超临界水氧化活性艳红M-2B染料废水动力学研究

用H2O2作为氧化剂,在595～704 K、18～30 MPa条件下,对活性染料废水进行超临界水氧化反应.实验结果表明,COD去除率随温度、压力、停留时间和氧化剂量的增加而上升,在704 K、28 MPa时,COD去除率可达到98.4%,停留时间小于35 s.COD、H2O2和水的反应级数分别为1、0和0;反应活化能Ea为37.21 kJ/mol;指前因子A为76.69 s-1.     

丙烯酸废水超临界水氧化动力学研究

用H2O2作为氧化剂,对丙烯酸生产废水进行超临界水氧化研究.得到了反应速率方程表达式.COD、H2O2和水的反应级数分别为1、0和0,指前因子A为4.97 s-1,反应活化能Ea为20.64 kJ/mol,诱导时间为8 s左右.     

Catalytic wet-air oxidation of a chemical plant wastewater over platinum-based catalysts.

Catalytic wet-air oxidation (CWAO) of wastewater (chemical oxygen demand [COD] = 1800 mg O2/dm3) from a fine chemicals plant was investigated in a fixed-bed reactor at T = 393-473 K under total pressure of 5.0 or 8.0 MPa. Catalysts containing 0.3% wt. of platinum deposited on two supports, mixed silica-titania (SM1) and carbon black composites (CBC) were used. The CBC-supported catalyst appeared to be more active than the SM1-supported one. A slow decrease of activity of the platinum on SM1 (Pt-SM1) during the long-term operation is attributed to recrystallization of titania and leaching of a support component, while the Pt-CBC catalyst is deteriorated, owing to combustion of the support component. The power-law-kinetic equations were used to describe the rate of COD removal at CWAO over the catalysts. The kinetic parameters of COD reduction for the wastewater were determined and compared with the kinetic parameters describing phenol oxidation over the same catalysts. Rates of COD removal for the wastewater were found higher than those for phenol oxidation over the same catalysts and under identical operating conditions.     

Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions

In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids.     

Fenton氧化-序批式膜生物反应器耦合处理干法腈纶废水

采用Fenton氧化-序批式膜生物反应器(SBMBR)组合工艺处理干法腈纶废水。结果表明,在废水初始pH值为3.0,H2O2投加量为90.0 mmol/L,Fe2+投加量为20.0 mmol/L,反应时间为2.0 h的条件下,Fenton氧化预处理对腈纶生产废水的COD去除率达到47.0%以上,COD由1 091 mg/L降至560 mg/L,废水的BOD5/COD由0.32升至0.69,废水的可生化性得到显著提高。Fenton处理出水与丙烯腈废水等比例混合后,采用SBMBR进行生化处理,在水力停留时间为24 h,90 min缺氧/150 min好氧交替运行的条件下,COD、NH4+-N和TN的平均去除率分别为71.7%、97.2%和47.4%,碳源不足是限制TN去除效果的主要影响因素。在无外加碳源的条件下,组合工艺处理后出水COD和NH4+-N浓度分别为117 mg/L和1.7 mg/L,出水水质可以稳定达到国家一级排放标准(GB8978-1996)。     

Electrochemical treatment of domestic wastewater using boron-doped diamond and nanostructured amorphous carbon electrodes

The performance of the electrochemical oxidation process for efficient treatment of domestic wastewater loaded with organic matter was studied. The process was firstly evaluated in terms of its capability of producing an oxidant agent (H₂O₂) using amorphous carbon (or carbon felt) as cathode, whereas Ti/BDD electrode was used as anode. Relatively high concentrations of H₂O₂ (0.064 mM) was produced after 90 min of electrolysis time, at 4.0 A of current intensity and using amorphous carbon at the cathode. Factorial design and central composite design methodologies were successively used to define the optimal operating conditions to reach maximum removal of chemical oxygen demand (COD) and color. Current intensity and electrolysis time were found to influence the removal of COD and color. The contribution of current intensity on the removal of COD and color was around 59.1 and 58.8 %, respectively, whereas the contribution of treatment time on the removal of COD and color was around 23.2 and 22.9 %, respectively. The electrochemical treatment applied under 3.0 A of current intensity, during 120 min of electrolysis time and using Ti/BDD as anode, was found to be the optimal operating condition in terms of cost/effectiveness. Under these optimal conditions, the average removal rates of COD and color were 78.9?±?2 and 85.5?±?2 %, whereas 70 % of total organic carbon removal was achieved.     

