La_(0.8)Sr_(0.2)MnO_3的燃烧法制备及对HMX热分解的影响(英文)

Perovskite-type La0.8Sr0.2MnO3 was prepared by stearic acid gel combustion method. The obtained powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scaning electron micrograph (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic activity of La0.8Sr0.2MnO3 was investigated on thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by thermal gravity-differential scanning calorimetry (TG-DSC) techniques. The experimental results show that La0.8Sr0.2MnO3 is an effective catalyst for HMX thermal decomposition. The surface-adsorbed species such as H2O, OH&;#61485; and adsorbed oxygen (Oad) could result in an advance in the onset temperature of HMX thermal decompo-sition. The mixture system of Mn3+ and Mn4+ ions and lattice oxygen could play key roles for the increase of the decomposition heat of HMX because these exothermic reactions could be catalyzed by La0.8Sr0.2MnO3 between CO and NOx (from the thermal decom-position of HMX) and the oxidation reaction of CO. According to the previous researches and our results, perovskite-type La0.8Sr0.2MnO3 may be used as a novel catalyst or modifier for nitrate ester plasticized polyether (NEPE) propellant.     

剩余活性污泥碱性发酵液用于厌氧交替好氧-缺氧序批式反应器生物除磷脱氮的碳源的研究(英文)

Activated sludge process has been widely used to remove phosphorus and nitrogen from wastewater. However, the nitrogen and phosphorus removal is sometimes unsatisfactory due to the low influent COD. Another problem with the activated sludge process is that large amount of waste activated sludge is produced, which needs further treatment. In this study, the waste activated sludge alkaline fermentation liquid was used as the main carbon source for phosphorus and nitrogen removal under anaerobic followed by alternating aerobic-anoxic conditions, and the results were compared with those using acetic acid as the carbon source. The use of alkaline fermentation liquid not only affected the transformations of phosphorus, nitrogen, intracellular polyhydroxyalkanoates and glycogen, but also led to higher removal efficiencies for phosphorus and nitrogen compared with acetic acid. It was observed that ammonium was completely removed with either alkaline fermentation liquid or acetic acid as the carbon source. However, the former resulted in higher removal efficiencies for phosphorus (95%) and nitrogen (82%), while the latter showed lower ones (87% and 74%, respectively). The presence of a large amount of propionic acid in the alkaline fermentation liquid was one possible reason for its higher phosphorus removal efficiency. Exogenous instead of endogenous denitrification was the main pathway for nitrogen removal with the alkaline fermentation liquid as the carbon source, which was responsible for its higher nitrogen removal efficiency. It seems that the alkaline fermentation liquid can replace acetic acid as the carbon source for phosphorus and nitrogen removal in anaerobic followed by alternating aerobic-anoxic sequencing batch reactor.     

Eco-friendly corrosion inhibitor from Pennisetum purpureum biomass and synergistic intensifiers for mild steel

Extracts of elephant grass(Pennisetum purpureum) blended with some intensifier halides like ammonium chloride(AMC) and potassium iodide(PTI) were investigated as corrosion inhibitor for mild steel.The corrosion process was monitored in 3.5% HCl by mass loss and electrochemical techniques at 30,40,50,60 and 90 °C.Addition of AMC and PTI increased the inhibition efficiency with the highest inhibition efficiency obtained with PTI blended extract.The blends behaved as mixed type inhibitors and were spontaneously adsorbed on mild steel surface in exothermic nature.Synergistic parameters of the intensifier ions revealed cooperative effect.Kinetic data treatment indicated increase in energy barrier by intensifier ions.The results demonstrate that elephant grass extract blended with halide ions can act as alternative ecofriendly inhibitor for mild steel at elevated temperatures.     

蜡状芽抱杆菌壬基苯酚降解酶的分离纯化及其酶学性质(英文)

An extracellular NP-degrading enzyme secreted by Bacillus cereus.Frankland was purified to homogeneity by a combination of ammonium sulfate precipitation,Phenyl-Sepharose hydrophobic-interaction chromatography and DEAE anion-exchange chromatography.On SDS(sodium dodecyl sulfate)-polyacrylamide gel electrophoresis analysis,the purified enzyme showed a relative molecular mass of 58.3 kDa.The depolymerzation of subunits was accompanied with the loss of NP-degrading enzyme activity,and removing denaturing factors by dialysis could restore the dimer structure and enzymatic activity.The enzyme had an isoelectric point of 5.5 and an optimal temperature of 60℃,and was the most active at pH 6.0.The enzymatic activity was stable at pH 4-8 and inhibited by Cu2+.TenN-terminal amino acids were determined to be ASVNSIKIGY,demonstrating that the purified enzyme was a novel one.The hydrolysis pattern of the purified enzyme indicated that the NP-degrading enzyme was an endo NP-degrading enzyme.The extraordinary thermo-stability provided the enzyme with a good prospect to be used as a new tool for clean-production process for textile industry.     

