Experimental study on explosion inhibition by heptafluoropropane and its synergy with inert gas

The inhibition effect of heptafluoropropane (CF₃CHFCF₃) on methane explosions under different inhibitor concentrations in a closed vessel was studied. A high-speed camera and a pressure sensor were adopted respectively to record flame propagation characteristics and pressure data. Results indicate that the relationship between flame propagation and pressure rising was correlated. As the equivalent ratio (ϕ)≤1, the pressure presented a trend of rising firstly and then decreasing with increasing CF₃CHFCF₃ concentration, and it was found that there existed a critical concentration for pressure decrease. As ϕ > 1, the pressure exhibited a decreasing trend. Although the pressure appeared to seemingly increase, the moment that the pressure began to rise (t_rise) and the moment that the maximum explosion overpressure appeared (t_Pmax) were obviously delayed. The average rate of pressure rise ((dP/dt)_ave) was decreased as the concentration of CF3CHFCF3 increased. It indicates that CF₃CHFCF₃ can effectively reduce the explosion reaction rate. The critical concentration of CF₃CHFCF₃ for complete inhibition was determined. Meanwhile, the synergy of CF₃CHFCF₃-inert gas can improve the inhibition effect. Compared with CF₃CHFCF₃–N₂, the synergy of CF₃CHFCF₃–CO₂ presented a better inhibition effect, and the inhibition effect was increased with increasing inert gas concentration. And the mechanisms of physical and chemical effects on explosion inhibition were analyzed.     

Evaluation of thermal reaction for two azo compounds by using 20-L apparatus and calorimetry

Azo compounds are widely involved in the industrial processes of dyes, pigments, initiators, and blowing agents. Unfortunately, these compounds have a bivalent unstable –NN– composition, which can be readily broken when the ambient temperature is elevated. Self-accelerating decomposition might cause a runaway reaction and lead to a fire, explosion, or leakage when the cooling system fails or other events occur. This study investigated the explosion properties, thermal stability parameters, and thermal hazard and mechanism of 2,2′–azobisisobutyronitrile (AIBN) and 2,2′–azobis–2–methylbutyronitrile (AMBN). We used a 20-L apparatus, vent sizing package 2, synchronous thermal analysis, and differential scanning calorimetry under explosive, adiabatic, and dynamic conditions to acquire the explosive curves, thermal curves, and thermodynamic parameters of the substances. Moreover, the differential isoconversional method (Friedman method) and ASTM E698 equation were employed to obtain the apparent activation energy E_a. All the experimental results revealed that AIBN is more dangerous than AMBN. The E_a of AIBN was lower than that of AMBN. The results can be used to construct an azo compound thermal hazard database for use for searches and reference examples by industry and related research areas.     

Co-treatment of fruit and vegetable waste in sludge digesters. An analysis of the relationship among bio-methane generation,process stability and digestate phytotoxicity

The co-digestion of a variable amount of fruit and vegetable waste in a waste mixed sludge digester was investigated using a pilot scale apparatus. The organic loading rate (OLR) was increased from 1.46 kg VS/m³ day to 2.8 kg VS/m³ day. The hydraulic retention time was reduced from 14 days to about 10 days. Specific bio-methane production increased from about 90 NL/kg VS to the maximum value of about 430 NL/kg VS when OLR was increased from 1.46 kg VS/m³ day to 2.1 kg VS/m³ day. A higher OLR caused an excessive reduction in the hydraulic retention time, enhancing microorganism wash out. Process stability evaluated by the total volatile fatty acids concentration (mg/l) to the alkalinity buffer capacity (eq. mg/l CaCO₃) ratio (i.e. FOS/TAC) criterion was <0.1 indicating high stability for OLR <2.46 kg VS/m³ day. For higher OLR, FOS/TAC increased rapidly. Residual phytotoxicty of the digestate evaluated by the germination index (GI) (%) was quite constant for OLR < 2.46 kg VS/m³ day, which is lower than the 60% limit, indicating an acceptable toxicity level for crops. For OLR > 2.46 kg VS/m³ day, GI decreased rapidly. This corresponding trend between FOS/TAC and GI was further investigated by the definition of the GI ratio (GIR) parameter. Comparison between GIR and FOS/TAC suggests that GI could be a suitable criterion for evaluating process stability.     

