Molecular investigation into the transformation of recalcitrant dissolved organic sulfur in refinery sour water during stripping process

Refinery sour water primarily originates from the tops of towers in various units and coker condensate,and cannot be discharged directly to a wastewater treatment plant due to high levels of chemical oxygen demand(COD)and organic sulfur contents.Even after the recovery of H_(2)S from the sour water by the stripping process,the effluent still contains a high concentration of dissolved organic sulfur(DOS),which can have a huge bad influence.While chemical composition of dissolved organic matter(DOM)in refinery wastewater has been extensively studied,the investigation of recalcitrant DOS from sour waters remains unclear.In the present study,chemical composition of sour water DOMs(especially DOS)was investigated using fluorescence spectroscopy(excitation-emission matrix,EEM)and mass spectrometry,including gas chromatography-mass spectrometry(GC-MS)and high-resolution Orbitrap MS.The GC-MS and EEM results showed that volatile and low-aromaticity compounds were effectively removed during the stripping process,while compounds with high hydrophilicity and humification degree were found to be more recalcitrant.The Orbitrap MS results showed that weak-polar oxygenated sulfur compounds were easier to be removed than oxygenated compounds.However,the effluent still contained significant amounts of sulfur-containing compounds with multiple sulfur atoms,particularly in the form of highly unsaturated and aromatic compounds.The Orbitrap MS/MS results of CHOS-containing compounds from the effluent indicate that the sulfur atoms may exist as sulfonates,disulfide bonds,thioethers.Understanding the composition and structure of sour water DOS is crucial for the development of effective treatment processes that can target polysulfide compounds and minimize their impact on the environment.

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.

Hydrometallurgical process for recovery of Zn,Pb,Ga and Ge from Zn refinery residues

Zn,Pb,Ga and Ge were separated and recovered from zinc refinery residues by stepwise leaching.In the first stage,by leaching with H2SO4 media,more than 90%of Zn and 99%of Ga were dissolved,leaving 92%of Ge in the leaching residue.In the second stage,by leaching with HCl media,approximately 99%of Pb and less than 2%of Ge were selectively dissolved.Finally,the remaining 90%of Ge was extracted in 1 mol/L NaOH solution by destroying the correlation between SiO2 and Ge.XRD pattern of the leaching residue demonstrated that ZnSO4·H2O,PbSO4 and SiO2 were removed sequentially through the stepwise leaching.The proposed process achieved high recoveries of Zn,Pb,Ga and Ge,thus presenting a potential industrial application.

Modeling and Multi-objective Optimization of Refinery Hydrogen Network

The demand of hydrogen in oil refinery is increasing as market forces and environmental legislation, so hydrogen network management is becoming increasingly important in refineries. Most studies focused on single-objective optimization problem for the hydrogen network, but few account for the multi-objective optimization problem. This paper presents a novel approach for modeling and multi-objective optimization for hydrogen network in refineries. An improved multi-objective optimization model is proposed based on the concept of superstructure. The optimization includes minimization of operating cost and minimization of investment cost of equipment. The proposed methodology for the multi-objective optimization of hydrogen network takes into account flow rate constraints, pressure constraints, purity constraints, impurity constraints, payback period, etc. The method considers all the feasible connections and subjects this to mixed-integer nonlinear programming （MINLP）. A deterministic optimization method is applied to solve this multi-objective optimization problem. Finally, a real case study is intro-duced to illustrate the applicability of the approach.

