炼油厂含油冷却水处理回用技术研究

开展了O3氧化和强碱性阴离子交换组合工艺用于炼油厂含油冷却水回用处理的实验研究。结果表明，O3氧化过程中的最佳pH值约为10．5，O3氧化的除油效率为86．7％(紫外法测定)，去除1mg石油类约需消耗5．7mgO3，O3氧化后产物以乙酸和丙酸等挥发性脂肪酸为主。离子交换处理后油的含量达到未检出的水平。研究结果表明，O3氧化和离子交换组合处理技术能使炼油厂含油冷却水达到回用水水质标准。     

Fe-Cu-C三元微电解—Fenton氧化深度处理含油废水的研究

以某石化厂实际生产中经隔油、三级气浮处理后的含油废水(含油量为20～30mg/L)为处理对象,采用Fe-Cu-C三元微电解—Fenton氧化组合工艺进行处理,确定Fe-Cu-C三元微电解体系、Fenton氧化体系的最佳工艺条件。结果表明,Fe-Cu-C三元微电解的最佳工艺条件:Fe/Cu/C为2∶1∶1(质量比),反应时间为45min,溶液初始pH为4,最佳工艺条件下出水除油率可达56%左右;三元微电解出水经Fenton氧化的最优条件:H2O2投加量为1.0mL/L,pH为5,氧化时间为40min,最优条件下的除油率可达到89%以上;采用Fe-Cu-C三元微电解—Fenton氧化组合工艺处理后总除油率可达94%～96%,最终出水含油量稳定在1～2mg/L。     

组合方法去除新型采油污水中有机污染物的研究

含聚丙烯酰胺采油污水的有效处理是近年来困扰油田三次采油生产的一个难题。研究采用移动床生物膜技术与O3/UV/H2O2高级氧化技术的组合方法来处理含聚丙烯酰胺采油污水。实验结果表明,移动床生物膜技术可以有效去除污水中的石油类有机物,但对聚丙烯酰胺几乎无效果。O3/UV/H2O2高级氧化技术可以降解污水中的聚丙烯酰胺。组合方法处理后的含聚丙烯酰胺采油污水水质可以达到污水综合排放标准中的一级要求。     

采气废水中有机物去除方法

新疆油田天然气开采过程中产生的大量高矿化度、高COD的含油废水,难以处理处置,严重影响了气田的正常生产活动,危害到气田周边土壤安全和荒漠植被的生存.为实现该类废水的达标排放,选取COD和总石油烃含量为考察指标,研究比较了紫外(UV)、臭氧(O3)及紫外臭氧联合处理(UV/O3)法对该类废水的处理效果,进一步考察了pH和O3发生量对UV/O3法处理效果的影响.研究结果表明,3种方法处理废水60 min后,废水COD由处理前的563 mg/L分别下降至处理后的479、334.9和314 mg/L,去除率分别达到14.9％、32.7％和44.2％;而总石油烃含量由处理前的3.86 mg/L分别降至处理后的3.05、1.26和0.20 mg/L,去除率分别达到21.2％、67.4％和94.8％;其中,UV/O3法处理90 min后废水COD降低至148 mg/L,达到《废水综合排放标准GB8978-1996》二级排放标准;pH为7,臭氧发生量为10 g/L时,UV/O3法可应用于采气废水的处理.     

氧化-混凝法处理碱性高砷废水的实验研究

对碱性高砷废水的处理进行了研究 ,针对常规混凝法除砷的缺点提出了氧化 混凝工艺。结果表明 ,用氧化 混凝工艺除砷效果显著 ,废水经处理后砷含量低于 0 5mg/L ,符合国家排放标准。氧化 混凝除砷的最佳工艺条件为 :pH值为 6— 7,H2 O2 用量为 2 5 % ,氧化时间为 10min ,Fe2 (SO4) 3 用量为 2 5g/L ,PAM用量为 11 2 5mg/L。     

