MIL-101（Cr）在H2O2氧化环己烷反应中的催化性能

采用水热合成法制备了MIL-101(Cr)催化剂,考察了反应条件对其在H2O2氧化环己烷反应中催化性能的影响。利用XRD、FT-IR和UV-Vis等手段对MIL-101(Cr)反应前后结构的变化进行了表征。结果表明,MIL-101(Cr)在所选择的反应体系中存在Cr析出现象,其结构在以H2O2为氧化剂的反应体系中不稳定,经反应后形成了无定型物质,但催化活性不仅远高于新鲜MIL-101(Cr),而且还在重复利用中表现出良好的稳定性。     

Oxidative Desulfurization of Dibenzothiophene Catalyzed by VO(acac)2 in Ionic Liquids at Room Temperature

A simple extraction and catalytic oxidative desulfurization (ECODS) system composed of VO(acac)₂, 30% H₂O₂, and 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF₄) has been found to be suitable for the deep removal of dibenzothiophene (DBT) in model oil at room temperature. The optimal conditions were as follows: [n(H₂O₂)/n(DBT)/n(catalyst) = 100:20:1], model oil = 5 mL, ionic liquid [IL] = 1 mL, T = 30°C, t = 2 hr. With the ECODS system, the sulfur removal of DBT could reach 99.6%, which was superior to that of the simple extraction with IL (15.6%) or oxidation without catalyst (17.1%). The IL could be recycled five times without a significant decrease in activity.     

天然气净化厂Cansolv尾气处理装置废水处理

目的 解决Cansolv尾气处理装置胺液净化单元(APU)废水高盐、高有机物与还原性硫的高浓水质特征影响水处理系统的稳定运行问题。方法 详细分析了两个天然气净化厂的文丘里和APU废水的水质特征,其中,APU废水成分复杂,是影响水处理系统稳定运行的关键。采用臭氧(O₃)、O₃耦合催化剂、臭氧/双氧水(O₃/H₂O₂) 3种氧化技术处理APU废水,通过废水中COD值和TOC值变化来评价有机物降解效果,研究了反渗透膜污堵原因和O₃/H₂O₂降解有机物机理。结果 O₃/H₂O₂氧化技术为去除废水中有机物的最优方法,当200 mL废水中O₃质量浓度为22 500 mg/L、H₂O₂投加量为2 mL、反应时间为60 min时,达到最佳处理效果,COD去除率为60.8%。结论 采用O_3<...     

超声波辐照浸渍法制备MnO2/γ-A12O3催化剂及其柴油催化氧化脱硫性能

 分别采用超声波辐照浸渍法和普通浸渍法制备了MnO₂/γ-Al₂O₃催化剂,运用电感耦合等离子体原子发射光谱（ICP-AES）和X射线衍射（XRD）对催化剂进行表征,在空气-异丁醛-MnO₂/γ-Al₂O₃体系中评价其对加氢柴油的氧化脱硫催化性能,并考察了反应温度、异丁醛用量、空气流量、溶剂类型和剂/油体积比对柴油氧化脱硫反应的影响。结果表明,超声波辐照浸渍法制备的MnO₂/γ-Al₂O₃催化剂对柴油氧化脱硫的催化性能明显优于普通浸渍法制备的催化剂。最适宜的催化柴油氧化脱硫反应的条件为：乙腈为溶剂、加氢柴油30 mL、温度35℃、异丁醛20 mmol、空气流量0.06 L/min、超声波辐照浸渍法制备的MnO₂/γ-Al₂O₃催化剂0.08 g、剂/油体积比1/6和催化氧化时间10 min。在此条件下可将柴油硫质量分数从542μg/g 降至31μg/g,柴油脱硫率和回收率分别为94.3%和93.3%。     

Oxidative Desulfurization of Fuel Oil: Modeling Based on Artificial Neural Network

