化学沉淀组合电催化氧化处理脱硫废液技术研究

真空碳酸钾脱硫工艺碱洗段废液因含有高浓度硫化物、COD等有毒成分而影响焦化废水后续生物处理。以焦化企业实际碱洗段废液为研究对象,选用化学沉淀和电催化氧化的组合方式对其进行预处理。结果表明,室温下当氧化铜的投加量为65 g/L、反应时间60 min时废液中S2-去除率可达93%,且经过高温灼烧可实现Cu O沉淀剂的再生使用。沉淀后出水经电催化氧化处理,在电流10 A、电压4.9 V、电解时间120 min的条件下,出水COD可降至2 400 mg/L,满足常规生化系统进水的要求。     

Kinetics characteristics of coal low-temperature oxidation in oxygen-depleted air

The longwall gob (mined-out) area is one of the main places that are prone to coal spontaneous combustion and most of the residual coal in it is in oxygen-depleted air as it is a semi-enclosed space. A DSC (Differential scanning calorimetry) test system was designed to accurately test the heat generation of coal oxidation in different oxygen concentration atmosphere, based on which the kinetics parameters (activation energy and pre-exponential factor) of coal low-temperature oxidation in oxygen-depleted air were solved out. The results show that the kinetics parameters present obvious stage features and the lower the oxygen concentration is, the smaller is the difference of the kinetics parameters that in different oxidation stages. When the oxygen concentration is lower than 5% and 3% for jet coal and meagre coal respectively, the kinetics parameters of slow oxidation start to be greater than that of rapid oxidation. Both in the slow oxidation and rapid oxidation stage, with the decrease of oxygen concentration, kinetics parameters present significant decline on the whole while in different oxygen concentration range, the decline rate is different. It's concluded that when assessing the residual coal's self-heating risk, we need to use the corresponding kinetics parameters of coal oxidation in the oxygen concentration of the location where the residual coal is and the safety factor will be greater to only use the kinetics parameters of coal oxidation in slow oxidation stage. This study is of great significance for the assessment and control of the self-heating risk of coal that in different oxygen concentration atmospheres of the longwall gob areas.     

Remarkable promotion effect of trace sulfation on OMS-2 nanorod catalysts for the catalytic combustion of ethanol

OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO₄ (OMS-2-SO₄) and Mn(CH₃COO)₂ (OMS-2-AC) as precursors. SO₄^2 −-doped OMS-2-AC catalysts with different SO₄^2 − concentrations were prepared next by adding (NH₄)₂SO₄ solution into OMS-2-AC samples to investigate the effect of the anion SO₄^2 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO₄ catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO₄^2 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO₄^2 − (SO₄/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH₃-TPD and H₂-TPR techniques. The results showed that the presence of a suitable amount of SO₄^2 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO₄ compared to OMS-2-AC is due to the presence of some residual SO₄^2 − species in OMS-2-SO₄ samples.     

Oxidation of Cr(III) on birnessite surfaces: The effect of goethite and kaolinite

Oxidation of Cr(III) by manganese oxides may pose a potential threat to environments due to the formation of toxic Cr(VI) species. At present, it was still unclear whether the extent of Cr(III) oxidation and fate of Cr(VI) would be changed when manganese oxides co-exist with other minerals, the case commonly occurring in soils. This study investigated the influence of goethite and kaolinite on Cr(III) oxidation by birnessite under acidic pH condition (pH 3.5) and background electrolyte of 0.01 mol/L NaCl. Goethite was found not to affect Cr(III) oxidation, which was interpreted as the result of overwhelming adsorption of cationic Cr(III) onto the negatively-charged birnessite (point of zero charge (PZC) < 3.0) rather than the positively-charged goethite (PZC = 8.8). However, more Cr(VI) would be retained by the surface with the increase in addition of goethite because of its strong ability on adsorption of Cr(VI) at low pH. Moreover, either Cr(III) oxidation or distribution of the generated Cr(VI) between the solid and solution phases was not affected by kaolinite (PZC < 3.0), indicating its low affinity for Cr species. Reactions occurring in the present mixed systems were suggested, which could be partly representative of those in the soils and further indicates that the mobility and risk of Cr(VI) would be decreased if goethite was present.     

组合工艺在养猪废水处理中的工程应用研究

针对某猪场养殖废水排放所造成的严重污染问题,采用“固液分离+ UBF厌氧反应器+接触氧化+曝气生物滤池”的组合工艺,对废水中的COD、BOD、氨氮、SS去除效果明显,去除率分别为93.7％、94.4％、95％、77.1％,处理后的水质达到《国家畜禽养殖业污染物排放标准》.该工程运行费用仅为1.509元/m3,处理成本低.同时UBF池中产生的沼气可以收集并利用,猪粪和污泥可制作有机肥,实现了废物资源化利用.     

Fenton法和类Fenton法降解土壤中的二苯砷酸

本文对Fenton法与类Fenton法降解土壤中的二苯砷酸(diphenylarsinic acid,DPAA)进行了研究.考察了H2O2投加量和催化剂种类(Fe2+/Fe3+)对红壤及黑土中DPAA降解效果的影响,并采用高效液相色谱-质谱联用法(HPLC-MS/MS)对降解中间产物进行了初步鉴定.结果显示,针对红壤与黑土分别采用类Fenton法与Fenton法,在H2O2投加浓度为1 mol·L-1,含铁催化剂浓度为0.25 mol·L-1,土水比为1∶3,反应时间为1h的条件下,红壤及黑土中DPAA的降解率均可达到65%以上.HPLC-MS/MS的分析结果表明,DPAA可脱苯环形成降解产物苯砷酸(phenylarsinic acid,PAA),而PAA进一步氧化生成无机砷,这可能是Fenton/类Fenton法降解DPAA的途径之一.     

