Molecular transformation of dissolved organic matter in refinery wastewaters: Characterized by FT-ICR MS coupled with electrospray ionization and atmospheric pressure photoionization

Dissolved organic matter(DOM)in refinery wastewater is an extremely complex mixture of various organic compounds.Using mass spectrometry,it is impossible to characterize all of the DOM molecules with only one ionization source.In this study,negative-ion,electrospray ionization(ESI),positive-ion ESI,and positive-ion atmospheric pressure photoionization(APPI)were coupled with Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS)to analyze the molecular composition of DOM in a refinery wastewater stream during the treatment process.There were obvious differences in the heteroatom composition,number of DOM constituents,and chemical properties in refinery wastewater under the three ionization modes.Acidic CHO and CHOS compounds detected by(+)ESI,basic CHN and CHON compounds detected by(þ)ESI,and hydrocarbons detected by(+)APPI were analyzed to determine the molecular transformations that occurred during treatment.In an anaerobic biological treatment process,acidic CHO and CHOS compounds with a high oxygen content were preferentially removed,and acidic CHO and CHOS compounds with a low oxygen content were produced.In an aerobic biological process,acidic CHO and CHOS compounds with a low oxygen content were preferentially removed,and acidic CHO and CHOS compounds with a high oxygen content were produced.The whole biological treatment process has a poor removal efficiency for CHN and CHON compounds,and hydrocarbons.An activated carbon(AC)adsorption process removed different heteroatom compounds mainly with a low oxygen content for acidic and basic compounds.The transformation mechanism of CHO and CHOS compounds in the biological treatment process was analyzed by the Kendrick mass defect(KMD)theory and a mass difference network analysis.In the anaerobic process,large amounts of oxygenated CHO and CHOS compounds were degraded by decarboxylation,deoxydation,demethoxylation,and dehydration reactions,and converted to lower oxygen content compounds.In the aerobic processes,these low oxygen CHO and CHOS compounds mainly underwent carboxylation and oxidation reactions.This study determined the transformation characteristics and mechanisms of different types of organic compounds in refinery wastewater during the treatment process.The results provide guidance for the design and optimization of technologies for refinery wastewater treatment.

Efficient ozonation of reverse osmosis concentrates from petroleum refinery wastewater using composite metal oxideloaded alumina

Novel Mn–Fe–Mg-and Mn–Fe–Ce-loaded alumina（Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3） were developed to catalytically ozonate reverse osmosis concentrates generated from petroleum refinery wastewaters（PRW-ROC）. Highly dispersed 100–300-nm deposits of composite multivalent metal oxides of Mn（Mn^2＋）, Mn^3＋,and Mn^4＋, Fe（Fe^2＋）and Fe^3＋ and Mg（Mg^2＋）, or Ce（Ce^4＋） were achieved on Al2O3 supports. The developed Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3 exhibited higher catalytic activity during the ozonation of PRW-ROC than Mn–Fe/Al2O3, Mn/Al2O-3, Fe/Al2O3, and Al2O3. Chemical oxygen demand removal by Mn–Fe–Mg/Al2O3-or Mn–Fe–Ce/Al2O3-catalyzed ozonation increased by 23.9% and23.2%, respectively, in comparison with single ozonation.Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3 notably promoted áOH generation and áOH-mediated oxidation. This study demonstrated the potential use of composite metal oxide-loaded Al2O3 in advanced treatment of bio-recalcitrant wastewaters.

