有机废水厌氧水解酸化工艺研究与工业应用现状

综述了厌氧水解酸化作为有机废水预处理工艺的研究和应用现状。指出,对于有机废水,特别是高浓度和难降解有机废水,水解酸化是一种有效的预处理手段,可明显提高有机废水的可生物降解性。其理论基本成熟,已进入对不同类型废水的广泛试验阶段,其工业应用前景广阔。

水解酸化—两级生物接触氧化工艺处理印染废水

纺织印染行业是水污染大户,且废水成分复杂,毒性强,色度高,pH波动大,难降解,组分变化大,一直是工业废水处理的难点。结合工程实例,介绍了水解酸化—两级生物接触氧化工艺处理印染废水的工艺流程、主要工艺参数以及工程的调试与运行情况。运行结果表明,该工艺处理效果良好,出水水质满足《污水海洋处置工程污染控制标准》(GB 18486—2001)。

水解酸化-MBR处理偶氮染料废水的膜污染与清洗

通过水解酸化-MBR处理偶氮染料活性艳红X-3B废水膜污染和膜清洗试验,分析膜污染过程和膜清洗方法与效果。对污染膜采用空曝气、脱脂绵擦拭膜表面的物理清洗方法,酸洗、碱洗的化学清洗方法。水解酸化-MBR工艺处理偶氮染料废水,从启动初期到运行初期,膜污染速度逐渐降低,第1周期40 h,第2周期16天,第3周期37天。各周期平均压差值也在逐渐降低,分别为605.2cm,263.6 cm,79.9 cm。采用物理和化学的膜清洗方法,可恢复膜的过滤能力。物理清洗法可使由污染造成的膜阻力减少95.34%,再经酸、碱化学法清洗后,污染所造成的膜阻力基本消除。污染膜阻力主要来自凝胶极化层,占72.88%,其次来自外部污染,占15.63%,膜的内部污染阻力较小,仅占总阻力的4.33%。

Self-repairing Al_(2)O_(3)-TiO_(2)coatings fabricated through plasma electrolytic oxidation with various cathodic pulse parameters

The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed bipolar waveforms with various cathodic duty cycles and cathodic current densities.The coatings were characterized by SEM,EDS,and XRD.EIS was applied to investigate the electrochemical properties.It was observed that the increase of cathodic duty cycle and cathodic current density from 20%and 6 A/dm^(2) to 40%and 12 A/dm^(2) enhances the growth rate of the inner layer from 0.22 to 0.75μm/min.Adding PTO into the bath showed a fortifying effect on influence of the cathodic pulse and the mentioned change of cathodic pulse parameters,resulting in an increase of the inner layer growth rate from 0.25 to 1.10μm/min.Based on EDS analysis,Si and Ti were incorporated dominantly in the upper parts of the coatings.XRD technique merely detectedγ-Al_(2)O_(3),and there were no detectable peaks related to Ti and Si compounds.However,the EIS results confirmed that the incorporation of Ti^(4+)into alumina changed the electronic properties of the coating.The coatings obtained from the bath containing PTO using the bipolar waveforms with a cathodic duty cycle of 40%and current density values higher than 6 A/dm^(2) showed highly appropriate electrochemical behavior during 240 d of immersion due to an efficient repairing mechanism.Regarding the effects of studied parameters on the coating properties,the roles of cathodic pulse parameters and PTO in the PEO process were highlighted.

Enhancing selectivity in acidic CO_(2) electrolysis:Cation effects and catalyst innovation

The electrochemical reduction of CO_(2)(eCO_(2)R)under ambient conditions is crucial for reducing carbon emissions and achieving carbon neutrality.Despite progress with alkaline and neutral electrolytes,their efficiency is limited by(bi)carbonates formation.Acidic media have emerged as a solution,addressing the(bi)carbonates challenge but introducing the issue of the hydrogen evolu-tion reaction(HER),which reduces CO_(2) conversion efficiency in acidic environments.This review focuses on enhancing the selectivity of acidic CO_(2) electrolysis.It commences with an overview of the latest advancements in acidic CO_(2) electrolysis,focusing on product selectivity and electrocatalytic activity enhancements.It then delves into the critical factors shaping selectivity in acidic CO_(2) electrolysis,with a special emphasis on the influence of cations and catalyst design.Finally,the research challenges and personal perspectives of acidic CO_(2) electrolysis are suggested.

