四溴双酚A的辐照降解研究

研究了甲醇-水溶液中四溴双酚A(TBBPA)的电子束辐照降解.通过测定辐照前后TBBPA的浓度变化来研究吸收剂量、初始浓度、pH、自由基清除剂对辐照降解效果的影响.结果表明,TBBPA在甲醇-水溶液的辐照降解是还原性逐步脱溴降解过程,自由电子在降解过程中起主导作用,降解反应遵循一级动力学方程.在辐照剂量为10 kGy时,20 mg.L-1的TBBPA有91.6%发生脱溴降解,当向辐照体系充入氮气并且加入叔丁醇,可将TBBPA的降解效率提高到100%,或者调节辐照体系溶液的pH值至12,TBBPA的降解效率也可以达到100%.辐照降解是处理TBBPA的一种有效手段.     

Removal of decabromodiphenyl ether (BDE-209) by sepiolite-supported nanoscale zerovalent iron

Nanoscale zerovalent iron (nZVI) synthesized using sepiolite as a supporter was used to investigate the removal kinetics and mechanisms of decabromodiphenyl ether (BDE-209). BDE-209 was rapidly removed by the prepared sepiolite-supported nZVI with a reaction rate that was 5 times greater than that of the conventionally prepared nZVI because of its high surface area and reactivity. The degradation of BDE-209 occurred in a stepwise debromination manner, which followed pseudo-first-order kinetics. The removal efficiency of BDE-209 increased with increasing dosage of sepiolite-supported nZVI particles and decreasing pH, and the efficiency decreased with increasing initial BDE-209 concentrations. The presence of tetrahydrofuran (THF) as a cosolvent at certain volume fractions in water influenced the degradation rate of sepiolite-supported nZVI. Debromination pathways of BDE-209 with sepiolite-supported nZVI were proposed based on the identified reaction intermediates, which ranged from nona- to mono-brominated diphenylethers (BDEs) under acidic conditions and nona- to penta-BDEs under alkaline conditions. Adsorption on sepiolite-supported nZVI particles also played a role in the removal of BDE-209. Our findings indicate that the particles have potential applications in removing environmental pollutants, such as halogenated organic contaminants.     

超/亚临界水中四溴双酚A的脱溴降解特性研究

在超/亚临界水及其碱溶液中对四溴双酚A进行了水热脱溴降解研究。考察了温度、时间和碱类型对降解特性的影响。结果表明,在纯水中温度是影响四溴双酚A降解的关键参数,350℃下反应180 min和400℃反应30 min,脱溴率分别达到98.7%和96.7%,降解产物中苯酚和4-丁基苯酚分别占50%和20%以上,另外还有少量的烷基酚;向反应体系中加入碱不仅可以中和反应过程中产生的氢溴酸以保护超临界反应釜,而且可以在较低温度下实现高的脱溴率,产物中苯酚含量达50%以上、4-异丙烯基苯酚占10%左右,可以实现脱溴同时回收化工产品的目的。与传统的热解技术相比,超/亚临界水处理TBBPA具有明显的优势,本研究为含溴电子废弃物的清洁高附加值资源化利用提供了一条新的途径。     

超临界丙酮降解废弃线路板中的溴化环氧树脂

探讨废弃线路板中溴化环氧树脂在超临界丙酮中的脱溴降解特性,重点考察了温度、反应时间和有机溶剂添加量对溴化环氧树脂降解特性的影响,确立的最佳实验条件为：温度260℃、保温时间1~2 h、丙酮添加量20~40 mL,系统压强3~6 MPa,此时溴化环氧树脂能够快速降解,脱溴率达到97.94%,降解产物主要为苯酚和异丙基苯酚,含量分别为60.99%和3.12%,降解产物中溴主要以HBr的形式存在于油相中,可以用碱液从油相中萃取脱除。线路板经超临界丙酮处理后,铜箔与玻璃纤维自动分层解离便于后续破碎回收,为废弃线路板的无害化处理和资源回收利用提供了一条新途径。     

