Aluminum-based ozone catalysts prepared by mixing method: Characteristics, performance and carbon emissions.

Green and low carbon is an essential direction for the development of water treatment technology. Ozone catalysts prepared by the mixing method have advantages in terms of energy consumption and CO2 emissions, but are considered to be insufficient in catalytic efficiency and stability. In this paper, an Mn-Cu-Ce/Al2O3 (MCCA) catalyst was prepared by optimizing the preparation conditions of the mixing method and the types and ratios of active components. Taking petrochemical secondary effluent (PCSE) as the treatment object, the performance of the catalyst and the carbon emission in the preparation process were studied; and compared with the impregnation method. Results showed that compared with catalysts loaded with other components, the MCCA had a higher removal efficiency for TOC (43.04%) and COD (53.18%), which was basically equivalent to the impregnation method, and the treated effluent reached the expected concentration. MCCA promoted the decomposition rate of O3 by ten times, and the main active species generated were found to be •OH and 1O. Similar to the catalytic ozonation by the catalyst prepared by the impregnation method, the adsorption sites and surface hydroxyl groups on the MCCA surface play a significant role in the degradation of pollutants. However, the carbon emission in the catalyst preparation process of the mixing method was 418.68 kg/ton, which was only 44% of the impregnation method (949.67 kg/ton). Under the global low-carbon transition, this study shows that the mixing method aligns more with the concept of green, clean, and efficient ozone catalyst preparation.

Effect of extrusion-spheronization granulation and manganese loading on catalytic ozonation of petrochemical wastewater.

The petrochemical secondary effluent (PSE) is typical refractory wastewater derived from the petrochemical industries, which requires advanced treatment due to the strict environmental protection policies. Catalytic ozonation is one of the most widely used advanced oxidation technologies in wastewater treatment because of its high mineralization rate, in which the alumina-based catalyst usually plays an important role. Extrusion-spheronization is a promising technique for the preparation of alumina spheres because the synthesized alumina particles have high sphericity, high specific surface aera and narrow particle size distribution. In this paper, two kinds of alumina-based catalysts (catalyst A: manganese nitrate added after alumina granulation and catalyst B: manganese nitrate added into alumina powder before granulation) were prepared by the extrusion-spheronization method and used for PSE treatment by catalytic ozonation. The prepared alumina samples were characterized by Brunauer-Emmett-Teller (BET) method, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM), while the wastewater samples were analyzed for Total organic carbon (TOC), UV254 and fluorescence spectroscopy. Results showed that manganese was uniformly distributed in both catalysts, and the specific surface area of two catalysts was 318.36 m2/g and 354.95 m2/g, respectively. Catalytic ozonation experiments were repeated nine times with each catalyst under the same conditions. The TOC removal rates for catalysts A and B in the first run were 48.88% and 49.06%, respectively, then it dropped to 28.05% for catalyst A but remained 47.81% for catalyst B after using for nine times. This implied that the long-term performance of catalyst B would be more stable than catalyst A. Similar result were found in three-dimensional fluorescence analysis. UV254 results indicated that the removal efficiency of aromatic and unsaturated substances by catalyst B was higher than catalyst A. A possible explanation is that the active component manganese oxide formed a catalyst skeleton in catalyst B, which makes it hard to dissolve. Effect of extrusion-spheronization granulation and manganese loading on advanced oxidant treatment of petrochemical wastewater.

[Enhanced Treatment of Petrochemical Secondary Effluent by Biological Aerated Filter (Fe2+)-Ozonation Process].

Two parallel biological aerated filters (BAF)-ozonation,named as number 1(feeding with FeSO4·7H2O) and number 2,were used to treat petrochemical secondary effluent.The effect of FeSO4·7H2O on COD and phosphorus removal by BAF-ozonation was studied.Molecular weight distribution,three-dimensional fluorescence scan and gas chromatography-mass spectrometry (GC-MS) were used to analyze water quality before and after BAF-ozonation.The results showed the average COD and TP concentrations were 82.91 mg·L-1 and 1.37 mg·L-1,respectively.When the dosage of FeSO4·7H2O was 9 mg·L-1,the average removal rates of COD and TP were 52.20% and 71.50%,respectively.The average COD removal rate in number 1 combined process was 17.15%,which was higher than that in number 2 combined process.The TP removal rate in number 1 combined process was increased by 51.81%.The percentage of dissolved organic matters with relative molecular weight less than 1×103 was 52% in the raw wastewater.However,the percentage increased to 75% when treated by number 1 combined process and the removal rate of various molecular weight organics was increased.Three-dimensional fluorescence analysis showed that the dosage of FeSO4·7H2O could improve the removal of fluorescent substances.GC-MS results showed that the number and concentration of organics were reduced after number 1 combined process in comparison with number 2 combined process.BAF-ozone could be enhanced by FeSO4·7H2O when treating petrochemical secondary effluent.