Abstract

Oxidative desulfurization of fuel oil was investigated using a process consisting of oxidation and distillation steps. In the oxidation step, various organic carboxylic acid/H₂ O₂ systems, especially acetic acid/H₂ O₂, were used as oxidant. They oxidize both easy and refractory sulfur compounds and convert them into oxidized sulfur compounds. The oxidized sulfur compounds are finally removed from fuel oil by distillation in the presence of water. The sulfur content of fuel oil was decreased to levels as low as 20 ppm (up to 90%) in a short contact time, ambient temperature, and atmospheric pressure. The results showed that applying this process did not have any deleterious influence on the distillation characteristic, composition, and content of fuel oil that was examined. An artificial neural network, using back propagation (BP), was also utilized for modeling oxidative desulfuration process of fuel oil. The comparison between the output of ANN modeling and the experimental data showed satisfactory agreement.     

Catalytic gasification of oil sludge with calcined dolomite

Abstract

Gasification of carbon-based residues for synthesis gas production is one of the most important strategies for clean energy production and environmental management. Currently, China is the world's largest net oil importer which is a result of China's added refinery capacity. In this article, a simulation model of oil sludge gasification with a combination of air and steam was developed using Aspen Plus software. Effect of dolomite as an active catalyst on gas composition was studied at various operating conditions. Results showed that H₂ and CO increased with reaction temperature, while CH₄ decreased from 9.1 to 4.71?vol% because of increased steam reforming of CH₄. By adding steam to the gasifier, H₂ content increased significantly, while CO content showed an opposite trend.     

介孔CuO/SiO2用于汽油氧化-吸附脱硫

 利用[(C₁₆H₃₃) N(CH₃)₃]₃-[PW₁₂O₄₀]双亲催化剂与H₂O₂组成的催化氧化体系对汽油进行氧化后,以介孔SiO₂为载体等体积浸渍法制备的介孔CuO/SiO₂为吸附剂,采用固定床连续流动式吸附脱硫评价装置,考察了CuO/SiO₂的CuO负载量、焙烧温度、焙烧时间和吸附温度对汽油脱硫率的影响,并对介孔CuO/ SiO₂吸附剂性质进行了XRD表征。结果表明,采用在焙烧温度为400℃、焙烧时间为2.0 h、CuO负载量为2%制备的CuO/SiO₂, 在吸附温度为120℃时,汽油氧化-脱硫的脱硫效果较好,汽油脱硫率可达56.82%。     

Oil Recovery from Petroleum Sludge by Solvent Extraction

Abstract

Technical problems associated with sludge deposition in storage units of petroleum industries are enormous. The conventional methods of management are laborious and uneconomical; the hydrocarbon contents are lost to the pits, causing environmental problems. Solvent recovery of the hydrocarbons from accumulated sludge in storage facilities of oil industries in the Niger delta area of Nigeria was carried out. A recovery of about 67.5% hydrocarbon oils was obtained, out of which 86.7% were aromatic. Gas chromatographic analysis of the extracted oil showed it contained the hydrocarbons in the range of C₉–C₂₅, which is good petrochemical industry feedstock. Hexane and xylene showed high potentials for hydrocarbon oil extraction from the sludge, reducing the quantity of solid waste to the barest minimum.     

氨基改性吸附剂在低CO2分压下吸附CO2的热力学研究

为了减少温室效应,应采取有效措施减少温室气体CO2的排放。氨基改性吸附剂是捕获烟道气中CO2的重要吸附材料。建立了描述氨基改性MCM-41吸附剂在低CO2压力下吸附等温线的平衡模型,并计算了吸附热力学参数。该模型基于Dual-site Langmuir模型,同时假设CO2吸附具有两种独立的吸附机理,分别是氨基基团的化学吸附和吸附剂表面的物理吸附,提出了一种基于未改性介孔材料吸附容量和比表面积计算改性材料的物理吸附量方法。结果表明,该模型能较好地拟合吸附等温线,计算得到的物理化学吸附热分别为-25.4kJ/mol和-41.9kJ/mol,总吸附热为-67.3kJ/mol,与实验数据一致,且氨基改性MCM-41-TEPA饱和吸附容量可达到7.79mmol/g。     

The extraction effect of CO2 injection on the flow properties of crude oil

During CO₂ flooding, extraction of lighter hydrocarbons from crude oil makes the remaining oil hard to be recovered. In this work, we design a new experimental method to characterize the effect of CO₂ extraction on crude oil. The experimental results show that, the volume of extracted hydrocarbons increases as system pressure increases. The hydrocarbons with wider carbon number can be extracted from crude oil at high pressures. Moreover, the wax precipitation and viscosity of the remaining oil increase with increasing pressure. This study is expected to provide the basic understanding of the mechanisms of CO₂ flooding for enhanced oil recovery.     