双金属系统还原脱溴降解多溴联苯醚(PBDEs)研究进展

多溴联苯醚(PBDEs)是一类新型持久性有机污染物。双金属系统催化还原脱溴技术作为一种处理环境中PBDEs的方法,具有出较好的应用前景。综述了双金属系统催化还原PBDEs脱溴的研究进展,详细阐述了双金属系统催化PBDEs脱溴降解的机理、途径以及不同双金属系统的脱溴效能。提出了利用双金属系统降解PBDEs存在的问题和发展前景。     

树脂D001负载纳米Pd/Fe双金属脱溴2,2＇,4,4＇-四溴联苯醚（BDE-47）的研究

采用大孔树脂D001交换吸附Pd2＋、Fe2＋并在厌氧条件下以硼氢化钠溶液还原吸附的钯铁离子制备成负载纳米Pd/Fe双金属树脂。利用该树脂对2,2＇,4,4＇-四溴联苯醚（BDE-47）进行脱溴反应,探讨了该法的可行性和特性。结果表明：当大孔树脂D001、氯化钯、硫酸亚铁用量分别为0.75 g、2μg和0.2 g时所制备的双金属树脂脱溴水-乙醇溶液中的BDE-47效果最佳,反应遵循准一级动力学,速率常数k约为0.161 d-1,半减期为1.21 d。负载Pd/Fe的D001连续3次脱溴反应都有较好的效果,水-乙醇溶液中超过90%以上的BDE-47在反应6 d后被降解。负载Pd/Fe双金属的树脂可以重复活化再生,但再生2次后其脱溴效率变差,反应6 d只有47.3%的BDE-47被降解。用气相色谱-质谱联用仪和离子色谱仪跟踪Pd/Fe双金属树脂脱溴BDE-47反应,可知产物包括溴离子、三溴联苯醚、二溴联苯醚、一溴联苯醚和联苯醚。     

Ca、Fe系添加剂对废线路板热解油脱溴改质效果的影响

为了达到废印刷电路板(WPCB)热解油的脱溴和轻质化的目的,在废印刷电路板非金属粉末(WPCBNP)的热解中应用不同的添加剂(脱溴剂、脱溴剂+催化剂).首先,研究了WPCBNP的热解三相产物产率.其次,测定了热解液体产物中有机溴和无机溴的含量.最后,分析了热解油中碳原子的组成分布和组分含量.试验结果表明,使用Fe_3O_4+4A分子筛时,热解油回收率可达12.23%.热解液相产物中的无机溴含量从283.04 mg·g~(-1)减少到10.19 mg·g~(-1)(Fe_3O_4+Al_2O_3),去除率为90.47%,有机溴含量从151.13 mg·g~(-1)减少到11.07 mg·g~(-1)(Fe_3O_4+Al_2O_3),去除率分别为90.47%和92.68%.应用Fe_3O_4+Al_2O_3可将C6~C9组分(或汽油组分)含量从61.07%提高到76.75%,C10~C14组分(或柴油组分)含量从10.66%提高到13.95%,而≥C15(或重油组分)含量从28.27%降低至9.30%.通过分析热解油成分,可知油中主要含溴有机物是2-bromoPhenol和2,4-dibromo-Phenol.应用不同添加剂/组合添加剂,2-bromo-Phenol含量可降至1.22%,而2,4-dibromo-Phenol未被检出.结果表明,Fe_3O_4+Al_2O_3在WPCBNP热解油的脱溴和轻质化方面效果最好,对WPCB资源化利用具有显著的效益.     

