生物法和化学法回收制革污泥中铬的对比研究

研究了嗜酸性硫杆菌(Thiobacillus)生物沥滤法和1:1硫酸化学沥滤法分离回收制革污泥中的铬.比较了嗜酸性硫杆菌生物沥滤法和化学沥滤法回收制革污泥铬过程中pH、氧化还原电位(ORP)、沉降比(SV)以及铬的沥滤率的变化.试验结果表明,pH是影响制革污泥中铬的沥滤率的关键因素.生物沥滤法在使污泥pH大幅度降低的同时,能很好地改善污泥的沉降性能,对铬的沥滤效果好于化学沥滤法.     

制革污泥生物沥浸液中铬回收的方法与效果研究

对制革污泥生物沥浸液加碱沉淀回收Cr时碱的类型与用量、加碱后混合液的沉降速度、沉降比以及上层清液悬浮性固体(SS)及Cr含量与pH关系等进行了研究.结果表明,氧化镁和氧化钙均能很好地沉淀制革污泥经生物沥浸处理后所得的铬液,而液碱效果较差.综合沉淀效果和经济成本考虑,氧化钙作沉淀剂更为合适.将含Cr 720 mg/L的铬液调至pH 7.0,消耗氧化钙的质量浓度为10.0 g CaO/L铬液,能使Cr从液相完全去除,混合液的沉降比达40%.     

皮革厂含铬污泥铬回收及资源化利用

以滨州某皮革厂产生的含铬污泥为研究对象,采用酸浸-加碱-氧化的方法提取污泥中的铬,通过实验探究获得最佳反应条件,铬回收率达到92.6%。回收得到的的铬盐红矾钠（Na2Cr2O7）可回用于制革产业中制备铬鞣剂。铬回收后污泥中的铬含量为10.88 mg·g-1,浸出毒性低于危险废物鉴别标准。     

铬的浸出毒性试验方法研究

以铬为分析指标,探讨了钻井废充泥浆在不同的提取剂、没的提取时间、不同的固液比以及不同的提取方式下铬的浸出毒性大小,提出了适合评价钻井废充泥浆中铬的浸出毒性的试验方法。     

Response of antioxidants in sunflower (Helianthus annuus L.) grown on different amendments of tannery sludge: its metal accumulation potential

The interaction of metals present in tannery waste and their tolerance in the plants of sunflower (Helianthus annuus L.) was studied in the present paper under field conditions. Effects of 100% tannery sludge and various amendments of tannery sludge (10%, 25%, 35%, 50%, 75%) along with one set of control were studied on the physiological and biochemical parameters of the plant along with their metal accumulation potential after 30, 60 and 90 d after sowing. The plants of H. annuus were found effective in the accumulation of metals (Cr, Fe, Zn and Mn) in roots, shoots and leaves, however, the level of toxic metal, Cr was found below detection limit in the seeds of the plant. The oil was extracted from the seeds of the plant and the level of oil content was increased up to 35% tannery sludge as compared to control followed by decrease at higher tannery sludge ratio. An increase in the chlorophyll, protein, cysteine, non-protein thiol and sugar contents was observed at the lower amendment of tannery sludge at initial exposure periods followed by decrease than their respective controls. Malondialdehyde content in the roots and leaves was increased beyond 50% sludge amendments at all the exposure periods as compared to control. However, proline and ascorbic acid contents of the roots and leaves of the plant increased at all the exposure periods and sludge amendments, compared to their respective controls.     

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。     

Ageing of chromium(III)-bearing slag and its relation to the atmospheric oxidation of solid chromium(III)-oxide in the presence of calcium oxide

