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.     

异戊醇低压热解的同步辐射真空紫外光电离质谱研究

作为新兴生物燃料,大分子醇类燃料在低压下的火灾安全基础迫切需要得到深入研究。热解过程作为火灾过程的初始阶段直接控制着火过程,火灾中碳烟颗粒的产生也依赖于热解反应,因此可燃物的低压热解研究在其低压火灾基础研究中具有重要意义。利用同步辐射真空紫外光电离质谱方法研究了异戊醇在0.2atm下的流动反应器热解,探测到了20余种热解产物,包括烯丙基自由基和C_4H_8O、C_5H_8、C_6H_6等同分异构体,并测量了其摩尔分数。基于实验结果,对燃料分解路径和主要产物的生成及消耗路径进行了探讨。与本组之前正戊醇热解实验的对比表明,由于存在支链结构,异戊醇在热解中比正戊醇更容易产生戊烯、丁烯和丙烯,但更少地产生乙烯。此外,异戊醇在热解中能够生成更多的丙炔和丙二烯等环状化合物前驱体,令其苯和1,3-环戊二烯的生成量更高,表明异戊醇比正戊醇更易于生成多环芳烃和碳烟。     

两种有机锌络合物处理棉花的霉变及热解行为研究

棉花是纺织业的重要原料,是人民群众生活不可或缺的必需品,同时也是我国进出口重要的商品。研究如何安全有效地进行棉花的储备具有十分重要的现实意义。棉纤维本身含有脂肪、蜡质和果胶等适合微生物生长繁殖的营养物质。在棉花储备中,高的回潮率会加速微生物的繁殖,进而产生热量。热量的累积会引起温度升高以及棉花霉变,不利于棉花的安全有效储存。因此,通过静电吸附法将安全无毒的有机锌络合物附着在棉纤维表面,研究表明,相同条件下,处理棉的霉变状况明显得到抑制。加速发霉条件下,未处理棉的相对于白纸的平均色差值为28.10,而双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别为5.16和5.86,下降了81.6%和79.1%。自然发霉条件下,双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别下降了53.8%和50.7%。同时研究了纯棉以及处理棉氮气下的热分解动力学,相比于未处理棉,双乙酸锌防霉处理后活化能下降了15.8%,而苯甲酸锌防霉处理后活化能下降了10.9%。此外,利用实时红外和热重红外联用技术得到了样品在热解过程中固相以及气相的裂解产物的红外谱图,发现防霉处理能一定程度上抑制棉花热解。     

定费用时尿素热解脱硝系统的可靠性研究

针对费用最小化理论在可靠性分配中的局限性,建立更切合实际的固定费用下可靠度极大化思想。将该思想运用到尿素热解脱硝系统中,针对系统结构功能特征及运行特点,深入分析各系统间逻辑功能关系,提出了完整的尿素热解脱硝系统可靠性分配模型。并引入可靠性成本预估函数,以固定费用为约束,建立数学模型,实现了系统可靠性指标的最优化分配。最后以脱硝系统为例,获得具有实际意义的数值解,证明了该方法的可用性及正确性。     

污水污泥裂解目标产物及残焦促进植物生长的研究

研究了污水污泥的低温裂解特性,考察了裂解终温和干燥到一定程度后污泥含水率对裂解产物分布及产物性质的影响,并分析了裂解产物中最合适的目标产物形式.经过分析比较,最终确定以污泥裂解残焦为目标产物并通过与普通土壤混拌进行了栽种大蒜和测试大蒜重金属浓度水平的实验,并考察残焦中重金属向植物迁移的情况.结果表明,干燥到一定程度的污水污泥在550℃下裂解时残焦的产率在40%以上,其中灰分含量在60%～65%之间,富含氮、 磷、 钾.该残焦中重金属含量符合有关土地使用规定,能明显促进大蒜植株的生长,实验组平均株高比普通组高出3～4　cm;但是快速生长的大蒜植株中重金属浓度略有增加.研究表明残焦是合适的污水污泥裂解目标产物,具有土地使用的前景,能够用于促进非食用目的的植物的生长.     