铜绿假单胞菌NY3好氧降解四溴双酚A的特性研究

为发掘铜绿假单胞菌NY3对有机污染物更多的降解功能,探究该菌好氧降解四溴双酚A(TBBPA)的特性。结果表明,NY3菌能以四溴双酚A为唯一碳源和能源好氧生长,并在TBBPA质量浓度为20 mg/L时,脱溴率达到51.90%。该菌生长量越大,对TBBPA降解率和脱溴率越高。TBBPA质量浓度为60 mg/L时,外加共代谢碳源葡萄糖、丙酮酸钠、乙酸钠、乳酸钠、柠檬酸钠、乙醇均能明显提高NY3菌生长量,且使脱溴率分别提高21.7%、13.4%、13.11%、18.5%、18.3%、17.1%。NY3菌好氧降解TBBPA优化条件为最佳氮源(NH4)2SO_4、pH=8.0、温度(30±1)℃、摇床转速150 r/min的条件下振荡培养。在NY3菌降解TBBPA过程中,转化的主要中间产物包括3,3',5-三溴双酚A、4-(2-羟基-异丙烷基)-2,6-二溴-苯酚、2,6-二溴-4-异丙烷基-苯酚、3,3',5-三溴-5'-羟基-双酚A、4,5-二羟甲基-5-(3,5-二溴-4-羟苯基)-2-己烯酸,根据转化产物分析,NY3菌降解TBBPA主要通过脱溴、羟基化,然后开环裂解,进一步脱羧等途径。这是首次报道铜绿假单胞菌具有降解含溴阻燃剂的功能,且质荷比为477和407的2种中间产物也鲜有报道。     

Uptake, translocation, and debromination of polybrominated diphenyl ethers in maize

Uptake, translocation and debromination of three polybrominated diphenyl ethers (PBDEs), BDE-28, -47 and -99, in maize were studied in a hydroponic experiment. Roots took up most of the PBDEs in the culture solutions and more highly brominated PBDEs had a stronger uptake capability. PBDEs were detected in the stems and leaves of maize after exposure but rarely detected in the blank control plants. Furthermore, PBDE concentrations decreased from roots to stems and then to leaves, and a very clear decreasing gradient was found in segments upwards along the stem. These altogether provide substantiating evidence for the acropetal translocation of PBDEs in maize. More highly brominated PBDEs were translocated with more difficulty. Radial translocation of PBDEs from nodes to sheath inside maize was also observed. Both acropetal and radial translocations were enhanced at higher transpiration rates, suggesting that PBDE transport was probably driven by the transpiration stream. Debromination of PBDEs occurred in all parts of the maize, and debromination patterns of different parent PBDEs and in different parts of a plant were similar but with some differences. This study for the first time provides direct evidence for the acropetal translocation of PBDEs within plants, elucidates the process of PBDE transport and clarifies the debromination products of PBDEs in maize.     

Electrocatalytic debromination of BDE-47 at palladized graphene electrode

Graphene electrodes （Ti/Gr） were prepared by depositing Gr sheets on Ti substrate, followed by an annealing process for enhancing the adhesion strength. Electrochemical impedance spectroscopies and X-ray dif- fraction patterns displayed that the electrochemical behavior of Ti/Gr electrodes can be improved due to the generation of TiO2 layer at Ti-Gr interface during the annealing process. The palladized Gr electrodes （Ti/Gr/Pd） were prepared by electrochemical depositing Pd nanoparticles on Gr sheets. The debromination ability of Ti/Gr/Pd electrodes was investigated using BDE-47 as a target pollutant with various bias potentials. The results indicated that the BDE-47 degradation rates on Ti/Gr/Pd electrodes increased with the negative bias potentials from 0V to -0.5 V （vs. SCE）. Almost all of the BDE-47 was removed in the debromination reaction on the Ti/Gr/Pd electrode at - 0.5 V for 3 h, and the main product was diphenyl ethers, meaning it is promising to debrominate completely using the Ti/Gr/Pd electrode. Although the debromination rate was slightly slower at -0.3 V than that under -0.5 V, the current efficiency at -0.3 V was higher, because the electrical current acted mostly on BDE-47 rather than on water.