An alternative treatment process for upgrade of petroleum refinery wastewater using electrocoagulation

An electrocoagulation treatment process was developed for treatment and upgrade of petroleum refinery effluent （wastewater）, instead of the conventional methods, which can consume higher amounts of chemicals and produce larger amounts of sludge. The effect of the operation parameters, such as current density, initial pH, anode material, anode dissolution, energy consumption and electrolysis time, on treatment efficiency was investigated. The experimental results showed that the effluent can be effectively treated under optimal conditions. Fourier transform infrared （FTIR） analysis of the effluent, and scanning electron microscopy （SEM） coupled with energy dispersive analysis of X-rays （EDAX） of the sludge produced, revealed that the unwanted pollutants can be eliminated. The electrocoagulation treatment process was assessed by using the removal efficiency of chemical oxygen demand （COD）, total suspended solids （TSS）, and the general physicochemical characteristics of wastewater, and the results showed that the electrocoagulation is an efficient process for recycling of petroleum wastewater; it is faster and provides better quality of treated water than the conventional methods.

An Optimization Model for the Production Planning of Overall Refinery

This article addresses a production planning optimization problem of overall refinery. The authors formulated the optimization problem as mixed integer linear programming. The model considers the main factors for optimizing the production plan of overall refinery related to the use of run-modes of processing units. The aim of this planning is to decide which run-mode to use in each processing unit in each period of a given horizon, to satisfy the demand, such as the total cost of production and inventory is minimized. The resulting model can be regarded as a generalized lot-sizing problem where a run-mode can produce and consume more than one product. The resulting optimization problem is large-sized and NP-hard. The authors have proposed a column generation-based algorithm called branch-and-price （BP） for solving the interested optimization problem. The model and implementation of the algorithm are described in detail in this article. The computational results verify the effectiveness of the proposed model and the solution method.

Radial Basis Function Neural Networks-Based Modeling of the Membrane Separation Process: Hydrogen Recovery from Refinery Gases

Membrane technology has found wide applications in the petrochemical industry, mainly in the purification and recovery of the hydrogen resources. Accurate prediction of the membrane separation performance plays an important role in carrying out advanced process control （APC）. For the first time, a soft-sensor model for the membrane separation process has been established based on the radial basis function （RBF） neural networks. The main performance parameters, i.e, permeate hydrogen concentration, permeate gas flux, and residue hydrogen concentration, are estimated quantitatively by measuring the operating temperature, feed-side pressure, permeate-side pressure, residue-side pressure, feed-gas flux, and feed-hydrogen concentration excluding flow structure, membrane parameters, and other compositions. The predicted results can gain the desired effects. The effectiveness of this novel approach lays a foundation for integrating control technology and optimizing the operation of the gas membrane separation process.

Analysis on Refinery System as a Complex Task-resource Network

Refinery system, a typical example of process systems, is presented as complex network in this paper. The topology of this system is described by task-resource network and modeled as directed and weighted graph, in which nodes represent various tasks and edges denote the resources exchanged among tasks. Using the properties of node degree distribution, strength distribution and other weighted quantities, we demonstrate the heterogeneity of the network and point out the relation between structural characters of vertices and the functionality of correspond- ing tasks. The above phenomena indicate that the design requirements and principles of production process contrib- ute to the heterogeneous features of the network. Besides, betweenness centrality of nodes can be used as an impor- tance indicator to provide additional information for decision making. The correlations between structure and weighted properties are investigated to further address the influence brought by production schemes in system con- nectivity patterns. Cascading failures model is employed to analyze the robustness of the network when targeted at- tack happens. Two capacity assignment strategies are compared in order to improve the robustness of the network at certain cost. The refinery system displays more reliable behavior when the protecting strategy considers heteroge- neous properties. This phenomenon further implies the structure-activity relationship of the refinery system and provides insightful suggestions for process system design. The results also indicate that robustness analysis is a _promising applicat!on of methodologies from complex networks to process system engineering..

