金矿区高浓度砷污染土壤的稳定化处理

以粉煤灰、干化污泥、粉碎花生壳、硫酸亚铁（Fe2SO4）和磷酸二氢钾（KH2PO4）为稳定剂对矿区高浓度As污染土壤进行处理,通过土壤理化性质、重金属形态和浸出浓度变化等综合评估稳定剂对高浓度砷污染土壤的稳定化处理效果。结果表明,添加稳定剂可以提高土壤pH值、有机质含量和阳离子交换量。粉煤灰、干化污泥、粉碎花生壳、硫酸亚铁对土壤中的As有较好的稳定化作用,其中硫酸亚铁对土壤中As的稳定效果最好。同时添加10%粉煤灰、10%干化污泥和1%硫酸亚铁后,土壤中可交换态As、碳酸盐结合态As、铁锰氧化物结合态As、有机结合态As含量显著降低,降幅分别为62.3%、55.2%、29.6%、58.2%,残渣态As含量增加8.1%。添加粉煤灰、干化污泥、硫酸亚铁能显著降低土壤中As的浸出浓度,而添加KH2PO4会使土壤中As浸出浓度增加,移动性增强。当同时添加10%粉煤灰、10%干化污泥、1%粉碎花生壳和1%硫酸亚铁后,As浸出浓度最低（0.93 mg·L-1）,稳定效果最好,稳定化效率达到了74.8%。土壤中As的浸出浓度与可交换态As和碳酸盐结合态As呈显著正相关,与残渣态As呈显著负相关,可交换态As、碳酸盐结合态As和残渣态-As含量是影响土壤中As浸出浓度变化的主要因素。     

Characteristics of leachate from pyrolysis residue of sewage sludge

The pyrolysis residue (SP) of sewage sludge (SS) produced at 500 degrees C was subjected to batch and column leaching tests to investigate the release of its organic and inorganic constituents and metals. For comparison, incineration ash (SI) obtained from a SS incinerator was also tested. Pyrolysis and incineration reduced organic matter of SS from 0.78 kg kg(-1)-dry SS to 0.16 and 0.01 kg kg(-1)-dry SS, respectively. Heavy metals remained in SP without being volatilized, although Cd and Pb were transferred into the off-gas during incineration. In the batch leaching test with the leaching liquid-to-solid mass ratio (L/S)=10, the pH of the SS, SP, and SI filtrates was 6.3, 7.9, and 11.0, respectively. The total organic carbon concentrations were in the order SS (877 l mg l(-1))>SP (99 mg l(-1))>SI (26 mg l(-1)). The SP and SI filtrates met the landfill standard for the Cd and Pb concentrations (<0.3 mg l(-1)). In the column tests, although the SP contained more organic matter than that of SI, its carbon discharge into the leachate under aerobic conditions was similar to that of SI under anaerobic conditions. The leaching of heavy metals, such as Cd, Cr, Pb, and Zn, was also suppressed in SP during the active decomposition of organic matter. We demonstrated that pyrolysis reduces the potential release of pollutants from sewage sludge in landfill, making it a promising method of treating sewage sludge before landfilling.     

Supercritical water oxidation of tannery sludge: Stabilization of chromium and destruction of organics

The supercritical water oxidation (SCWO) of industrial tannery sludge was investigated to understand the simultaneous destruction of organic pollutants and recovery of high content chromium. Experiments were performed in a batch reactor at temperatures of 350–500 °C, reaction time of 150–300 s and different oxygen ratios, to exhibit the effect of operation conditions. Results showed that removal efficiency of chemical oxygen demand (COD) increased with higher temperature, larger oxidant amount and reaction time; a maximum value of 96% was obtained. Meanwhile, destruction yield was much higher under supercritical conditions than that in subcritical water. In addition, removal efficiency of Cr from sludge reached more than 98% under all conditions; higher temperature played a positive role. Further, leaching toxicity tests of heavy metals in solid products were conducted based on toxicity characteristic leaching procedure. All heavy metals except nickel showed a greatly reduced leaching toxicity through their stabilization. The chromium oxide recovered in ash was amorphous below 550 °C, so that the structure of Cr could not be identified by X-ray diffraction pattern. Special attention should be paid on nickel as its leaching toxicity increased due to the corrosion of reactor surface under severe reaction conditions.     

