再生铜冶炼过程中重金属排放特征和控制

再生铜冶炼是重要的重金属排放源,为掌握再生铜冶炼过程中重金属的排放特征和控制效果,通过固定源等速采样装置采集不同冶炼阶段的烟气样品,利用电感耦合等离子体质谱仪测定烟气和飞灰中重金属的浓度,并估算重金属的排放因子.结果表明,在冷却阶段烟气中重金属和颗粒物的浓度较高,经过布袋除尘器和吸附塔等污染控制装置后,重金属和颗粒物被协同脱除,脱除效率达80%～99%.排放烟气中重金属的浓度在阳极炉不同工艺段中的排序为：加料熔融段>氧化段≈还原段,且As、 Pb、 Cr、 Sn、 Sb和Cd的平均排放因子分别为2.6×10³、2.4×10³、2.7×10³、5.6×10²、34.1和9.8 mg·t^-1,烟气中重金属和颗粒物的浓度均满足行业排放标准.飞灰中Cu和Zn的浓度较高,具有回收利用价值.     

Interactions Among the Copper Species and Forms in Sea Water/Sediments and Copper Bioaccumulation in Oysters

Abstract

Earlier papers indicated that the first incident of green discoloration in oysters (Crassostrea gigas) and the mass mortality observed in 1986 along the Taiwan Erhjin Chi coastal area were caused by the higher contents of total copper and copper species (mainly bioavailable and free ion) in sea water. the copper in sea water would be sorbed by suspended matter and transferred to sediments, and the copper in the sediments would also be desorbed to sea water. Processes of copper adsorption and desorption are the major factors influencing the contents of total copper and copper species in sea water and sediments. in this study, the Erhjin Chi sediments were mixed with sea water by a shaker technique. When the mixture was shaken for one hour, analogous to tidal mixing in estuaries, only copper desorption from sediments was observed. If the shaking time is increased for more than 3 hours, the copper released from the sediments was resorbed to the remaining solid phases. the higher the contents of mud (91.71%) and total copper (701 mg kg^?1) in sediments, the higher the copper desorption rate (1.86 ppm hr^?1) and copper adsorption rate (0.50 ppm hr^?1) were observed. in sediments containing lower mud (0.80%) and lower copper (43.5 mg kg^?1), the copper desorption and adsorption rates were 0.83 ppm hr^?1 and 0.22 ppm hr^?1, respectively. the interactions among the total copper and copper species in sea water and sediments, chemical and ecological parameters, and copper bioaccumulation in oysters in the Erhjin Chi estuarine and coastal area are also discussed.     

Modeling Flow Through a One-Dimensional Multi-Layered Soil Profile Using the Method of Lines

The vertical flow of water through horizontal layers of soil is considered using the Method of Lines. Continuity of mass principles are used to develop the interface boundary conditions, by introducing fictitious points at the interface, and the boundary conditions are handled using explicit and iterative approximations. Both the pressure based, and the water content based forms of Richards' equation are solved using the Method of Lines. The solutions obtained are compared with some particular analytic solutions obtained from the literature, and the results show that good accuracy can be achieved. It is also shown that the water content model can handle a large discontinuity at the interface when compared against the analytical solution. This result is also confirmed against a numerical example from the literature, and was effective for relatively dry initial conditions.     

SnAgCu焊料中Sn元素在模拟土壤溶液中的浸出行为

研究了Sn-3.5Ag-0.75Cu无铅焊料及其与Cu基板的钎焊接头在模拟土壤的NaCl,NaCl-Na2SO4和NaCl-Na2SO4-Na2CO3溶液中Sn元素的浸出行为.结果表明:焊料在NaCl-Na2SO4-Na2CO3溶液中Sn的浸出相对严重;而接头在NaCl溶液中Sn的浸出量最多.在Sn浸出量多的焊料和接头表面形成厚而疏松的腐蚀产物,XRD分析表明其产物主要由SnO,SnO2和Sn4(OH)6Cl2组成.动电位极化测试分析表明接头中Cu基板与焊料合金之间的电偶腐蚀是焊料合金与接头在同种溶液中Sn元素浸出差异的主要原因.     

重金属铜在砂质壤土土柱中运移的数值模拟

通过室内土柱出流实验,分析了重金属离子铜在饱和砂质壤土中的运移行为,发现高浓度的入流液有利于铜离子的运移。同时借助于软件包CXTFIT,用确定性平衡模型和非平衡两区模型对铜离子的出流动态进行了拟合,并预测了土柱不同深度处铜离子浓度随时间的变化过程。结果表明,室内饱和均质条件下,应用确定性平衡模型拟合参数模拟精度要高于非平衡两区模型,可以不用考虑不动水体对铜离子运移的影响。     

配碳还原回收铜渣中铁、铜的影响因素探讨

采用配碳还原和熔融造渣方法回收铜渣中铁和铜,研究了CaO、Al2O3、CaF2、Na2CO3成分对铁和铜回收效果的影响。在碳氧比1.5和1 450℃条件下,CaO加入量约30%时,铁和铜的回收率较高,分别是93.85%和92.73%。实验表明:添加Al2O3、Na2CO3均降低铁和铜的回收效果,使渣中含铁量增加;CaF2添加量小于2%时,有利于铜渣中铁的回收,CaF2添加量较大时不利于铁和铜的回收。     

