提高重铬酸盐法化学需氧量测定精度的方法研究

重铬酸盐法测定COD的步骤较为固定,但影响测定精度的因素比较多,对影响测定精度的因素进行研究,是提高重铬酸盐法测定COD精度的有效方法。通过理论研究和实验,发现操作前将水样摇匀、使用0.025 mol/L(COD含量小于50 mg/L低浓度水样)或0.250 mol/L(COD含量大于50 mg/L高浓度水样)的重铬酸钾溶液作为氧化剂、加入掩蔽剂硫酸汞有效除去氯离子的干扰、加热回流120分钟,滴定前自然冷却至室温,这些操作对于提高重铬酸盐法测定COD精度的操作具有积极的作用。     

COD测定中氯离子干扰的影响与消除

在测定COD的过程中,水样中存在的氯离子极易被氧化剂氧化,从而消耗氧化剂的量,导致测量结果偏高,同时由于氯离子与Ag2SO4反应生成AgCl沉淀会造成催化剂中毒,因此氯离子成为废水COD测定的主要影响因素,所以目前执行的《水质化学需氧量的测定重铬酸钾法》（GB11914—89）不适用于含氯离子大于1000mg／L（稀释后）的水样,尤其是对于高氯低COD的废水,如不进行干扰消除,     

分光光度法与滴定法测定COD比对实验

通过分光光度法与滴定法测定COD比对实验,COD浓度含量较大的天然水样,用分光光度法可以在短时间内得到较稳定的数据。滴定法在测高COD含量的天然水样时因为加热不均匀及高浓度重铬酸钾法计算方式对误差的放大作用导致结果精密度差。COD浓度40 mg/L以下的水样,分光光度法的精密度及可信性较差。     

小型密封管法测定地表水中低浓度化学需氧量的适用性检验技术浅探

化学需氧量(简称COD)是指在一定的条件下,用强氧化剂处理水样时所消耗氧化剂的量,以每升氧的毫克数表示,是反映水体水质、判断水体受有机物污染程度的重要指标。目前,检测COD的国家标准方法为重铬酸盐法(GB11914-1989),该方法采用敞开式加热回流装置消解水样,水样经回流氧化处理后,用硫酸亚铁铵滴定剩余重铬酸钾,测定结果准确,重现性较好。然而,该方法     

钢筋锈蚀氯离子临界浓度研究进展

鉴于钢筋锈蚀氯离子临界浓度对钢筋混凝土结构的使用寿命有很大影响,从钢筋锈蚀氯离子临界浓度的表达形式、测试方法、影响因素等方面对国内外氯离子临界浓度的研究进展进行综述,给出了已有研究成果得到的氯离子临界浓度值和有关国家标准中限定的氯离子浓度,提出氯离子临界浓度的影响机理、测试方法、影响因素的耦合作用、计算模型和提高方法等有待进一步研究的问题。     

用新催化剂测定化学需氧量(COD)

COD是指水中还原性物质(一般指有机还原性物质)被强氧化剂氧化时所需的氧量O_2毫克/升)。常用重铬酸钾回流法测定COD,此法氧化率高,重现性好。但加热回流时间长,且所用催化剂是贵重试剂(硫酸银),价格高。为此我们采用酸式磷酸锰作催化剂,以磷酸氢二钠作助催化剂,对成分较复杂的印染废水COD进行了试验测定。通过初步试验证明,新催化剂的优点是测定时间短(由原来回流两小时缩短为25分钟);     

水质中化学需氧量（COD）的快速测定

采用恒温箱加热、重铬酸钾吸光光度法来快速测定COD值。此方法与经典回流滴定法比较。除了快速、简便、还能减少试剂用量,减少环境的2次污染。使用于COD值在10mg/L以下的水样。     

紫外-可见光谱法水质COD检测技术研究——以大凌河水质检测为例

对于在水质的检测来说,水体中氯离子对COD测定的影响不容忽视。重铬酸钾具有强氧化性,能氧化大部分物质中的有机物。但它通常是用来确定水体COD大于30mg/L,和氯离子易受影响。因此,在高氯浓度废水中,通常采用氯离子对氯离子影响较小的碱性高锰酸钾法。在潮汐河口,通常采用酸性高锰酸钾法在上游和碱性高锰酸钾法下游。不同的检测方法导致水质评价不一致。文章选择大凌河的水质检测为案例,对紫外-可见光谱法水质COD检测技术进行了详细的研究。     

流动分析法检测水中CODcr的实验条件探究

文中使用AA3型连续流动分析仪COD模块,测定标准样品中的化学需氧量CODcr,并对其相关实验条件进行了探究,同时在不同浓度重铬酸钾存在的条件下增加样品浓度,从而确定了AA3连续流动分析仪的检测上限.文中还对不同浓度氯离子存在对样品结果的影响进行了探究,实验结果表明,氯离子的存在对样品结果的测定有一定影响.     

