LPWCO method for the treatment of high concentrated organic wastewater

Based on wet air oxidation (WAO) and Fenton reagent, thispaper raises a new low pressure wet catalytic oxidation(LPWCO)which requires low pressure for the treatment of highlyconcentrated and refractory organic wastewater. Compared withgeneral wet air oxidation, the pressure of the treatment(0.1-0.6MPa) is only one of tens to percentage of latter(3.5-10MPa). Inaddition, its temperature is no more than 180℃.Compared withFenton reagent, while H2O2/COD(weight ratio) less than 1.2, theremoval of COD in the treatment is over twenty percents more thanFenton's even the value of COD is more than 14000mg/L. In thispaper, we study the effect factor of COD removal and the mechanismof this treatment. The existence of synergistic effect (catalytic oxidation and carbonization) for COD removal in H2SO4-Fenton reagent system under the condition of applied pressure and heating (0.1-0.6MPa, 104-165℃) was verified. The best condition of this disposal are as follows:H2O2/COD(weight ratio)=0.2-1.0, Fe2+ 0.6×10-3 mol, H2SO4 0.5mol, COD>1×104mg/L, the operating pressure is 0.1-0.6MPa and temperature is 104-165℃. This method suit to dispose the high-concentrated refractory wastewater, especially to the wastewater containing H2SO produced in the manufacture of pesticide, dyestuff and petrochemical works.     

有机物对厌氧氨氧化系统的冲击影响

接种稳定运行300余天的厌氧氨氧化污泥,通过批次试验,研究了不同浓度乙酸钠和不同种类有机物对厌氧氨氧化系统的冲击影响.结果表明:在初始NO2--N浓度为35mg/L左右,乙酸钠浓度为0~200mg/L时,乙酸钠的冲击不会抑制厌氧氨氧化菌的活性,且一定程度上促进厌氧氨氧化反应的进行,最大比氨氧化速率与乙酸钠浓度呈正相关性;不同有机物对厌氧氨氧化系统的促进作用不同,氨氧化速率从高到低依次为乙酸钠、蛋白胨、葡萄糖和淀粉;反硝化作用伴随整个反应过程,但硝态氮还原速率[0.0155~0.0442mgN/(L?min)]小于氨氧化速率[0.1090~0.1498mgN/(L?min)],因此厌氧氨氧化菌在系统中一直占主导地位.在有机物的冲击下,厌氧氨氧化反应可协同反硝化反应去除系统中的总氮,提高系统总氮的去除率,从而改善出水水质.     

Removal of formaldehyde over MnxCe1-xO2 catalysts: Thermal catalytic oxidation versus ozone catalytic oxidation

MnxCe1- xO2（x： 0.3–0.9） prepared by Pechini method was used as a catalyst for the thermal catalytic oxidation of formaldehyde（HCHO）. At x = 0.3 and 0.5, most of the manganese was incorporated in the fluorite structure of Ce O2 to form a solid solution. The catalytic activity was best at x = 0.5, at which the temperature of 100% removal rate is the lowest（270°C）. The temperature for 100% removal of HCHO oxidation is reduced by approximately 40°C by loading 5 wt.% Cu Oxinto Mn0.5Ce0.5O2. With ozone catalytic oxidation, HCHO（61 ppm） in gas stream was completely oxidized by adding 506 ppm O3 over Mn0.5Ce0.5O2 catalyst with a GHSV（gas hourly space velocity） of 10,000 hr-1at 25°C. The effect of the molar ratio of O3 to HCHO was also investigated. As O3/HCHO ratio was increased from 3 to 8, the removal efficiency of HCHO was increased from 83.3% to 100%. With O3/HCHO ratio of 8, the mineralization efficiency of HCHO to CO2 was 86.1%. At 25°C, the p-type oxide semiconductor（Mn0.5Ce0.5O2） exhibited an excellent ozone decomposition efficiency of 99.2%,which significantly exceeded that of n-type oxide semiconductors such as Ti O2, which had a low ozone decomposition efficiency（9.81%）. At a GHSV of 10,000 hr-1, [O3]/[HCHO] = 3 and temperature of 25°C, a high HCHO removal efficiency（≥ 81.2%） was maintained throughout the durability test of 80 hr, indicating the long-term stability of the catalyst for HCHO removal.     