Rapid aerobic granulation using biochar for the treatment of petroleum refinery wastewater

Aerobic granular sludge technology has great potential for the treatment of petroleum refinery wastewater.However,strategies to shorten the granulation time and improvement the stability still need to be developed.In this work,biochar was prepared from waste petroleum activated sludge(biochar-WPS) and used in a sequencing batch reactor for the treatment of petroleum refinery wastewater.Biochar-WPS presented the surface area of 229.77 m2/g,pore volume of 0.28 cm3/g,H/C and O/C atomic ratios of 0.42 and 0.21,respectively.The porous structure and a high degree of hydrophilicity were found to facilitate microbial colonization and adhesion as well as particle aggregation.Application of biochar-WPS resulted in the formation of more substantial and stable aerobic granules(~66% of granules> 0.46 mm diameter) 15 days earlier compared with the control.The addition of biochar-WPS enhanced the average removal efficiency of chemical organic demand(~3%),oil(~4%)and total nitrogen(~10%) over the control.Increased microbial richness and diversity were observed within the formed granules and had an increased(~4%) proportion of denitrifying bacteria.These results indicate that an aerobic granulation mechanism using biochar-WPS is a feasible option for the treatment of petroleum refinery wastewater.

Pretreatment of super viscous oil wastewater and its application in refinery

Wastewater from super viscous oil processing cannot be effectively treated by conventional wastewater treatment plants in refineries because of its high concentration of various organic pollutants. In order to resolve this problem, a number of investigations were conducted in our work to understand the physicochemical properties, sedimentation, demulsification and pretreatment of such super viscous oil refinery wastewater. The results showed that the key issues for pretreatment of this wastewater were： （1） Optimized process parameters were used in the sedimentation and demulsification processes for oil removal to effectively recover oil and remove scum from wastewater; （2） A suitable flocculation process was selected to minimize oil, suspended solids （SS） and chemical oxygen demand （CODcr）. A pretreatment process including three continuous steps： oil removal by sedimentation, oil removal by demulsification, and flotation separation, was proposed and applied in Liaohe Petrochemical Company, PetroChina and the oil content in effluents was less than 200 mg/L and CODcr less than 2,500 mg/L, which completely met the requirement for influent of the conventional wastewater treatment plant, and the recovered super viscous oil reached 5,873 tons in the initial year in Liaohe Petrochemical Company, PetroChina.

Microbial community dynamics at high organic loading rates revealed by pyrosequencing during sugar refinery wastewater treatment in a UASB reactor

The performance and rnicrobial community structure in an upflow anaerobic sludge blanket reactor （UASB） treating sugar refinery wastewater were investigated. The chemical oxygen demand （COD） removal reached above 92.0% at organic loading rates （OLRs） of 12.0-54.0 kgCOD/（m^3· d）. The volatile lhtty acids （VFAs） in effluent were increased to 451.1 mg/L from 147.9 mg/L and the specific methane production rate improved by 1.2 2.2-1bid as the OLR increased. The evolution of microbial comnmnities in anaerobic sludge at three different OLRs was investigated using pyrosequencing. Operational taxonomic units （OTUs） at a 3% distance were 353,337 and 233 for OLRI2, OLR36 and OLR54, respectively. When the OLR was increased to 54.0 kgCOD/（m^3· d） from 12.0 kgCOD/ （m^3· d） by stepwise, the microbial community structure were changed significantly. Five genera （Bacteroides, Trichococcus, Cho,seobacterium, Longilinea and Aerococcus） were the dominant fermentative bacteria at the OLR 12-0 kgCOD/（m^3· d）. However, the sample of OLR36 was dominated by Lacmcoccus, Trichococcus, Anaer-arcus and Veillonella. At the last stage （OLR = 54.0 kgCOD/ （m^3· d）, the diversity and percentage of femlentative bacteria were markedly increased. Apart from fermentative bacteria, an obvious shift was observed in hydrogen-producing acetogens and non- acetotrophic methanogens as OLR increased. Svntrophohacter, Geobacter and Methanomethylovor- ans were the dominant hydrogen-producing acetogens and methylotrophic methanogens in the samples of OLRI2 and OLR36. When the OLR was increased to 54.0 kgCOD/（m^3· d）, the mare hydrogen-producing acetogens and hydrogenotrophic methanogens were substituted with Destd/bvi- brio and Methanospillum. However, the composition of acetotrophic methanogens （Methanosaeta） was relatively stable during the whole operation period of the UASB reactor.

