锌粉对聚氯乙烯的机械化学还原脱氯

以锌粉为还原剂进行了聚氯乙烯（PVC）的机械化学还原脱氯（简称脱氯）探索研究,考察了球磨转速、球料比（磨球与试样的质量比）、锌粉与PVC质量比等对脱氯率的影响,并对脱氯产物进行了X射线衍射、红外光谱等分析。实验结果表明,最佳工艺条件为球料比33、球磨转速528r／min、锌粉与PVC质量比9;产物中未形成结晶性氯化锌,且锌粉被氧化成ZnO;行星球磨比搅拌球磨对PVC的脱氯效果好,球磨时间超过3h,PVC的脱氯率可接近100％。     

1,2,4-三氯苯环境污染修复技术研究进展

综述了物理修复、化学修复、微生物修复及联合修复等几种主要的1,2,4-三氯苯(1,2,4-TCB)环境污染修复技术的研究进展。阐述了各种修复方法的反应原理、修复条件和效果,对比了各种修复方法的优缺点。提出今后的研究方向:解决物理吸附法修复1,2,4-TCB污染后的吸附剂的后续处理问题;优化化学降解1,2,4-TCB的工艺条件,避免二次污染,进行现场试验,实现工程应用;分离、培育1,2,4-TCB的优势降解菌种;深入研究联合修复技术的降解机理,实现1,2,4-TCB的高效、彻底降解。     

用铜钨合金废料制备氧化亚铜

用硝酸浸取铜钨合金废料中的铜,再用亚硫酸钠还原硝酸铜制备氧化亚铜。采用X射线衍射仪对氧化亚铜进行表征,考察了氧化亚铜产品对溶液中甲基橙的光催化效果,并与分析纯五水硫酸铜制备的氧化亚铜进行了对比。实验结果表明:在硝酸浓度为5.6 mol/L,硝酸用量为2.5 m L/g(为理论用量的1.5倍),浸取温度为40℃,浸取时间为6 h的最优浸取条件下,铜浸取率稳定在87%以上;在还原反应温度为80℃、还原反应时间为4h、硝酸铜浓度为0.8 mol/L的条件下,可制备得到较高纯度的氧化亚铜;在甲基橙质量浓度为20 mg/L、氧化亚铜加入量为2 g/L,500 W氙灯照射时间为2.5 h的条件下进行光催化反应,甲基橙降解率可达93%以上。与分析纯五水硫酸铜制备的氧化亚铜相比,两者形貌相似、光催化效果基本相当。     

钯负载泡沫镍电极电化学还原水中三氯乙酸

采用非电沉积法制备了钯负载泡沫镍电极,运用SEM技术对其进行了表征,并以其阴极、铂丝为阳极进行了电化学还原三氯乙酸的研究,考察了工艺条件对三氯乙酸降解效果的影响,并对反应动力学和反应机理和进行了探讨。结果表明:钯负载泡沫镍电极具有较高的比表面积和良好的储氢性能;以20 mmol/L硫酸钠为电解质,在电解温度为20℃、钯负载量为4.5 mg/cm~2的条件下恒流(10 mA)电解240 min,三氯乙酸降解率达99.76%,氯原子脱除率达73.86%;三氯乙酸的电化学还原反应过程以及三氯乙酸上未脱除氯原子浓度的变化均符合拟一级反应动力学方程;三氯乙酸在电化学还原过程中逐个脱除氯原子。     

钯/铁双金属对六氯乙烷的催化还原脱氯

用钯／铁双金属对水溶液中的六氯乙烷（HCE）进行催化还原脱氯,考察了各种因素对脱氯效果的影响。实验结果表明,在厌氧环境、饱和HCE溶液体积80mL、钯与铁质量比0．03％、钯／铁双金属质量3g、反应时间130min的条件下,脱氯率可达98．8％。采用气相色谱-质谱联用仪对HCE及其脱氯产物进行分析,结果表明,HCE的脱氯中间产物主要是四氯乙烯,四氯乙烯进一步脱氯的中间产物未检出。     