润滑油废白土的应用探索

针对炼油企业废白土排放污染环境问题,在实验室中利用溶剂进行脱油处理,其脱油率及脱油废渣活性度都较高,但再生后的脱油废渣仍难以重复利用。而利用废白土作型砂添加剂的试验研究,其工业试验结果较为理想,且能彻底解决废渣的污染问题,实现其环保利用。     

有机难溶盐膜抑制黄铁矿氧化的研究

２５℃及ｐＨ３ 、５ 和７ 时，黄铁矿（ＦｅＳ２）经０－１ ｍｏｌ·Ｌ－１ Ｈ２Ｏ２ ＋ ０－０５ ％ 有机螯合剂混合液淋洗后，表面可形成黑色的保护膜，该膜能有效抑制黄铁矿氧化．淋洗４００ ｍｉｎ 后，黄铁矿剩余百分率分别为９９－７８％ 、９９－５４ ％ 和９９－５０ ％ ，而对照处理却分别为９５－７９ ％ 、９７－４５ ％ 和９９－７０ ％ ．在３ 种ｐＨ 条件下，经混合液淋洗４８０ ｍｉｎ 的黄铁矿再经ｐＨ３ 的０－１ ｍｏｌ·Ｌ－１ Ｈ２Ｏ２ 溶液淋洗４００ ｍｉｎ 后，样品的剩余百分率分别从对照的９４－９２ ％ 、９６－１７％ 和９８－１６ ％ 提高到９８－３１ ％ 、９８－８４ ％ 和９８－９１ ％ ．     

催化湿式过氧化氢氧化处理垃圾渗滤液及其DOM光谱分析

采用催化湿式过氧化氢氧化法对转运站垃圾渗滤液进行了处理,研究了影响催化湿式过氧化氢氧化效果的多个因素,并采用三维荧光和紫外-可见光谱对催化湿式过氧化氢氧化处理后水样中的溶解性有机物(DOM)成分变化进行了表征分析.结果显示,在最优实验条件下,COD去除率可达90%以上.光谱分析结果表明,渗滤液中的DOM组分降解效果明显,含有芳香环、双键和羰基共轭体系的有机物的去除效果也比较显著.     

高浓度难降解有机废水的催化氧化技术发展

在催化氧化法的研究发展中,产生的湿式催化氧化法,光催化氧化法,均相催化氧化法和多相催化氧化法４个分支,在实质上,它们都对氧化剂的分解产生催化作用,以加快放心水中与氧化剂之间的化学反应。由于某些强氧化可要催化作用下产生更强氧化性的基团,能够使一些高浓度难解的有机物氧化分解,因此催化氧化法成为处理高深度难降解有机废水一项重要的新技术。本文将对催化氧化法的研究发展,应用情况分类予以介绍。     

UV-catalytic treatment of spent caustic from ethene plant with hydrogen peroxide and ozone oxidation

The performance of UV/H2O2, UV/O3 and UV/H2O2/O3 oxidation systems for treating spent caustic from an ethylene plant was investigated, in UV/H2O2 system, with the increase of H202 dosage, removal efficiencies of COD and the ratio of biochemical oxygen demand(BOD) to chemical oxygen demand(COD) of the effluent were increased and a better performance was obtained than the H2O2 system alone. In UV/H2O2 system, removal efficiency of COD reach 68% under the optimum condition, and BOD/COD ratio was significantly increased from 0.22 to 0.52. In UV/O3 system, with the increase of O3 dosage, removal efficiency of COD and BOD/COD ratio were increased, and a better performance was obtained than the O3 system alone. Under the optimum condition, removal efficiency of COD was 54%, and BOD/COD ratio was significantly increased from 0.22 to 0.48. In UV/H2O2/O3 system, COD removal efficiency was found to be 22.0% higher than UV/O3 system.     