微波-Fenton氧化-PAFSi絮凝法处理含油废水

采用微波-Fenton氧化-PAFSi絮凝法处理含油废水，结果表明，200mL水样先经微波辐射6rnin，在pH=2，H2O2（30％）3．5g／L，Fe2＋ 1．3g／L的条件下氧化4h后，采用聚硅酸铝铁（Al：Fe：Si=10：2：1）和聚丙烯酰胺在pH：8时进行絮凝实验，处理后废水浊度、SS、COD、含油量和色度分别降低了99．46％、96．66％、91．94％、97．97％和95．00％，且经处理后废水的BOD5／COD由原水的0．04提高到0．53。实验还分析了含油废水的降解机理。     

Fenton氧化与生化组合技术处理油田采油废水的研究

采用Fenton氧化与生化组合技术处理生物难降解的采油废水的研究结果表明 ,Fenton氧化技术不但对采油废水中有机质有较好的去除率 ,而且大大地改善了废水的可生化性 ,在H2 O2 的投加浓度和Fe2 + 与H2 O2 的摩尔比分别为10mmol/L和 0 .1的条件下 ,经过 30min氧化后可使废水BOD值由原来的 5mg/L上升至 4 0mg/L ;同时随着氧化时间的延长 ,废水中残余的有机物分子量逐渐降低。 30min氧化后的废水经过生物处理 ,其出水COD值为 10 2mg/L ,可以满足国家综合污水外排标准 ,经济分析结果表明 ,该技术处理采油废水的运行成本为 1 4 7元 /t。这一技术在解决石油行业采油废水的外排达标方面具有很好的应用前景。     

Fenton试剂处理电厂离子交换树脂再生废水

采用 Fenton试剂对电厂离子交换树脂再生废水进行催化氧化处理 ,实验结果表明 ,当溶液 p H=2 .0、H2 O2 ( 30 % )投加量为 6 0 m L/L、F e SO4· 7H2 O投加量为 4.5 g/L、H2 O2 投加次数为 4、反应时间为 1.5 h时 ,废水的处理效果最佳     

Fenton氧化-前置反硝化缺氧好氧池(A/O)处理荧光增白剂废水中试研究

采用Fenton氧化-前置反硝化缺氧好氧池(A/O)对荧光增白剂废水IC出水进行中试实验研究。实验表明,在Fe2+投加量为0.003 mol/L,进水pH值为3,[H2O2]/[Fe2+]为4∶1,反应时间为2 h的条件下,Fenton氧化法对COD的去除率可以达到46%以上,出水BOD5/COD的值由0.26提高到0.58。氧化后废水进入前置反硝化生物脱氮系统进行生化处理,该系统采用间歇式进水,水力停留时间为2 d,实验结果表明,A/O系统对COD、氨氮和总氮的去除率分别达41%、90%以上和86%。该组合工艺对COD的总去除率可达到67%,出水氨氮在20 mg/L以下,总氮在37 mg/L以下。     

城市污水生化处理水UV/O3法深度处理效果及影响因素研究

研究城市污水生化处理水的深度处理技术及其影响因素,对于减轻环境污染和实现废水回用具有重要理论意义和实用价值。考察了UV／O3法对城市污水生化处理水深度处理的效果及其影响因素。结果表明,由于UV／O3过程具有氧化能力强,反应无选择性等优点,使其在城市污水生化处理水深度处理方面较普通O3氧化更具有优势,50min时CODCr去除率达到90％以上,达到了深度处理的目的。对于难氧化有机物,UV／O3法处理时几乎大部分都被氧化分解残留量很少,而O3法处理时仍有较多难氧化有机物残留。UV／O3法处理城市污水生化处理水时,在pH=6～9时,CODCr去除率随pH的升高而降低,表明较低pH（pH=5）有利CODCr的去除。有机污泥对CODCr去除率基本没有影响。但无机悬浮物SiO2对CODCr去除率影响较大,投加70mg／L的SiO2后CODCr氧化速率和去除率有较明显下降。随溶液碱度的增加,CODCr的去除率下降,碱度越高对CODCr去除的影响也越明显。     