油田油泥与煤在流化床中的混烧

基于小型流化床焚烧实验平台,通过含油污泥与煤混合燃烧,分析气体污染物排放浓度以及灰渣特性。含油污泥与煤混烧后NOx、SO2的排放浓度均低于危险废物焚烧排放标准。根据灰渣中组分分析,煤中碱金属化合物能抑制SO2的排放。渣样的浸出毒性均在标准范围内,灰样的浸出毒性高于渣样,主要因为飞灰中更容易富集挥发和易溶形态的重金属。基于小试实验的结果,油泥在小型流化床上的燃烧不充分导致了CO排放浓度较高,且灰的灼减率较高,因此,在后续中试以及示范工程中,应保证油泥的充分燃烧,为灰渣的综合利用提供理论基础。     

Phosphate removal from digested sludge supernatant using modified fly ash

The removal of phosphate in digested sludge supernatant by modified coal fly ash was investigated in this study. Modification of the fly ash by the addition of sulfuric acid could significantly enhance its immobilization ability. The experimental results also showed that adsorption of phosphate by the modified fly ash was rapid with the removal percentage of phosphate reaching an equilibrium of 98.62% in less than 5 minutes. The optimum pH for phosphate removal was 9 and the removal percentage increased with increasing adsorbent dosage. The effect of temperature on phosphate removal efficiency was not significant from 20 to 40 degrees C. X-ray diffraction and scanning electron microscope analyses showed that phosphate formed an amorphous precipitate with water-soluble calcium, aluminum, and iron ions in the modified fly ash.     

不同pH控制策略下剩余污泥中NH4^＋-N、PO4^3--P、COD溶出研究

污水处理厂的剩余污泥中富含氮、磷、COD,在其水解酸化过程中对pH条件进行控制,使污泥中的氮、磷、COD溶出到上清液中并进行回收利用是可行的。在22～25℃的温度条件下,1#反应器中剩余污泥先调节为酸性（pH=3）,在实验第8 d氨氮、磷酸盐溶出量最多后调节为碱性（pH=10）;3#反应器中剩余污泥先调节为碱性（pH=10）,在实验第8 dCOD溶出量最多后调节为酸性（pH=3）;2#反应器为对照实验,pH不进行调节。结果表明：若要以回收污泥中的氨氮、磷酸盐为主,剩余污泥由碱性（pH=10）调节为酸性（pH=3）优于由酸性（pH=3）调节为碱性（pH=10）;若要回收污泥上清液中的COD为主,剩余污泥由酸性（pH=3）调节为碱性（pH=10）优于由碱性（pH=10）调节为酸性（pH=3）。     

电镀污泥回收重金属的新工艺

合理、经济地处理混合电镀污泥,回收其中有价值的金属具有重要意义。以不同的酸作为浸出剂对电镀污泥中的金属进行了浸出效果实验。结果表明,在相同条件下,各酸的浸出效果顺序为:硫酸>盐酸>王水>硝酸;液体水与固体电镀污泥比为3,干污泥为5 g,硫酸加入量为15 mL,时间1 h条件下,混合电镀污泥中金属铜锌的浸出率最大,达到97.38%。分别采用铁和铁锰合金还原剂常温还原低熔点重金属离子铜、锌,浸出液中99%以上含量的铜、锌沉淀,使低熔点重金属与黑色金属铁、锰、铬有效分离。低熔点混合重金属可以用来做铜合金添加剂使用,最后沉淀的混合黑色金属氢氧化物处理后可以用来做炼钢合金添加剂使用。     

污水处理厂脱水污泥中磷的形态及其溶出规律

运用化学连续提取法(standards-method of measurements and testing,SMT)对北京市3座污水处理厂污泥中的磷进行形态和组成分析,以低温热解、投加酸碱和投加EDTA 3种方式处理污泥,研究磷的溶出规律。结果表明：污泥中的磷主要以无机磷形态存在,占总磷的71.7%~89.3%;非磷灰石是无机磷的主要形态,占50%左右。低温热解时,在50 ℃条件下,污泥总磷的溶出率最高,达50%以上。酸性或碱性条件下,污泥磷溶出效果优于中性条件,pH为4时,污泥的磷溶出效率最高,在40%左右;碱性条件下,污泥中非磷灰石态无机磷会大量溶出。投加EDTA,磷灰石态无机磷的溶出率大于非磷灰石态无机磷。综合以上结果,根据磷的形态设置合理的条件进行污泥磷溶出,有利于提高溶出效率。     

Leaching of heavy metals and alkylphenolic compounds from fresh and dried sewage sludge

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP₁EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP₁EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.     