MO_x-CeO_2/HZSM-5催化剂催化氧化含氯挥发性有机物研究

采用浸渍法制备了不同过渡金属掺杂的MOx-CeO2/HZSM-5（M分别表示Cr、Mn、Fe、Co、Ni和Cu）催化剂,研究了各催化剂对1,2-二氯乙烷（DCE）的催化降解性能.结果表明,过渡金属掺杂后,MOx-12%CeO2/HZSM-5催化剂催化氧化1,2-二氯乙烷（DCE）的活性明显提高.各催化剂（记为M-CeO...     

Distribution and sources of solvent extractable organic compounds in PM2:5 during 2007 Chinese Spring Festival in Beijing

The solvent extractable organic compounds (SEOC), including n-alkanes, polycylic aromatic hydrocarbons, fatty acids, anddicarboxylic acids in PM2.5 during the 2007 Chinese Spring Festival in Beijing, were measured via gas chromatography-massspectrometry for determining the characteristics and sources of these organic pollutants. The concentrations of total n-alkanes, PAHs,and organic acids before Chinese Spring Festival Eve (1025.5, 95.9, and 543.3 ng/m3, respectively) were higher than those after (536.6,58...     

FCC废催化剂中的金属污染物及其环境风险

采集国内不同地区的19套流化催化裂化(FCC)装置产生的FCC废催化剂样品,分析其金属浓度及浸出浓度,探讨FCC废催化剂中的主要金属污染物、污染特性及潜在风险。结果表明:FCC废催化剂中主要金属为镍、钒、锑、钴和锌;不同装置采集的FCC废催化剂中主要金属浓度与浸出浓度差别较大,其中镍、钒、锑浸出浓度较高,分别为0.004~3.171、0.130~39.490、0.042~8.099 mg/L;FCC废催化剂中金属浸出浓度不影响其作为危险废物填埋,而浸出pH过低需要进行预处理后才能进入危险废物填埋场;当FCC废催化剂长期堆存在地面时,锑会释放出来,危及地下水,存在一定健康风险,而镍没有类似影响。     

电解催化氧化法处理毒死蜱废水的研究

采用电解氧化和Fenton技术耦合的电解催化氧化法对毒死蜱废水进行处理,考察了该法对毒死蜱废水的处理效果和出水的生化性能。结果表明:采用H₂O₂溶液用量逐步增加的方式,经过420 min电解催化氧化反应,废水COD_Cr仅由初始的7 920 mg/L降至5 880 mg/L,反映出毒死蜱废水的难降解特性。电解氧化单独处理毒死蜱废水时,在初始20 min内COD_Cr迅速下降,削减量为1 892 mg/L,随后COD_Cr变化不大;反应至80 min时,随着Fenton氧化反应的加入,废水COD_Cr开始逐步下降,有机物得到进一步降解。结合电解催化氧化出水的可生物降解COD_Cr(BCOD_Cr)和废水处理要求(生化出水预期COD_Cr为500~600 mg/L,满足DB 33/923—2014《生物制药工业污染物排放标准》排放限值),将其分别稀释3和4倍后进行好氧生化试验,反应动力学常数分别为383.4和298.3 min ^-1,该好氧生化反应过程可能更多受浓度控制而非毒性抑制。电解催化氧化出水稀释3倍后进行21 d水解酸化-好氧连续流试验,出水COD_Cr为512~673 mg/L,去除率基本保持在60%以上;出水TP浓度后期稳定在20~30 mg/L,去除率在45%左右;出水NH₃-N浓度为2.8~5.3 mg/L,去除率可达95%以上。     