Removal of Heavy Metals （Copper, Manganese and Zinc） from Industrial Wastewater of Baiji Refinery by Granular Activated Carbon

The aim of the present work is to remove heavy metals （copper, manganese, and zinc） from industrial wastewater of Baiji refinery using GAC （granular activated carbon）. The most important factors affecting adsorption process have been studied, which are granular activated carbon thickness, H, inlet pollutant concentration, Cv, and liquid hourly space velocity, LHSV. All experiments were performed under constant temperature at 25℃ and pH = 7. The experimental apparatus was designed and constructed to enable controlling of the operating conditions. Employing five levels for each of H and LHSV and three levels for Co required 75 runs for each metal. Box-Wilson method was used to reduce the number of experiments to 15 for each metal. The results indicated that copper, manganese, and zinc can be completely removed from wastewater using activated carbon. However, breakthrough time for zinc is low. It is also shown that breakthrough time （TB） and exhaustion time （TE） are inversely proportional with pollutant concentration and LHSV （liquid hour space velocity） while it is directly proportional with the thickness of activated carbon column.

A comprehensive evaluation of re-circulated bio-filter as a pretreatment process for petroleum refinery wastewater

Conventional biological treatment process is not very efficient for the treatment of petroleum refinery wastewater （PRW） that contains high-concentration of organic contaminants. Prior to biological treatment, an additional pretreatment process for PRW is required for the effluent to meet the discharge standards. While re-circulated bio-filter （RBF） has been applied as a pretreatment process in several PRW treatment plants, its effects have not been comprehen- sively evaluated. In this study, the parameters of operation, the changes in pollution indexes and contaminant composition in an engineered RBF have been investigated. We found that mainly highly active de-carbonization bacteria were present in the RBF, while no nitrification bacteria were found in the RBF. This indicated the absence of nitrification in this process. The biodegradable organic contaminants were susceptible to degradation by RBF, which decreased the Biological Oxygen Demand （BODs） by 83.64% and the Chemical Oxygen Demand （CODcr） by 54.63%. Consequently, the alkalinity and pH value of RBF effluent significantly increased, which was unfavorable for the control of operating parameters in subsequent biological treatment. Along with the decrease of CODcr, the RBF effluent exhibited a reduction in biodegradability. 834 kinds of recalcitrant polar organic contaminants remained in the effluent; most of the contaminant molecules having complex structures of aromatic, polycyclic and heterocyclic rings. The results of this study showed that RBF could efficiently treat PRW for biodegradable organic contaminants removal; however, it is difficult to treat bio-refractory organic contaminants, which was unfavorable for the subsequent biological treatment process operation. An improved process might provide overall guarantees for the PRW treatment.

Waveband Selection with Equivalent Prediction Performance for FTIR/ATR Spectroscopic Analysis of COD in Sugar Refinery Waste Water

The level of chemical oxygen demand(COD)is an important index to evaluate whether sewage meets the discharge requirements,so corresponding tests should be carried out before discharge.Fourier transform infrared spectroscopy(FTIR)and attenuated total reflectance(ATR)can detect COD in sewage effectively,which has advantages over conventional chemical analysis methods.And the selection of characteristic bands was one of the key links in the application of FTIR/ATR spectroscopy.In this work,based on the moving window partial least-squares(MWPLS)regression to select a characteristic wavelength,a method of equivalent wavelength selection was proposed combining with paired t-test equivalent concept.The results showed that the prediction effect of the selected wavelength was very close to that of the MWPLS method,while the number of wavelength points was much smaller.SEPAve,RP,Ave,SEPStd,and RP,Std which characterized the modeling effect were 26.3 mg L^-1,0.969,3.49 mg L^-1,and 0.006,respectively.The validation effect V-SEP and V-RP were 28.64 mg L^-1 and 0.960,respectively.The selected waveband was between 1809 cm^-1 and 1568 cm^-1.The method was of more reference value for the design of FTIR/ATR spectral instrument for COD detection.