二氧化氯处理中药废水的氧化特性研究

采用稳定性二氧化氯溶液氧化降解中药废水,运用正交设计方法考察了常温、常压(291～298 K,1.013×10~5Pa)下ClO_2起始浓度([ClO_2]:COD)、pH、氧化反应时间等因素对中药废水处理效果的影响。研究表明,(1)当[ClO_2]:COD在1.0～0.4范围时,COD的平均去除率42%;当[ClO_2]:COD大于1.0或小于0.4时,COD平均去除率仅为27%～35%;(2)pH=2～4时,COD去除率可以达到40%以上,且pH≥10时,COD去除率高达59%;(3)COD去除率随着反应时间的延长而升高,氧化反应30 min左右,COD去除率能达到40%以上,105 min后处理效率达到63%;(4)ClO_2处理中药废水的最佳工艺条件是[ClO_2]:COD为0.7:1,反应pH值6,反应时间75 min。     

废椰壳制备活性炭负载CuO处理活性艳红X-3B废水的工艺优化

为了综合利用废椰壳,进行了废椰壳制备活性炭并负载氧化铜处理活性艳红X-3B废水的研究。采用正交实验法,以COD和色度去除率为目标函数确定了活性炭的最佳制备工艺条件为：磷酸浓度65%（质量百分数）,m（磷酸）/m（椰壳）比3∶1,活化时间2.5 h,活化温度500℃。在该活性炭上负载氧化铜处理活性艳红X-3B染料废水,其COD和色度去除率分别为83.70%和99.72%。用扫描电镜（SEM）和X衍射仪（XRD）对裸活性炭和载铜活性炭样品表面形貌和结构进行了表征和分析。通过单因素实验法确定了废水处理的最佳工艺条件为：pH值5,曝气时间4 h和催化剂用量0.55 g,在此条件下,COD和色度去除率分别为86.70%和99.75%,相应的出水指标为75 mg/L和32稀释倍数。     

微波辐照活性炭/铁屑处理橡胶促进剂生产废水

通过微波辐照活性炭与废铁屑的混合物处理橡胶促进剂生产废水。考察了炭铁混合物投加量、炭铁质量比、废水初始pH值、微波功率和微波辐照时间等对废水COD去除率的影响。结果表明,工艺的最佳参数为:炭铁混合物投加量65 g/L,炭铁质量比2∶1,微波功率200 W,微波辐照5 min,此条件下的废水COD去除率为76%;反应的表观过程近似符合一级动力学规律,动力学方程为:ln(C0/C)=0.1012t+0.8887,速率常数k=0.1012 min-1,半衰期t1/2=6.85 min;橡胶促进剂生产废水的微波辐照活性炭/铁屑处理工艺比单纯微波辐照及活性炭/铁屑处理工艺有明显的优越性。     

三维电极电化学氧化法深度处理DOP生产废水的研究

采用以铁板作阴、阳极,活性炭作填充粒子的三维电极电化学氧化法深度处理DOP生产废水。探讨了废水的pH、槽电压、极板间距、活性炭投加量和反应时间等因素对COD去除率的影响,并通过正交实验确定了处理DOP废水的最佳工艺条件,还对COD的降解动力学规律进行了初步探讨。结果表明,三维电极电化学氧化法处理DOP生产废水的最佳工艺条件为:pH值为5、电极间距为4 cm、槽电压为25 V、活性炭投加量为12 g/L、电解时间为90 min。在此条件下,COD去除率可达71.5%,出水COD浓度为50.9 mg/L,达到国家污水综合排放标准(GB8978-1996)的一级标准。三维电极电化学氧化法对COD的降解反应呈表观一级反应,降解速率方程为C=C0e-0.0124t。     

