Polymer hydrogels with enhanced stability and heterogeneous Fenton activity in organic pollutant removal

Polymer hydrogel-based materials have been shown to act as novel Fenton catalysts for water treatment, but the rational design of hydrogel-based catalysts with good stability has been a great challenge. To increase the stability and activity of polymer-based Fenton catalysts, uniform urchin-like α-Fe_2O_3 was grown in situ in a PVA carrier matrix here. PVA molecules promoted the growth of urchin-like α-Fe_2O_3, and then the PVA hydrogel acted as a barrier and carrier to reduce agglomeration. Through coordination by hydroxyl groups,PVA had good combination with Fe ions and α-Fe_2O_3. The formation of Fe–O–C bonds between iron oxides and polymers was reported for the first time, enhancing the material stability during catalysis. Under higher PVA concentrations, the resulting composite hydrogel could generate more ˙OH due to the increase in the number of active sites because of the hairy urchin-like structure. In tetracycline degradation through a heterogeneous Fenton reaction, the resulting material had good catalytic activity from pH 2 to pH 10 with low iron leaching, good reusability and remained at a level of nearly 90%after five consecutive cycles. Density functional theory calculations were used to further prove the mechanism of structural change of the iron oxides. The HOMO and LUMO energies of the iron oxides changed from 5.428 and 4.899 eV to 5.926 and 5.310 eV,indicating that the presence of PVA could influence the charge of the iron atom. The results provide new insights into the preparation of polymer hydrogel-based heterogeneous Fenton catalysts with enhanced stability for water treatment.     

无起爆药雷管内管装药密度对燃烧转爆轰的影响研究

起爆药雷管生产中产生大量有毒废水,且其运输、贮存存在安全隐患。为克服这些困难,笔者自行制备无起爆药雷管。采用圆筒式金属内管中装填超细PETN(季戊四醇四硝酸酯),作为起爆元件,代替起爆药部分,研究装药密度对内管燃烧转爆轰(DDT)的影响。研究结果表明,在内管壁厚1～2 mm,内径Φ4.0 mm,长25 mm,装压密度为0.8～1.14 g/cm3的范围内,内管能可靠实现燃烧转爆轰。     

约束空间可燃气体燃烧爆轰特性的数值研究

在可燃气体的输送、贮存、加工和使用过程中,容易发生可燃气体的燃烧和爆炸事故。文中基于有限体积方法,采用五阶WENO格式进行左右状态量的重构后,利用ROE格式进行空间离散,自行开发程序对甲烷氧气的气相爆轰波传播过程进行了数值研究。计算结果表明:在CH4质量分数为10%的混合气体中,高温高压气团可诱导气相发生爆轰,爆轰波以2133.3 m/s的速度传播。在带有障碍物的约束空间内,文中分析了障碍物不同高度、不同间距条件下爆轰波传播时波的绕射、马赫反射等现象,给出障碍物表面压力随时间变化历程和冲量值,揭示波与障碍物的相互作用机理以及由此引发流场的变化规律,为有效地控制可燃气体的燃烧速率、防治爆炸灾害的发生提供理论依据。     

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.     

Removal of ofloxacin antibiotic using heterogeneous Fenton process over modified alginate beads

The aim of this work is to study the heterogeneous oxidative degradation of ofloxacin antibiotic using a composite material prepared from sodium alginate and cyclohexane dinitrilo tetraacetic acid(CDTA). The characterization tests indicated the successful incorporation of metal chelator and iron. It was also demonstrated that the synthesized beads are mesoporous. The influence of several experimental parameters(i.e.: H2O2 dose,working temperature, beads loading and initial drug concentration) on the process performances was evaluated. The reaction temperature significantly affects the drug conversion efficiency. It was also observed that the synthesized material was efficient toward the target antibiotic degradation in the presence of small quantities of hydrogen peroxide. Under optimum conditions(0.05 g of granules, initial drug concentration = 10 mg/L,25 μL of 10 mmol/L H2O2), conducted in a batch reaction, 94% degradation of ofloxacin was reached. The results also indicate that the composite material showed a reasonable stability;a relatively low decrease of activity after four successive runs(only 9%) and a negligible iron leaching(0.8%) have been observed. The synthesized composite material offered interesting advantages in terms of simplicity, good stability, ease of recovery from the liquid medium after use and its efficiency in the presence of low quantities of oxidant. It constitutes a good candidate in the water treatment area.     

