肥煤自燃全过程热动力学特征参数研究

实验测定了林西矿肥煤样品30~900℃煤自燃全过程热动力学特征参数,得出:TG/DTG曲线显示煤样DTG初始临界温度45℃,干裂温度122℃,活性温度195℃,增速温度265℃,质量极大值温度342℃,着火温度465℃,最大热失重速率温度515℃和燃尽温度690℃;DSC曲线显示,煤样初始放热温度60℃、最大热释放速率温度511℃。结合TG-DTG-DSC曲线综合分析可知,煤温达到510℃左右时煤样反应最剧烈。由煤自燃标志气体测定实验系统得出:煤温130℃后CO,CO 2释放量迅速增加,210℃增加速度下降;CH 4,C 2 H 6含量变化具有规律性且两者变化相近;C 2 H 4出现温度为130℃;C 2 H 4/C 2 H 6比值在190~350℃有较强的规律性,呈上升趋势且上升速度较快;350℃之后,CH 4,C 2 H 6,C 2 H 4体积分数均开始急剧增大;C 2 H 4/CO与C 2 H 4/CO 2变化趋势大致相同,在130~350℃时缓慢增长,达到350℃后比值呈指数形式上升。经拟合曲线,得到活化能的3个突变点温度:70,180,220℃,其中180℃与交叉点温度相吻合。通过以上研究,得到了肥煤自燃全过程的热力学特征参数,为实际生产中防治煤自燃提供了理论依据。     

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.     

去除城市生活污泥中有机络合态金属强化其厌氧生物制气

为提高城市生活污泥厌氧消化沼气产率,本文考察了通过金属络合剂EDTA预处理污泥,以去除城市生活污泥中有机络合态金属,强化其厌氧生物制气的效果.结果表明,经EDTA预处理去除金属后的污泥(实验组)较未预处理的污泥(对照组)的有机络合态金属含量减少[(5.09±0.57)%~(1.37±0.20)%,以TS计],溶解性有机质显著提高(SCOD提升627%),暗示该预处理方法能够极大地去除有机络合态金属并强化污泥有机质的溶出.通过测定污泥有机质溶出表观活化能发现,实验组污泥有机质溶出表观活化能比对照组降低36%,表明预处理能够有效降低有机质溶出反应的能量壁垒.污泥厌氧发酵研究发现,在16d的污泥厌氧产酸实验中,实验组VFAs浓度高于对照组,较对照组最大提升42%;在22 d的污泥厌氧产甲烷测试实验(BMP)中,实验组单位有机质累积甲烷产量比对照组增加48%,表明EDTA预处理对提高污泥厌氧消化产沼气具有重要的作用.通过进一步产沼气动力学研究发现,实验组的产沼气限速步骤在产甲烷阶段,而对照组限制于水解阶段,表明经EDTA预处理能有效地破除城市生活污泥厌氧消化过程的水解限速.     

热活化镁砂的表征、吸附性能及其对含油废水的处理效果研究

通过对镁砂进行改性试图提高其吸附性能,并用于处理含油废水。对镁砂进行热活化处理,并对处理前后的镁砂进行了X射线衍射分析、TG-DSC热分析及扫描电镜分析。再将热活化后的镁砂用于处理模拟含油废水,考察了焙烧温度、吸附剂用量、pH、温度等因素对模拟含油废水中COD去除效果的影响。根据实验结果,确定镁砂的热活化温度为500℃,利用热活化后的镁砂吸附去除模拟含油废水中的COD,处理后出水COD浓度可满足GB 8978—1996《污水综合排放标准》一级标准。     

固体云爆剂热分解性能研究

目的研究固体云爆剂的热分解特性。方法利用差示扫描量热(DSC)和热重分析(TG)测定该固体云爆剂的热分解过程。分别得到固体云爆剂在不同温度下的DSC和TG曲线,以及同一温度下云爆剂不同组分的DSC和TG曲线。结合线性回归分析的方法,利用Ozawa法、Starink法以及Kissinger法计算了反应活化能。结果其表观活化能为208 k J/mol左右。结论该固体云爆剂的热分解是一个连续的过程,具有良好的安定性。     

