Modelling diffusion and adsorption of As species in Fe/GAC adsorbent beds

BACKGROUND: Arsenic decontamination of drinking water by adsorption is a simple and robust operation. When designing packed bed adsorbers for arsenic, the main problems are the slow diffusion kinetics of As in microporous media and the lack of simple equations for predicting the performance of the equipment. Commercial iron‐doped granular activated carbon adsorbents (Fe/GAC) for groundwater arsenic abatement were studied in this work. Basic parameters for arsenate (As^V) adsorption were measured and their performance at larger scale was simulated with an approximate analytical model. RESULTS: In the 0–300 µg_As L^?1 range, the As^V adsorption isotherm on Fe/GAC was found to be approximately linear. Assuming Henry's law for adsorption and homogeneous surface diffusion with constant diffusivity for intrapellet mass transfer, an approximate model for flow and adsorption of arsenate inside packed bed adsorbers was developed, and reduced to an analytic compact solution using the quasi‐lognormal distribution (Q‐LND) approximation. The use of this model with fitted and reported parameters enabled the approximate simulation of industrial adsorbers and home point‐of‐use filters. Results show that industrial adsorbers meet the breakthrough condition with incomplete utilization of the adsorbent unless convenient process configurations are used. In point‐of‐use systems with short residence times intraparticle diffusion would drastically reduce the adsorbent performance. CONCLUSION: Assuming linear adsorption of As^V over Fe/GAC, an analytical approximate solution for flow and adsorption in packed beds can be obtained. The model seems to represent correctly the main features of industrial and home filters, however, more experimental data is necessary for scale‐up purposes. Copyright © 2011 Society of Chemical Industry     

氢化物发生-原子荧光光谱法测定载金炭中砷

用硝酸和硫酸消解载金炭样品,通过加热消解除去样品中的炭基体,以硫脲-抗坏血酸为还原剂,使溶液中的As(Ⅴ)还原为As(Ⅲ),用氢化物发生-原子荧光光谱法测定载金炭中砷含量。方法检出限为0.093 mg/L。选取5个不同含量的样品进行测定,测定结果的相对标准偏差在1.59%~5.52%之间(n=7),加标回收率在96%~101%之间。     

Selective removal of As from arsenic-bearing dust rich in Pb and Sb

The selective removal of arsenic from arsenic-bearing dust containing Pb and Sb in alkaline solution was studied. The influence of NaOH concentration, temperature, leaching time, liquid to solid ratio, and the presence of elemental sulfur on the dissolution of As, Sb and Pb in NaOH solution was investigated. The results indicate that the presence of elemental sulfur can effectively prevent leaching of lead and antimony from arsenic. The Sb₂O₃, As₂O₃ and Pb₅(AsO₄)₃OH in the raw material convert to NaSb(OH)₆ and PbS in the leaching residue, while arsenic is leached out as As(III) or As(V) ions in the leaching solution. Arsenic leaching efficiency of 99.84% can be achieved under the optimized conditions, while 97.82% of Sb and 99.97% of Pb remain in the leach residue with the arsenic concentration of less than 0.1%. A novel route is presented for the selective removal of arsenic and potential recycle of lead and antimony from the arsenic-bearing dust leached by NaOH solutions with the addition of elemental sulfur.     

电感耦合等离子体串联质谱法测定高温合金中痕量砷

高温合金中Co含量较高,采用电感耦合等离子体质谱(ICP-MS)测定高温合金中As时,⁵⁹Co¹⁶O⁺会严重干扰As的分析,这一直是ICP-MS测定高温合金中痕量As的研究难点。在串联四极杆(MS/MS)模式下向碰撞/反应池内通入O₂,设置一级质量过滤器(Q1)m/z=75,⁷⁵As⁺可以与O₂反应生成⁷⁵As¹⁶O⁺,而干扰离子不能与O₂发生反应,将二级质量过滤器(Q2)设置为m/z=91,仅⁷⁵As¹⁶O⁺通过并被检测器检测,从而避免了⁵⁹Co¹⁶O⁺的质谱干扰。据此,建立了电感耦合等离子体串联质谱法(ICP-MS/MS)测定高温合金中痕量As的方法。采用As质量浓度为1.000 ng/mL、Co质量浓度为1.000~1 000 μg/mL的系列标准溶液考察了单四极杆和MS/MS两种模式下Co对As测定的质谱干扰。结果表明,在MS/MS模式下,As的回收率均在100%左右,这说明在MS/MS质量转移模式下,采用O₂为反应气,通过两次质量选择,可以成功消除Co基体带来的严重干扰。对O₂流速进行了优化,选择O₂流速为0.375 mL/min。方法线性范围为1.00~100 ng/mL,线性相关系数为1.000 0,检出限为0.006 7 μg/g,定量限为0.023 μg/g。选择纯钴标准样品为测定对象,按照实验方法对其中As进行测定,并进行加标回收试验,回收率在96%~102%之间。采用所建立的方法对镍基高温合金标准物质和高温合金样品中As进行测定,测定结果分别与认定值或原子荧光光谱法测定值基本一致,实际样品测定结果的相对标准偏差(RSD,n=6)为1.6%～2.8%。     