Appling hydrolysis acidification-anoxic-oxic process in the treatment of petrochemical wastewater: From bench scale reactor to full scale wastewater treatment plant.

A hydrolysis acidification (HA)-anoxic-oxic (A/O) process was adopted to treat a petrochemical wastewater. The operation optimization was carried out firstly by a bench scale experimental reactor. Then a full scale petrochemical wastewater treatment plant (PCWWTP, 6500 m(3) h(-1)) was operated with the same parameters. The results showed that the BOD5/COD of the wastewater increased from 0.30 to 0.43 by HA. The effluent COD was 54.4 mg L(-1) for bench scale reactor and 60.9 mg L(-1) for PCWWTP when the influent COD was about 480 mg L(-1) on optimized conditions. The organics measured by gas chromatography-mass spectrometry (GC-MS) reduced obviously and the total concentration of the 5 organics (1,3-dioxolane, 2-pentanone, ethylbenzene, 2-chloromethyl-1,3-dioxolane and indene) detected in the effluent was only 0.24 mg L(-1). There was no obvious toxicity of the effluent. However, low acute toxicity of the effluent could be detected by the luminescent bacteria assay, indicating the advanced treatment is needed. The clone library profiling analysis showed that the dominant bacteria in the system were Acidobacteria, Proteobacteria and Bacteriodetes. HA-A/O process is suitable for the petrochemical wastewater treatment.

[Treatment of Petrochemical Treatment Plant Secondary Effluent by Fenton Oxidation].

Fenton oxidation was applied to treat the petrochemical treatment plant secondary effluent by the continuous flow configuration. The effect of Fenton agent dosage on the COD and phosphorus removal and the variation of the dissolved organic matter characteristics during the treatment process were investigated. The results showed the average COD and PO(4)3- -P concentrations were 64.8 mg.L-1 and 0. 79 mg.L-1, respectively. When the dosage of H2O (30%), FeSO4.7H2O and PAM were 0. 4 mL.L-1, 0. 8 mg.L-1 and 0. 9 mg.L-1 and the residence time was 30 min, the average removal rate of COD and PO(4)3- -P were 24. 3% and 95. 5% respectively. The effluent COD was lower than 50 mg.L-1. The percentage of dissolved organic matters with molecular weight less than 1 x 10(3) was 80. 4% in the raw wastewater, however, the percentage increased to 95. 6% when treated by Fenton oxidation. Three-dimensional fluorescence analysis showed that the Fenton oxidation can effectively remove protein and phenols. GC-MS results showed that there were about 117 kinds of organic matters detected in the secondary effluent, while the number reduced to 27 after oxidation by Fenton. The organics containing unsaturated bond had a better removal than those of other types of organics. Fenton oxidation can be used in the advanced treatment of petrochemical secondary effluent.

Improving hydrolysis acidification by limited aeration in the pretreatment of petrochemical wastewater.

Petrochemical wastewater was pretreated by hydrolysis acidification to improve the biodegradation and treatability on limited aeration conditions. The results showed limited aeration with DO from 0.2 to 0.3mg/L (average ORP was -210 mV) was the best condition. The BOD5/COD of influent was 0.23, and it increased to 0.43 on this condition. Limited aeration can obviously reduce the reduction of SO4(2-), reducing the generation of toxic gas H2S, and almost no H2S can be detected in the off-gas. The sulfate reducing bacteria (SRB) diversity and abundance on limited aeration condition was obviously inhibited. Limited aeration condition was benefit for the removal of benzene ring organics, such as benzene, toluene, ethylbenzene and xylenes (BTEX), improving the toxicity and treatability of the wastewater. Based on the experiment results, an anaerobic hydrolysis acidification tank (100,000 m(3)) has been transformed into limited aeration hydrolysis acidification tank and it runs well.

Understanding the granulation process of activated sludge in a biological phosphorus removal sequencing batch reactor.