酸化冲击解堵技术的改进与应用

油井堵塞问题一直制约着油井的正常生产,锦州采油厂从建厂以来一直使用机械解堵类技术对中低渗稀油油藏进行解堵,解除近井地带污染,恢复油井产能。经过多年现场试验,根据投入产出对比现场应用效果,优选和改进适合锦州采油厂的解堵技术,从而实现油层改造,解决油层污染,恢复油井产能。

组合工艺处理重质原油废水的中试

对重质原油废水采用气浮+水解酸化+A/O+Fenton+BAF的组合工艺进行了中试试验,结果表明所采用的组合式处理工艺对该类废水中的COD、氨氮、石油类等污染物均有较好的处理效果,处理出水可达到《城镇污水处理厂污染物排放标准》(GB 18918—2002)中的一级A类排放标准。

Separation and recovery of Cu and As during purification of copper electrolyte

Cu, As, Sb and Bi in copper electrolyte could be efficiently removed by reducing with SO2 followed by evaporative crystallization. As2O3 and CuSO4·5H2O were obtained after crystallized product was treated by dissolution, oxidation, neutralization, sedimentation, filtration and evaporative crystallization. The removal rates of Cu, As, Sb and Bi are 87.1%, 83.9%, 21.0% and 84.7%, respectively, when As （Ⅴ） in copper electrolyte is fully reduced to As （Ⅲ） by SO2, and the H2SO4 in concentrated copper electrolyte is 645 g/L. The removal rate of As is 92.81% when 65 g crystallized product is dissolved in 200 mL water at 30 ℃. The CuSO4·5H2O content is 98.8% when the filtrate is purified under the conditions that n（Fe）：n（As） is 1.2, the dosage of H2O2 is 19 times the stoichiometric needed, temperature is 45 ℃, time is 40 min, pH is 3.7, and then is evaporation crystallized.

Kinetic model for calcium sulfate decomposition at high temperature

A modified shrinking unreacted-core model,based on thermogravimetric analysis,was developed to investigate CaSO4 decomposition in oxy-fuel combustion,especially under isothermal condition which is difficult to achieve in actual experiments due to high-temperature corrosion.A method was proposed to calculate the reaction rate constant for CaSO4 decomposition.Meanwhile,the diffusion of SO2 and O2,and the sintering of CaO were fully considered during the development of model.The results indicate that the model can precisely predict the decomposition of CaSO4 under high SO2 concentration（1100×10-6）.Concentrations of SO2 and O2 on the unreacted-core surface were found to increase first and then decrease with increasing temperature,and the average specific surface area and porosity of each CaO sintering layer decreased with increasing time.The increase of SO2 and/or O2 concentration inhibited CaSO4 decomposition.Moreover,the kinetics of CaSO4 decomposition had obvious dependence on temperature and the decomposition rate can be dramatically accelerated with increasing temperature.

