废弃锂离子电池中金属的回收及钴酸锂的湿法合成

采用湿法回收并合成锂离子电池中钴酸锂。考察了不同的有机溶剂溶解粘结剂PVDF、不同酸浸条件对钴酸锂浸出效果的影响、碳酸钴和碳酸锂共沉淀物的焙烧条件，并对所获得的钴酸锂进行结构分析。结果表明，N-甲基吡咯烷酮（NMP）作为溶解PVDF的溶剂效果最佳；当硫酸浓度6％、固液比1：30、30％的H2O：1．4mL／g、温度80℃、反应120min时为硫酸浸出最佳条件，此时钴的浸出率为92．3％，锂的浸出率为92．0％；合成LiCoO2时的焙烧温度在750℃较为合适。SEM分析表明，颗粒粒度小，分散性好。     

废旧锂离子电池中钴的回收

采用高温煅烧-酸浸-化学沉淀工艺回收废旧锂离子电池中的钴,根据电极材料的热重性质确定煅烧温度,探究不同因素对钴的浸出和沉淀效果的影响,利用响应面技术优化酸浸过程,并对酸浸液进行回收处理。实验结果表明:煅烧温度为500℃时可充分去除黏结剂;优化实验得出H_2SO_4+H_2O_2体系浸出钴的最佳实验条件为液固比(m L:g)6.15,浸出温度96.34℃,浸出时间44.52 min,H_2SO_4浓度1.20 mol·L~(-1),浸出率97.51%;当浸出液pH为1.5,[C_2O_4~(2-)]/[Co~(2+)]比值为1.10,反应温度为70℃,沉淀时间为50 min时,钴的沉淀率为95.69%。回收得到的Co C2O4纯度高,晶体结构较好。     

氧化氨浸工艺回收硫化砷渣中的铜

对在(NH4)2S2O8-NH3-H2O体系中氧化浸出硫化砷渣(砷渣)中的铜进行热力学分析;讨论了浸出温度、c(NH3)/c(NH+4)、液固比、浸出时间及总氨浓度对铜浸出率的影响,确定了从砷渣中回收铜最佳浸出工艺条件;采用XRD和SEM对浸出渣进行表征。结果表明,氧化氨浸回收铜工艺具有热力学可行性;在浸出温度35℃,c(NH3)/c(NH+4)1∶7,液固比6∶1,浸出时间3 h,总氨浓度4 mol/L的条件下,铜的浸出率为70.74%;大量S0均匀分布在浸出渣中。     

钴钛层柱粘土催化剂催脱除零价汞简

采用钴-钛层柱粘土催化剂，向烟气中添加HCl气体进行零价汞的催化脱除实验研究。考察了反应温度及催化剂的焙烧温度、Ti/粘土、活性组分（Co）负载量等制备条件对零价汞催化脱除效果的影响。研究表明，在HCl含量20×10^-6的模拟烟气中，焙烧温度为400℃、Ti/粘土为15 mmol/g、Co含量为5 wt%（以CoO计）的钴钛层柱粘土催化剂（Co-Ti-PILCs）在空速为1.0×10⁴ h^-1、温度为300℃时零价汞脱除效率为86.7%。     

助剂(C_2H_4、NH_3)添加对AC/DC流光放电等离子体脱硝效果的影响

等离子体法脱硝被认为是一种非常环保有效的脱硝技术,为了探究等离子体对NO_x的作用过程,选用AC/DC流光放电等离子体及模拟烟气,考察了烟气流量和NO初始浓度、添加剂的种类与含量以及SO_2对等离子体脱硝的影响。结果表明:NO的脱除过程由氧化过程和还原过程同时作用,在同一功率下,NO_x脱除率随流量的增加而降低,NO初始浓度对NO_x脱除率无直接影响。氨的添加可以促进NO_x的还原脱除,乙烯的添加可以促进NO氧化转化为NO_2。烟气中SO_2存在会导致NO_x脱除效率降低,此时氨助剂的加入可以显著提高NO_x脱除率。当NH3∶SO_2=2∶1时,在15 W下SO_2脱除率可达100%,NO_x脱除率60%。     

