单阳膜氧化降解乐果废水及动力学分析

针对乐果废水C0D高、污染严重、可生化性差的特点,研究了单阳膜技术氧化降解乐果废水的效果.研究结果表明,采用单阳膜技术氧化降解乐果废水,COD去除率较高.在本试验条件下,乐果模拟废水的COD去除率受电解时间、操作电压、NaCl导电介质浓度及超声辅助的影响.通过试验确定的最佳试验条件为:操作电压9V、电解时间50min、NaCl质量浓度5 g·L-1、超声辅助处理.采用以上条件处理乐果模拟废水,COD去除率达79.87%.反应动力学分析发现,乐果模拟废水的降解反应符合2级动力学,反应动力学方程为Ct=C0/1×10-5C0t+1.     

Fenton氧化法降解HMX废水中有机物的氧化反应动力学

用Fenton氧化技术研究了降解HMX废水中有机物的工艺及氧化反应动力学。结果表明,适宜的降解工艺条件为:H2O2投加量2mol/L,H2O2与Fe2+摩尔比为40∶1,pH值为3,反应温度20℃,反应时间1.5h。在上述条件下HMX废水的COD去除率为68.5%。在研究的温度范围内,用Fenton氧化法降解HMX废水中有机物的氧化反应为一级反应,反应的活化能和指前因子分别为7.03kJ/mol和0.067 7min-1。     

TNT在超临界水中的氧化反应动力学

利用超临界水氧化(SCWO)实验装置,氧气为氧化剂,对废水中的TNT在超临界水中的氧化反应进行了研究,用幂函数法则建立了COD去除率宏观动力学方程。结果表明,SCWO技术可有效消除废水中的TNT,随着反应温度的升高和停留时间的延长,TNT模拟废水的COD去除率显著增大。在温度为673~823K、压力24MPa、300%过氧量、TNT浓度为5.7×10-4mol/L的实验条件下,有机物的反应级数为1.18,活化能Ea为96.85kJ/mol,指前因子A为4.87×103s-1。     

几种硝胺炸药在熔态TNT和DNP中的溶解性及其结晶晶型

为研究硝胺类炸药在熔铸载体中的溶解性并分析溶解后硝胺类炸药的相变,采用物理分离的方法分别测出了RDX、HMX和CL-20在90℃的2,4,6-三硝基甲苯(TNT)和3,4-二硝基吡唑(DNP)中的溶解度;通过拉曼光谱对溶解后回收的硝胺类炸药进行了表征。结果表明,90℃下,RDX、HMX和CL-20在TNT中的溶解度分别为3.35、0.24和4.99g/100g,在DNP中的溶解度分别为12.28、2.64和7.03g/100g;RDX在TNT、DNP中溶解冷却后的晶型均为β型,HMX在TNT、DNP中溶解冷却后的晶型均为α型,RDX、HMX在TNT、DNP中溶解前后晶型一致,均未发生变化;CL-20在TNT、DNP中溶解后回收的晶型均由ε型变为β型,说明CL-20在熔铸炸药载体中由于温度与溶剂的作用晶型不稳定,硝胺类炸药在熔铸载体中溶解并发生相变将会严重影响炸药的性能。     

催化协同高压脉冲气相放电降解TNT废水

采用多针-板式高压脉冲气相放电体系处理TNT废水,结合向反应器中投加催化剂来强化TNT的降解效果,考察了不同催化剂及投加量对TNT降解效果的影响.结果表明,在脉冲峰值电压为9.8kV、脉冲频率为125Hz的试验条件下,初始浓度为30 mg·L-1的TNT水溶液处理60 min后,降解率为66.1%.Fe2 的添加促进了TNT的降解,当Fe2 为0.15 mmol·L-1时,催化效果最好,比单独高压脉冲放电处理TNT的降解率提高了17.9%.添加H2O<,2>对TNT降解有抑制作用,尤其在反应初期.初始浓度为100 mg·L-的TNT废水处理2 h后,TNT降解率为87%,COD降解率为80%,表明高压脉冲放电等离子体技术可以有效降解TNT废水.     

超临界水氧化处理HMX废水

实验在400～550℃的反应温度、22～25MPa的反应压力下对HMX炸药废水进行超临界水氧化技术处理,有机物COD去除率在99%以上。采用单因素法分析反应温度、压力、反应时间对超临界水氧化HMX废水的影响,确定超临界水氧化法处理HMX废水的最佳实验运行条件：反应温度500℃,压力为22.4MPa,反应时间为150s。通过液相色谱检测,得出主要污染物的去除率为99.88%。     

Fenton法处理全自动喷漆线废水的工艺特性及动力学模型

实验研究了Fenton氧化技术降解全自动喷漆线废水可溶性有机物的工艺特性,建立了氧化反应动力学模型。结果表明,Fenton法可有效降解喷漆线废水的可溶性有机物,COD的去除率与n(H_2O_2):n(Fe~(2+))、n(COD):n(H_2O_2)、温度和时间呈正相关关系,与初始pH呈负相关关系;在5因素上的1:0.33、1:3、3、40℃和180 min最佳水平下,COD去除率超过86%;在293.15～313.15 K范围内,Fenton试剂氧化喷漆线废水有机物的反应为准一级反应,活化能为8.73 kJ/mol,指前因子为0.39 min~(-1)。     