Germination Characteristics and Secondary Metabolism Regulation of Scutellaria baicalensis Georgi Seeds under Different Temperatures

[Objective] To study the germination characteristics and secondary metabolism of Scutellaria baicalensis Georgi seeds under different temperatures.[Method]The activities of superoxide dismutase（SOD）and peroxidase（POD）were determined with lactoflavine-NBT method and guaiacol-colorimetry assay,respectively.The catalase（CAT）,ascorbate peroxidase（APX）,phenylalanine ammonia-lyase（PAL）and cinnamic acid 4-Hydroxylase（C4H）were determined with ultraviolet spectrophotometry.The secondary metabolites were detected by High Performance Liquid Chromatography（HPLC）.[Result]The germination percentage,germination potentiality and germination index were seriously affected by low or high temperature.The proper germination temperature was 20-25 ℃.The activities of SOD,POD and CAT were significantly decreased as comparison to suitable temperature.The activities of PAL and C4H were also significantly decreased as comparision to suitable temperature which was accordance to the secondary metabolites.There was a positive correlation between the flavonoids content and the PAL and C4H activity（r=0.956,r=0.951,P0.05）.[Conclusion]The quality of the skullcaps could be improved by improving the activity of PAL and C4H.The proper temperature for the seed germination and the formation of secondary metabolites was 20 ℃.

Comparison of electrochemical dissolution of chalcopyrite and bornite in acid culture medium

The electrochemical dissolution process of chalcopyrite and bornite in acid bacteria culture medium was investigated by electrochemical measurements and X-ray photoelectron spectroscopy（XPS） analysis. Bornite was much easier to be oxidized rather than to be reduced, and chalcopyrite was difficult to be both oxidized and reduced. The relatively higher copper extraction of bornite dissolution can be attributed to its higher oxidation rate. Covellite（CuS） was detected as the intermediate species during the dissolution processes of both bornite and chalcopyrite. Bornite dissolution was preferred to be a direct oxidation pathway, in which bornite was directly oxidized to covellite（CuS） and cupric ions, and the formed covellite（CuS） may inhibit the further dissolution. Chalcopyrite dissolution was preferred to be a continuous reduction-oxidation pathway, in which chalcopyrite was initially reduced to bornite, then oxidized to covellite（CuS）, and the initial reduction reaction was the rate-limiting step.

Role of Sb(V) in removal of As, Sb and Bi impurities from copper electrolyte

The function mechanism of Sb（V） in As, Sb and Bi impurities removal from copper electrolyte was investigated by adding Sb（V） ion in a synthetic copper electrolyte containing 45 g/L Cu2＋, 185 g/L H2SO4, 10 g/L As and 0.5 g/L Bi. The electrolyte was filtered, and the precipitate structure, morphology and composition were characterized by chemical analysis, SEM, TEM, EDS, XRD and FTIR. The results show that the precipitate is in the shape of many irregular lumps with size of 50-200 μm, and it mainly consists of As, Sb, Bi and O elements. The main characteristic bands in the FTIR spectra of the precipitate are As-O-As, As-O-Sb, Sb-O-Bi, Sb-O-Sb and Bi-O-Bi. The precipitate is the mixture of microcrystalline of AsSbO4, BiSbO4 and Bi3SbO7 by XRD and electronic diffraction. The removal of As, Sb and Bi impurities by Sb（V） ion can be mainly ascribed to the formation of antimonate in copper electrolytes.

Changes of Primary and Secondary Metabolism during the Seed Germination of Scutellaria baicalensis Georgi

[Objective] To investigate the primary and secondary metabolism during the seed germination of Scutellaria baicalensis Georgi. [Method] The activities of SOD and POD were determined with lactoflavine-NBT method and guaiacol-colorimetry as- say, respectively. The activities of CAT, APX,PAL and C4H were determined with ultraviolet spectrophotometry. The contents of secondary metabolites were detected by High-performance Liquid Chromatography （HPLC）. [Result] The results indicate that the soluble sugar content decreased during the first 5 days and then increased when the cotyledons formed. The contents of PAL, C4H and CHS continuously in- creased at different stages during the seed germination process. The secondary metabolites also showed the consistent variation trend. In addition, the contents of secondary metabolites had significant positive correlation with the key enzyme activi- ty. [Conclusion] The formation of secondary metabolites is significantly positively cor- related with the key enzyme during the seed germination process. Therefore, the key enzyme activity can be enhanced by adopting appropriate measures to improve the secondary metabolites, thereby obtaining high-quality medicinal materials.