SBR-电催化组合工艺处理己内酰胺废水试验研究

通过小试试验研究芬顿法、序批式活性污泥(SBR)生化法和电催化氧化法对己内酰胺废水中有机物的去除效果;采用SBR-电催化组合工艺现场中试,研究其对己内酰胺废水中有机物的去除效果,分析其运行的稳定性与经济性。结果表明:芬顿法在氧化剂投加量为3.0%时,COD_Cr去除率可达90.0%,但氧化剂成本较高;SBR生化法在适宜能耗时对COD_Cr的去除率为56.1%,单一工艺难以达到处理要求;电催化氧化法在适宜能耗时对COD_Cr的去除率为43.5%,单一工艺难以达到处理要求且单位耗电量较大;SBR-电催化氧化组合工艺对COD_Cr的去除率超过90.0%,出水COD_Cr降至200~300 mg/L,废水处理成本降低至5.15元/m ³,技术与经济方面均可行。     

Advanced molecular-fingerprinting analysis of dissolved organic sulfur by electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry using optimal spray solvent

Molecular level characterization of dissolved organic sulfur(DOS) by electrospray ionizationFourier transform ion cyclotron resonance mass spectrometry(ESI-FTICR MS) is necessary for further understanding of the role of DOS in the environment. Here, ESI spray solvent, a key parameter for ion production during ESI process, was investigated for its effect on the molecular characterization of DOS by ESI-FTICR MS. 100% MeOH as spray solvent was found for the first time to remarkably enhance the ioni...     

Supercritical water oxidation of polyvinyl alcohol and desizing wastewater：Influence of NaOH on the organic decomposition

Polyvinyl alcohol is a refractory compound widely used in industry. Here we report supercritical water oxidation of polyvinyl alcohol solution and desizing wastewater with and without sodium hydroxide addition. However, it is difficult to implement complete degradation of organics even though polyvinyl alcohol can readily crack under supercritical water treatment. Sodium hydroxide had a significant catalytic effect during the supercritical water oxidation of polyvinyl alcohol. It appears that the OH ion participated in the C-C bond cleavage of polyvinyl alcohol molecules, the CO2-capture reaction and the neutralization of intermediate organic acids, promoting the overall reactions moving in the forward direction. Acetaldehyde was a typical intermediate product during reaction. For supercritical water oxidation of desizing wastewater, a high destruction rate (98.25%) based on total organic carbon was achieved. In addition, cases where initial wastewater was alkaline were favorable for supercritical water oxidation treatment, but salt precipitation and blockage issues arising during the process need to be taken into account seriously.     

Size distribution and chemical composition of secondary organic aerosol formed from Cl-initiated oxidation of toluene

Secondary organic aerosol (SOA) formed from Cl-initiated oxidation of toluene was investigated in a home-made smog chamber. The size distribution and chemical composition of SOA particles were measured using aerodynamic particle sizer spectrometer and the aerosol laser time-of-flight mass spectrometer (ALTOFMS), respectively. According to a large number of single aerosol diameter and mass spectra, the size distribution and chemical composition of SOA were obtained statistically. Experimental results showed that SOA particles created by Cl-initiated oxidation of toluene is predominantly in the form of fine particles, which have diameters less than 2.5 m (i.e., PM2.5), and glyoxal, benzaldehyde, benzyl alcohol, benzoquinone, benzoic acid, benzyl hydroperoxide and benzyl methyl nitrate are the major products components in the SOA. The possible reaction mechanisms leading to these products are also proposed.     

20种水溶性有机溶剂对发光菌的毒性效应

以新型淡水发光菌——青海弧菌Q67(Vibrio-qinghaiensis sp.Q67)为检测生物,应用VeritasTM微孔板光度计测定了甲醇等20种常见水溶性有机溶剂对Q67的毒性效应.结果表明,乙腈、甲醇、乙醇、丙酮、乙醚、四氢呋喃和异丙醇7种有机溶剂具有非单调J型剂量-效应关系,其他13种为典型S型剂量-效应关系.分别采用Biphasic、Logit和Weibull等非线性函数进行曲线模拟,利用模拟函数可有效估算有机溶剂的各个效应浓度Ecx值.不同组成和结构的有机溶剂对淡水发光菌的毒性效应不同,官能团相同的直链溶剂含碳数越多毒性越大.     

