Effective removal of coordinated copper from wastewater using a new dithiocarbamate-type supramolecular heavy metal precipitant

A new dithiocarbamate-type heavy metal precipitant, sodium 1,3,5-hexahydrotriazinedithiocarbamate (HTDC), was prepared and used to remove coordinated copper from wastewater. In the reported dithiocarbamate-type precipitants, HTDC possesses the highest percentage of the effective functional groups. It could effectively precipitate copper to less than 0.5 mg l⁻¹ from both synthetic and actual industrial wastewater containing CuEDTA in the range of pH 3–9. UV–vis spectral investigation and elemental analysis suggested that the precipitate was a kind of coordination supramolecular compound, [Cu₃(HTDC)₂]_n. The toxicity characteristic leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) indicated that the supramolecular precipitate was non-hazardous and stable in weak acid and alkaline conditions. Tests of an anion exchange resin D231 provided a clue to simultaneously remove excess HTDC and residual CuEDTA in practical process of wastewater treatment.     

Antioxidative response to Cd in a newly discovered cadmium hyperaccumulator, Arabis paniculata F

A hydroponic experiment was carried out to study the effect of cadmium (Cd) on growth, Cd accumulation, lipid peroxidation, reactive oxygen species (ROS) content and antioxidative enzymes in leaves and roots of Arabis paniculata F., a new Cd hyperaccumuator found in China. The results showed that 22-89 microM Cd in solution enhanced the growth of A. paniculata after three weeks, with 21-27% biomass increase compared to the control. Cd concentrations in shoots and roots increased with increasing Cd supply levels, and reached a maximum of 1662 and 8670 mg kg(-1) Cd dry weight at 178 microM Cd treatment, respectively. In roots, 22-89 microM Cd reduced the content of malondialdehyde (MDA), superoxide (O(2)(-1)) and H(2)O(2) as well as the activities of superoxide dismutase (SOD), guaiacol peroxidase (GPX), ascorbate peroxidase (APX) and glutathione reductase (GR). In leaves, the contents of MDA, O(2)(-1) and H(2)O(2) remained unaffected by 22-89 microM Cd, while 178 microM Cd treatment significantly increased the MDA content, 69.5% higher than that of the control; generally, the activities of SOD, catalase (CAT), GPX and APX showed an increasing pattern with increasing Cd supply levels. Our present work concluded that A. paniculata has a great capability of Cd tolerance and accumulation. Moderate Cd treatment (22-89 microM Cd) alleviated the oxidative stress in roots, while higher level of Cd addition (178 microM) could cause an increasing generation of ROS, which was effectively scavenged by the antioxidative system.     

中国省域森林公园旅游产业竞争力的时空演化特征及影响因素

分析我国各省森林公园旅游产业竞争力演变及其影响因素,有助于为处于不同发展阶段和不同发展水平的省份提供产业竞争力方面的指导。首先构建我国港澳台外31省（市、自治区）森林公园的旅游产业竞争力指标体系,然后计算各省旅游产业竞争力得分并分析其时空演变特征,最后采用分位数回归研究影响森林公园旅游产业竞争力空间差异的主要因素。结果表明：中国森林公园旅游产业平均竞争力值较低,区域差异较大,呈现东部向中西部递减的状态;2004~2014年期间西部各省森林公园旅游产业竞争力进步较小,主要原因是受到“短板效应”的制约,表现为西部各省在产业效益方面与东、中部省份存在较大差距;中国的森林公园存在东北和东南两个高层次旅游产业竞争力集聚中心,并存在逐渐向周边地区扩散,带动周边省份提升发展的趋势;回归表明,国家扶持力度、管理投入、资源禀赋、经济基础、品牌效应和交通便利性会在不同分位点上对各省森林公园旅游产业竞争力产生影响。森林公园旅游产业竞争力在不同分位点上影响因素的差异为有针对性的提高各地区竞争力提供了良好的参考。     

Multiple copper adsorption and regeneration by zeolite 4A synthesized from bauxite tailings