废旧镍钴锰酸锂电池正极材料闭环回收

提出了一种闭环回收废旧镍钴锰酸锂电池正极活性物质的方法。采用H_2SO_4为浸出剂,H_2O_2为还原剂,浸出回收4种金属离子。结果表明:硫酸浓度为1.5 mol·L~(-1),反应温度为70℃,反应时间为25 min,反应固液比为20∶1 (g∶L),过氧化氢体积分数为1%时,金属镍、钴、锰和锂的浸出率分别为96.8%、96.2%、93.8%和99.1%;动力学分析显示,Ni、Co、Mn、Li浸出反应表观活化能分别为51.75、44.90、46.77和36.08 kJ·mol~(-1),属于化学反应控制。分离浸出滤液中Ni、Co、Mn离子后,制备Li_2CO3终端产品,其XRD图谱显示产品成分较纯,可用于制备锂离子电池正极材料的前驱体。该工艺可实现废旧镍钴锰酸锂正极材料回收较高的经济和环境效益。     

钒硅催化脱硫脱硝的研究

考察了经10% H2-90% Ar(体积分数)还原的钒硅催化剂在固定床石英玻璃反应器中的脱硫脱硝活性,研究了反应温度、SO2/NO摩尔比及O2浓度对SO2和NO脱除率的影响.结果表明,还原后的钒硅催化剂的平均NO脱除率提高了15%左右;反应温度对脱硫脱硝影响较大,当温度为400℃以上时SO2和NO脱除率基本保持稳定;SO2/NO摩尔比为2和5时,钒硅催化剂的NO脱除率较高;模拟烟气中有O2条件下的脱硫脱硝活性明显高于无O2条件,O2体积分数为6.00%时SO2和NO脱除率达到最大.     

鼓泡反应器中液相络合催化同时脱硫脱硝的研究

在鼓泡反应器中考察了[Co(en)3]2+同时吸收去除SO2和NO的影响因素,实验结果表明,pH值和脱硫剂种类是影响乙二胺合钴同时脱除NO和SO2的最重要影响因素,烟气中的氧促进乙二胺合钴吸收NO和SO2,烟气中的SO2,CO2和NO2对乙二胺合钴吸收NO具有抑制作用。在实验条件温度为20℃,pH为13.0,[Co(en)3]2+浓度为0.025 mol/L,加入1 g NH3.H2O的脱硝率更好,连续吸收60 min,脱硝率均保持在93.5%,加入NaOH和NH3.H2O的脱硫效果最好。乙二胺合钴络合同时脱除NO和SO2完全可以在一个装置中完成。     

超临界水氧化处理棉纺织品印染废水

在温度400～600℃、压力25 MPa、停留时间10～45 s、过氧比0%～400%条件下,用超临界水氧化（SCWO）法在连续管式反应器中处理棉纺织品印染废水。分析了工艺条件对总有机碳（TOC）及氨氮（NH3-N）降解效率的影响。研究表明,温度是影响TOC降解的最重要因素,不同温度下,降解率随过氧比变化的趋势不同。在450℃、停留时间20 s、过氧比300%时,废水TOC降解达98.94%。NH3-N的降解与反应温度和氧化剂量密切相关。当过氧比300%,温度从400℃上升到600℃时,NH3-N的浓度从55.42 mg/L下降到3.31 mg/L,而600℃没有氧化剂存在时氨不易降解。450℃时随着过氧比增大NH3-N浓度略有下降,在该温度下停留时间延长对NH3-N降解无显著影响。     

Mn-La-Ce-Ni-O_x/P84一体化滤布的低温脱硝影响因素

将550℃煅烧的Mn-La-Ce-Ni-O_x(Mn/La/Ce/Ni=2.5∶2.5∶1∶1)粉体均匀分散在蒸馏水中,采用P84滤料浸渍吸附复合氧化物分散液,经干燥、喷洒聚四氟乙烯乳液固定化,制备除尘脱硝一体化Mn-La-Ce-Ni-O_x/P84滤布。研究了Mn-La-Ce-Ni-O_x/P84滤布低温选择性催化还原(SCR)NO的活性。分别考察了反应温度、NH_3/NO摩尔比、O_2体积分数、复合氧化物负载量和SO_2等因素对Mn-La-Ce-Ni-O_x/P84滤布NH3-SCR脱除NO活性的影响。结果表明,当催化剂负载量大于250 g·m-2时,在100~200℃温度范围内一体化滤布催化活性均大于90%,200℃时脱硝活性达98.3%。当氧含量6%、NH3/NO≤1.0时,一体化滤布脱硝活性随NH3/NO摩尔比的增大而增大,NH_3过量与氧过量时无影响。200℃时,通入300×10-6SO_2对Mn-La-Ce-Ni-O_x/P84滤布脱硝活性有一定地抑制作用,脱除NO_x效率最低下降到88.6%,停止通入SO_2后,脱硝活性逐渐恢复。     