白假丝酵母PDY-07厌氧生物降解4-氯酚的研究

Candida albicans PDY-07 was isolated from activated sludge under anaerobic conditions and identified as a member belonging to the genus Candida. Pure culture of C. albicans PDY-07, biodegradation of 4-chlorophenol (4-CP) was carried out under anaerobic conditions in Erlenmeyer flasks at 35℃, with an initial pH of 7.0—7.2 and a starting inoculum of 10% (by volume). The results showed that, under the above-mentioned conditions, C. albicans PDY-07 could thoroughly biodegrade 4-CP up to a concentration of 300mg•L－1 within 244h and that it had a high tolerance potential of up to 440mg•L－1 for 4-CP. With the increase in the initial concentrations of 4-CP, substrate inhibition was obviously enhanced. There was increased consumption of 4-CP, which was not assimilated by the cell for growth but was used to counteract the strong substrate inhibition. In addition, the cell growth and substrate-degradation kinetics of 4-CP as the sole source of carbon and energy for the strain in batch cultures were also investigated over a wide range of substrate concentrations (2.2—350mg•L－1), using the proposed cell growth and degradation kinetic models. The results recorded from these experiments showed that the proposed kinetic models adequately described the dynamic behavior of 4-CP biodegradation by C. albicans PDY-07.     

厌氧／缺氧SBR反硝化除磷过程的研究

Removal of denitrifying phosphorus was verified in a laboratory anaerobic/anoxic sequencing batch reactor (A/A SBR). The results obtained demonstrated that the anaerobic/anoxic strategy can enrich the growth of denitrifying phosphorus removing bacteria (DPB) and take up phosphate under anoxic condition by using nitrate as the electron acceptor. The phosphorus removal efficiency was higher than 90% and the effluent phosphate concentration was lower than 1mg·L^-1 after the A/A SBR was operated in a steady-state. When the chemical oxygen demand(COD) of influent was lower than 180mg·L^-1, the more COD in the influent was, the higher efficiency of phosphorus removal could be attained under anoxic condition. However, simultaneous presence of carbon and nitrate would be detrimental to denitrifying phosphorus removal. Result of influence of sludge retention time (SRT) on denitrifying phosphorus removal suggested that the decrease of SRT caused a washout of DPB and consequently the enhanced biological phosphorus removal decreased with 8 days SRT. When the SRT was restored to 16 days, however, the efficiency of phosphorus removal was higher than 90%.     

Immobilized laccase on magnetic nanoparticles for enhanced lignin model compounds degradation

As a natural aromatic polymer, lignin has great potential but limited industrial application due to its complex chemical structure. Among strategies for lignin conversion, biodegradation has attracted promising interest recently in term of efficiency, selectivity and mild condition. In order to overcome the issues of poor stability and non-reusability of enzyme in the biodegradation of lignin, this work explored a protocol of immobilized laccase on magnetic nanoparticles(MNPs) with rough surfaces for enhanced lignin model compounds degradation.Scanning electron microscope with energy dispersive spectrometer(SEM-EDS), flourier transformation infrared spectroscopy(FTIR) and thermal gravimetric analysis(TGA) were utilized to characterize the immobilization of laccase. The results showed a maximum activity recovery of 64.7% towards laccase when it was incubated with MNPs and glutaraldehyde(GA) with concentrations of 6 mg·ml~(-1) and 7.5 mg·ml~(-1) for 5 h, respectively. The immobilized laccase showed improved thermal stability and pH tolerance compared with free laccase, and remained more than 80% of its initial activity after 20 days of storage at 4 ℃. In addition, about 40% residual activity of the laccase remained after 8 times cycles. Gas chromatography–mass spectrometry(GC–MS) was utilized to characterize the products of lignin model compound degradation and activation, and the efficiency of immobilized laccase was calculated to be 1–5 times that of free laccase. It was proposed that the synergistic effect between MNPs and laccase displays an important role in the enhancement of stability and activity in lignin model compound biodegradation.     

Simultaneous heterotrophic nitrification and aerobic denitrification at high initial phenol concentration by isolated bacterium Diaphorobacter sp. PD-7