Slag arising in ferrochromium and stainless steel production is known to contain residual levels of trivalent chromium. As the chromium is normally bound in the slag matrix in various silicate or spinel phases, and hence not easily mobilised, utilisation or controlled disposal of such slag is generally considered unproblematic. Experimental test work with a number of slag materials indicates, however, that very gradual oxidation of trivalent to hexavalent chromium does occur when the slag is exposed to atmospheric oxygen, rendering a quantifiable but small portion of chromium in this much more mobile and toxic form. Mechanisms and rates of the oxidation reaction were investigated in a number of long-term studies using both original slag materials and artificial mixes of chromium and calcium oxides. Powders of these materials, some of them rolled into balls, were left to age under different conditions for periods of up to 12 months. In the slag samples, which contained between 1 and 3 wt.% chromium, 1000–10 000 μg Cr(VI) were found per gram of chromium within 6–9 months of exposure to an ambient atmosphere. The rate of the oxidation reaction decreased exponentially, and the reaction could generally be said to have ceased within 12 months. In mixtures of calcium and chromium oxides the oxidation reaction is presumed to occur at the boundaries between chromium oxide and calcium oxide phases through diffusion of oxygen along the grain boundaries and of Cr³⁺ across the boundaries, resulting in the formation of calcium chromate. In the slags, where calcium and chromium oxide can form a solid solution, the oxidation is likely to occur at the exposed surface of grains containing this solution.     

气封壁高浓度有机污染物超临界水氧化处理系统

利用干燥空气替换亚临界水作为蒸发壁流体,对传统蒸发壁超临界水氧化反应器进行了改进,即将干燥空气用作污染物超临界水氧化反应氧化剂的同时,又作为该超临界水氧化反应体系的密封介质,避免其与反应器内壁的直接接触,以改善超临界水氧化反应器的耐腐蚀性能。通过对采用城市活性污泥和异丙醇配制的高浓度难降解污染物悬浮液进行超临界水氧化处理后,发现反应器内衬陶瓷管在实验前后无论是外观形貌,还是结构组成均未发生明显变化;处理后液体COD降至80 mg/L以下,去除率达到99.6%以上,固体残渣量约为污染物总量的1%,且体系运行过程中压力和温度控制准确,可操作性强。进一步验证了将干燥空气作为超临界水氧化体系的密封介质具有可行性,同时表明,该气封壁超临界水氧化反应系统可用于高浓度难降解有机污染物的环境处理。     

微波预处理对制革污泥絮凝脱水性能的影响

分别采用微波、絮凝剂和微波联合絮凝剂对制革污泥进行脱水预处理,考察不同处理条件下制革污泥沉降速率(SV30)、毛细吸水时间(CST)和污泥比阻(SRF)的变化,并通过粘度、水分分布和微观结构的变化探讨相关的脱水机理。结果表明,在微波输出功率为648 W、辐射时间为60 s的预处理条件下,阳离子聚丙烯酰胺(CPAM)投加剂量为8 mg/L时,污泥脱水性能达到最佳。与单独添加絮凝剂的污泥脱水相比,该条件下的SV30、CST和SRF分别降低了25.0%、48.9%和34.7%。污泥絮凝脱水前进行微波预处理能够进一步提高污泥的脱水性能,微波辐射联合CPAM进行污泥脱水时,CPAM则起主要脱水作用。微波辐射通过破坏污泥絮体结构,改变污泥中的水分分布,降低污泥的粘度,从而提高污泥的脱水性能。     

制革废水处理过程中微生物代谢产物特征及铬分布的解析

制革废水生化处理后的出水仍残留低浓度的铬,为揭示微量铬在活性污泥胞外聚合物(EPS)中的分布及胞外聚合物在生物处理过程中的转化,通过改良热提取法提取生物处理过程中EPS和SMP,测定各组分中多糖、蛋白质、总铬等含量,分析制革废水生物处理中EPS组分的特征、金属铬的分布和EPS各组分含量。结果表明：一级生物处理中EPS的蛋白质和多糖含量均逐渐降低,二级生物处理中EPS含量增加,活性污泥SMP与邻近沉淀池出水组分及溶解性有机物含量具有较强的相似性;铬在不同来源污泥EPS中的分布存在差异,污泥表面吸附及EPS对铬的络合富集、EPS的水解及代谢组分外排的行为均影响铬的迁移;通常,水体中铬首先被S-EPS吸收,经LB-EPS运输渗透至TB-EPS中储存。根据Pearson分析结果,总铬的分布与胞外聚合物中PS/PN及PS含量呈显著正相关(P<0.01)。以上研究结果可为制革废水铬排放总量控制和深度处理提供参考。     

