基于FMEA和HAZOP的综合分析方法及应用研究

氯乙烯聚合生产过程复杂、设备众多,事故风险高,诸多危险因素极易引发火灾、爆炸、中毒等事故,导致生产停顿、设备损坏,甚至会造成大量人身伤亡和巨额财产损失。本文将故障类型和影响分析（FMEA）和危险性和可操作性研究（HAZOP）相结合,对某氯碱生产企业氯乙烯聚合生产过程的生产设备和工艺的危险性进行了系统安全分析,并科学的提出了一系列预防控制措施。这两种评价方法优势互补,不仅可以更全面合理的找出可能导致事故发生的不安全因素,而且更为系统安全分析提供了一种新的途径,使得系统的危险性分析更科学、完整和全面,这为有效预防和减少事故的发生提供了理论支撑。     

Recent advances in the electrochemical oxidation water treatment: Spotlight on byproduct control

• Byproduct formation mechanisms during electrochemical oxidation water treatment. • Control byproduct formation by quenchers. • Process optimization to suppress byproduct formation. Electrochemical oxidation (EO) is a promising technique for decentralized wastewater treatment, owing to its modular design, high efficiency, and ease of automation and transportation. The catalytic destruction of recalcitrant, non-biodegradable pollutants (per- and poly-fluoroalkyl substances (PFAS), pharmaceuticals, and personal care products (PPCPs), pesticides, etc.) is an appropriate niche for EO. EO can be more effective than homogeneous advanced oxidation processes for the degradation of recalcitrant chemicals inert to radical-mediated oxidation, because the potential of the anode can be made much higher than that of hydroxyl radicals (E_OH = 2.7 V vs. NHE), forcing the direct transfer of electrons from pollutants to electrodes. Unfortunately, at such high anodic potential, chloride ions, which are ubiquitous in natural water systems, will be readily oxidized to chlorine and perchlorate. Perchlorate is a to-be-regulated byproduct, and chlorine can react with matrix organics to produce organic halogen compounds. In the past ten years, novel electrode materials and processes have been developed. However, spotlights were rarely focused on the control of byproduct formation during EO processes in a real-world context. When we use EO techniques to eliminate target contaminants with concentrations at μg/L-levels, byproducts at mg/L-levels might be produced. Is it a good trade-off? Is it possible to inhibit byproduct formation without compromising the performance of EO? In this mini-review, we will summarize the recent advances and provide perspectives to address the above questions.     

Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

An assessment of the effectiveness and impact of electrokinetic remediation for pyrene-contaminated soil

The effectiveness of electrokinetic remediation for pyrene-contaminated soil was investigated by an anode-cathode separated system using a salt bridge. The applied constant voltage was 24 V and the electrode gap was 24 cm. Two types of soil （sandy soil and loam soil） were selected because of their different conductive capabilities. The initial concentrations of pyrene in these soil samples were 261.3 mg/kg sandy soil and 259.8 mg/kg loam soil After treatment of the sandy soil and loam soil for seven days, 56.8% and 20.1% of the pyrene had been removed respectively. Under the same power supply voltage, the removal of the pollutant from the sandy soil was greater than that from the loam soil, due to the higher current and lower pH. Further analysis revealed that the effectiveness of electrokinetic remediation was affected by the energy expenditure, and was associated with changes in soil properties.     

Electrochemical oxidation of 1H,1H,2H,2H-perfluorooctane sulfonic acid (6：2 FTS) on DSA electrode：Operating parameters and mechanism

The 6:2 FTS was the substitute for perfluorooctane sulfonate(PFOS) in the chrome plating industry in Japan. Electrochemical oxidation of 6:2 FTS was investigated in this study. The degradabilities of PFOS and 6:2 FTS were tested on the Ti/SnO2–Sb2O5–Bi2O3anode. The effects of current density,potential,and supporting electrolyte on the degradation of 6:2 FTS were evaluated. Experimental results showed that 6:2 FTS was more easily degraded than PFOS on the Ti/SnO2–Sb2O5–Bi2O3anode. At a low current density of 1.42 mA/cm2,6:2 FTS was not degraded on Ti/SnO2–Sb2O5–Bi2O3,while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm2. The degradation of 6:2 FTS at current density of 6.80 mA/cm2 followed pseudo first-order kinetics with the rate constant of 0.074 hr-1. The anodic potential played an important role in the degradation of 6:2 FTS,and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO2–Sb2O5–Bi2O3was contaminated after electrolysis at constant potential of 3 V,while the fouling phenomenon was not observed at 5 V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer(UPLC–MS/MS) were shorter chain perfluorocarboxylic acids. The 6:2 FTS was first attacked by hydroxyl radical,and then formed perfluorinated carboxylates,which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.     