离子交换树脂处理三乙胺废水

采用离子交换树脂对废水中三乙胺进行吸附。探讨了静态及动态吸附三乙胺的影响因素,考察了树脂的脱附条件及其吸附稳定性。实验结果表明:RX01型树脂对三乙胺的吸附性能优于HD-81型和D155型树脂;在三乙胺初始质量浓度为1 500 mg/L、初始pH为11.5、吸附时间为2 h、吸附温度为298 K的静态吸附条件下,三乙胺去除率为96.3%,饱和吸附量为145 mg/g,等浓度条件下阳离子影响的大小顺序为Ca~(2+)Mg~(2+)K~(+)Na~(+);当三乙胺初始质量浓度为1 500 mg/L、废水流量为60 BV/h、动态吸附柱高径比为5.37时,穿透体积为70 BV,出水三乙胺质量浓度小于3 mg/L,三乙胺去除率高达99.5%;以2 mol/L的HCl溶液为脱附剂,脱附剂流量为1 BV/h、出水体积为4 BV时,三乙胺的脱附率达94.8%;在最优动态吸附-脱附条件下重复使用10次,树脂性能稳定。     

NDA-66树脂对邻苯二甲酸的吸附及脱附性能

研究了NDA-66新型超高交联树脂对邻苯二甲酸的吸附及脱附性能。实验结果表明：静态吸附过程中,在初始邻苯二甲酸质量浓度1 000 mg/L、溶液pH=2.0、吸附时间600 min的条件下,吸附量可达190 mg/g;动态吸附过程中,处理11吸附床层体积倍数（BV）的邻苯二甲酸溶液,当溶液流量为1.5 BV/h时,吸附率可达100%;动态脱附过程中,在w（NaOH）= 6%、脱附温度328 K的最佳脱附条件下,脱附率可达99%以上。     

NDA-66树脂对邻苯二甲酸的吸附及脱附性能

研究了NDA-66新型超高交联树脂对邻苯二甲酸的吸附及脱附性能。实验结果表明:静态吸附过程中,在初始邻苯二甲酸质量浓度1 000 mg/L、溶液pH=2.0、吸附时间600 min的条件下,吸附量可达190 mg/g;动态吸附过程中,处理11吸附床层体积倍数(BV)的邻苯二甲酸溶液,当溶液流量为1.5 BV/h时,吸附率可达100%;动态脱附过程中,在w(NaOH)=6%、脱附温度328 K的最佳脱附条件下,脱附率可达99%以上。     

铁系金属对氯代有机物的还原脱氯研究进展

介绍了金属还原法中铁系金属还原脱氯去除氯代有机物的机理及研究现状,概括总结了催化剂类型、两种金属的比率、氯代有机物种类、溶液pH、反应温度、污染物初始浓度等因素对脱氯效果的影响,针对目前存在的问题提出了未来发展的方向。     

电气石对脱氯菌降解三氯乙烯的影响

以电气石作为环境微生物强化介质材料,协同以Dehalococcoides spp.为主体的脱氯混合菌群(简称脱氯菌)对水中的三氯乙烯(TCE)进行降解,探讨了电气石对降解效果的影响。实验结果表明:电气石可调节水溶液的p H使之趋向于中性并提高水溶液的电导率;在脱氯菌接种量为8%、电气石加入量为5.0 g/L的条件下降解20mg/L的TCE,84 h时TCE已全部降解,而未加电气石体系只降解了54.7%;外加电子供体甲醇和外加电气石均可明显提高脱氯菌对TCE的降解速率,且外加电气石的降解效果更好,说明电气石可能在促进微生物生长繁殖的同时也能为其提供合适的电子供体,这对降解地下水中的TCE具有重要意义。     

The effect of solvent concentration on the use of palladized-iron for the step-wise dechlorination of polychlorinated biphenyls in soil extracts