The granulation of activated sludge was investigated using two parallel sequencing batch reactors (SBRs) operated in biological nitrogen and phosphorus removal conditions though the reactor configuration and operating parameters did not favor the granulation. Granules were not observed when the SBR was operated in biological nitrogen removal period for 30d. However, aerobic granules were formed naturally without the increase of aeration intensity when enhanced biological phosphorus removal (EBPR) was achieved. It can be detected that plenty of positive charged particles were formed with the release of phosphorus during the anaerobic period of EBPR. The size of the particles was about 5-20 µm and their highest positive ζ potential was about 73 mV. These positive charged particles can stimulate the granulation. Based on the experimental results, a hypothesis was proposed to interpret the granulation process of activated sludge in the EBPR process in SBR. Dense and compact subgranules were formed stimulated by the positive charged particles. The subgranules grew gradually by collision, adhesion and attached growth of bacteria. Finally, the extrusion and shear of hydrodynamic shear force would help the maturation of granules. Aerobic granular SBR showed excellent biological phosphorus removal ability. The average phosphorus removal efficiency was over 95% and the phosphorus in the effluent was below 0.50 mg L(-1) during the operation.

Enhanced biological phosphorus removal by granular sludge: from macro- to micro-scale.

In this study, phosphorus accumulating microbial granules were successfully cultivated in a sequencing batch reactor (SBR) using synthetic wastewater. The average diameter of the granules was 0.74 mm and the diameter distribution fitted well with normal distribution with a correlation coefficient of 0.989. Good performance of biological phosphorus removal (BPR) was obtained in the granular system. The average phosphorus removal efficiency was over 94.3% and the level of phosphorus in the effluent was below 0.50mg/L during 300 days of operation. Particle analysis showed that positive charged particles were formed with the release of phosphorus in the anaerobic stage. These particles served as the cores of granules and stimulate the granulation. The maturated granules had a well-formed micro-pore structure with an average pore width between 291.5 nm and 446.5 nm. The spatial distribution of phosphorus decreased gradually from the surface to the center of the granules. Smaller granules had a higher specific area, pore width and phosphorus removal activity than bigger granules.

[Influence of carbon source on EBPR metabolism and microorganism communities].

A SBR was used in this study for investigating the influence of carbon source on EBPR metabolism and microorganism communities when feeding with acetate and propionate. The SBR was operated with a cycle time of 8 h and each cycle consisted of 4 min feeding, 2 h anaerobic period, 5 h aerobic period, 35 min setting, 15 min decanting and 6 min waiting. The COD of influent was kept at 300 mg/L during the experiment. Acetate and propionate were used as the sole carbon source for operation of 60 days, respectively. The phosphorus release/ COD consumption in the end of anaerobic phase were 0.35 and 0.27 when acetate and propionate were used as the carbon source, respectively. The PHA composition was different when different carbon source was dosed. PHB accounted for 92.6% in the end of anaerobic phase but the value for PHV was only 7.4% when acetate was selected as the carbon source. No PH2MV was detected during this process. The compositions of PHA were PHB (10.2%), PHV (35.8%) and PH2MV (54.0%) in the end of anaerobic cycle when propionate was used as the sole carbon source. There was variation of microorganism communities during this process for the results of DGGE combined with SEM micrographs and PHA staining. Coccus morphotype PAOs were accumulated in acetate-fed phase and rod morphotype PAOs were accumulated in propionate-fed stage. Different PAOs were accumulated and the metabolic pathways were different when different carbon sources were used, but good EBPR could be achieved during all these conditions.

[Influence of carbon source on biological nutrient removal in A2O process].

A 52.5 L pilot-scale biosystem, based on A2O configaration, was employed to investigate the effect of carbon source on biological nutrient removal and its metabolism process. Acetic acid and propionic acid were selected as the sole carbon source in different step. The COD was about 250 mg/L and NH4(+) -N was about 52 mg/L in the influent. The results showed that the removal efficiency of TN was about 65% and without any relationship to the carbon source. The TP viariation along the reactor, PHA formation and content were determined by different carbon source. When acetic acid was the sole carbon source, more phosphate was released in the anaerobic phase compared to propionic acid as the carbon source and the content of PHA was mainly PHB and PHV. The amount of PHB and PHV was almost equal. PHB was depleted in the following anoxic and aerobic phase for phosphorus removal but PHV was almost constant along the reactor. When propionic acid was the sole carbon source, less phosphate was released in the anaerobic phase and the content of PHA was mainly PHV. Almost no PHB and PH2MV were formed. PHV was depleted in the following anoxic and aerobic phase for phosphate uptake. Besides, the glycogen formation, variation and amount were different when different carbon source was dosed. More glycogen was depleted and formed in anaerobic and anoxic/aerobic phase when acetic acid was used as carbon source. Compared to acetic acid, propionic acid was more suitable for biological nutrient removal in wastewater treatment systems.