Copper ions were first adsorbed by zeolite 4A synthesized from bauxite tailings, the desorption of Cu(II) using Na₂EDTA solutions was performed, and the recycling of zeolite 4A in adsorption and desorption was systematically investigated. It was observed that the Cu(II) removal efficiency was directly dependent on the initial pH value. The maximum removal efficiency of Cu(II) was 96.2% with zeolite 4A when the initial pH value was 5.0. Cu(II) was completely absorbed in the first 30 min. It was also observed that the desorption efficiency and zeolite recovery were highly dependent on the initial pH and concentration of Na₂EDTA in the solution. The desorption efficiency and percent of zeolite recovered were 73.6 and 85.9%, respectively, when the Na₂EDTA solution concentration was 0.05 mol L^?1 and the pH value was 8. The recovered zeolites were pure single phase and highly crystalline. After 3 cycles, the removal efficiency of Cu(II) was as high as 78.9%, and the zeolite recovery was 46.9%, indicating that the recovered zeolites have good adsorption capacity and can repeatedly absorb Cu(II).

     

O3-H2O2氧化法处理印染废水

采用O₃-H₂O₂氧化法对印染废水进行氧化处理,比较了O₃氧化法和O₃-H₂O₂氧化法对印染废水的处理效果,考察了初始废水pH、H₂O₂加入量、O₃流量和反应时间对废水的色度去除率和COD去除率的影响。实验结果表明：O₃-H₂O₂氧化法对废水的COD和色度的去除效果比O₃氧化法更好;在初始废水pH为11、H₂O₂加入量为13mmol/L、O₃流量为6g/h、反应时间为60min的最佳工艺条件下,处理后废水COD为61.50mg/L,COD去除率为95.73%,废水色度为5倍,色度去除率为99.75%,TOC为37.84mg/L,TOC去除率为85.10%,BOD₅为22.76mg/L,BOD₅去除率为90.20%,BOD₅/COD为0.37。     

半胱氨酸合钴溶液膜吸收法处理NO废气

在中空纤维膜接触器中以半胱氨酸合钴溶液为吸收液,采用膜吸收法处理NO废气。研究了对传质系数和NO去除率的影响因素,以及吸收液循环使用效果。实验结果表明:在进气流速为0.005 m/s、进气中NO质量浓度为650.14 mg/m3、吸收液pH为9、吸收液中半胱氨酸合钴浓度为0.017 mol/L、吸收液流速为0.003 m/s、吸收液温度为50℃的优化工艺条件下,吸收时间在55 min之内时,NO去除率保持在98%以上;吸收时间超过55 min之后,NO去除率迅速下降。吸收液经SO2还原处理后可多次循环使用,吸收效果基本不变。     

烟气脱硫溶液中硫酸根的去除

分别采用石灰乳化学沉淀法和低温结晶法去除烟气脱硫溶液中的SO42-。实验结果表明：在室温、CaO溶液质量分数25%的条件下,石灰乳化学沉淀法对SO42-的去除率仅为59.51%,且向溶液中引入了Ca2+,产生的硫酸钙固体废物难以再生利用;采用低温结晶法处理烟气脱硫溶液,在结晶温度7 ℃、结晶时间3 h、NaOH加入量34.8 g/L的条件下,SO42-的去除率为82.04%、滤液中的ρ（Na+）为3.88 g/L。在现场工业应用试验中,采用低温结晶法去除烟气脱硫溶液中的SO42-,平均SO42-的去除率可达70.00%以上,滤液中的ρ（Na+）小于15.00 g/L。该法可有效抑制烟气脱硫溶液中SO42-含量的增加。     

膜电解法退镀废ABS电镀件及回收铜和镍

采用膜电解法对废丙烯腈-丁二烯-苯乙烯（ABS）电镀件进行退镀处理。以退镀废液作为阴极液和阳极液,在阳极室退镀ABS电镀件,在阴极室电解退镀废液,进行铜镍分离,回收铜粉和NiCl₂。实验结果表明：在阴极电流密度为500 A/m²、初始铜离子质量浓度为24.00 g/L的条件下电解160 min,阴极铜回收率可达97.65%,电流效率达86.60%,得到的铜粉纯度为97%~99%,处理1 L退镀废液可回收铜粉20.0 g,2 mol/L盐酸0.87 L,NiCl₂晶体43.8 g;在阳极电流密度为500 A/m²、液固比为6的条件下电解60 min, ABS电镀件的退镀率为77.22%。