铁炭微电解-Fenton试剂法预处理半焦废水

采用铁炭微电解／Fenton试剂法对半焦废水进行预处理，探索材料粒径、铁炭比、废水pH、H2O2用量以及反应时间对处理效果的影响。结果表明，在铁屑粒径为5～7mm，活性炭粒径为2～3mm，铁炭体积比为1：1，微电解反应90min，进水pH为8．0～9．0，H2O2投加量为4mL／L，Fenton试剂反应90min的条件下，半焦废水COD去除率可达55％以上，B／C由处理前的0．24提高到0．43，可生化性能良好，铁炭微电解／Fenton试剂法可作为半焦废水一种有效的预处理方式。     

臭氧/活性炭联合工艺深度处理焦化废水

采用臭氧/活性炭联合工艺对焦化废水A2/O出水进行深度处理。考察了溶液初始pH值、臭氧投加量、活性炭投加量及使用次数、反应时间对焦化废水处理效果的影响。实验结果表明,活性炭的使用可显著提高臭氧对焦化废水COD的去除率,在溶液初始pH值为10.25、臭氧投加量为7.5 mg/min、活性炭投加量50 g/L、反应时间为30 min条件下,COD去除率达到73.51%。同时,在活性炭重复使用10次时,COD去除率为70.85%,仅降低了2.66%。     

实用型深度光氧化设备对几种染料和多菌灵农药废水的处理

利用HFS 1型深度光氧化废水处理设备对活性艳蓝K3R、酸性红 3B、活性黑KNB、酸性红A、直接耐酸大红4BS等 5种染料的水溶液和多菌灵农药废水进行了深度光氧化处理。结果表明 :(1)染料在处理 5min后 ,脱色率都在 90 %以上 ;处理 15min后 ,CODCr的去除率除活性艳蓝K3R较低外 ,其余的都在 80 %以上 ;BOD5/CODCr的值都有所增大。 (2 )多菌灵农药废水 (经稀释 )处理 4 0min后CODCr的去除率为 5 7.0 % ,BOD5/CODCr的值由 0 .2 0增加到 0 .4 4。 (3)采用深度光氧化 -絮凝的工艺处理多菌灵农药废水 ,CODCr的去除率为 5 7.5 %。     

废铁屑处理难生物降解染料废水

研究了用废铁屑处理难生物降解的染料废水，考察了进pH值、曝气时间、固液比、铁屑粒度对废水处理效果的影响，并确定了适宜实验条件。实验证明，该法可以有效去除染料废水的色度和CODcr，在实验考察范围内，脱色率和CODcr去除率分别可达90％、61.7%。同时废水可生化性也得到了改善，BOD5／CODcr从19.6%上升到29.5%，提高了50％,有利于后续生化处理。该法以废治废，是一种很有实用价值的废水处理方法。     

Incomplete oxidation of ethylenediaminetetraacetic acid in chemical oxygen demand analysis.

Ethylenediaminetetraacetic acid (EDTA) was found to incompletely oxidize in chemical oxygen demand (COD) analysis, leading to incorrect COD values for water samples containing relatively large amounts of EDTA. The degree of oxidation depended on the oxidant used, its concentration, and the length of digestion. The COD concentrations measured using COD vials with a potassium dichromate concentration of 0.10 N (after dilution by sample and sulfuric acid) were near theoretical oxygen demand values. However, COD measured with dichromate concentrations of 0.010 N and 0.0022 N were 30 to 40% lower than theoretical oxygen demand values. Similarly, lower COD values were observed with manganic sulfate as oxidant at 0.011 N. Extended digestion yielded somewhat higher COD values, suggesting incomplete and slower oxidation of EDTA, as a result of lower oxidant concentrations. For wastewater in which EDTA is a large fraction of COD, accurate COD measurement may not be achieved with methods using dichromate concentrations less than 0.1 N.     