用LC/APCI/MS方法检测粉尘中的炸药成分

采用高选择性和灵敏度的LC(液相色谱)/APCI(大气压化学电离源)/MS(质谱)方法定量分析粉尘样品中的HMX、RDX、PETN、CE、NQ和TNT。采用ASE萃取,GPC净化浓缩作为前处理方法,在粉尘中分别添加所测炸药组分,用丙酮作为ASE萃取溶剂,乙酸乙酯和环己烷(体积比为1∶1)作为GPC净化时的流动相并抛弃杂质500s,收集1 520s。在LC/MS分析时,通过在流动相中添加1mmol/L甲酸与样品形成[M+HCOO]-的甲酸加合离子。结果表明,HMX、RDX、PETN、CE、NQ、TNT的方法检测限分别为0.78,1.44,1.69,0.77,1.06,1.72ng/mL,回收率为49.0%～88.4%,相对标准偏差为3.5%～10.3%。该方法可以用来系统排查及定量分析爆炸残留物及环境样品中的NQ、RDX、PETN、CE、HMX、TNT成分。     

Fenton氧化降解焦化废水的影响特性及动力学模型

为研究Fenton试剂氧化降解焦化废水的影响特性及动力学机理,采用小试烧杯实验考察初始COD、H2O2投加量、Fe2+投加量和反应温度等因素对处理效果的影响。结果表明,原水COD为260 mg/L、H2O2投加量为666mg/L、Fe2+投加量为200 mg/L、温度为298 K时,COD去除率达到89.53%;反应初始阶段COD氧化降解的表观反应动力学模型与实验数据得到较好的拟合,因此该动力学模型能较好地预测Fenton试剂对焦化废水的氧化降解情况;反应总级数为2.001 7,其中H2O2的反应分级数(0.568 5)高于Fe2+的反应分级数(0.494 0),说明Fenton氧化降解COD过程中H2O2浓度的影响比Fe2+的大;较低的反应活化能说明反应较易进行。     

纳米铝粉对硝胺炸药热分解催化性能的影响

采用直流电弧等离子体蒸发法制备了高纯度的纳米铝粉,并用比表面积分析仪和扫描电子显微镜(SEM)对样品进行了表征.将纳米铝粉与硝胺炸药HMX和RDX用研磨混合法制成混合粒子,用DSC对单质HMX和RDX炸药以及纳米铝粉/硝胺炸药混合物进行催化特性测试,并对样品的热分解动力学和热力学参数进行了计算和对比.结果表明,加入纳米铝粉后,HMX和RDX在不同升温速率(2、5、10、20 K/min)下的放热峰峰温降低,活化能分别降低15和16 kJ/mol,热力学参数都有明显变化.纳米铝粉对HMX和RDX有明显的热分解催化作用.     

Degradation of TNT,RDX, and HMX Explosive Wastewaters Using Zero‐Valent Iron Nanoparticles

The high‐energy explosives 2,4,6‐trinitrotoluene (TNT), hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX), and the high melting explosive octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) are common groundwater contaminants at active and abandoned munitions production facilities causing serious environmental problems. A highly efficient and environmentally friendly method was developed for the treatment of the explosives‐contaminated wastewaters using zero‐valent iron nanoparticles (ZVINs). ZVINs with diameters of 20–50 nm and specific surface areas of 42.56 m² g⁻¹ were synthesized by the co‐precipitation method. The explosives degradation reaction is expressed to be of pseudo first‐order and the kinetic reaction parameters are calculated based on different initial concentrations of TNT, RDX, and HMX. In addition, by comparison of the field emission scanning electron microscopy (FE‐SEM) images for the fresh and reacted ZVINs, it was apparent that the ZVINs were oxidized and aggregated to form Fe₃O₄ nanoparticles as a result of the chemical reaction. The X‐ray diffraction (XRD) and X‐ray absorption near edge structure (XANES) measurements confirmed that the ZVINs corrosion primarily occurred due to the formation of Fe₃O₄. Furthermore, the postulated reaction kinetics in different concentrations of TNT, RDX, and HMX, showed that the rate of TNT removal was higher than RDX and HMX. Furthermore, by‐products obtained after degradation of TNT (long‐chain alkanes/methylamine) and RDX/HMX (formaldehyde/methanol/hydrazine/dimethyl hydrazine) were determined by LC/MS/MS, respectively. The high reaction rate and significant removal efficiencies suggest that ZVINs might be suitable and powerful materials for an in‐situ degradation of explosive polluted wastewaters.     