Treatment of Slightly Polluted Wastewater in an Oil Refinery Using a Biological Aerated Filter Process

The slightly polluted wastewater from oil refinery contains some COD, oil pollutants and suspended solids （SS）. A small-scale fixed film biological aerated filter （BAF） process was used to treat the wastewater. The influences of hydraulic retention time （HRT）, air/water volume flow ratio and backwashing cycle on treatment efficiencies were investigated. The wastewater was treated by the BAF process under optimal conditions： the HRT of 1.0 h, the air/water volume flow ratio of about 5 ： 1 and the backwashing cycle of every 4-7 days. The results showed that the average removal efficiency of COD, oil pollutants and SS was 84.5%, 94.0% and 83.4%, respectively. And the average effluent concentration of COD, oil pollutants and SS was 12.5, 0.27, 14.5 mg·L^-1, respectively. The experimental results demonstrated that the BAF process is a suitable and highly efficient method to treat the wastewater.

Virtual Reality Based Process Integrated Simulation Platform in Refinery:Virtual Refinery and Its Application

With the combination between system simulation and virtual reality,we have established an integrated virtual refinery simulation platform,and analyzed the overall design and principal architecture.This paper introduces a simulation algorithm about a refinery based on virtual reality,and explains how the algorithm can be applied to the virtual refinery integrated simulation platform in detail.The virtual refinery simulation platform,which consists of a three-dimensional scene system,an integrated database system and a dynamic-static simulation system,has many applications,such as dynamic-static simulation of key process unit used as process control and oil tank blending simulation for scheduling.With the visualization and human-computer interaction for acquiring production and process data,this platform can provide effective supports on staff training related with monitoring,control and operation in refinery.Virtual refinery can also be web published through the internet and it is helpful for the distance training and education.

Application of organic polymeric flocculants in centrifugal dewa-tering of oil refinery sludge

In order to evaluate the applicability of the organic polymeric flocculants(OPF) in the treatment of oil refinery sludge, experiments were conducted to show that OPF have better performance of flocculation than inorganic flocculants. Both the anionic and cationic OPF have satisfactory flocculation efficiency in oil sludge treatment, but the latter are more cost efficient. Among the over 20 types of flocculants tested, 2 OPF(CPAM 2 and HPAM 2) were selected as the treatment agents, based on their good treatment performances, oil resistance and economic feasibility. It was demonstrated in the industrial scale centrifugal dewatering experiments that the application of either CPAM 2 or HPAM 2 could achieve high treatment efficiency of the oil sludge dewatering and reduce the COD of centrifugal liquid to less than 1000 mg/L.

Hydrolysis and acidification of activated sludge from a petroleum refinery

The cost-effective treatment of activated sludge that is generated by refining petroleum is a challenging industrial problem.In this study, semi-continuous stirred tank reactors(CSTRs) containing petroleum refinery excess activated sludge(PREAS)were used to comparatively investigate hydrolysis and acidification rates, after the addition of heneicosane(C_(21)H_(44))(R1)and 1-phenylnaphthalene(C16 H12)(R2) to different and individual reactors. Operation of the reactors using a sludge retention time(SRT) of 6 days and a pH of 5.0, resulted in the maintenance of stable biological activity as determined by soluble chemical oxygen demand(SCOD), volatile fatty acids(VFAs) production and oil removal efficiency. The optimum conditions for hydrogen production include a SRT of 8 days, at pH 6.5. Under these conditions, hydrogen production rates in the control containing only PREAS were 1567 mL/L(R0), compared with 1365 mL/L in Rl and 1454 mL/L-PREAS in R2.Coprothermobacter, Fervidobacterium, Caldisericum and Tepidiphilus were the dominant bacterial genera that have the potential to degrade petroleum compounds and generate VFAs. This study has shown that high concentrations of heneicosane and 1-phenylnaphthalene did not inhibit the hydrolytic acidification of PREAS.

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.

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.