化工污泥焚烧灰渣基功能材料中Cr的溶出

研究自制稳定剂对化工污泥焚烧灰渣制备环保功能材料过程中Cr的物理封闭效应和化学稳定效应的影响,并通过BCR修正法和XRD对灰渣基功能材料中Cr形态进行了分析。结果表明,投加自制稳定剂并经高温处理后,Cr的残渣态含量高达98%,ZMN稳定剂加强了功能材料体系对重金属的物理封闭作用和对酸环境、氧化环境的缓冲能力,有助于保持重金属的稳定性,功能材料中生成了钙铬磷酸盐、镁尖晶石和钠钙长石等新物质,有利于降低Cr的溶出。     

Effect of reducing conditions on sludge melting process

The objective of this study was to compare the effects of CO/CO(2) reducing conditions with those of air oxidizing conditions on the pouring temperature of the sludge melting process and the heavy metal leachability of the resultant sludge slag. Synthetic sludge ash composed of SiO(2), CaO and Al(2)O(3), as well as sewage sludge ash generated from a laboratory incinerator was employed. The experimental results indicated that the pouring temperatures are significantly reduced under the reducing conditions of CO/CO(2), or 24 and 77 degrees C lower than under air conditions for synthetic and sludge ash, respectively. The heavy metal leaching tests further indicate lower heavy metal concentrations present in the leachate under the reducing conditions, notably an order of magnitude lower in Zn. However, X-ray diffractogram indicates similar peaks for these two slags produced under different conditions.     

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。     

污泥活性炭对复合染料的脱色及其重金属浸出毒性

用自制的污泥活性炭处理亚甲基蓝与酸性品红组成的染料废水,研究了pH、吸附时间、温度等因素对复合组分染料废水脱色率的影响,测试分析了污泥活性炭在处理亚甲基蓝与酸性品红复合组分染料废水过程中的重金属浸出毒性。结果表明:与处理单一组分染料废水相比较,处理复合染料废水时pH的影响较为复杂,2种染料在污泥活性炭上存在竞争吸附,但是污泥活性炭对复合组分染料的脱色效果较好。污泥活性炭对复合染料的吸附过程符合Langmuir型吸附。在处理染料废水的过程中,污泥活性炭中的重金属镉、锌及铬会浸出,重金属镉、锌的浸出浓度符合国家标准,但铬的浸出浓度已接近国家标准上限。     

含重金属水处理污泥的固化和浸出毒性研究

工业危险固体废物在进行安全填埋前需要进行固化稳定处理。针对电镀厂和皮革厂含重金属的水处理污泥 ,用不同比例的水泥、粉煤灰进行固化稳定处理。考虑酸雨环境 ,浸出实验采用TCLP标准。电镀厂污泥单独固化时 ,其浸出液中铜离子浓度由 78 0mg/L下降到 1 5mg/L ;镍离子浓度由 2 2 4 5mg/L下降到 2 2 2mg/L ,高于危险废物允许进入填埋区 15mg/L的控制限值。电镀厂污泥与皮革厂污泥混合后固化 ,浸出液毒性明显降低。铜离子的浸出浓度降低到1 98mg/L ,镍离子降低到 4 10mg/L ,总铬降低到 0 4 0mg/L ,各项指标均低于国家危险废物允许进入填埋区的控制限值 ,可安全填埋。     

含重金属污泥制砖毒性的浸出

污泥中的重金属是影响污泥处置利用的重要因素,污泥制砖可以有效固结重金属。采用污水厂污泥与页岩按一定配比混合制备烧结砖,通过毒性浸出实验,研究烧结砖对重金属的固化程度以及重金属浸出稳定性,从而评定烧结制砖的安全性。结果表明,在浸出液为中性和酸性条件下,Cu、Cr、As和Pb的浸出浓度基本保持稳定,浸出时间的影响不大,而Zn的初始浸出浓度相对较大,最终逐渐降低;碱性条件下,Cr、Cu和Pb的浸出浓度随时间变化不大,而Zn和As的浸出浓度则在浸提时间内无明显变化规律;但不同pH浸出液下的重金属浸出浓度均远低于国家限值,污泥制砖重金属固化效果好,安全可靠。     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验,测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣,并为矿区重金属污染土壤的修复提供技术支持,采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理;通过浸出毒性实验对固化/稳定化处理效果进行综合分析,试图寻求一种最佳的稳定剂。结果表明,无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加,样品浸出液的pH都有升高,As、Cd的浸出浓度都有明显下降,而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中,粉煤灰混合堆肥化污泥的处理效果最好,浸出液的pH值达到7.82,As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳,同时具有以废治污的资源化生态效能。     