This report describes the application of palladized iron (Pd/Fe) to the dechlorination of polychlorinted biphenyls (PCBs) at ambient temperature. Experiments supported by congener-specific analyses demonstrated that dechlorination occurs in a step-wise fashion with the meta-chlorines being more reactive than ortho-chlorines. Over the course of the laboratory experiments, complete conversion to biphenyl was observed. The process was also tested with PCBs dissolved in high (40-60%) concentrations of ethanol and isopropanol as a means of simulating solutions generated by commercial soil and solid waste extraction processes. The reaction rate was sensitive to the percentage of solvent but complete dechlorination was still indicated. Tests with soil extracts from a contaminated site demonstrated that there were no apparent interferences from asphalt and other miscellaneous debris. Short-duration tests with highly contaminated PCB solutions from a hazardous waste site demonstrated efficient dechlorination although there was a reduction in reaction rate with time.     

防腐漆涂装含锌废水中锌粉的回收与利用

从水性环氧富锌涂料工业涂装废水中回收废锌粉,通过加热二甲基亚砜来溶解包覆于废锌粉表面的环氧树脂漆膜,得到回收锌粉,并将其再利用制防腐漆。在沉降时间12 h、热处理温度110 ℃、热处理时间60 min的条件下,废锌粉表面上的环氧树脂被去除,可直接以金属锌粉的形态加以回收利用,回收锌粉达到GB/T 6890—2012《锌粉》中的二级标准。使用后的溶剂经旋转蒸发后可再次使用,对锌粉的回收效果无影响。回收锌粉制备的防腐漆,其防腐蚀性能良好,可比市售锌粉。     

High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas–liquid fluidized bed reactor

In this research a gas–liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas–liquid fluidized bed reactor was running at 280–320 °C, where hot N₂ was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N₂ to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N₂ gas was set around 0.47–0.85 Nm³ kg^?1 for the molten PVC. Larger N₂ flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N₂ flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas–liquid fluidized bed reactor for dechlorination.     

草酸浸取废SCR催化剂制备光催化剂

采用草酸浸取废SCR催化剂,得到钛钨粉,制备Bi₂WO₆/钛钨粉复合光催化剂,考察了其对罗丹明B的光催化降解性能。制备光催化剂的优化工艺条件为：采用聚乙烯吡咯烷酮为表面活性剂,n（Bi₂WO₆）∶n（钛钨粉）=2∶1,前驱液pH为5,水热反应时间为18 h。在此条件下制备的光催化剂在可见光下降解罗丹明B,反应 60 min,罗丹明B降解率达94.30%。表征结果显示：钛钨粉小颗粒散落在Bi₂WO₆片表面,为光催化反应提供了更多的活性位点;Bi₂WO₆和钛钨粉两者结合可提高光生电子和空穴的分离效率,进而提高催化剂的光催化活性。Bi₂WO₆/钛钨粉光催化剂对罗丹明 B 的降解符合一级反应动力学规律。     

Relation between mechanochemical dechlorination rate of polyvinyl chloride and mill power consumption

A sample of polyvinyl chloride (PVC) powder was milled with CaO powder in a planetary mill for various mill operational parameters. The milled product consisted of dechlorinated hydrocarbon and water-soluble CaOHCl. The dechlorination rate of PVC was determined by the concentration of Cl⁻ ions measured in solution after dispersing the milled product in water. To evaluate the power consumption during PVC dechlorination, the mill power consumption was measured during each experimental run. In addition, media motion during planetary milling was simulated using the discrete element method (DEM), enabling calculation of the mill power consumption. The power consumption calculated by the DEM simulation compared well with the power consumption measured experimentally. The dechlorination rate correlated well with the specific mill power consumption, regardless of the sample weight. The dechlorination rate of PVC when milled with oyster shells (CaCO₃) was observed to be faster than that of the PVC/CaO system, and oyster shells could be used as a reactant for the treatment of PVC wastes. This work should be useful for the design of a reactor for the dechlorination of PVC. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Investigation on thermal dechlorination and catalytic pyrolysis in a continuous process for liquid fuel recovery from mixed plastic wastes