A strain capable of phenol degradation, heterotrophic nitrification and aerobic denitrification was isolated from activated sludge of coking-plant wastewater ponds under aerobic condition. Based on its morphology, physiology, biochemical analysis and phylogenetic characteristics, the isolate was identified as Diaphorobacter sp. PD-7. Biodegradation tests of phenol showed that the maximum phenol degradation occurred at the late phase of exponential growth stages, with 1400 mg·L-1 phenol completely degraded within 85 h. Diaphorobacter sp. PD-7 accumulated a vast quantity of phenol hydroxylase in this physiological phase, ensuring that the cel s quickly utilize phenol as a sole carbon and energy source. The kinetic behavior of Diaphorobacter sp. PD-7 in batch cultures was investigated over a wide range of initial phenol concentrations (0–1400 mg·L-1) by using the Haldane model, which adequately describes the dynamic behavior of phenol biodegradation by strain Diaphorobacter sp. PD-7. At initial phenol concentration of 1400 mg·L-1, batch experiments (0.25 L flask) of nitrogen removal under aerobic condition gave almost entirely removal of 120.69 mg·L-1 ammonium nitrogen within 75 h, while nitrate nitrogen removal reached 91%within 65 h. Moreover, hydroxylamine oxidase, periplasmic nitrate reductase and nitrite reductase were successful y expressed in the isolate.     

在不分隔的反应器中原位电生成活性氯氧化降解蒽醌染料

The purpose of this paper was to investigate the possibility of treating C. I. Reactive Blue 19 wastewater by electrochemical oxidation via electrogenerated active chlorine, using metallic oxide coatings （dimensional stable anode, DSA） as anode. The electrolysis for the simulated wastewater was conducted at a constant current. Absorbances at 592 nm and 255 nm were measured to follow the decolorization of the dye and the degradatin of its aromatic ring. After 4 h of electrolysis under the experimental conditions： current density of 15 A·m^-2, 0.2 mol·L^-1 NaCl, 0.1 mol·L^-1 Na2SO4, 0.1 mmol·L^-1 dye, initial pH=6.4 and T=30℃, 100% decolorization of the dye and about 45% degradation of its aromatic ring were achieved, while no obvious change of total organic carbon was observed. The experimental results suggest that the decolorization of the dye and degradation of its aromatic ring were directly affected by current density, temperature, concentrations of the dye and sodium chloride, while slightly affected by initial pH and sodium sulfate concentration; the decolorization of the dye and degradation of its aromatic ring followed pseudo-first-order kinetics; and indirect electrooxidation, using electrogenerated active chlorine, predominated in the electrochemical oxidation.     

Degradation of hexahydro‐1,3,5‐trinitro‐1,3, 5‐triazine (RDX) by anaerobic mesophilic granular sludge from a UASB reactor

BACKGROUND: This study investigated the performance of anaerobic mesophilic granular sludge for the degradation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). Batch tests were conducted to investigate the effects of different supplements on the RDX degradation ability of anaerobic granular sludge, as well as the contributions of both physicochemical and biological processes involved in RDX removal from aqueous solution. RESULTS: Anaerobic granular sludge exhibited good performance in treating RDX as the sole substrate. Biodegradation was the main mechanism responsible for RDX removal. Ammonium had no significant promoting effect on the degradation process. The presence of glucose was found to enhance the degradation of RDX by anaerobic granular sludge, while the addition of sulfate and nitrate had adverse effects on the reductive transformation of RDX. CONCLUSIONS: Anaerobic granular sludge is capable of removing RDX from aqueous solution with high efficiency. This study showed good prospects for high‐rate anaerobic processes in the treatment of munition wastewater. The results can be used for the design and optimization of high rate anaerobic systems for the elimination of RDX. Copyright © 2010 Society of Chemical Industry     

Selective Extraction of N‐Heterocyclic Precursors of 1,3,5,7‐Tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) Using Molecularly Imprinted Polymers

N‐heterocyclic compounds are key nitration precursors for some high energy density explosives such as 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX). Nitration of 1,3,5,7‐tetraacetyl‐1,3,5,7‐tetraazacyclooctane (TAT) yields HMX in high yields and purity. However, the analogue 1,3,5‐triacetyl‐1,3,5‐triazacyclohexane (TRAT) is easily co‐produced via the condensation of acetonitrile and 1,3,5‐trioxan. To selectively extract TAT from a mixture of TAT and TRAT, the molecular imprinting technology (MIT) was developed in this study. The capacity of the dry polymer is 16 mg g⁻¹ and the recovery surpasses 75 %.     

Analysis of Polar Precursors of 1,3,5,7‐Tetranitro‐1,3,5,7‐tetrazocine (HMX) Using Hydrophilic Interaction Chromatography

Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) is currently one of the most widely used explosives. 1,3,5,7‐Tetraacetyl‐1,3,5,7‐tetraazacyclooctane (TAT) is an attractive precursor for the synthesis of HMX; the nitration of this key precursor results in both high yield and purity under mild condition. TAT can be prepared either by acetylation of 2,6‐diacetyl‐pentamethylenetetramine (DAPT) or by the condensation of ACN and 1,3,5‐trioxane. However, TAT and DAPT are polar compounds, and are difficult to analyze using reverse phase liquid chromatography. Herein, a chromatography method for the direct separation of these polar compounds was developed using hydrophilic interaction chromatography (HILIC) using a Venusil HILIC column, with ACN/water (95/5, v/v) as the mobile phase. The chromatographic analysis and identification of these polar compounds provide valuable information for the optimization of the synthetic process of TAT.     