Influence of oxidation heat on hard anodic film of aluminum alloy

The special experimental device and sulfuric acid electrolyte were adopted to study the influence of anodic oxidation heat on hard anodic film for 2024 aluminum alloy. Compared with the oxidation heat transferred to the electrolyte through anodic film, the heat transferred to the coolant through aluminum substrate is more beneficial to the growth of anodic film. The film forming speed, film thickness, density and hardness are significantly increased as the degree of undercooling of the coolant increases. The degree of undercooling of the coolant, which is necessary for the growth of anodic film, is related to the degree of undercooling of the electrolyte, thickness of aluminum substrate, thickness of anodic film, natural parameters of bubble covering and current density. The microstructure and performance of the oxidation film could be controlled by the temperature of the coolant.

Effects of Dilute Acid-intensified Hydrolysis on Fermentative Biohydrogen Production Capacity of Maize Stalk

[Objective] This study was to explore the effects of dilute acid hydrolysis on fermentative biohydrogen production capacity of maize stalk. [Method] Using maize stalks subjected to mechanical disintegration,steam explosion and dilute acid hydrolysis as experimental materials,we measured and analyzed the effects of different treatments and particle size of maize stalk were analyzed. [Result] The optimal fermentative biohydrogen production was found under following parameters：pretreatment of 0.8% dilute H2SO4 following steam explosion,particle size of maize stalk of 0.425-0.850 mm,liquid-solid ratio [0.8% H2SO4 （M）：stalk （W）] of 10：1. [Conclusion] Post steam explosion,dilute 0.8% dilute H2SO4 intensified hydrolysis on maize stalk could produce fermentative biohydrogen production capacity.

Thermal decomposition of ammonium hexafluoroaluminate and preparation of aluminum fluoride

The thermal decomposition process of （NH4）3AlF6 was studied by DTA-TGA method and the related thermodynamic data were obtained. The results show that AlF3 is obtained after three-step decomposition reaction of （NH4）3AlF6, and the solid products of the first two decomposition reactions are NH4AlF4 and AlF3（NH4F）0.69, respectively. The three reactions occur at 194.9, 222.5 and 258.4 ℃, respectively. Gibbs free energy changes of pertinent materials at the reaction temperatures were calculated. Enthalpy and entropy changes of the three reactions were analyzed by DSC method. Anhydrous aluminum fluoride was prepared. The XRD analysis and mass loss calculation show that AlF3 with high purity can be obtained by heating （NH4）3AlF6 at 400 ℃ for 3 h.

复合式生物处理技术处理印染废水实验研究

复合式生物处理技术将生物悬浮生长的活性污泥工艺和固定生长的生物膜工艺有机的结合起来,发挥了悬浮生长法效率高和固定生长法适宜性强和稳定性好的优点,提高了生物量,从而有效地提高生物反应器的容积利用效率,使其在高效率和高稳定性条件下运行.采用复合式水解酸化反应器和复合式好氧生物反应器处理印染废水,研究结果表明,水解酸化反应器可以显著改善废水的可生化性.经过8h水解酸化后接8h复合式好氧生物处理后,系统出水可以达标排放.

Germination Characteristics and Secondary Metabolism Regulation of Scutellaria baicalensis Georgi Seeds under Different Light Intensities

[Objective] This study aimed to investigate the primary and secondary metabolisms during the germination of Scutellaria baicalensis Georgi seeds under different light intensities. [Method] The activities of CHL, soluble sugar, PAL, C4H and CHS were determined with ultraviolet spectrophotometry. The secondary metabolites were detected by High Performance Liquid Chromatography （HPLC）. [Result] The results indicate that the germination of Scutellaria baicalensis Georgi seeds is not sensitive to light and the seedlings were very sensitive to light. The CHL, soluble sugar, PAL, C4H and CHS continuously increased with light intensity. The content of secondary metabolites also increased. [Conclusion] Light increased the formation of leaf photosynthetic pigment, thereby affecting the primary metabolites. The activities of PAL, C4H and CHS significantly increased with the development of light intensity. Finally the secondary metabolites of medicinal plants increased sharply. Therefore, the quality of Scutellaria baicalensis Georgi materials can be improved by increasing the light intensity moderately.