丁二烯球罐中聚合物形成的影响因素

根据丁二烯聚合物形成的机理,通过自行搭建的实验装置,研究并确定了丁二烯过氧化物生成的影响因素。通过研究确定了温度对丁二烯过氧化物生成的影响,确定了氧含量和铁锈对丁二烯过氧化物生成的影响。根据不同因素对丁二烯过氧化物的影响,确定了球罐内丁二烯储存的临界温度和储存时间。丁二烯聚合的特点表明球罐内丁二烯二聚体含量偏高时,球罐发生爆聚的风险增加。为确保丁二烯球罐安全,必须严格控制球罐内二聚体含量、温度、铁锈含量和氧含量,紧急情况下须采取有效措施抑制丁二烯聚合。     

High aspect ratio micromachining of glass by electrochemical discharge machining (ECDM)

Micromachining of glass is essential for several microfluidic components, micro-pumps, micro-accelerometers, micro-reactors, micro-fuel cells and several biomedical devices. Unique properties such as high chemical resistance, thermal stability and transparency give glass scope for additional applications. However, poor machinability of glass is a major constraint, especially in high aspect ratio applications of glass in microsystem technology. Micro electrochemical discharge machining (micro ECDM) is an emerging nontraditional fabrication method capable of micromachining ceramic materials like glass. While surface features less than 100 μm have been successfully machined on glass, machining high aspect features is a challenge. Machining accuracy at high depths is severely affected due to overcut and tool wear. In this paper, high aspect ratio microtools fabricated in-house have been used for deep microhole drilling on glass using low electrolyte concentration. An aspect ratio of 11 has been achieved. The results show that lower electrolyte concentration reduced overcut by 22%, thus increasing the aspect ratio of the micro holes. Lowering the electrolyte concentration also reduced the tool wear and hole taper by 39% and 18% respectively.     

锌离子印迹聚合物的合成及固相萃取特性研究

为了达到对溶液中目标痕量金属离子的分离和分析,采用了硅胶表面金属离子印迹聚合技术,活化硅胶表面羟基后,在硅烷偶联剂(APS)存在条件下合成了Zn(Ⅱ)离子印迹聚合硅胶。对其进行表征和吸附、再生等性能及合成机理研究,并将所得Zn(Ⅱ)离子印迹聚合物填充于市售空白小柱制成Zn(Ⅱ)离子印迹聚合物固相萃取小柱,并对其固相萃取性能进行了初步研究表征结果表明,Zn(Ⅱ)成功印迹于活化硅胶表面。与非离子印迹硅胶相比,Zn(Ⅱ)离子印迹聚合硅胶具有更高的选择性,其最大静态吸附容量可达12.87 mg/g,并可反复利用10次以上保持吸附率不低于95%。所得Zn(Ⅱ)离子印迹聚合物固相萃取小柱在不同初始条件下对Hg的相对选择因子可达15.5和13.8。Zn(Ⅱ)离子印迹聚合硅胶是一种新型高效低成本的聚合物,可将其用于水溶液中Zn(Ⅱ)的分离和分析。     

EGCG消毒过程中氧化聚合作用对色度的影响研究

为探究茶多酚消毒时的色度问题,采用茶多酚中具有抑菌作用的主要成分表没食子儿茶素没食子酸脂(Epicatechin gallate,EGCG)为消毒剂,在不同条件下(消毒剂投加量、接触时间、水样p H、光照条件),测试EGCG氧化聚合反应对水样色度变化的影响。研究表明,非酶促氧化聚合反应主要受EGCG的投加量、水样p H的影响,其影响色度的方式是通过影响反应平衡进而控制聚合物的生成量;酶促氧化聚合反应的条件是存在多酚氧化酶(PPO),水中细菌可提供PPO,而光照条件是影响PPO活性的主要因素,水样p H的变化对于二聚醌(dimer quinone)进一步发生亲核加成反应起着关键作用。