高压蒸汽消化法测定废水的化学需氧量

针对目前采用重铬酸钾氧化回流法测定化学需氧量（COD）过程中存在的某些不足之处，提出采用高压蒸汽消化法测定COD，重点研究了重铬酸钾、催化剂银和硫酸的浓度大小以及加热时间长短对测定COD的影响．     

Activity of sulphate reducing bacteria according to COD/SO4(2-) ratio of acrylonitrile wastewater containing high sulphate.

This study was performed to evaluate the biodegradability of acrylonitrile wastewater, microbial inhibition effect of acrylonitrile wastewater on removal efficiency and the activity of sulphate reducing bacteria (SRB) according to COD/sulphate ratio. Acrylonitrile wastewater was hardly biodegradable in a biodegradability test, however, SRB activity was 57% for overall consumption of electron donor and it was relatively high value compared to 17% of reference test with glucose. COD removal of acrylonitrile wastewater was improved to 57% and 61% from 20% as the COD/sulphate ratio were 0.5 and 0.3 by sulphate addition to acrylonitrile wastewater. First order reaction rate constants k on organic removal of acrylonitrile wastewater were 0.001, 0.004 and 0.004 at each COD/sulphate ratio of 0.9, 0.5 and 0.3. Thus it was suggested that the activity of SRB was a significant factor for removing organics and sulphate simultaneously in acrylonitrile wastewater.     

Simultaneous removal of ammonium-nitrogen and sulphate from wastewaters with an anaerobic attached-growth bioreactor.

Some industrial wastewaters may contain ammonium-nitrogen and/or sulphate, which need to be removed before their discharge into natural water bodies to eliminate their severe pollution. In this paper, simultaneous removal of ammonium-nitrogen and sulphate with an anaerobic attached-growth bioreactor of 3.8 L incubated with sulphate reducing bacteria (SRB) was investigated. Artificial wastewater containing sodium sulphate as electron acceptor, ammonium chlorine as electron donor and glucose as carbon source for bacteria growth was used as the feed for the bioreactor. The loading rates of ammonium-nitrogen, sulphate and COD were 2.08 gN/m3 x d, 2.38 gS/m3 x d, 104.17 gCOD/m3 x d, respectively, with a N/S ratio of 1:1.14. The results demonstrated that removal rates of ammonium-nitrogen, sulphate and COD could reach 43.35%, 58.74% and 91.34%, respectively. Meanwhile, sulphur production was observed in effluent as well as molecular nitrogen in biogas, whose amounts increased with time substantially, suggesting the occurrence of simultaneous removal of ammonium-nitrogen and sulphate. This novel reaction provided the possibility to eliminate ammonium-nitrogen and sulphate simultaneously with accomplishment of COD removal from wastewater, making wastewater treatment more economical and sustainable.     

Pretreatment and biotreatment of saline industrial wastewaters.

Wastewater from an Akzo Nobel production site contains more than 50 g/l total dissolved salts, mainly chlorides and sulphates, and is currently being treated after 10-20 x dilution. Biological treatment of undiluted or less diluted wastewater is very desirable for environmental and economic reasons. Possibilities were investigated in laboratory scale reactors to treat this highly saline and high strength wastewater aerobically, either after long adaptation or after removing part of the salts by a pretreatment. Adaptation and selection from mixed activated sludge populations took approximately 40 days to finally achieve a COD removal in aerobic treatment of 55-65% at two times dilution (11-16 g/l chloride and 5-7 g/l sulphate). Undiluted wastewater was not treatable. A higher removal percentage (> 80%) was possible at the original high salt concentration only when the sludge load was limited to approximately 0.4-0.5 kg COD/kg sludge/day. A longer adaptation time was required. Nanofiltration (NF) and crystallization could be used as a pretreatment to remove and recover up to 80% of the sulphate in the form of crystallized Glauber salt. Recovery strongly depended on the sulphate and chloride concentration in the NF concentrate and on crystallization temperature. The salt (sulphate) reduction through the NF improved the removal efficiency of a consecutive biotreatment only at a relatively low chloride level, demonstrating that the combination of nanofiltration-crystallization-aerobic biodegradation is less feasible for very saline wastewaters. Anaerobic pretreatment of saline waters turned out to be rather sensitive to high salinities. Only wastewater diluted to 10 g/l chloride could be treated well: sulphate concentration decreased by 80% and COD by 40%. Removal efficiencies of the combined anaerobic-aerobic treatment were approximately 80-85%, proving that this was a feasible route for 2-3 x diluted wastewater. The study has shown that several alternatives are available for treatment of the very saline wastewaters at a much lower degree of dilution than currently practiced.     