应用臭氧氧化技术深度处理油船含油压载水的实验研究

油船含油压载水大量排放入海会对海洋生态环境产生较大的危害。在研究中,通过强电离放电技术制取高浓度臭氧,应用臭氧氧化方法来深度处理含油压载水,模拟实验表明在臭氧投加浓度达到120mg/L,在较短的接触时间(2min)内,臭氧对不同浓度的含油压载水中的油去除率可达到50%以上,同时使芳香族类物质显著减少,降低含油污水的生物毒性,处理方法具有可观的应用前景。     

Detection of naphthenic acids in fish exposed to commercial naphthenic acids and oil sands process-affected water

Naphthenic acids are a complex mixture of carboxylic acids that occur naturally in petroleum. During the extraction of bitumen from the oil sands in northeastern Alberta, Canada, naphthenic acids are released into the aqueous phase and these acids become the most toxic components in the process-affected water. Although previous studies have exposed fish to naphthenic acids or oil sands process-affected waters, there has been no analytical method to specifically detect naphthenic acids in fish. Here, we describe a qualitative method to specifically detect these acids. In 96-h static renewal tests, rainbow trout (Oncorhynchus mykiss) fingerlings were exposed to three different treatments: (1) fed pellets that contained commercial naphthenic acids (1.5mg g(-1) of food), (2) kept in tap water that contained commercial naphthenic acids (3mg l(-1)) and (3) kept in an oil sands process-affected water that contained 15mg naphthenic acids l(-1). Five-gram samples of fish were homogenized and extracted, then the mixture of free fatty acids and naphthenic acids was isolated from the extract using strong anion exchange chromatography. The mixture was derivatized and analyzed by gas chromatography-mass spectrometry. Reconstructed ion chromatograms (m/z=267) selectively detected naphthenic acids. These acids were present in each fish that was exposed to naphthenic acids, but absent in fish that were not exposed to naphthenic acids. The minimum detectable concentration was about 1microg naphthenic acids g(-1) of fish.     

Influence of pH and ozone dose on the content and structure of haloacetic acid precursors in groundwater

This study investigated the effects of pH (6-10) and ozone dose [0.4-3.0?mg O(3)/mg dissolved organic carbon (DOC)] on the content and structure of haloacetic acid (HAA) precursors in groundwater rich in natural organic matter (NOM; DOC 9.85?±?0.18?mg/L) during drinking water treatment. The raw water was ozonated in a 2 L glass column. NOM fractionation was carried out using XAD resins. HAA formation potential (HAAFP) was determined according to standard EPA Method 552. NOM characterization revealed it is mostly hydrophobic (65?% fulvic and 14?% humic acids). Hydrophobic NOM significantly influences HAA formation, as confirmed by the high HAAFP (309?±?15?μg/L). Ozonation at pH?6-10 led to changes in NOM structure, i.e. complete humic acid oxidation, and increased the hydrophilic NOM fraction content (65-90?% achieved using 3.0?mg O(3)/mg DOC). The highest degree of NOM oxidation and HAA precursor removal was achieved at pH?10 (up to 68?% HAAFP). Ozonation pH influenced the distribution of HAA precursor content, as increasing the pH from 6 to 10 increased the reactivity of the hydrophilic fraction, with the HAAFP increasing from 19.1?±?6.0?μg/mg DOC in raw water to 152?±?8?μg/mg DOC in ozonated water. The degree of HAA precursor removal depends on the dominant oxidation mechanism, which is related to the applied ozone dose and the pH of the oxidation process. Ozonation at pH?10 favours the mechanism of radical NOM oxidation and was the most effective for HAAFP reduction, with the efficacy of the process improving with increasing ozone dose.     