以印刷电路板废粉末料制取碱式碳酸铜的研究

印刷电路板废粉末料的资源化和无害化问题日益得到重视。以报废印刷电路板经机械粉碎和分选后的非金属粉(铜含量1%～5%)为原料,采用"氨浸—脱氨—干燥"的工艺制备碱式碳酸铜,设计了实验装置,考察了氨浸分离工艺条件,通过实验验证了其可靠性:铜的回收率达到98.8%以上,获得了纯度不小于98.0%的碱式碳酸铜,采用X射线粉末衍射(XRD)﹑扫描电镜(SEM)和能谱(EDS)方法对产品进行了分析和表征。     

铜前驱体对Cu/SSZ-13催化剂选择性催化氧化NH3性能的影响

采用浸渍法制备了一系列Cu/SSZ-13(X)催化剂,考察不同铜前驱体对催化剂选择性催化氧化氨(NH_3-SCO)性能的影响,并通过ICP、N_2吸附-脱附、XRD、XPS、EPR、UV-Vis、NH_3-TPD和H_2-TPR等手段对催化剂进行物化性质表征.活性测试结果表明,不同铜前驱体制备的Cu/SSZ-13催化剂活性顺序为Cu/SSZ-13(N) Cu/SSZ-13(AC) Cu/SSZ-13(Cl) Cu/SSZ-13(O).其中Cu/SSZ-13(N)具有最佳的低温活性,在200℃反应温度下NH_3转化率达85.5%,且N_2选择性达到80%以上.XRD、EPR和UV-Vis分析表明,CuO和孤立Cu~(2+)是Cu/SSZ-13催化剂的主要铜物种.NH_3-TPD分析表明,以硝酸铜为前驱体制备的Cu/SSZ-13(N)具有更多的酸性位点,有利于提高催化剂的NH_3吸附能力.H_2-TPR结果表明,Cu/SSZ-13(N)的氧化还原性最强,具有最优异的NH_3活化能力,从而使催化剂呈现最好的低温NH_3-SCO活性.     

铜胁迫对黄芪幼苗的生理学毒性与凹凸棒黏土的缓解作用

为探究黄芪幼苗对铜离子（Cu²⁺）胁迫的耐性机理以及凹凸棒黏土对Cu²⁺污染的缓解作用,研究了不同浓度CuSO₄（2~20mmol/L）胁迫对黄芪幼苗的生理学毒性与凹凸棒黏土的缓解作用.结果表明,2mmol/L CuSO₄胁迫使得根系Cu²⁺含量、H₂O₂（过氧化氢）含量、MDA（丙二醛）含量分别较对照显著上升1.82倍、1.04倍、2.14倍.CuSO₄胁迫浓度达8mmol/L时,根系SOD（超氧化物歧化酶）活性、根尖膜损伤程度和叶片Cu²⁺含量分别较对照显著上升1.13倍、1.12倍和2.62倍;同时,叶片PS Ⅱ（光系统II）实际光化学效率[Y（II）]、光化学淬灭系数（qP）、PSⅡ电子传递速率（ETR）和叶绿素含量较对照分别显著降低22.88%、24.44%、21.49%和28.31%,而NPQ和qN（非光化学荧光猝灭系数）则较对照分别显著上升2.35倍和1.58倍.根系POD（过氧化物酶）和CAT（过氧化氢酶）活性、可溶性糖和可溶性蛋白含量在8mmol/L CuSO₄处理下达到最高值后呈下降趋势.CuSO₄浓度为15~20mmol/L时,根系APX活性和叶片光适应下PS II潜在最大光化学效率（F_v'/F_m'）,以及幼苗全株鲜重、全株干重、地下部鲜重、地下部干重较对照显著下降.在非CuSO₄胁迫条件下,基质中凹凸棒黏土的存在使得幼苗根系MDA含量较对照显著降低15.93%,但未对其它所测生理学指标产生显著影响;在20mmol/L CuSO₄胁迫条件下,基质中凹凸棒黏土的存在使得幼苗根系和叶片中Cu²⁺含量分别显著下降30.78%和23.12%;同时显著缓解了20mmol/L CuSO₄胁迫对根系活性氧水平、抗氧化酶活性、膜脂质过氧化程度、根尖膜损伤程度、可溶性蛋白和可溶性糖含量,叶片PS II光化学活性和叶绿素含量的不良影响,以及对幼苗生长的抑制作用.研究结果表明,培养基质中凹凸棒黏土的存在能够显著降低幼苗组织中Cu²⁺的生物有效性,继而缓解CuSO₄胁迫对黄芪幼苗的生理学毒性作用.     

载铜氮化碳纳米片对单质汞的吸附脱除特性

用简易热剥离法合成了氮化碳纳米片（CNNS）,再通过等体积浸渍法将铜负载于CNNS表面合成了载铜CNNS吸附剂,用于低温下吸附脱除气态单质汞（Hg⁰）.利用氮气吸附-脱附、X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）等手段对吸附剂进行表征.结果表明：CNNS对Hg⁰具有良好的吸附性能,吸附温度为120℃时,脱汞效率约为54.2%;载铜修饰可极大提高CNNS的脱汞活性,脱汞效率在40~240℃温度范围内均大于82.3%,这归因于铜与氮化碳间的紧密接触.煅烧温度对载铜CNNS的脱汞活性影响较大,最佳煅烧温度为200℃.通过载铜修饰可有效活化CNNS,提高其对Hg⁰的氧化能力,这可能归因于铜离子与氮化碳之间的莫特-肖特基电子转移效应.SO₂和水蒸气对载铜CNNS的脱汞性能有抑制作用.