低温下废铁屑对厌氧氨氧化系统的影响

考察了在低温条件下(<20℃)废铁屑及其投加方式对厌氧氨氧化反应器脱氮性能和微生物群落的影响.结果表明,当废铁屑投加量为10g/L时,直接(R2)和间接(R3)投加方式均会对厌氧氨氧化反应造成短期抑制,总氮去除率分别降低4.7%和3.4%;30d连续运行后,2组反应器总氮去除率均提升至70%左右;反应器稳定运行阶段,R2的R_s(NO₂^--N与NH₄⁺-N去除量之比)和R_p(NO₃^--N生成量与NH₄⁺-N去除量之比)为1.57和0.22, R3的R_s和R_p为1.49和0.23,比R2更接近厌氧氨氧化反应理论值.废铁屑在水中发生腐蚀,降低DO并提高pH值,且R2,R3污泥中铁含量分别为对照组的1.64倍和1.93倍,废铁屑不仅改善了厌氧氨氧菌的生境,还满足了其对铁元素的需求.高通量测序结果显示,在20~50d的运行过程中, R1,R2,R3中优势厌氧氨氧化菌属Candidatus_Kuenenia的相对丰度分别增加-1.05%,0.14%和0.96%,废铁屑的投加促进了厌氧氨氧化菌在低温下的生长,且间接投加促进效果更为显著.     

Dosing low-level ferrous iron in coagulation enhances the removal of micropollutants, chlorite and chlorate during advanced water treatment

Drinking water utilities are interested in upgrading their treatment facilities to enhance micropollutant removal and byproduct control. Pre-oxidation by chlorine dioxide (ClO₂) followed by coagulation-flocculation-sedimentation and advanced oxidation processes (AOPs) is one of the promising solutions. However, the chlorite (ClO₂^–) formed from the ClO₂ pre-oxidation stage cannot be removed by the conventional coagulation process using aluminum sulfate. ClO₂^– negatively affects the post-UV/chlorine process due to its strong radical scavenging effect, and it also enhances the formation of chlorate (ClO₃^–). In this study, dosing micromolar-level ferrous iron (Fe(II)) into aluminum-based coagulants was proposed to eliminate the ClO₂^– generated from ClO₂ pre-oxidation and benefit the post-UV/chlorine process in radical production and ClO₃^– reduction. Results showed that the addition of 52.1-µmol/L FeSO₄ effectively eliminated the ClO₂^– generated from the pre-oxidation using 1.0 mg/L (14.8 µmol/L) of ClO₂. Reduction of ClO₂^– increased the degradation rate constant of a model micropollutant (carbamazepine) by 55.0% in the post-UV/chlorine process. The enhanced degradation was verified to be attributed to the increased steady-state concentrations of HO^· and ClO^· by Fe(II) addition. Moreover, Fe(II) addition also decreased the ClO₃^– formation by 53.8% in the UV/chlorine process and its impact on the formation of chloro-organic byproducts was rather minor. The findings demonstrated a promising strategy to improve the drinking water quality and safety by adding low-level Fe(II) in coagulation in an advanced drinking water treatment train.     

Biological methane production coupled with sulfur oxidation in a microbial electrosynthesis system without organic substrates

Methane is produced in a microbial electrosynthesis system (MES) without organic substrates. However, a relatively high applied voltage is required for the bioelectrical reactions. In this study, we demonstrated that electrotrophic methane production at the biocathode was achieved even at a very low voltage of 0.1 V in an MES, in which abiotic HS⁻ oxidized to SO₄²⁻ at the anodic carbon-cloth surface coated with platinum powder. In addition, microbial community analysis revealed the most probable pathway for methane production from electrons. First, electrotrophic H₂ was produced by syntrophic bacteria, such as Syntrophorhabdus, Syntrophobacter, Syntrophus, Leptolinea, and Aminicenantales, with the direct acceptance of electrons at the biocathode. Subsequently, most of the produced H₂ was converted to acetate by homoacetogens, such as Clostridium and Spirochaeta 2. In conclusion, the majority of the methane was indirectly produced by a large population of acetoclastic methanogens, namely Methanosaeta, via acetate. Further, hydrogenotrophic methanogens, including Methanobacterium and Methanolinea, produced methane via H₂.     

Identification and characterization of Fe3O4/peroxodisulfate advanced oxidation products from sulfameter

Sulfonamides (SAs) are one of the most widely used antibiotics and their residuals in the environment could cause some negative environmental issues. Advanced oxidation such as Fenton-like reaction has been widely applied in the treatment of SAs polluted water. Degradation rates of 95%-99.7% were achieved in this work for the tested 8 SAs, including sulfisomidine, sulfameter (SME), phthalylsulfathiazole, sulfamethoxypyridazine, sulfamonomethoxine, sulfisoxazole, sulfachloropyridazine, and sulfadimethoxine, in the Fe₃O₄/peroxodisulfate (PDS) oxidation system after the optimization of PDS concentration and pH. Meanwhile, it was found that a lot of unknown oxidation products were formed, which brought up the uncertainty of health risks to the environment, and the identification of these unknown products was critical. Therefore, SME was selected as the model compound, from which the oxidation products were never elucidated, to identify these intermediates/products. With liquid chromatography-high resolution tandem mass spectrometry (LC-HRMS/MS), 10 new products were identified, in which 2-amino-5-methoxypyrimidine (AMP) was confirmed by its standard. The investigation of the oxidation process of SME indicated that most of the products were not stable and the degradation pathways were very complicated as multiple reactions, such as oxidation of the amino group, SO₂ extrusion, and potential cross-reaction occurred simultaneously. Though most of the products were not verified due to the lack of standards, our results could be helpful in the evaluation of the treatment performance of SAs containing wastewater.