A continuous system (feeding rate >1 kg/h) consisting of thermal dechlorination pre-treatment and catalytic pyrolysis with Fe-restructured clay (Fe-RC) catalyst was developed for feedstock recycling of PVC-containing mixed plastic waste. The vented screw conveyor which was specially designed for continuous dechlorination was able to achieve dechlorination efficiency of over 90 % with a feedstock retention time longer than 35.5 min. The chlorine content of the pyrolytic oil obtained after dechlorination was in the range of 6.08–39.50 ppm, which meet the specification for reclamation pyrolytic oil in Japan. Fe-RC was found to significantly improve the yield of pyrolytic oil (achieved to 83.73 wt%) at the optimized pyrolysis temperature of 450 °C and catalyst dosage of 60 g. With the optimized parameters, Fe-RC showed high selectivity for the C₉–C₁₂ and C₁₃–C₁₉ oil fraction, which are the major constituents of kerosene and diesel fuel, demonstrating that this catalyst can be applied in the pyrolysis of mixed plastic wastes for the production of kerosene and diesel fuel. Overall, the continuous process exhibited high stability and consistently high-oil yield upon reaching steady state, indicating its potential up-scaling application in the industry.     

Impact of iron concentration and ph on zero‐valent iron dechlorination of DDT for brownfields

Soil contamination with persistent pesticides such as dichloro‐diphenyl‐trichloroethane (DDT) is a major issue at many brownfield sites. A technology that can be used to treat DDT‐contaminated soil using surfactants is to enhance the migration of the contaminants from the soil phase to the liquid phase, followed by the dechlorinating of the mobilized DDT in the liquid phase using zero‐valent iron (ZVI). The DDT degradation using ZVI occurs under anaerobic conditions via reductive reactions. The effect of the iron concentration on the dechlorination rate is assessed in the range of 1 to 40 percent (weight to volume) for remediation of a DDT‐contaminated site in Ontario, Canada. The optimum percentage of iron is found to be 20 percent at which the dechlorination rates of DDT and 1,1‐dichloro‐2,2‐bis(p‐chlorophenyl)ethane (DDD) were 4.5 and 0.6 mg/L/day, respectively. While mixing of the reaction solution is shown to be important in providing the iron surface available for the dechlorination reaction throughout the reaction solution, there is no significant difference between batch and fed‐batch mode of adding iron to the dechlorination process. Low pH values (pH = 3) increased the dechlorination rates of DDT and DDD to 6.03 and 0.75 mg/L/day, respectively at a 20 percent iron concentration, indicating increased dechlorination rates in acidic conditions. © 2010 Wiley Periodicals, Inc.     

Recovery of yttrium from fluorescent powder of cathode ray tube,CRT: Zn removal by sulphide precipitation

This work is focused on the recovery of yttrium and zinc from fluorescent powder of cathode ray tube (CRT). Metals are extracted by sulphuric acid in the presence of hydrogen peroxide. Leaching tests are carried out according to a 2² full factorial plan and the highest extraction yields for yttrium and zinc equal to 100% are observed under the following conditions: 3 M of sulphuric acid, 10% v/v of H₂O₂ concentrated solution at 30% v/v, 10% w/w pulp density, 70 °C and 3 h of reaction.Two series of precipitation tests for zinc are carried out: a 2² full factorial design and a completely randomized factorial design. In these series the factors investigated are pH of solution during the precipitation and the amount of sodium sulphide added to precipitate zinc sulphide. The data of these tests are used to describe two empirical mathematical models for zinc and yttrium precipitation yields by regression analysis. The highest precipitation yields for zinc are obtained under the following conditions: pH equal to 2–2.5% and 10–12% v/v of Na₂S concentrated solution at 10% w/v. In these conditions the coprecipitation of yttrium is of 15–20%.Finally further yttrium precipitation experiments by oxalic acid on the residual solutions, after removing of zinc, show that yttrium could be recovered and calcined to obtain the final product as yttrium oxide. The achieved results allow to propose a CRT recycling process based on leaching of fluorescent powder from cathode ray tube and recovery of yttrium oxide after removing of zinc by precipitation. The final recovery of yttrium is 75–80%.