pH对污水污泥中污染物浸出的影响

研究pH对污泥中污染物浸出的影响可以为投海过程中海洋水体酸碱性变化对污泥中污染物浸出的影响及其变化规律提供理论依据。为了得出不同pH值对污泥中污染物浸出的影响，采用CEN/TS 14429：2005浸出实验对上海5个污水处理厂脱水污泥中重金属、溶解性有机碳、溶解性硫化物和主要离子的浸出情况进行了研究，同时分别以超纯水和海水为浸提剂研究在相应pH范围内盐度对上述指标浸出的影响。结果表明，Zn、Cd、Pb和As在酸性和碱性条件下浸出量较高，在中性或接近中性条件下浸出量则最低，且海水中Zn和Cd的浸出量比超纯水中高；Cu在碱性条件下的浸出量明显比酸性条件高；在所研究的pH范围内，5个污泥样品中溶解性有机碳的浸出量均随pH的升高而增高；仅酸挥发性硫含量最高的S5在海水中有较明显的溶解性硫化物浸出；部分污泥样品中的氮在酸性纯水中有较高的浸出量，海水中浸出量较少；而无论海水或纯水中，磷在强酸和强碱条件下均有明显浸出。     

施用垃圾堆肥土壤重金属在不同温度和酸雨条件下的淋溶特征

采用淋洗法,研究了垃圾堆肥中重金属在不同温度与模拟酸雨条件下的淋溶特征。结果表明,随着淋洗次数的增加,淋洗液中Cd、Cr、Cu、Ni和Pb的含量都有很大程度的减少。Cd、Cr、Cu和Ni 4种金属在模拟酸雨的情况下淋出量明显高于蒸馏水的情况,增幅都在116%和351%之间,差异显著(P<0.05)或极显著(P<0.01),而酸雨对Pb的淋出影响较小。在酸雨淋洗下,重金属的淋出率在30℃时达到最大,其中Ni随着温度的变化相对较小。而在蒸馏水淋洗下,重金属的淋出率随着温度的变化相对平稳。此外,5种重金属的淋出率明显不同,其中Cr和Ni的淋出率相对较大,Pb最小。     

氧化亚铁硫杆菌浸铜作用研究

为研究氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,简称A.f)对铜浸出的作用,从某煤堆积水中分离得到A.f菌,利用该菌对铜进行浸出实验,设置3个处理,3个处理的浸出液分别为9 K培养基(简称S),成熟菌液(简称MS)和过滤除菌液(简称FS)。结果表明,3个处理中铜都得到了浸出,浸出铜浓度按S、FS和MS依次递增分别为4 433、5 377和6 296 mg/L;浸出初期,MS中的铜,浸出速度最快,过滤除菌液中次之,而培养基中的速度比较稳定,比前两者均慢,24 h后三者浸铜速度趋近一致;三者中pH、Eh变化相似,pH均先升高至3.4左右保持相对稳定,Eh均先迅速下降至280 mV后保持稳定。由实验可知,氧化亚铁硫杆菌主要在浸出初期促进了铜的浸出,且菌液中溶解氧氧化Fe2+以及酸性条件下氧化Cu0对铜的浸出作用不容忽视。     

活性炭对细菌浸出线路板中金属铜的影响研究

研究了活性炭对细菌生长和浸出铜的效应影响。结果表明活性炭的添加对细菌的生长有一定的抑制作用,但这种作用随着添加量的增加而减弱。Fe3+对Cu浸出速率较快,活性炭对浸出速率有一定的促进作用,但效果不明显,且最终Cu的浸出率只达到87%。活性炭的添加增大了浸出体系中的生物量,加速了对Fe2+的氧化速率,从而保持溶液中较高的Fe3+浓度,可以提高铜的浸出速率。但这种促进作用需要较高浓度的活性炭添加量才比较明显。     

改性钢渣吸附氨氮和磷的特性研究

利用钢渣与氢氧化铝以4∶3质量配比混合,在700℃下进行2 h煅烧,得到改性钢渣。通过批次吸附实验,研究了改性钢渣在不同初始pH值、振荡时间和温度下对水溶液中氨氮和磷酸根的吸附情况,进而分析了改性钢渣对氨氮和磷酸根的吸附等温线、热力学和动力学特性。结果表明,改性钢渣脱氮除磷能力比原钢渣显著增强,且最适pH值为4～8。改性沸石对氨氮和磷酸盐的吸附均符合Langmuir等温吸附方程,氨氮(以N计)最大吸附量在10、20和30℃下分别为1.67、2.59和3.24 mg/g,磷酸根(以P计)的最大吸附量在10、20和30℃下分别为1.02、1.19和1.37 mg/g。热力学参数ΔG0、ΔH0和ΔS0表明,该吸附是一个自发、吸热、熵增型反应过程,且磷的吸附是化学吸附为主,氨氮的吸附是以离子交换吸附和物理吸附为主。改性钢渣对磷和氨氮的吸附动力学符合伪二级方程(R2>0.999)。     