去除污泥中重金属铬的生物淋滤反应器设计与应用

用微生物方法去除污泥中重金属(生物淋滤法)是近年来发展的新技术,探索工程化的条件有重要的应用价值。设计了一套容积为1 m3的生物淋滤反应器,由生物淋滤池、搅拌器、曝气器和空气压缩机等构成。其中,搅拌叶轮由平叶桨和斜叶桨组合而成。利用制革污泥进行了半连续的生物淋滤试验,结果表明,在反应器中污泥与菌体和营养物质能充分混匀,经过2~5 d的处理,污泥pH持续下降到2.0以下,污泥中铬的溶出率达90%~99.5%。     

去除污泥中重金属铬的生物淋滤反应器设计与应用

用微生物方法去除污泥中重金属（生物淋滤法）是近年来发展的新技术，探索工程化的条件有重要的应用价值。设计了一套容积为1m^3的生物淋滤反应器，由生物淋滤池、搅拌器、曝气器和空气压缩机等构成。其中，搅拌叶轮由平叶桨和斜叶桨组合而成。利用制革污泥进行了半连续的生物淋滤试验，结果表明，在反应器中污泥与菌体和营养物质能充分混匀，经过2-5d的处理，污泥pH持续下降到2．0以下，污泥中铬的溶出率达90％-99．5％。     

SUFR系统活性污泥特性及稳定性研究

通过实验考察了SUFR系统中活性污泥的特性及进水COD浓度、SRT和停运对稳定性的影响。结果表明：SUFR系统的污泥颗粒直径多在0.7～0.9 mm之间,属于小颗粒污泥,污泥沉降性能良好;对氮、磷有较好的去除效果。SUFR系统氮的去除对SRT有一定的耐冲击负荷,但受进水COD的影响较大;磷的去除对进水COD和SRT有较好的冲击能力;系统在经过72 h停运后污泥沉降性、脱氮与除磷效果都有较大降低,但基本在1周内就可恢复。     

Study of the chemistry of an acid soil column and of the corresponding leachates after the addition of an anaerobic municipal sludge

A column leaching study was carried out over a period of 77 days to determine the changes in the chemistry of an acid soil and of the corresponding leachates after the addition of an anaerobic sludge (equivalent to 69 Mg DW ha⁻¹). By the end of the experiment, the addition of the sludge to the soil had induced an increase in soil pH (from pH 3.6–4.0 to pH 4.1–4.8), in spite of the pronounced decrease in pH detected in the leachates by day 18 of the experiment. The decrease in pH (down to pH 3.3) occurred at the same time as leachate SO₄ and Fe peaked. Once the acidification attributed to sulphide oxidation ceased, the “liming effect” of the sludge became evident and counteracted further proton production – such as that associated with oxidation of NH₄ – at least for the duration of the study. Concentrations of Zn, Cd, Ni, and to a lesser extent, Pb in leachates displayed pulses at the beginning of the experiment (first 12 days), whereas the concentration of Cu followed a more irregular pattern; the concentrations of these metals never surpassed the European threshold values for drinking water. In contrast, concentrations of NO₃, Mn, and Cr in leachates had increased by the end of the experiment – in parallel with an increase in dissolved organic C (DOC) – and surpassed the European threshold for drinking water. Mineralisation of native soil organic C (SOC) was enhanced by the addition of this N-rich residue, and the organic C mass balance at the end of the experiment was negative. Nitrogen mass balance, although positive, exhibited a loss of 77% of the N added to the system. The results obtained indicate that application of this sewage sludge to a soil with a pH < 5, at the loading rate used here, and without liming (i.e., non fulfilment of the requirements of the present European Directive) may pose a risk in terms of groundwater contamination.     