Structure and corrosion resistance of modified micro-arc oxidation coating on AZ31B magnesium alloy

A hydrophobic surface was fabricated on a micro-arc oxidation (MAO) treated AZ31 Mg alloys via surface modification with myristic acid. The effects of modification time on the wettability of the coatings were investigated using the contact angle measuring device. The surface morphologies and structure of the coatings were evaluated using SEM, XRD and FT-IR. The corrosion resistance was investigated by potentiodynamic polarization curves and long-term immersion test. The results showed that the water contact angle (CA) increases gradually with modification time from 0 to 5 h, the highest CA reaches 138° after being modified for 5 h, and the number and size of the micro pores are decreased. The modification method hardly alters crystalline structure of the MAO coating, but improves the corrosion resistance based on the much positive potential and low current density. Moreover, the corrosion resistance and hydrophobicity can be enhanced with increasing the alkyl chain. The wetting and spreading for the alkylcarboxylate with low surface energy become easier on the micro-porous surface, and alkylcarboxylate monolayer will be formed through bidentate bonding, which changes the surface micropores to a sealing or semi-sealing structure and makes the MAO coating dense and hydrophobic. All the results demonstrate that the modification process improves the corrosion protection ability of the MAO coating on AZ31B Mg alloy.

Heterogeneous catalytic activation of peroxymonosulfate for efficient degradation of organic pollutants by magnetic Cu^0/Fe_3O_4 submicron composites

Magnetic Cu^0/Fe3O4 submicron composites were prepared using a hydrothermal method and used as heterogeneous catalysts for the activation of peroxymonosulfate（PMS） and the degradation of organic pollutants.The as-prepared magnetic Cu^0/Fe3O4 submicron composites were composed of Cu^0 and Fe3O4 crystals and had an average size of approximately 220 nm.The Cu^0/Fe3O4 composites could efficiently catalyze the activation of PMS to generate singlet oxygen,and thus induced the rapid degradation of rhodamine B,methylene blue,orange Ⅱ,phenol and 4-chlorophenol.The use of0.1 g/L of the Cu^0/Fe3O4 composites induced the complete removal of rhodamine B（20 μmol/L） in15 min,methylene blue（20 μmol/L） in 5 min,orange Ⅱ（20 μmol/L） in 10 min,phenol（0.1mmol/L） in 30 min and 4-chlorophenol（0.1 mmol/L） in 15 min with an initial pH value of 7.0 and a PMS concentration of 0.5 mmol/L.The total organic carbon（TOC） removal higher than 85%for all of these five pollutants was obtained in 30 min when the PMS concentration was 2.5 mmol/L.The rate of degradation was considerably higher than that obtained with Cu^0 or Fe3O4 particles alone.The enhanced catalytic activity of the Cu^0/Fe3O4 composites in the activation of PMS was attributed to the synergistic effect of the Cu^0 and Fe3O4 crystals in the composites.Singlet oxygen was identified as the primary reactive oxygen species responsible for pollutant degradation by electron spin resonance and radical quenching experiments.A possible mechanism for the activation of PMS by Cu^0/Fe3O4 composites is proposed as electron transfer from the organic pollutants to PMS induces the activation of PMS to generate ^1O2,which induces the degradation of the organic pollutants.As a magnetic catalyst,the Cu^0/Fe3O4 composites were easily recovered by magnetic separation,and exhibited excellent stability over five successive degradation cycles.The present study provides a facile and green heterogeneous catalysis method for the oxidative removal of organic pollutants.