Explosion characteristics of micron- and nano-size magnesium powders

Explosion characteristics of micron- and nano-size magnesium powders were determined using CSIR-CBRI 20-L Sphere, Hartmann apparatus and Godbert-Greenwald furnace to study influence of particle size reduction to nano-range on these. The explosion parameters investigated are: maximum explosion pressure (P_max), maximum rate of pressure-rise (dP/dt)_max, dust explosibility index (K_St), minimum explosible concentration (MEC), minimum ignition energy (MIE), minimum ignition temperature (MIT), limiting oxygen concentration (LOC) and effect of reduced oxygen level on explosion severity. Magnesium particle sizes are: 125, 74, 38, 22, 10 and 1 μm; and 400, 200, 150, 100, 50 and 30 nm. Experimental results indicate significant increase in explosion severity (P_max: 7–14 bar, K_St: 98–510 bar·m/s) as particle size decreases from 125 to 1 μm, it is maximum for 400 nm (P_max: 14.6 bar, K_St: 528 bar·m/s) and decreases with further decrease of particle size to nano-range 200–30 nm (P_max: 12.4–9.4 bar, K_St: 460–262 bar·m/s) as it is affected by agglomeration of nano-particles. MEC decreases from 160 to 30 g/m³ on decreasing particle size from 125 to 1 μm, its value is 30 g/m³ for 400 and 200 nm and 20 g/m³ for further decrease in nano-range (150–30 nm). MIE reduces from 120 to 2 mJ on decreasing the particle size from 125 to 1 μm, its value is 1 mJ for 400, 200, 150 nm size and <1 mJ for 50 and 30 nm. Minimum ignition temperature is 600 °C for 125 μm magnesium, it varies between 570 and 450 °C for sizes 38–1 μm and 400–350 °C for size range 400–30 nm. Magnesium powders in nano-range (30–200 nm) explode less violently than micron-range powder. However, likelihood of explosion increases significantly for nano-range magnesium. LOC is 5% for magnesium size range 125–38 μm, 4% for 22–1 μm, 3% for 400 nm, 4% for 200, 150 and 100 nm, and 5% for 50 and 30 nm. Reduction in oxygen levels to 9% results in decrease in P_max and K_St by a factor of 2–3 and 4–5, respectively, for micron as well as nano-sizes. The experimental data presented will be useful for industries producing or handling similar size range micron- and nano-magnesium in order to evaluate explosibility of their magnesium powders and propose/design adequate safety measures.     

容积负荷对ABR-MBR工艺反硝化除磷性能的影响

采用连续流ABR-MBR组合工艺处理生活污水,研究不同容积负荷(volume loading rate,VLR)对该工艺反硝化除磷性能的影响,获得最佳工艺参数.试验考察ABR进水容积负荷(以COD计,下同)分别为0.76、1.01、1.51和2.27 kg·(m~3·d)~(-1)时系统去碳脱氮除磷的性能,并在各ABR容积负荷条件下考察MBR容积负荷对MBR反应器硝化性能的影响.结果表明,在ABR进水容积负荷为1.51 kg·(m~3·d)~(-1)的条件下,系统A2隔室COD去除量最大,并在MBR容积负荷为0.462 kg·(m~3·d)~(-1)时,MBR反应器中实现了短程硝化,系统NH_4~+-N和TN去除率分别达到90%和72%以上,厌氧释磷量为7.41 mg·L~(-1),缺氧吸磷量达到15.42 mg·L~(-1),出水PO_4~(3-)-P浓度低于0.5 mg·L~(-1),这表明短程硝化更有利于强化ABR-MBR系统的反硝化除磷性能.     

福建省重点城市路面尘负荷及化学组成研究

采集并分析了福建省重点城市厦门、漳州、泉州和莆田城区具有代表性的57个地面扬尘和16个土壤样品的26种无机元素、8种水溶性离子和碳成分等组成.不同城市粒径≤100μm的路面尘负荷平均值在6.99 g.m-2与10.11 g.m-2之间,而粒径≤2.5μm的路面尘(PM2.5)负荷平均值在4.0 mg.m-2和12.5 mg.m-2之间.不同城市土壤尘和路面尘PM2.5中浓度最高的元素都是Si、Ca、Al、Fe和K,路面尘中Ca元素明显富集,而主要人为来源的重金属元素如Cu、Pb、Zn、Cr在路面尘PM2.5中的浓度显著高于土壤尘.漳州城区路面尘PM2.5中二次离子NH4+、NO3-和SO24-的含量明显高于其它地区,厦门、漳州和泉州城区路面尘PM2.5中Mg2+和Ca2+之间都存在显著的正相关关系.四城市路面尘中有机碳(OC)的含量均高于济南、石家庄以及北京地面扬尘OC的含量,元素碳(EC)的含量均低于北京地区路面扬尘EC的含量.泉州和莆田两地OC和EC的相关性较好,说明路面尘中OC和EC有相同或相似的来源.质量平衡结果显示泉州和莆田路面尘PM2.5中含量最高的是土壤尘,其次为有机物.按化学组成特征对路面尘PM2.5进行聚类解析,得到受大气沉降影响、受土壤尘影响、受大气沉降和土壤尘共同作用以及受土壤尘和建筑尘共同作用4类样品.     