Comprehensive characterization of oil refinery effluent-derived humic substances using various spectroscopic approaches

Refinery effluent-derived humic substances (HS) are important for developing refinery effluent reclamation techniques and studying the environmental chemistry of wastewater effluents. In this study, dissolved organic matter (DOM) from refinery effluent was concentrated using a portable reverse osmosis (RO) system. HS were isolated from RO retentates with XAD-8 resin. A variety of approaches such as specific UV absorbance at 254nm (SUV(254)), elemental analysis, size exclusion chromatography (SEC), solid-state cross polarization magic angle spinning (13)C nuclear magnetic resonance spectrometry ((13)C CPMAS NMR), Fourier transform infrared spectrometry (FTIR), and electrospray ionization/ion trap/mass spectrometry (ESI/ion trap/MS) were employed for characterization of HS. The portable RO system exhibited high yield and recovery of DOM for concentrating refinery effluent. The concentration of dissolved organic carbon (DOC) in the refinery effluent was 9.9mg/l, in which humic acids (HA) and fulvic acids (FA) accounted for 2.3% and 34.6%, respectively. Elemental and SUV(254) analyses indicated relative high amounts of aliphatic structures and low amounts of aromatic structures in refinery effluent-derived HS. Refinery effluent-derived HS displayed lower molecular weight than natural HS. The number-average molecular weight (M(n)) and the weight-average molecular weight (M(w)) of HA were 1069 and 2934, and those of FA were 679 and 1212 by SEC, respectively. By ESI/ion trap/MS, the M(n) and the M(w) of FA were 330 and 383. Four kinds of carbon structures (aliphatic, aromatic, heteroaliphatic, and carboxylic carbons) were found in refinery effluent-derived HS by (13)C NMR analysis. The quantitative results support the interpretation that these HS are rich in aliphatic carbons and poor in aromatic carbons. Proteinaceous materials were identified by FTIR analysis in refinery effluent-derived HS.     

O3氧化工艺处理黄连素制药废水研究

采用臭氧（O3）氧化法处理含高浓度黄连素和COD的制药废水，探讨了废水初始pH、O3投加量及初始黄连素浓度等因素对O3氧化过程的影响，确定了O3氧化技术处理黄连素制药废水的最佳操作条件。结果表明，O3能够有效分解废水中的黄连素，降低其COD浓度；黄连素浓度为700mg／L、COD为3500mg／L、pH为0．88的废水，进气O3浓度为14．05mg／（L·min），处理时间为180rain（即投加量为2529mg／L）时，黄连素和COD的降解率分别可达77．46％和41．28％，BOD，／COD比（B／C比）从0．06提高到0．34，增加了4．7倍；随着废水中初始黄连素浓度的升高，废水COD降解率逐渐降低。O3氧化法是一种有效的黄连素制药废水预处理技术，可以大大提高废水的可生化性。     

微气泡曝气O3／H2O2处理RO浓水的效能及影响因素

采用O3／H2O2高级氧化工艺处理炼油厂反渗透（RO）浓水，用溶气泵加压溶气并产生微气泡强化传质，确定装置运行条件，考察气体中臭氧浓度、O3／H2O2初始摩尔比、pH和温度对O3／H2O2处理RO浓水效果的影响，并对RO浓水处理效能进行研究。结果表明，随着气体中臭氧浓度的增加，COD的去除率基本呈线性增加；加入适当量H，0，能提高臭氧氧化RO浓水的效果，O3／H2O2初始摩尔比在0～0．8范围内，COD的去除率先增加后下降，O3／H2O2初始摩尔比为O．5时COD去除率最大；pH从6．84增加到9．01，COD去除率逐渐增大，pH为10．03时COD去除率反而降低；在14～28℃范围内，温度低时，升高温度COD去除率增加较大，温度较高时，升高温度对COD去除率的影响较小。为考察该工艺的稳定性，在H：0：／0，初始摩尔比为O．5、溶液pH为8～9、臭氧浓度为80～100mg／L、温度为10-28℃条件下，对COD为90～140mg／L的RO浓水氧化处理4～10h，出水COD维持在39．9～49．9mg／L，达到《城镇污水处理厂污染物排放标准（GB18918—2002）》中的一级A标准；去除1gCOD消耗031．4～3．3g，消耗0，与H，02的总氧量为2．2～4．4g。     