煤中砷的分布和赋存规律研究

在较全面系统地收集了已发表的资料和检测了我国西南、西北和华北地区147个煤样中砷含量的基础上,对代表性矿区煤中砷的成因机理及其与有机质的亲和性、与硫的亲和性以及煤变质程度的关系作了分析。我国西南地区第三纪富砷褐煤受大断裂热液影响为主,砷主要以有机质 结合态赋存;华北地区石炭二叠纪煤中砷分布受沉积环境影响明显,当海水入侵沼泽还原环境,黄铁矿含量增高的同时,砷含量相应升高,砷主要以类质同象置换赋存于黄铁矿中。岩浆侵入活动的高温气液是导致高变质程度煤中砷元素富集的直接原因之一;西北地区侏罗纪煤中砷含量水平低,是我国最好的环保煤。     

超声对铁锰氧化物吸附废水中无机砷的强化效应

快速吸附去除废水中无机砷的技术,由于其高效性成为污水处理领域亟需的一种技术。采用草酸沉淀法制备了不同铁锰比（物质的量比）的铁锰复合草酸盐,以铁锰复合草酸盐为前驱体通过热分解得到铁锰元素均匀分布的复合氧化物,以铁锰复合氧化物为吸附剂吸附去除废水中的无机砷。在超声波辅助下,铁锰复合氧化物对废水中无机砷的去除效果显著。实验结果表明,铁锰物质的量比为6:4的铁锰复合氧化物,因具有较高的比表面积（396.6 m²/g）和独特的形貌,超声辅助1 min对废水中无机砷的吸附率可达95%以上。吸附动力学研究表明,该吸附过程符合准二级动力学模型,吸附速率常数为1.11 g/（mg·s）。吸附剂再生实验表明,将吸附砷的吸附剂采用碳酸氢钠溶液洗脱重复用于吸附实验,吸附剂重复使用3次对砷的吸附率仍可达到83.6%。     

含砷金铜矿熔炼电尘灰酸性氧化浸出工艺研究

含砷金铜精矿火法熔炼电尘灰是铜冶炼熔炼车间产出的中间产物,成分复杂,较难处理,属于典型危废。以山东某冶炼公司含砷金铜矿熔炼产出的中间产物电尘灰为原料,采用双氧水为氧化剂进行酸性氧化浸出,最佳浸出工艺条件为：双氧水用量120 kg/t、酸性氧化浸出时间2 h、浸出温度80 ℃、酸度60 g/L,铜和砷的浸出率分别达到92.30%、87.50%以上。为铜冶炼企业湿法处理电尘灰提供了一条新途径。     

铁粉预还原—硫化亚铁脱除高酸性硫酸铁溶液中的砷

焙烧氰化法提金尾渣经酸浸后产出大量酸性硫酸铁溶液,因其中含有较高的砷而限制了其高值化利用。采用铁粉预还原—硫化亚铁脱砷对溶液中的砷进行脱除研究。结果表明,溶液中砷的存在形式及分布与溶液体系电位密切相关,铁粉可以有效降低溶液电位,经铁粉预还原后硫酸铁溶液中的砷可用硫化亚铁有效脱除。当铁粉添加量为溶液中铁含量的0.6倍,溶液加入36.6g/L的FeS,搅拌30min,可使溶液中砷含量由0.253g/L降低至4.79mg/L。空气对脱砷过程有不利影响。     

As-NaOH-ClO~-体系脱砷试验

提出了在As-NaOH-ClO体系脱砷的方法,并以含砷镍烟灰为原料,系统研究了该体系下的脱砷效果。结果表明:在液固比L/S=10、NaClO浓度4.1%、NaOH浓度3%、反应温度50℃、反应时间1h的最优条件下,砷脱除率达到75%以上,镍损失率小于0.03%,可实现砷的无害化处理和金属镍的回收。     

皖南地区的早期矿冶遗址以及三种合金技术

对皖南地区的早期矿冶遗址进行综合考察研究,发现存在着配制锡青铜、砷青铜、锑青铜的3种合金技术。青铜冶炼流程为两步法,所用铜料、砷料、锑料应来自当地,锡料推测来自长江中游的赣北且主要以锡砂形式添加。研究还发现,以皖南为代表的长江下游是中国早期又一处重要的砷青铜冶金区,其生产流行的资源背景应与该地区缺乏锡矿有关。研究进一步预示长江流域存在着相当规模且独具特色的早期青铜冶金业,而与黄河流域的中原地区有明显区别。