杂质对废塑料裂解产物及污染物排放的影响

从垃圾中分选出的废塑料混有大量杂质,杂质对现有废塑料裂解工艺有直接的影响.针对这一问题,对混有厨余、纸、织物和渣土等杂质的废塑料裂解产物和污染物排放进行了研究.同时检测和分析了厨余、纸、织物和沙土等常见杂质所含N、Cl、S元素向裂解油、裂解气中的迁移规律.研究表明,厨余的混入将对裂解油的产物产生严重不利影响,如热值降低至27 MJ/kg,油品的含水率高达25%以及多环芳烃含量大大提高,因而应在分选过程中除去.厨余、织物和纸张等杂质的混入导致裂解气体中污染物浓度的显著上升.渣土的混入对气体产物有有利影响,对油品无明显不利影响.     

微波诱导热解制备小麦秸秆吸附剂及响应面优化工艺研究

以氯化锌为活化剂,通过微波诱导热解法制备小麦秸秆吸附剂,并以微波功率、热解时间和氯化锌质量分数为影响因素,碘吸附值为响应值,采用响应面法对小麦秸秆吸附剂的制备工艺进行优化。结果表明,热解时间和微波功率对碘吸附值的交互作用明显。响应面优化工艺分析,发现当热解时间4.03 min、微波功率569.0 W,氯化锌质量分数为31.24%时,碘吸附值最大,为643.33 mg/g。另外,小麦秸秆吸附等温线与I型相似,吸附剂的微孔容积为0.238 4cm³/g,吸附剂的BJH孔径分布表现窄小,最高峰出现在2.1nm左右。处理Cr(VI)废水的吸附试验,发现Cr(VI)的去除率可以达到70%以上。研究表明,微波诱导热解法及响应面优化工艺制备的小麦秸秆吸附剂技术可行且具有良好的重金属废水处理应用前景。     

热分析-质谱联用分析生物垃圾热解机理

采用热分析-质谱联用技术研究了城市生活垃圾中三种生物质成分的热解过程,并采用Freeman-Carroll法定量分析了三种生物质热重动力学参数。结果表明木屑、落叶和菜叶这类生物质热解过程分为三个阶段,先是水分析出的微小失重阶段,之后是因纤维素等大分子进行交联缩聚的快速热解阶段,表现为放热效应,逸出的气体主要有H2O、CO2、C2H6/C2H4和CH4,最后是吸热脱链解聚的缓慢热解过程,逸出的小分子气体主要有CO2。     

Characterization of organic matter in total suspended particles by thermodesorption and pyrolysis-gas chromatography-mass spectrometry

The organic matter in tropospheric aerosol plays an important role in atmospheric physical and chemical processes. The bulk of organic matter, representing a significant proportion of the total suspended particulate (TSP) mass, is bound to polymeric material whose structure and properties are largely unknown. Here we used thermodesorption gas chromatography/mass spectrometry (Td- GC/MS) to study organic compounds of low molecular mass and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) to characterize the chemical structure of macromolecules in TSP samples collected in di erent seasons from di erent sites in Guangzhou. n-Alkanes, fatty acids and nitriles were the predominant compounds in the thermodesorption products, whereas aromatics, fatty acids, nitriles and n-alkanes/alkenes were the major compounds in the pyrolysates. The results indicated that aromatics were main units in macromolecules. The fatty acids and nitriles formed from carboxylic ammonium salts were detected in both thermodesorption products and pyrolysates at a certain concentration, indicating the importance of these compounds in TSP formation. The TSP source mainly determined the occurrence of compounds in samples from urban, suburban and forest sites, whereas the TSP source and formation process maybe controlled the seasonal variation in compounds detected. High levels of nitriles in summer samples from suburban and forest sites coincide with the release of ammonium from the land and of fatty acids from vegetation at these sites.     

基于微波辐射研究城市污水污泥脱水特性

选用沈阳市仙女河污水处理厂和北部污水处理厂污水污泥作为微波脱水试验物料,分析物料性质、辐射强度、辐射时间以及添加剂投入量等对污泥脱水率和有机质损失率的影响. 结果表明:污泥中水分含量高的脱水效果最好,经过微波处理后的污泥有机质含量仍较高;辐射时间是最主要的影响因素,在540 W下辐射2～5 min即可达到良好效果;在合适的辐射时间下540～900 W都能达到良好的脱水效果,但在900 W时有机质的损失率较大,达到65.64%;添加剂投入量对污泥脱水基本不起作用,但可改变污泥微波干燥后的性状. 同时,运用灰色关联分析得到决定微波试验运行系统的主次因素,最后建立了影响因素对污泥脱水率和有机质损失率的经验公式.