氧化铈/活性炭催化臭氧氧化技术去除水中邻苯二甲酸二甲酯

用浸渍法在活性炭(AC)上负载氧化铈(CeO2)制备催化刺CeO2/AC催化臭氧氧化去除邻苯二甲酸二甲酯(DMP),考察了臭氧投加量,DMP初始浓度和溶液初始pH的影响.结果表明,CeO2/AC催化臭氧氧化去除DMP的最佳臭氧投加量为50mg/h,DMP初始浓度和溶液初始pH对CeO2/AC催化臭氧氧化DMP过程都有一定的影响.在DMP初始质量浓度为30 mg/L、溶液初始pH为5、臭氧投加量为50 mg/h、反应60 min时,CeO2/AC的加入(1.5g/L)有利于催化臭氧氧化DMP过程中总有机碳(TOC)的去除,TOC去除率由AC催化臭氧氧化的48%提高到68%.而单独臭氧氧化过程中的TOC去除率仅22%;且单独臭氧氧化与AC、CeO2/AC催化臭氧氧化DMP的矿化过程均符合二级反应动力学方程,CeO2/AC催化臭氧氧化DMP时TOC降解的二级反应动力学常数为0.0015L/(mg·min),分别是AC催化臭氧氧化的2.5倍和单独臭氧氧化的7.5倍.     

Ozonation of oil sands process water removes naphthenic acids and toxicity

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).     

Sensitivity of urban ozone formation to chlorine emission estimates

Recent evidence has demonstrated that chlorine radical chemistry can enhance tropospheric volatile organic compound oxidation and has the potential to enhance ozone formation in urban areas. In order to investigate the regional impacts of chlorine chemistry in southeastern Texas, preliminary estimates of atmospheric releases of atomic chlorine precursors from industrial point sources, cooling towers, water and wastewater treatment, swimming pools, tap water, reactions of chlorides in sea salt aerosols, and reactions of chlorinated organics were developed. To assess the potential implications of these estimated emissions on urban ozone formation, a series of photochemical modeling studies was conducted to examine the spatial and temporal sensitivity of ozone and a unique marker species for chlorine chemistry, 1-Chloro-3-methyl-3-butene-2-one (CMBO), to molecular chlorine emissions estimates. Based on current estimates of molecular chlorine emissions in southeastern Texas, chlorine chemistry has the potential to enhance ozone mixing ratios by up to 11–16 ppbv. Impacts varied temporally, with emissions from cooling towers primarily responsible for a morning enhancement in ozone mixing ratios and emissions from residential swimming pools for an afternoon enhancement. Maximum enhancement in CMBO mixing ratios ranged from 59 to 69 pptv.     

The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater

The process by which sulphur dioxide is oxidised in atmospheric droplets has been studied in laboratory experiments designed to collect a large amount of chemical data pertinent to the atmospheric situation. Thus the oxidation of sodium sulphite solutions by oxygen, ozone and hydrogen peroxide has been studied at different pH's and temperatures. In all cases the reaction is first order with respect to sulphite ion but the order with respect to oxidant differs. For oxygen the order is zero whereas the order for ozone and hydrogen peroxide is one. Varying the hydrogen ion concentration has little effect on the oxygen reaction rate between pH 6 and 9; the ozone reaction rate is inversely proportional to the square root of the hydrogen ion concentration and the hydrogen peroxide rate is almost directly proportional to the hydrogen ion concentration. These last two observations are very important since in the case of ozone it indicates that the reaction proceeds via a free radical mechanism involving hydroxyl radicals and in the case of hydrogen peroxide it is the only oxidation process of sodium sulphite so far investigated that shows a positive response to the presence of hydrogen ions.The experimental data was used to calculate the rate of sulphate formation in water droplets under atmospheric conditions for each of the three oxidants. If it is assumed that the ozone and hydrogen peroxide gas phase concentrations are initially 50 parts in 10⁹ and 1 part in 10⁹ by volume respectively, then the rates of sulphate formation are equal in cloud water at pH 5.8. Above this pH the ozone reaction is faster and below it the hydrogen peroxide reaction is faster due to the positive catalysis by hydrogen ions; the oxygen rate is unimportant by comparison at all pH's below 7. The rate of hydrogen peroxide reaction is such that substantial amounts of sulphate can still be formed rapidly in water droplets at pH values from 3 to 5, and thus this process will be very important in creating acidity in rainwater.