Acidification of a Solonetzic soil by nitrogenous fertilizers

Annual applications of (NH4)2SO4, NH4NO3 and urea on a Solonetzic soil at 112 kg N/ha for 10 consecutive years reduced pH levels from 5.6 for the check to 4.4, 4.9 and 5.3, respectively for (NH4)2SO4, NH4NO3 and urea. (NH4)2SO4 generated twice as much exchange acidity as NH4NO3 and four times as much as urea. Net extractable cations leached from the Ap horizon closely approximated the amount of exchange acidity generated by (NH4)2SO4 and NH4NO3 fertilizers. The levels of soil extractable Al and Mn were greatly enhanced by (NH4)2SO4 as were plant contents. Similar acidifying effects to that produced by the (NH4)2SO4 occurred when NH4NO3 was applied at 300 kg N/ha annually for 12 consecutive years in another field experiment on the same soil. Liming samples of the field (NH4)2SO4 acidified soils in the greenhouse, significantly increased yields and lowered the Al and Mn contents of the plants to normal levels.     

Anion and cation leaching or desorption from activated carbons from municipal sludge and poultry manure as affected by pH.

The conversion of municipal sludge and poultry manure to activated carbon results in a significant ash fraction that contains several different anions and cations. The objectives of this study were to determine whether the select ions are released or leached from virgin carbon into the sorption medium at different pH values. Activated carbon was placed in solutions of pH 1, 5, or 7, and the leaching of six cations (cadmium, chromium, copper, nickel, lead, and zinc) and two anions (arsenate and selenate) was recorded. Considerable quantities of zinc and copper were removed at pH 1 from all carbon sources. However, the amounts leached at pH 5 and 7 were small or undetectable. Our results indicate that leaching or desorption from carbons made from municipal sludge or poultry manure is pH-dependent and occurs readily under highly acidic conditions but minimally under pH conditions typically seen in contaminated water or wastewater.     

Leaching of bisphenol A (BPA) from polycarbonate plastic to water containing amino acids and its degradation by radical oxygen species

In this study, (1) the change in the concentration of bisphenol A (BPA) leached from polycarbonate plastic (PCP) tube to water samples containing phosphate, sodium barbital, glycine, methionine or albumin at 37 degrees C as a function of time, and (2) the degradation rate of BPA leached from PCP tube to amino acid solutions in the presence of radical oxygen species (ROS) were investigated. The BPA leaching velocity (BPA-LV) from PCP tube to 50 mM glycine at pH 6 or 7 was twice that to control water, and the leaching was enhanced above pH 8. At pH 11, BPA-LV was significantly higher in 50 mM glycine and methionine solutions than in 50 mM NaOH. These results indicate that basic pH and amino acids contained in water could accelerate BPA leaching. The BPA-LV in phosphate buffer was different from the BPA-LVs in other buffers (barbital and glycine) at the same pH. BPA leached to the glycine or methionine solutions at pH 11 was degraded time dependently in a similar manner as the control water in the presence of ROS. The degradation of leached BPA was inhibited in the glycine solution, but was accelerated in the methionine solution. However, degradation of BPA added to freshly prepared methionine was inhibited in a similar manner to BPA in glycine. BPA degradation could be influenced by some kinds of amino acids, but glycine and methionine might be involved in BPA degradation in different ways.     

Dissolution of trace metals from particles of industrial origin and its influence on the composition of rainwater

The dissolution of trace metals (Fe, Mn, Cu, Zn, Ca and Mg) from pulverized fuel ash and steel dust particles in aqueous suspensions was studied as a function of solution pH and aerosol mass loading. The rate of dissolution, the final concentration and the fraction of the metal leached increased with decreasing pH over the range of pH 2.5→ 5. The leaching of aerosol particles is an important source of trace metals in rainwater, and the results of the leaching experiments were found to be consistent with the observations of these metals in urban rainwater. Alkaline materials such as Ca and Mg leached from particles may be important in the electroneutrality balance of rainwater and they could affect the solution pH. The dissolution of metals such as Fe and Mn may provide catalysts which could be important in the aqueous oxidation of SO₂, and the leaching of Ca and Mg may have a ‘buffering’ effect in reacting cloud and aerosol droplets.