion pressure P_m of the stearic acid dust was larger in low concentration ranges and decayed to an even smaller pressure than with lauric acid when the concentration exceeded 500 g/m³. The rate of explosion pressure rise (dP/dt)_m of the stearic acid dust was always larger in the experimental concentration range. The stearic acid dust explosion possessed a higher P_max, (dP/dt)_max and K_st mainly because of a larger pre-exponential factor A related to more active sites participating in the pyrolysis and oxidation reaction. Consequently, the active chemical reaction occurred more violently, and the temperature and overpressure rose faster, indicating a higher explosion hazard class for stearic acid dust.     

城市生活垃圾热解产气特性的试验研究

在外热式固定床试验台上,针对城市生活垃圾中的典型组分,进行了不同条件下的热解试验研究。试验测量不同条件下产物的产气量和产气速率,分析了热解气的组分和气体热值。分析发现,物料的挥发分、加热方式以及热解终温等对产气影响大,随温度的增加产气中H2含量逐渐增多,C2H4和C2H6的含量逐渐下降,气体热值有一个最大值。     

聚氨酯泡沫材料阴燃发展过程的特性分析

分析对比了相同加热条件下的聚氨酯泡沫材料在有氧和无氧气氛下的升温过程,并对不同加热条件下的聚氨酯泡沫材料的阴燃传播速度进行研究.结果表明:沿着反应进行的方向,分离点的温度越来越低,不同热流条件下的温度分离曲线斜率在实验稳定发展段的变化规律表现得很相似,并在分离点出现后,有氧气氛中的该位置温度在短时间内急剧上升;在阴燃不稳定传播阶段时,热解前锋的速度小于氧化前锋的速度,在稳定传播阶段时,热解前锋速度与氧化前锋速度近乎相等.     

Cr(Ⅵ)污染土壤的热解还原无害化处理

提出了用热解还原法对含铬土壤进行无害化处理的新技术,研究了热解温度、热解时间及土壤有机质对铬无害化处理的影响,分析了热解前后土壤中铬的元素形态的变化.同时还探讨了热解还原过程中Cr(Ⅵ)的无害化机制.结果表明,土壤中的有机质在热解还原过程中产生的挥发分对Cr(Ⅵ)的无害化起核心作用;在200～600℃范围内,Cr(Ⅵ)的还原量随着热解温度升高而增大,500.0℃最适合于经济有效地实现Cr(Ⅵ)的热解还原处理;Cr(Ⅵ)的热解还原过程较快.铬的形态分析结果表明,热解后可交换态和碳酸盐结合态铬量大大降低,大部分铬转化成了活性低的残渣态,极大地降低了铬的危害.     

污水污泥裂解及其性能的研究

以碘吸附值为裂解残渣吸附性能的指标,通过单因素实验和正交实验,确定了制备裂解残渣的最佳工艺条件,并对残渣的表面元素组成、孔结构组成、晶相组成和吸附性能等性质进行了表征。结果显示：以浓度均为5 mol/L的ZnCl₂和H₂SO₄作活化剂、复配比2∶1、活化温度600℃、活化时间1 h、固液比1∶2.5,制得的裂解残渣酸洗后碘值平均值可达892.8 mg/g;用制备的裂解残渣对苯酚废水进行处理,室温下振荡5 min,苯酚去除率即可达到87.9%,且符合Langmuir吸附等温线方程和Freundlich吸附等温线方程。     

生活垃圾催化热解液体产物特性

为探索生活垃圾催化热解液体产物特性变化规律,选取Na2CO3、CaO、Fe2O33种催化剂,利用固定床实验、红外分析(FT-IR)进行生活垃圾热解液体产物产率和组分特性研究.结果表明,热解终温600℃无催化剂时,生活垃圾热解液产率为39.80 wt％,添加3种催化剂后热解液产率均降低;生活垃圾分别添加1％的Na2CO3和CaO后,热解油氧含量由22.49％分别降低到20.12％和18.53％,低位热值由30.30 MJ/kg分别提高到33.79和32.74 MJ/kg;无催化剂时热解油成分为脂肪类、含氧化合物及少量芳香类混合物,加催化剂后热解油中芳香类物质峰面积比例显著增加,而含氧化合物峰面积比例降低,羟基类及羧酸类含氧化合物峰面积比例明显减少,其他含氧物峰面积比例却增加;CaO催化效果较明显,生活垃圾添加1％的CaO热解油中芳香类物质峰面积比例从4.36％增加到29.46％,含氧化合物峰面积比例由49.42％降低到23.12％,其中羟基类和羧酸类化合物峰面积比例分别由34.03％和10.65％降低到0.00％和3.34％,其他含氧化合物峰面积比例由4.73％增加到19.77％.     

微波辐射对生物质热解过程的影响

自行设计加工了微波热重实验装置,研究了在微波辐射下菜籽粕热解过程特征及其产物产出规律.在此基础上,对比分析了菜籽粕微波热解与电热热解产物产出率之间的差异.结果发现,在菜籽粕微波热解过程中,半纤维素的反应区间为180 ～ 370℃,其转化率可以达到87.0％;纤维素的热解反应区间为370 ～ 550℃,其热解转化率32.8％.表明在微波作用下,纤维素的热稳定性远高于半纤维素.在菜籽粕的微波热解过程中,冷凝液的产生主要集中在100 ～400℃的温度范围内,热解得到的生物质油类主要是菜籽粕的半纤维素热解生成的.不凝气的产生主要集中在300 ～ 600℃的温度范围内,并且主要为纤维素与木质素的热解反应产生的.与电热方式相比,菜籽粕的微波热解升温速率较快,菜籽粕微波热解生物质炭的产出率较高,冷凝液产出率相对较低.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure,biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, ¹³C and 1H Nuclear Magnetic Resonance Spectrometry (¹³C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) ¹³C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

印刷线路板废弃物的热解与动力学实验研究

分别应用管式炉反应器和热重分析手段对印刷线路板废弃物的热解行为和热解动力学进行了实验研究。在管式炉中，研究不同的热解温度：700～950℃，对产物分布和气体成分分布的影响。实验结果表明：PCB热解气体的主要成分是H2和CO2，气体的热值较低，仅为2．09～5．41MJ/m^3，PCB不适合以气体产物为目标的能源利用方式。应用Friedman方法对PCB的热解动力学进行了研究，求得PCB的热解动力学参数分别是：表观活化能190．92kJ/mol，反应级数5．97，指前因子lnA47．14min^-1。