不同锆负载量锆改性膨润土对水中磷酸盐吸附作用的对比

通过实验对比考察了不同锆负载量的锆改性膨润土对水中磷酸盐的吸附作用.结果表明,锆改性膨润土对水中磷酸盐的吸附动力学过程符合准二级动力学模型,整个过程可以分为快速吸附阶段、缓慢吸附阶段和平衡吸附阶段,其中缓慢吸附阶段的吸附速率受膜扩散和颗粒内扩散所控制.锆改性膨润土对水中磷酸盐的吸附等温实验数据可以采用Langmuir、Freundlich、Sips和Dubinin-Radushkevich等温吸附模型进行拟合.实验条件下,磷酸盐吸附性能随pH增加而降低.溶液共存的Na~+、K~+和Ca~(2+)促进了锆改性膨润土对磷酸盐的吸附,并且Ca~(2+)的促进作用远远大于Na~+和K+,而溶液共存的HCO-3和SO2-4一定程度上抑制了锆改性膨润土对磷酸盐的吸附.锆改性膨润土吸附水中磷酸盐的主要机制为配位体交换并形成内层磷酸盐配合物.锆改性膨润土对水中磷酸盐的吸附能力随着锆负载量的增加而增加,而锆改性膨润土中单位质量ZrO_2对水中磷酸盐的吸附量则随着锆负载量的增加而降低.当ZrO_2负载量由3.61%增加到13.15%时锆改性膨润土的最大单层单位吸附量(以P计)显著地由3.83 mg·g~(-1)增加到9.03 mg·g~(-1),而继续增加ZrO_2负载量至19.63%时锆改性膨润土的最大单层单位吸附量则缓慢地提高到9.66 mg·g~(-1)(以P计).当ZrO_2负载量由3.61%逐渐增加到19.63%时,锆改性膨润土中单位质量ZrO_2的磷酸盐最大吸附量[m(P)/m(ZrO_2)]由106 mg·g~(-1)逐渐下降到49.2 mg·g~(-1).综合考虑吸附剂的经济成本和吸附容量,ZrO_2负载量为13.15%锆改性膨润土更为适合作为吸附剂去除水中磷酸盐.     

氯化磁性凹土树脂的制备与表征研究

利用表面负载的方法将有机化磁性凹土与苯乙烯、二乙烯苯等制备磁性凹土树脂;对磁性凹土树脂进行氯甲基化改性,制备出氯化磁性凹土树脂.表征了样品的形貌、结构以及表面积,研究了树脂对天然有机物(腐殖酸)的吸附性能.结果表明:氯化后的磁性凹土树脂的比表面积是原有的1.9倍,对附腐殖酸的饱和吸附能力也从原有的41.84 mg/g提高到了51.02 mg/g,这表明改性后的树脂增强了其对腐殖酸的去除能力.     

生态高负荷土地快速渗滤系统处理猪场废水的效能及微生态

以经过厌氧反应器处理后的猪场废水为研究对象,探讨了新型生态高负荷土地快速渗滤系统对废水中COD、氨氮及总氮的去除情况;同时分析了该系统中的微生物群落结构以及过氧化氢酶、脲酶、硝酸盐还原酶的含量.结果表明,在水力负荷为11 cm·d~(-1)、进水COD为700 mg·L~(-1)左右的条件下,一级土地渗滤柱与二级土地渗滤柱对COD的去除率分别为78.8%与63.0%,总去除率达到了92.6%;而当水力负荷增大到22 cm·d~(-1)时,总的COD去除率仍在90.0%以上;该系统对于氨氮的去除更为显著,去除率可达99%左右.一级土地快速渗滤系统中上、中、下部的过氧化氢酶含量分别为1.899、0.990、0.323 m L·g~(-1),表明猪场废水中的有机物主要在该系统的上部与中部得以去除;二级土地快速渗滤系统上、中、下部的硝酸盐还原酶含量分别是3.453、3.831、1.971 m L·g~(-1),表明脱氮作用主要发生二级土地快速渗滤系统的上部与中部.该土地快速渗滤系统中微生物以Gram Negative与Gram Positive为主,特别是在二级土地快速渗滤系统中,AM Fungi与Actinomycetes占有一定比例,为猪场废水中难降解有机物的去除提供了保障.     

有机负荷条件对间歇式气提内循环反应器中好氧颗粒污泥形成的影响

在R1、R2和R3共3组气提式内循环序批式反应器中启动好氧颗粒污泥工艺,探讨在无选择压作用下有机负荷对好氧颗粒污泥的形成及稳定性的影响.其中,R1、R2分别以7 kg.(m3.d)-1和3 kg.(m3.d)-1的目标COD负荷直接启动,R3以1.5kg.(m3.d)-1逐步增加至3 kg.(m3.d)-1的递增COD负荷方式启动.结果表明,3组反应器在启动期中均能快速形成好氧颗粒污泥,但以目标负荷启动方式易使好氧颗粒污泥反应器产生丝状菌污泥膨胀.通过对颗粒形成过程、粒径、性质以及胞外多聚物等指标分析,认为递增负荷的启动方式可有效抑制启动初期丝状菌污泥膨胀,且形成的颗粒更为稳定,生物降解效率更高.