深圳市典型溶剂使用源VOCs排放特征、治理现状与减排对策

为强化工业企业VOCs的综合整治,选取工业经济发达的深圳市作为研究区域,通过实地调研和现场检测的方式探讨了橡胶和塑料制品行业、印刷行业、表面涂装行业、电子元件制造业等典型溶剂使用源的VOCs排放特征和末端治理现状,并就源头替代和末端管理提出了具体的减排对策。结果表明：深圳市典型溶剂使用源VOCs的平均排放量为表面涂装（51.8 t/a）>电子元件（36.5 t/a）>印刷（21.0 t/a）>橡胶塑料（17.4 t/a）,不同排放规模的橡胶塑料企业和印刷企业对各自行业的排放贡献较为均匀,而排放量>300 t/a的涂装企业、电子企业对各自行业的贡献率则分别占63.9%、44.9%;受水性原料替代和末端治理设施等控制政策的影响,四大行业固定排放源VOCs组分以OVOCs为主（排放量占比为76.8%~97.0%）,特征污染物为甲醛和乙醛;四大行业末端工艺类型均以UV光解、水喷淋、活性炭吸附的低效组合工艺为主,占比约51.4%~69.6%;评估结果显示,所测试的典型组合工艺中,78%的设施平均处理率均低于35%,治理方案缺乏针对性、运行管理缺乏规范性是造成溶剂使用源VOCs末端削减率偏低的主要因素。因此,为控制未来溶剂使用源VOCs排放量,应当推动源头排放控制从“底线约束”向“先进带动”持续转变;末端治理应统筹考虑技术可行性和管理有效性,确保实现行业VOCs排放总量的高效削减。

     

萃取在含盐有机废水焚烧处理中的应用

提出并研究了萃取-焚烧工艺在蒸发残液焚烧处理中的应用.以乙酸乙酯为萃取剂,水油体积比为5时,将含30 g·L-1氯化钠、1 g·L-1对硝基苯酚的模拟废水剧烈振荡1min,静置10 min后进行萃取,一级萃取效率和二级萃取效率分别为97.12%和99.89%.随着水油比的升高,一级萃取效率和二级萃取效率都有所下降,但是经过二级萃取之后,有机物的萃取率均在99.00%以上.废水中的氯化钠对萃取效率有提高作用,当氯化钠浓度从60g·L-1升高到200 g·L-1时,一级萃取效率和二级萃取效率分别从94.76%和99.82%上升到97.53%和99.92%.正辛醇的萃取效率较乙酸乙酯低.经过萃取脱盐的有机相,蒸发回收有机溶剂后得到有机物残渣,有机物残渣与有机废水蒸汽一起进入流化床焚烧炉进行焚烧处理;当焚烧炉的温度从700℃提高到850℃时,有机废水蒸汽单独焚烧的焚烧效率从86.34%上升到99.96%,而有机废水蒸汽和有机残渣混合焚烧时的焚烧效率则从90.16%上升到99.99%.     

Catalytic wet air oxidation for the treatment of emulsifying wastewater

The wet air oxidation (WAO) and catalytic WAO(CWAO) of the high strength emulsifying wastewater containing nonionic surfactants have been investigated in terms of COD and TOC removal. The WAO and homogeneous CWAO processes were carried out at the temperature from 433 K to 513 K, with initial oxygen pressure 1.2 MPa. It was found that homogeneous catalyst copper(Cu(NO3)2) had an fairly good catalytic activity for the WAO process, and the oxidation was catalyzed when the temperature was higher than 473K. Moreover, several heterogeneous catalysts were proved to be effective for the WAO process. At the temperature 473 K, after 2h reaction, WAO process could achieve about 75% COD removal and 66% TOC removal, while catalysts Cu/Al2O3 and Mn-Ce/Al2O3 elevated the COD removal up to 86%-89% and that of TOC up to 82%. However, complete elimination of COD and TOC was proved to be difficult even the best non-noble catalyst was used. Therefore, the effluent from WAO or CWAO process need to be further disposed. The bioassay proved that the effluent from WAO process was amenable to the biochemical method.