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.     

Micro Videographic Analysis of the Melt Layer of Self‐Deflagrating HMX and RDX

Micro videographic analysis of the thin molten layer on the surface of HMX (Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine) and RDX (Hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine) during self deflagration were performed. This was done to gain a better understanding of the physical structure present in this 100–300 μm layer and give a visual picture for the development of computational models. During steady‐state combustion, RDX had a consistent melt layer with vigorous bubble formation. There was a continuous liquid layer throughout combustion and no foam was formed. The surface of HMX during steady‐state combustion at ambient initial temperatures was an uneven layer of foam. Foam appeared to convect across the surface in undulating waves. At elevated initial temperatures, the HMX molten layer was a consistent foam layer in both time and space. Micro videography was also done with a diagnostic laser sheet as illumination to measure the melt layer thickness. The RDX bubbling layer was about 217±30 μm thick. The HMX foam thickness varied from almost nothing to 660 μm, with an average value of about 234±106 μm.     

Kinetic Deuterium Isotope Effects in the combustion of formulated nitramine propellants

The kinetic deuterium isotope effect was used to investigate the rate-limiting process in the combustion of formulated nitramine propellants. Model propellant formulations containing either octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), or their deuteriated analogues were pressed into pellets and burned under nitrogen pressure in a window bomb. The magnitudes of the observed deuterium isotope effects indicate that the HMX and RDX exert significant control over the combustion phenomenon of the propellants studied. Furthermore, assuming a consistent mechanism between decomposition and combustion, the observed isotope effects suggest that a carbon-hydrogen bond rupture in HMX or RDX is the rate-controlling step in the combustion of the model nitramine propellants. Observed isotope effect values for HMX-CW5 and RDX-CW5 formulated propellants at 1000 psig (6.99 MPa) pressure were 1.29 ± 0.09 and 1.24 ± 0.07, respectively, compared to a theoretical estimate of 1.29 for a primary effect due to C H bond rupture at 673 K.     

Study of Plastic Explosives based on Attractive Cyclic Nitramines,Part II. Detonation Characteristics of Explosives with Polyfluorinated Binders

A series of plastic bonded explosives (PBXs) based on Viton A and Fluorel binders were prepared using four nitramines, namely RDX (1,3,5‐trinitro‐1,3,5‐triazinane), β‐HMX (β‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole), and ε‐HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane). The detonation velocities, D, were determined. Detonation parameters were also calculated by means of modified Kamlet & Jacobs method, CHEETAH and EXPLO5 codes. In accordance with our expectations BCHMX based PBXs performed better than RDX based ones. The Urizar coefficient for Fuorel binder was also calculated.     

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。     

Study of Plastic Explosives based on Attractive Cyclic Nitramines Part I. Detonation Characteristics of Explosives with PIB Binder

Four plastic explosives based on energetic nitramines and a non‐energetic binder were prepared and studied. The nitramines were RDX (1,3,5‐trinitro‐1,3,5‐triazine), HMX (1,3,5,7‐tetranitro‐1,3,5,7‐tetrazine), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole) and HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane, ε‐CL‐20). The binder was in all cases polyisobutylene (PIB) as in the standard composition C‐4. These powerful plastic explosives were compared to standard PETN‐based commercially available explosives Semtex 1A and Sprängdeg m/46. The detonation velocities were experimentally measured and compared to the ones calculated by the Kamlet–Jacobs method, CHEETAH and EXPLO5 Codes. The experimental detonation velocities as well as the calculated detonation parameters decrease in the following order: HNIW‐PIB>HMX‐PIB≥BCHMX‐PIB>RDX‐PIB>Sprändeg m/46≥Semtex 1A. Urizar coefficients for the various binders were calculated from experimental data.     

Determination of Binary Mixtures of Nitramines by aSpectrophotometric Method Using Partial Least Squares Multivariate Calibration

The UV‐absorption spectra of cyclo‐1,3,5‐trimethylene‐2,4,6‐trinitramine (RDX) and cyclo‐1,3,5,7‐tetramethylene‐2,4,6,8‐tetranitra mine (HMX) are strongly overlapping and do not allow their direct determination without previous separation by conventional methods. A partial least squares method (PLS) in a multicomponent analysis provides a sensitive and accurate technique for the analysis of complex mixtures with strong overlapping spectra. The experimental calibration matrix was designed with 15 samples. The concentration varied between 0.584 μg/ml and 10.220 μg/ml for HMX, and between 0.400 μg/ml and 8.000 μg/ml for RDX. The cross‐validation method was used to select the number of factors. To check the accuracy of the proposed method, the optimized model obtained by using PLS‐2 was applied to the determination of these compounds in industrial samples.