低温热碱破解低有机质污泥及磷形态分析

以低温热碱破解低有机质污泥,考察了不同热碱条件下低有机质污泥破解情况,通过DNA释放量分析了污泥细胞破解效果,同时,研究了污泥中磷形态分布与变化。结果表明,从污泥破解程度（DD）与DNA释放量来看,热碱联合可强化污泥破解,而pH比温度起更重要作用,尤其对污泥破解释磷起关键作用。高pH条件下,污泥中有机磷（OP）和非磷灰石无机磷（NAIP）以磷酸盐的形式大量溶解,而磷酸盐与钙离子反应导致磷灰石（AP）含量升高。研究认为,仅加碱pH=13即可有效破解低有机质污泥,操作简单,有利于污泥减量,且磷回收潜力大。     

污泥施入黄土后重金属Cu、Zn、Cd的淋滤迁移

污泥土地利用是目前国内外污泥处置的主要方式和鼓励方向,在中国西北黄土地区更有前景和意义.污泥富含有机质和营养元素可弥补黄土的贫瘠缺陷,改善黄土肥力、增加植物产量.污泥施入黄土后,灌溉水对污泥重金属的淋滤迁移和污染风险是值得研究的课题之一.研究旨在了解重金属Cu、Zn、Cd在黄土层中的淋滤迁移特征,为黄土地区污泥的土地利用及重金属污染控制提供实验依据.实验选择污泥中含量或毒性大的Cu、Zn、Cd 3种重金属作为研究对象,通过室内模拟土柱对表层堆肥污泥中2种源强的重金属进行1年灌溉用水量的淋滤对比实验,测定淋滤前后土柱中和渗出液的Cu、Zn、Cd总量、有机质及pH值,以期分析重金属在黄土中的淋滤、迁移特征.结果表明,淋滤作用可使堆肥污泥Cu、Zn、Cd发生少量迁移并富集于土柱中、上部,大部分或绝大部分重金属仍滞留于耕作层(0~20 cm);淋滤使堆肥污泥Cd与Cu向下迁移约30 cm,Zn向下迁移约20 cm;渗出液呈弱碱性,其中Cu、Zn、Cd 3种重金属的浓度较入渗水均有增多,但随渗出液从黄土柱中溶出的重金属量极少.实验表明,耕作层重金属源强对Cu、Zn、Cd在土柱剖面中的淋滤、迁移和滞留作用以及溶出量均有不同程度的影响,堆肥污泥土地利用可以明显改善黄土肥力,灌溉对耕作层污泥有机质的淋滤损失量较小.并得出,堆肥污泥在黄土地区的土地利用是可行的.     

微生物电解池从剩余污泥热碱水解液中回收鸟粪石

通过鸟粪石的形式回收城市污水处理厂剩余污泥中的氮磷,不仅可减少对环境的污染,而且可以实现氮磷的资源化。利用微生物电解池(microbial electrolysis cell, MEC)开展了回收剩余污泥热碱水解液中鸟粪石的研究,实验结果表明,剩余污泥通过热碱水解促进了磷酸盐的释放,经MEC处理后可形成鸟粪石沉淀。扫描电镜-能谱分析(SEM-EDS)结果表明,阴极沉淀物为斜方晶,主要成分为N、O、P、Mg,符合鸟粪石的成分组成及晶体特征。双室MEC的鸟粪石生成速率远大于单室MEC的,双室MEC对磷酸盐的去除率最高可达77%,而单室MEC对磷酸盐去除率最高为56%。在双室MEC中,随着外加电压的升高,鸟粪石的生成速率增大,当外加电压为0.95 V时,鸟粪石生成速率为0.37 g/(m2·h);当外加电压为1.15 V时,鸟粪石生成速率为0.61 g/(m2·h)。微生物电解池为剩余污泥中鸟粪石的回收提供了一种新的处理方法。     

Hydrometallurgical recovery of zinc from ashes of automobile tire wastes

Study has been performed on the investigation of metal leaching behavior for fly and bottom ashes from automobile tire wastes using acid and alkaline solutions from both viewpoints of environmental protection and resource utilization. The two ashes were found to contain substantial amounts of zinc and iron along with small quantities of cobalt, manganese, magnesium, copper, titanium and aluminum. The fly ash contained a much larger amount of zinc than the bottom ash, and seems to be a promising secondary source for the metal. Effects of such experimental parameters as temperature, time and solid-liquid ratio on the leaching behavior were investigated. Using three mineral acids and citric acid, selective leaching of zinc was successfully attained; the concentration of zinc in the leach liquors from the fly ash reached as high as 20 g l(-1) while the iron leaching was much suppressed. Selective separation of zinc was also attained in the leaching with alkaline solutions, though the percent leaching was lower than that in the acid leaching. Moreover, solvent extraction and precipitation were applied to the metal-loaded leach liquors as downstream processing to evaluate the feasibility of zinc recovery.