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 (C₂₁H₄₄) (R1) and 1-phenylnaphthalene (C₁₆H₁₂) (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 R1 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.     

Petroleum Hydrocarbons Extraction Efficiency of Carbon Tetrachloride and Trichlorotrifluoroethane: A Comparative Study

Abstract

Petroleum hydrocarbons (PHC) contaminated water samples, prepared in laboratory, were analyzed using infrared spectroscopy to compare PHC extraction efficiency of carbon tetrachloride (CCl₄) and trichlorotrifluoroethane (C₂Cl₃F₃) solvents. The comparison of the results illustrated that PHC extraction efficiency of CCl₄ was greater than C₂Cl₃F₃. The higher extraction efficiency of CCl₄ was ascribed to its more non-polar nature and higher polarity index. This study supported the selection and use of CCl₄ for extraction and quantification of PHC of groundwater samples of the projects carried out in the department.     

不同铁基催化剂活化过硫酸钠修复石油污染土壤

目的 在活化过硫酸钠(Na2 S2 O8)体系处理石油污染土壤中,采用不同形态的铁基材料作为催化剂,进行石油烃的去除研究.方法 通过室内模拟实验,比较了3种铁基催化剂(柠檬酸亚铁、零价铁、四氧化三铁)活化Na2 S2 O8处理石油污染土壤,探究了氧化剂的持续性、污染物去除的有效性、可溶性碳氮含量和pH值的变化.结果 外...     

Applying Pebax-1657/ZnO mixed matrix membranes for CO2/CH4 separation

Abstract

Membrane technologies as conservative approaches have absorbed much attention in chemical and petroleum engineering, recently. The current research presents the preparation of effectively mixed matrix membranes (MMMs) using polyether-block-amide (Pebax-1657) as a polymeric matrix and zinc oxide (ZnO) nanoparticles with various contents (0.0, 2.5, 5.0, 7.5, and 10.0?wt%) as a filler. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and field emission scanning microscopy (FESEM) were conducted to characterize the prepared membranes. The membrane performance was evaluated by caring out permeation experiments of the CO₂ and CH₄ at a pressure of 3?bar and temperature of 30?°C. Based on the obtained results, the CO₂ permeability and ideal CO₂/CH₄ selectivity increased about 13 and 21%, respectively at 10.0?wt% loading of ZnO in the polymer matrix.     

Electrochemical degradation of petroleum hydrocarbons (PAHS) from synthetic aqueous solutions

Water separated from crude oil and wastewater discharge from petroleum oil refineries contains significant quantity of dissolved hydrocarbons. Polycyclic aromatic hydrocarbons (PAHs) are major toxicants in wastewater of refineries. It is difficult to treat wastewater containing PAHs due to their recalcitrant property and low solubility. Conventional techniques for the treatment of wastewater are still a concern of toxicity. Electrochemical oxidation process has been found to be a favorable for treating wastewater. Electrodes with high stability and electrocatalytic activity are important factors for a successful electrochemical oxidation of toxic organics in wastewater. In this study titanium anodes were coated with tin, antimony and iridium oxide mixture from their respective salts by thermal decomposition method. FESEM and XRD used for surface characterization of Ti/SnO₂–Sb₂O₅–IrO₂ anode. Quantification of PAHs was done using GC–MS. Results confirm the presence of respective oxides on anode surface. Their electrocatalytic capability was tested for degradation of 16 priority PAHs in aqueous solution. Results reveal the complete degradation of naphthalene, acenaphthylene, acenaphthene and fluorene without using NaCl electrolyte. While in the presence of NaCl naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene were completely removed. About 98% of total PAHs removal was found at all initial pH values 3, 6, and 9 in the presence of electrolyte. Current study will be helpful in improving quality of petroleum industry wastewater containing PAHs.     