高速撞击流技术制备炸药超细微粉的研究

介绍了利用高速撞击流技术制备出亚微米级超细炸药颗粒的方法及基本原理,并给出了超细ＨＭＸ和ＲＤＸ的粒度测试结果。     

纳米HMX/微米RDX复合炸药撞击感度的性能研究

在超声波的环境下制备了不同配比的纳米HMX(奥克托今)/微米RDX(黑索今)复合炸药,并对纯RDX炸药和自制炸药的撞击感度进行了比较。结果发现,在实验配比范围内,纳米HMX/微米RDX复合炸药比纯RDX炸药敏感,且随HMX含量的增加,撞击感度降低。     

RDX and HMX with Reduced Sensitivity Towards Shock Initiation–RS‐RDX and RS‐HMX

Reduced Sensitivity RDX (RS‐RDX) has received a lot of attention and interest from the explosive community in the recent years. There are several producers of RS‐RDX, most of them using a direct nitration (Woolwich process) for the RDX synthesis, while Chemring Nobel uses the Bachmann process. The processes for obtaining the RS properties probably differ between the various producers. Chemring Nobel has also developed an HMX quality that shows Reduced Sensitivity (RS‐HMX) of different particle size distributions. The shock sensitivity is at the same level as for RS‐RDX in comparable compositions. Reduced shock sensitivity has been obtained for RS‐RDX and Reduced Sensitivity (RS‐HMX) in both pressable and cast‐cured compositions. By using a pressable composition, it is possible to get the results from a BICT gap test faster than from a cast‐cured composition that has to go through a curing process. Chemring Nobel in cooperation with FFI have performed an extensive accelerated ageing testing of RS‐RDX produced by the Bachmann process. The samples have been aged at 60 and 70 °C and the shock sensitivity tested by two different gap tests. The results demonstrate that the Chemring Nobel RS‐RDX retain the insensitivity towards shock during ageing and show no degradation at all. Accelerated ageing testing of RS‐HMX has also been performed and shows no degradation in the shock sensitivity.     

密度分级法分离废旧梯黑铝炸药中的RDX与铝粉

为了研究分离回收废旧梯黑铝炸药中各成分的高效低成本的物理方法,采用控温离心和控温水洗结晶,回收梯黑铝炸药中的TNT组分;再根据RDX与铝粉的密度差异,使用密度分级法,分离RDX与铝粉,优化了分离条件,对回收物质进行DSC和XRD表征,并测试其撞击感度。结果表明,在密度为2.0g/cm3的溴化锌溶液中,控温30℃、离心转速2500r/min等条件下,回收RDX和铝粉回收率分别为67.6%和86.5%,纯度分别为77.2%和94.6%;回收的RDX热安定性良好,存在少量铝粉和TNT与RDX的共熔物,且基本没有独立存在的TNT组分,其撞击感度为90%;回收铝粉中含有微量氧化铝粉和炸药成分;两种回收物组分中均不含溴化锌。该物理方法可有效实现废旧梯黑铝炸药各组分的高效绿色回收。     

梯黑铝混合装药提取铝的反应动力学研究

采用"颗粒不变收缩芯模型"研究了梯黑铝装药中Al的酸解反应动力学行为,考察了反应温度、硫酸浓度及炸药粒度对反应速率的影响。结果表明,A l的酸浸过程符合动力学方程g(x)=1-(1-x)1/3=kt,为化学反应控制类型,表观活化能为42.392 kJ/mol。在此基础上,经线性回归分析,发现表观反应速率常数k与硫酸初始浓度C0及炸药粒径1/r20成正比例关系。     

Modification of W/O Emulsions by Demilitarized Composition B

A series of W/O emulsion explosives containing 30–50 wt‐% of the demilitarized mixture RDX/TNT (Composition B 50/50) was prepared. Detonation velocities and relative explosive strengths of these mixtures were determined and their detonation characteristics were calculated according to the EU standard methods for commercial explosives. Thermal reactivities of the most reactive components of these W/O mixtures were examined by means of differential thermal analysis and outputs were analyzed according to the Kissinger method. The reactivities, expressed as the E_a ⋅ R⁻¹ slopes of the Kissinger relationship, correlate with the squares of the detonation velocities of the corresponding explosive mixtures. It was found that fortification of the W/O emulsions by the demilitarized mixture RDX/TNT allows modification of detonation velocities of the resulting emulsion explosives within relatively broad limits. However, the effect of this admixture on the relative explosive strength is not well defined. Nevertheless, fortification in this sense can give rock‐blasting explosives with a performance on the level of industrial powdered amatols.     

RDX和HMX单晶的压痕断裂韧性

使用纳米压痕仪在HMX、RDX单晶表面进行压痕实验,并用不同压痕方程计算了单晶的断裂韧性.计算得到HMX晶体(010)面与RDX晶体(020)、(210)面间断裂韧性分别力0.092543、0.097387、0.10072 MPa·m1/2.结果表明,实验单晶的KIC值遵循Palmqvist系裂纹系统shetty方程,...