含表面活性剂的采油废水催化氧化处理

对含有表面活性剂的废水(以下简称表活废水)进行了傅里叶红外光谱分析(FTIR),结果表明,废水中所含表面活性剂主要为环烷酸钠。采用次氯酸钙(Ca(ClO)2)和活性炭-Ni催化氧化处理,在Ca(ClO)2投加量为4 500 mg/L,活性炭-Ni投加量为7 000 mg/L时,反应90 min,出水COD为158.91 mg/L,去除率达62.92%。催化氧化出水经沸石吸附处理,在pH为6.85,吸附时间为2 h,沸石投加量为17 g/L的条件下,吸附出水COD和油含量分别为88.92 mg/L和2.53mg/L,去除率分别为45.65%和90.02%,均达到《污水综合排放标准(GB8978-1996)》的一级标准要求。催化剂活性炭-Ni和吸附剂沸石均具有较稳定的活性,在重复使用20次后,出水COD的去除率仅分别降低了1.16%和1.32%。     

蒸发壁式超临界水氧化反应器处理分散红和活性红染料废水的比较

采用蒸发壁式超临界水氧化反应器对染料分散红C.I.60和活性艳红M-2B配制的模拟废水进行降解实验.实验结果表明,2种染料的COD和TN去除率随着反应温度、氧化剂过量比(r)的升高而上升.COD去除率活性红要高于分散红,而TN去除率则相反.根据GC-MS分析和陶瓷膜SEM图像,分析测得2种染料主要反应中间产物均含有苯酚和苯甲酸,2种染料的反应对陶瓷膜均有轻微的腐蚀.     

焦化废水生物处理尾水的活性炭吸附及条件优化研究

国内焦化企业废水生物处理尾水中COD、色度等指标超标的现象大多是由残留的难降解有机物造成的。针对这种现象,通过采用不同种类和孔结构的活性炭、改变炭表面化学性质、优化吸附环境3种方式对生物处理尾水中的COD成分进行强化吸附,考察炭型、表面化学性质及pH值等因素的影响,以明确焦化废水吸附法深度处理的合理炭型及其优化的条件。把已稳定运行的1 320 m3/d处理规模焦化废水A/O/H/O工艺实际工程生物处理尾水作为研究对象,试验了13种活性炭品种的吸附去除COD及色度的效果,发现甲基蓝值和丹宁酸值大的炭型其吸附容量高;而某一种炭样的吸附特性实验中,不同化学改性时表面酸性官能团含量少的活性炭有利于提高其吸附容量,低pH值条件的吸附能力高于碱性条件,曝气混合方式能够缩短吸附平衡时间。经过优选的活性炭在适宜的反应条件下能够将焦化废水生物处理尾水中的COD值及色度值分别降低至60 mg/L及20倍以下,在较低的运行费用条件下使出水达到工业循环冷却水的水质要求。     

聚乙烯醇在超临界水氧化中降解

以H2O2为氧化剂用间歇式超临界水氧化装置对聚乙烯醇(PVA)废水进行降解研究。通过正交实验,考察了反应温度、压力、时间及氧化剂过氧倍数对降解效果的影响,并且采用GC/MS对液相降解产物进行表征推测其可能降解途径。结果表明:PVA在SCWO体系中能完全降解,反应温度440℃、压力28 MPa、氧化剂过氧倍数4、反应40 min时,COD去除率为99.03%,出水COD=89.09 mg/L。PVA在SCWO体系中降解为烯烃、烯酮、醇和羧酸类中间产物、最终降解为小分子的饱和直链烷烃类液相产物。     

粉末活性炭对三烯丙基异氰脲酸酯的吸附性能简

用静态吸附法考察粉末活性炭对水中三烯丙基异氰脲酸酯（CAIC）的吸附行为，采用单因素分析法对活性炭吸附化工废水中TAIC的工艺条件进行研究。实验结果表明，在TAIC模拟废水中，其TAIC初始浓度为800 mg/L，pH为7，在温度为298 K、转速为150 r/min的条件下，当活性炭的投加量达到4.4 g/L，吸附反应时间为50 min时，TAIC的去除效率最高为96.17%；对于实际废水，其TAIC初始浓度为1 500 mg/L，溶液pH为3，在温度为298 K、转速为150 r/min的条件下，当活性炭投加量达到10 g/L，吸附反应时间为2 h时，TAIC的去除效率最高为46.8%。这也是由于实际废水组分复杂，其他有机物存在一定的吸附竞争机制。