金湖凹陷原油轻烃的地球化学特征及意义

对金湖凹陷40个原油样品进行轻烃组分、Mango参数和成熟度等研究。甲基环己烷指数指示出该凹陷原油的干酪根类型为Ⅰ-Ⅱ型;C₅轻烃特征显示有机质来源既有腐泥型也有腐殖型;Mango轻烃参数K₁值基本符合轻烃稳态催化动力学轻烃成因模式,暗示着该凹陷原油有着相似的沉积环境;C₅-C₇轻烃三环优势大于五环和六环优势,表明该地区原油主要来源于湖相沉积环境的烃源岩;原油轻烃组分中的庚烷值和异庚烷指数都较低,原油成熟度低,原油形成温度在120~128℃之间。为进一步认识金湖凹陷原油和烃源岩的地球化学特征提供科学依据。     

Effects of magnesium compounds on the gasification of petroleum coke

The magnesium compounds are used as catalysts for petroleum coke-CO₂ gasification. The effect of catalyst type, catalyst addition amount and gasification temperature on petroleum coke-CO₂ gasification is studied by using thermogravimetric analyzer. It is shown that the catalytic activity of MgCl₂ is higher than other magnesium catalyst. The catalytic activity of the catalyst increases with the increase of temperature. At the same temperature, the time required for complete gasification of petroleum coke decreases with the increase of catalyst dosage. There is a limit to the amount of catalyst added, and the best amount of magnesium chloride is 5%.     

Changes in the properties of conventional crude oil before and after CO2 flooding

Abstract

In order to enhance oil recovery of a conventional oil reservoir by CO₂ flooding, the changes in the properties of the crude oil before and after CO₂ flooding are systematically investigated by on-site sampling and experimental testing. The results show that, after CO₂ flooding, the light hydrocarbons of the produced crude oil is increased and the heavy hydrocarbons of the produced crude oil is decreased due to the deposition of resins and asphaltenes in the pores of the formation. In addition, the produced fluid (a mixture of oil and water) has a high water separation rate, the oil- water interface has a high tension value, and the crude oil has a high acid value and a low viscosity. The conclusions can provide a certain guidance for high-efficiency development of a conventional oil reservoir by CO₂ flooding.     

H6P2W18O62/MCM-48催化剂的制备、表征及催化绿色合成己二酸

以MCM-48为载体,通过浸渍法制备了H6P2W18O62/MCM-48催化剂,并采用FT-IR、XRD、SEM、EDS对催化剂进行表征。以微波促进30%(质量分数)H2O2氧化环己酮合成己二酸反应为探针,考察了H6P2W18O62/MCM-48的催化性能,并通过正交实验确定了优化的工艺条件。结果表明,采用H6P2W18O62负载量40%的H6P2W18O62/MCM-48催化剂,在优化的合成己二酸的工艺条件下,即催化剂质量分数(以环己酮质量计)5.1%、n(C6H10O)∶n(H2O2)∶n(H2C2O4.2H2O)=100∶450∶1.88、反应温度95℃、微波功率300 W、反应时间3.5h,己二酸收率可达81.3%;催化剂重复使用5次,己二酸收率仍可达到64.6%。     

TiO_2基硫磺回收催化剂表面化学特性研究

随着炼油工业和天然气工业的快速发展,针对SO2排放的环保要求日益严格。对于炼油加工和天然气净化过程所产生的含硫酸性气体,硫磺回收加尾气处理工艺是主要的治理方式,其中TiO2基硫磺回收催化剂逐步得到广泛应用。通过一系列的XPS、XRD、TEM、FT-IR、CO2-TPD、NH3-TPD和吡啶红外分析表征手段,进一步认识到钛基催化剂的表面化学特性,其活性组分为锐钛矿相TiO2,晶粒为纳米级晶粒,具有弱碱性位和中强碱性位。