A decision tree based decomposition method for oil refinery scheduling

Refinery scheduling attracts increasing concerns in both academic and industrial communities in recent years.However, due to the complexity of refinery processes, little has been reported for success use in real world refineries. In academic studies, refinery scheduling is usually treated as an integrated, large-scale optimization problem,though such complex optimization problems are extremely difficult to solve. In this paper, we proposed a way to exploit the prior knowledge existing in refineries, and developed a decision making system to guide the scheduling process. For a real world fuel oil oriented refinery, ten adjusting process scales are predetermined. A C4.5 decision tree works based on the finished oil demand plan to classify the corresponding category(i.e. adjusting scale). Then,a specific sub-scheduling problem with respect to the determined adjusting scale is solved. The proposed strategy is demonstrated with a scheduling case originated from a real world refinery.

Experimental Study on Refinery Gas Desulfurization Using Gas-Liquid Membrane Contactor

Gas-liquid contactors equipped with polytetrafluoroethylene （PTFE） or polypropylene （PP） hydrophobic membranes were applied for removal of sulfur dioxide from refinery gas. Pure water, NaOH solution and MDEA were adopted as the absorbents. The performance of the two kinds of membranes for separation of SO2 was evaluated in terms of the concentration of absorbent solution, the concentration of SO2, and the feed flow rate. The efficiency for removal of SO2 increased with an increasing absorbent concentration. Upon increasing the concentration of SO2 and the feed flow rate, the desulfurization efficiency was decreased.

Leaching behavior of zinc and copper from zinc refinery residue and filtration performance of pulp under the hydrothermal process

This study aims to investigate the leaching behavior and filtration performance of zinc refinery residue under hydrothermal conditions. The relationships between the structure and morphology of silicon in the leaching residue and the pulp filtration performance were explored by determining the pulp filtration speed, analyzing quantitatively the silicon content in the leachate, and characterizing the leaching residue structure. The results show that hydrothermal leaching induces the coagulation–hydrolysis of the silicon in solution, consequently altering the microstructure of the leaching residue, and that silicon oxygen tetrahedra([SiO_4]^(4-)) form the main skeleton structure of the residue. The results obtained also show that the leaching rates of zinc and copper are 98.1% and 98.7%, respectively, and that the filtration speed is 526.32 L/(m^2·h) under the conditions of sulfuric acid concentration of 140 g/L, leaching temperature of 160°C, leaching time of 3.0 h, oxygen partial pressure of 0.75 MPa, stirring speed of 600 r/min, and a liquid-to-solid ratio of 10 mL/g.

Preliminary Discussion on the Construction and Development of Modern Refinery in China

Sustainable development of refinery is an important problem that refining industry faces in the21st Century. The situation and challenges in front of refining industry are analyzed and illustrated byexamples in this paper. It is also recognized that large-scale, clean, light-oriented and integrated refinery isthe mode of development in future, and also an important measure for the sustainable development ofpetroleum resource.

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.

Selecting Suitable Heat Source in Refinery for Multi-effect Distillation Based on Grey System Theory

For dealing with high-salinity wastewater in the refinery, the high cost of driving heat source is the disadvantage of multi-effect distillation (MED) so it is of great importance to evaluate the performance of low-temperature heat source for conducting MED and select the optimal temperature for it. Both the MED and the low-temperature heat sources studied in this paper were from a typical refinery located in northwestern China. Besides, a new methodology to evaluate heat sources as the optimal candidate was proposed for MED based on the grey system theory. Five process units, which included 18 fluids of the refinery, were named as the evaluation projects. Three factors, which included safety effects, total costs and characteristics of low-temperature heat sources were determined as the evaluation indexes, the values of which were established through the analyses. The results obtained through the grey correlation analyses have revealed that the grey correlation degrees of these units were 0.661(AVDU), 0.732 (#1 FCCU), 0.618 (#2 FCCU), 0.535 (#1 DCU), and 0.572 (#2 DCU), respectively. Thus, the optimal heat source was provided from #1 FCCU. Through further analyses of the fluids from #1 FCCU, the grey correlation degrees of the fluids were 0.597 (oil and gas at top of tower), 0.714 (recycle oil and gas), and 0.512 (diesel), respectively. Thus, the optimal heat source was the oil and gas recycle stream.