建构筑物周边爆破施工安全控制距离及分析方法研究

为研究在居民区附近开展大面积爆破施工的安全可行性以及安全控制距离标准,采用数值模拟方法,分析了地铁车辆段爆破施工对周边高压线及居民楼的影响,根据分析结果,给出了安全控制距离及关键控制指标,说明采用数值模拟的方法适用于类似工况的可行性。另外,研究发现,在居民楼附近进行地铁车辆段爆破施工风险较高,建议在距建构筑物100 m范围内采用静态爆破或机械开挖的方式进行施工。     

炸药爆轰气体产物中无机组份的离子色谱分析方法研究

采用超纯水、Na2CO3-NaHCO3NaOH3种不同的吸收液吸收爆轰气体产物、离子色谱进行样品分离、外标法定量,建立了爆轰气体产物中HF、HCl、HCN无机污染物的离子色谱分析方法。研究表明,炸药爆轰气体中合有一定量的HF、HCl和少量的HCN,选择3．2mmol／LNa2C03与1．0mmol／LNaHCO3混合溶液作为爆轰产物中无机组份的吸收液,吸收效率均值太于90％;离子色谱分析方法的相对标准偏差（RSD）小于5．0％,相关系数达到0．9990以上;进样量为100μL时,HF、HCl、HCN的检测限分别为0．04mg／m^3、0．03mg／m^3、0．05mg／m^3。该方法灵敏度高,回收率好,且样品预处理简单。     

爆炸形成过程中火焰加速的试验研究

为预防和控制工业爆炸事故,并为脉冲爆轰发动机的研究提供理论指导,分析火焰加速导致的燃烧转爆轰过程的影响因素。采用爆轰管探讨障碍物的阻塞比、混合物的组成、初始压力和点火能等4个因素对爆炸性气体火焰速度和爆轰压力的影响规律。试验结果表明:障碍物的存在能大大提高火焰速度和爆轰压力;爆轰压力随管内障碍物阻塞比的增大先变大后减小,并在阻塞比为0.498,燃料种类为天然气,化学当量比为1时达到最大;爆轰压力还随混合气体初始压力的增大和点火能的提高而增大。选择适宜的条件可大大提高火焰加速速率,促进燃烧向爆轰过程转变。     

Efficient degradation of Rhodamine B by magnetically recoverable Fe3O4-modified ternary CoFeCu-layered double hydroxides via activating peroxymonosulfate

Environment-friendly nano-catalysts capable of activating peroxymonosulfate (PMS) have received increasing attention recently. Nevertheless, traditional nano-catalysts are generally well dispersed and difficult to be separated from reaction system, so it is particularly important to develop nano-catalysts with both good catalytic activity and excellent recycling efficiency. In this work, magnetically recoverable Fe₃O₄-modified ternary CoFeCu-layered double hydroxides (Fe₃O₄/CoFeCu-LDHs) was prepared by a simple co-precipitation method and initially applied to activate PMS for the degradation of Rhodamine B (RhB). X-ray diffraction (XRD), fourier transform infrared spectrometer (FT-IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller method (BET), and vibrating sample magnetometer (VSM) were applied to characterize morphology, structure, specific surface area and magnetism. In addition, the effects of several key parameters were evaluated. The Fe₃O₄/CoFeCu-LDHs exhibited high catalytic activity, and RhB degradation efficiency could reach 100% within 20 min by adding 0.2 g/L of catalyst and 1 mmol/L of PMS into 50 mg/L of RhB solution under a wide pH condition (3.0-7.0). Notably, the Fe₃O₄/CoFeCu-LDHs showed good super-paramagnetism and excellent stability, which could be effectively and quickly recovered under magnetic condition, and the degradation efficiency after ten cycles could still maintain 98.95%. Both radicals quenching tests and electron spin resonance (ESR) identified both HO? and SO₄^?? were involved and SO₄^?? played a dominant role on the RhB degradation. Finally, the chemical states of the sample's surface elements were measured by X-ray photoelectron spectroscopy (XPS), and the possible activation mechanism in Fe₃O₄/CoFeCu-LDHs/PMS system was proposed according to comprehensive analysis.     

Influence of physical properties of ammonium nitrate on the detonation behaviour of ANFO

In order to obtain a better understanding of the non-ideal detonation behaviour of ammonium nitrate based explosives, detonation velocities of ANFO (ammonium nitrate and fuel oil) prepared with different kinds of ammonium nitrate (AN) were measured in steel tubes. In this series of test six kinds of AN were used and the influence of the pore diameter, the pore volume and the particle diameter of the AN particle on the detonation velocity of ANFO was investigated.

It was found that the pore diameter and the pore volume had a strong influence on the detonation velocities of ANFO. In the case of ANFO samples which were prepared with AN that had the same pore diameter and the pore volume, when tested the highest detonation velocity (3.85 km/s) was observed when the smallest particle diameter (<0.85 mm) was used. This value corresponded to 75% of the ideal detonation velocity, which was theoretically predicted by the CHEETAH code with the JCZ3-EOS.

The 12 months aging showed the change of the detonation velocities of ANFO and the reaction of ANFO was influenced both by the physical and the chemical properties of AN particles and oil during the storage period.