活化温度对SCAC制备过程中副产物生成规律的影响

文章研究了污泥-玉米芯活性炭(SCAC)制备过程中,活化温度对副产物(热解气和热解油)生成规律的影响。热解气和热解油分别采用气相色谱仪和气质联用仪进行分析检测。试验结果表明,随着活化温度的升高,SCAC的产量逐渐降低,热解气与热解油的产量则随之增多。不同温度条件下,热解气的主要成分均为H2和CO2,热解气中H2所占的体积百分数随着活化温度的升高而增加,而CO2则相应降低。此外,热解气中CH4的含量也会随着活化温度的上升而略有提高,说明较高的活化温度更有利于热解气的资源利用。热解油组分较为复杂,每个温度条件下的液态产物都包括上百种化合物,可分为烷烃,烯烃,苯类,酚类,腈类,杂环化合物,多环芳烃,有机酸,酰胺,酯类,甾体,醇,酮以及其他类共14大类型,其中以有机酸、腈类和甾体类有机物含量居多。随着活化温度的升高,有机酸和多环芳烃的含量有所增加,而酚类化合物的含量则有所降低;当活化温度升高至650℃以上时,甾体类有机物含量明显降低。     

Oxidation inhibition of sulfite in dual alkali FGD system

A laboratory-scale well-mixed thermostatic reactor with continuously blasting air was used to investigate the oxidation inhibition of sulfite in dual alkali flue gas desulfurization （FGD） system. The effects of operating parameters such as pH value and catalyst concentration on the oxidation were studied. Sodium thiosulfate was used in the system, and was found that it significantly inhabited the sulfite oxidation. In the absence of catalyst, sodium thiosulfate at 12.67 mmol/L had an inhibition efficiency of approximately 98%. While in the presence of catalyst, sodium thiosulfate at 26.72 mmol/L had an inhibition efficiency less than 85.0%. The oxidation reaction order of sulfite in the sodium thiosulfate was determined to be -1.90 and 4）.55 in the absence and presence of the catalyst, respectively. Apparent activation energy of oxidation inhibition was calculated to be 53.9 kJ/mol. Pilot tests showed that the consumption rate of thiosulfate agreed well with the laboratory-scale experimental results.     

Kinetics of selective catalytic reduction of NO by NH3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction (SCR) of nitric oxide (NO) with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results show that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3, respectively, at 350-450℃. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.     

铅在棉秆基活性炭上的吸附动力学与热力学

以棉秆与棉秆纤维为原料,利用磷酸活化法制备了低成本的高比表面微孔棉秆基活性炭,通过静态实验研究了活性炭对水溶液中铅的吸附特性,测定了溶液pH值、吸附时间、溶液温度对吸附的影响,探讨了吸附动力学、热力学及吸附机制.根据低温液氮(N2/77K)吸附测定数据,以BET方程、BJH法及H-K法对活性炭孔结构进行了表征,以Boehm滴定、FTIR、零电荷点pHPZC测定及元素分析定量表征活性炭表面含氧官能团.结果表明,以棉秆和棉秆纤维为原料制备的活性炭的比表面积分别为1570和1731m2·g-1,含氧酸官能团含量分别为1.43和0.83mmol·g-1,均高于商业活性炭ST1300.静态吸附实验表明,棉秆基活性炭对铅有较大的吸附容量和吸附效率,最大吸附量超过120mg·g-1,溶液pH对吸附有较大的影响,吸附量随时间增大而增大,在5min内可达饱和吸附量的80%;吸附动力学数据符合假二级方程,Freundlich方程能更好地描述等温吸附行为;热力学研究表明,吸附吉布斯自由能(ΔG0)0,而焓变(ΔH0)0,说明吸附为吸热的自发反应过程,升温有利于吸附,离子交换可能在吸附过程中起了重要作用.     

Antimicrobial activity of thin metallic silver flakes, waste products of a manufacturing process

The aim of the research was to develop new products and processes from a manufacturing waste from an Italian metallurgic company. The company produced thin silver metallic films and the production scraps were silver flakes. The possibility to use the silver flakes in water disinfection processes was studied. The antimicrobial activity of the flakes was investigated in batch using Escherichia coli as Gram-negative microorganism model. The flakes did not show any antimicrobial activity, so they were activated with two different processes: thermal activation in reducing atmosphere and chemical activation, obtaining, respectively, reduced flakes (RF) and chemical flakes (CF). The flakes, activated with either treatment, showed antimicrobial activity against E. coli. The kill rate was dependent on the type of activated flakes. The chemical flakes were more efficient than reduced flakes. The kill rate determined for 1 g of CF, 1.0 ± 0.2 min⁻¹, was greater than the kill rate determined for 1 g of RF, 0.069 ± 0.004 min⁻¹. This was confirmed also by the minimum inhibitory concentration values. It was demonstrated that the antimicrobial capability was dependent on flakes amount and on the type of aqueous medium. Furthermore, the flakes maintained their properties also when used a second time. Finally, the antimicrobial activities of flakes were tested in an effluent of a wastewater treatment plant where a variety of heterotrophic bacteria were present.