Anaerobic pond treatment of wastewater containing sulphate.

Anaerobic ponds are usually used for treatment of industrial and agricultural wastes which contain high organic matter and sulphate. Competition for substrate between sulphate reducing bacteria and methane producing archaea, and the inhibitory effects of sulphide produced from microbial sulphate reduction reported in the literature varied considerably. In this research, a laboratory scale column-in-series anaerobic pond reactor, consisting of five cylindrical columns of acrylic tubes, was operated to evaluate the effect of COD and sulphate ratio on pond performance treating wastewater containing high organic matter and sulphate from a tapioca starch industry. The result depicted that no adverse effect of COD:SO4 ratios between 5 and 20 on overall COD removal performance of anaerobic pond operated with organic loading rate (OLR) of 150 to 600 g COD/m3d. Sulphate reducing bacteria could out-compete methane producing archaea for the same substrate at COD:SO4 ratio equal to or lower than 5 and OLR greater than 300 g COD/m3d. Sulphide inhibition was not observed on overall performance of pond up to an influent sulphate concentration of 650 mg/L.     

UASB treatment of liquid residues from grass bioraffination.

In 2001 the first green biorefinery started operation in Switzerland with a design load of 5,000 tons dm of grass per year and a combined output of fibres (0.4 tons per ton input), protein (160 t/t) and bioenergy (500 kWh/t). Bioenergy was produced in a 570 m3 UASB reactor which has been monitored intensively during its first year of operation. Anaerobic treatment of liquid residues with > 80% degradation of organics was shown up to high f/m ratios and loading rates of 12 -15 kg COD/m3 d and specific biogas production of 0.5-0.65 Nm3 of gas per kg of COD added. A mass flow analysis of solids and pellets leads to the conclusion, that due to a low sludge bed volume of only 16% of the reactor combined with a low actual organic loading of 1.5 kg COD/m3 d there was a restricted adsorption and a low degradation of substrate solids.     

Application of anaerobic biological treatment for sulphate removal in viscose industry wastewater.

Long term lab-scale and bench-scale experiments were performed to investigate the feasibility of the anaerobic process to treat wastewater from a pulp and viscose fibre industry. Anaerobic wastewater treatment enables an advantageous combination of COD, sulphate and zinc removal from viscose wastewater. The aim of the investigations was to evaluate the influence of the free sulphide concentration on COD and sulphate removal efficiency and on the substrate competition between sulphate reducing and methanogenic bacteria. Since the wastewater did not contain enough COD for complete sulphate removal it was of major interest to determine favourable process conditions to steer the substrate competition in favour of sulphate reduction. Further experiments at bench-scale permitted us to evaluate applicable COD-loading rates and gain fundamental information about process stability and optimization for large-scale implementation. The present work will deal with the most relevant experimental results achieved and with important technological aspects of anaerobic treatment of viscose wastewater.     

Microbial sulphate reduction during anaerobic digestion: EGSB process performance and potential for nitrite suppression of SRB activity.

The present study investigated mesophilic anaerobic treatment of sulphate-containing wastewater in EGSB reactors and assessed the inclusion of nitrite in the reactor influent as a method for control of biological sulphate reduction. Two EGSB reactors, R1 and R2, were operated for a period of 581 days at varying volumetric loading rates, COD/SO4(2-) ratios and influent nitrite concentrations (R2 only). COD removal efficiencies of > 93% were achieved in both reactors at influent sulphate concentrations of up to 3,000 mg l(-1). A two-fold increase in the influent sulphate concentration, giving an influent COD/SO4(2-) ratio of 2, resulted in a reduction in reactor COD removal efficiency to 84% and 89%, in R1 and R2, respectively. Despite inclusion of nitrite in the R2 influent at concentrations up to 500 mg NO2-N l(-1), sulphate reduction proceeded similarly in R2 and R1, suggesting the ineffectiveness of nitrite as a potential inhibitor of SRB     

Treatment of industrial wastewater using photooxidation and bioaugmentation technology.