热处理对脱水污泥溶解特性及厌氧消化性能的影响

分别对脱水污泥在100、130和170℃条件下进行热处理,研究热处理对脱水污泥溶解特性的影响。此外,在半连续式完全混合反应器中进行厌氧消化实验研究不同热处理污泥的厌氧消化性能。实验结果表明,在100、130和170℃条件下,污泥COD溶解率由处理前的5.23%分别提高至20.08%、22.50%和27.20%,脱水污泥热处理规律和效果与高含水率污泥(总固体含量<5%)基本一致。经130℃2 h和170℃30 min高温热处理后污泥甲烷产率显著提高,较原泥分别提高24.64%和38.61%,沼气中甲烷含量稍有降低。     

PAM对制药污泥脱水性能改善及毒性削减

制药污泥的脱水处理及毒性削减是当前业界的研究热点。以污泥脱水性能(污泥比阻和泥饼含固率)和污泥综合急性毒性为评价指标,对2种不同型号PAM处理污泥的投加量进行优化,讨论了污泥絮凝脱水和毒性削减的机理。研究结果表明,处理100 mL原污泥,当制药污水厂现场使用的德国天使PAM和拓普戴克TOP8321型PAM投加量分别为4mg/L和12 mg/L时,污泥脱水性能达到最佳,此时污泥比阻从0.730×1012cm/g分别降低至0.126×1012cm/g和0.034×1012cm/g,泥饼含固率从16.32%分别提高至46.89%和34.98%;在毒性削减方面,2种混凝剂都可将污泥上清液毒性由微毒降至无毒,但对污泥毒性的削减效果不明显。对2种PAM的处理成本进行估算发现,污水厂现场使用的PAM对处理该制药污泥效果更佳,且费用相对较低,但要大幅度削减制药污泥的毒性需串联相应毒性削减技术和混凝沉淀单元。     

电渗脱水对污泥性质及结合水含量的影响

为探究电渗脱水对污泥理化性质及内部结合水的影响,采用电渗脱水技术处理机械脱水后的污泥,研究了电渗脱水后污泥的含水率、pH、总氮、总磷及结合水的含量变化。结果表明,随着脱水实验的进行,污泥的含水率均呈下降趋势,其中阳极下降最快,最低含水率可降至50.4%。阴极pH上升至9.1,中部变化不明显,而阳极持续下降至5.8。总氮含量表现为阴极和中部缓慢上升,而阳极持续下降;总磷含量的变化为阳极缓慢上升,而阴极和中部持续下降。电渗脱水后污泥中结合水含量较原泥降低,其中阳极结合水含量最低,结合水与干物质的质量之比由初始的2.67降低至0.76。同时发现,结合水含量越少,其所需的融化热就会越高,脱除难度越大。     

Fenton活化制备污泥炭对水中Cr (Ⅵ)的吸附性能

利用Fenton活化法活化脱水污泥制备活性炭,研究了Fenton试剂投加量、活化时间、炭化温度、炭化时间和升温速率5种因素对制备污泥炭的影响。污泥炭的最佳制备工艺：Fenton试剂投加量为150 mL,活化时间为2.5 h,炭化温度为350℃,炭化时间为1 h,升温速率为20℃·min-1。污泥炭碘吸附值达到331.90 mg·g-1,BET比表面积为24.265 m2·g-1。总孔容为0.146 cm3·g-1,微孔率为17%。分析了吸附时间、pH值和吸附温度3种因素对污泥炭吸附水中Cr（Ⅵ）的影响。在吸附时间为90 min,pH=3,吸附温度为50℃时,污泥炭对Cr（Ⅵ）的吸附量为9.93 mg·g-1。吸附动力学符合准二级动力学模型描述,吸附过程符合Langmuir和Tempkin等温吸附模型描述。     

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）。     

污泥提取液与普通小球藻相互影响的特性

本研究将普通小球藻低成本培养与污泥提取液处理相结合,探讨使用污泥提取液与BG11混合培养普通小球藻,以实现养藻成本的降低与污泥资源化利用的目的。通过测定小球藻细胞密度、叶绿素a、中性油脂等生长特性以及污泥提取液中总氮(TN)、总磷(TP)、总有机碳(TOC)和毒性等降解指标的变化,来验证污泥提取液与普通小球藻生长的相互影响。结果表明,污泥提取液占总培养基(提取液与BG11)体积的20%(v/v)时,普通小球藻细胞密度最大,细胞中中性油脂积累较好,但不利于藻细胞叶绿素a的合成;普通小球藻对污泥提取液中的TN、TP、总有机碳(TOC)、毒性等都有显著的去除效能,在污泥提取液含量为20%、培养240 h时,TN、TP、毒性的去除率分别为89.91%、92.31%和63.08%。