The versatile metabolism of microorganisms has an played important role in the biodegradation of recalcitrant toxic compounds entering into the natural environment. The biodegradability of organics can be enhanced using bioaugmentation and advanced oxidation processes (AOP) for aerobic/anaerobic treatment programs. Wastewater from a bulk drug (cresol) plant had high levels of TDS, COD and BOD, whilst the levels from a pigment plant low. Both contained organics difficult to degrade. AOP using hydroxyl radical generated in 1 L glass reactor using UV and H2O2 efficiently oxidised phenol and cresol. COD and sulphite reduction in cresol containing wastewater were 20-60% in 1-6 h. A twenty to thirty percent reduction in copper phthalocyanine pigment effluents was achieved in 6 h using AOP. Strains of Micrococcus, Pseudomonas, and Nocardia degrading phenol, cresol were isolated from soil and sludge. Mixed biomass of these organisms removed phenols (1,000 ppm) and cresols (500 ppm) completely in 24 and 72 h, respectively. The COD and BOD reductions under the optimum nutritional and physiological conditions were in the range of 70 to 90%. When added to the bioreactor, 20% of the developed biomass of mixed strains of Micrococcus, Nocardia and Pseudomonas increased the rate of COD and BOD reduction gradually and stabilised at 80-90%. Added biomass improved the overall efficiency of the aerobic process.     

Integration of sulphate reduction, autotrophic denitrification and nitrification to achieve low-cost excess sludge minimisation for Hong Kong sewage.

An integrated anaerobic-aerobic treatment system of sulphate-laden wastewater was proposed here to achieve low sludge production, low energy consumption and effective sulphide control. Before integrating the whole system, the feasibility of autotrophic denitrification utilising dissolved sulphide produced during anaerobic treatment of sulphate rich wastewater was studied here. An upflow anaerobic sludge blanket reactor was operated to treat sulphate-rich synthetic wastewater (TOC=100 mg/L and sulphate=500 mg/L) and its effluent with dissolved sulphide and external nitrate solution were fed into an anoxic biofilter. The anaerobic reactor was able to remove 77-85% of TOC at HRT of 3 h and produce 70-90 mg S/L sulphide in dissolved form for the subsequent denitrification. The performance of anoxic reactor was stable, and the anoxic reactor could remove 30 mg N/L nitrate at HRT of 2 h through autotrophic denitrification. Furthermore, sulphur balance for the anoxic filter showed that more than 90% of the removed sulphide was actually oxidised into sulphate, thereby there was no accumulation of sulphur particles in the filter bed. The net sludge productions were approximately 0.15 to 0.18 g VSS/g COD in the anaerobic reactor and 0.22 to 0.31 g VSS/g NO3- -N in the anoxic reactor. The findings in this study will be helpful in developing the integrated treatment system to achieve low-cost excess sludge minimisation.     

Electrolytic degradation of biorefractory organics and ammonia in leachate from bioreactor landfill.

Electrochemical oxidation was applied to treat the effluent from bioreactor landfill with leachate recirculation, characterised as poor biodegradability and high NH3-N concentration. In this study, the effluent was electrolysed in a batch reactor with Ti/TiO2-IrO2-RuO2 anode and stainless steel cathode. The oxidation of dissolved organic matter (DOM) during electrolysis was evaluated based on the evolution of molecular weight grade, hydrophilic fractionation (humic acid, fulvic acid and hydrophilic fractions), specific ultraviolet absorbance (SUVA254) and AOX. The impact of the initial NH3-N concentration on the oxidation was discussed. The results showed that at a current density of 100 mA/cm2, electrolysis time of 1.5 h and electrode gap of 1 cm, NH3-N with an initial concentration of 1.2 g/L could be completely eliminated and 56% of COD with an initial concentration of 1.2 g/L could be removed, which illustrated that the electrolysis-produced chlorine preferentially oxidised ammonia. The electrolysis mainly resulted in the degradation of humic substances and other high molecular DOM, followed by the increase of BOD/COD ratio and decline of SUVA254 of the leachate. The current efficiencies for COD and ammonia oxidation gradually decreased during the electrolysis, with the latter obviously higher than the former. At the optimal electrolysis time of 1.5 h, NH3-N could be totally removed and the BOD/COD ratio could be enhanced to 0.3, which was also favourable to control the AOX at a reasonable level.