柴油理化性质与烃族组成关联

 摘要：柴油的主要组分为烃类物质,包括链烷烃、一环烷烃、二环烷烃、三环烷烃、烷基苯、四氢萘、茚类、萘、烷基萘、苊类、苊烯类和三环芳烃。笔者采用相关分析法,考察了上述各烃类物质对中国成品柴油理化性质的影响规律,并采用逐步线性回归方法,建立了油品理化性质与其烃类组成的关联方程。F检验表明,上述方程可行,可以准确预测其中15项理化性质。根据关联方程确定了影响柴油理化性质的主要烃类物质,其中柴油的氧化安定性主要由苊烯类决定,低温流动性能主要由一环烷烃决定,十六烷值、密度和热值主要由链烷烃决定,润滑性主要由茚类决定。     

Conversion of Mixed Lower Olefins and Paraffins on Galloaluminosilicate

At many oil refineries and gas processing plants, the C₂–C₅ fractions obtained as by–products do not have any qualified application. These hydrocarbons can be converted into valuable products on zeolite–based catalysts from the pentasil family. The characteristics of conversion of mixed C₂–C₄ olefins and paraffins into aliphatic and aromatic C₅₊ hydrocarbons in the presence of a galloaluminosilicate catalyst with the structure of pentasil were investigated. The temperature intervals of formation of isoparaffins from ethylene and propylene and aromatic hydrocarbons from mixed C₂–C₄ olefins and paraffins were found. Key words: C₂–C₄ olefins and paraffins, aliphatic and aromatic hydrocarbons, zeolites of the pentasil family, galloaluminosilicates.     

生物工程用稠环芳烃衍生物

对应用于生物工程的萘、芴、芘、蒽、苊等稠环芳烃衍生物作了概括介绍。     

In situ bioremediation of crude oil contaminated site: A case study in Jianghan oil field,China

A bacterial consortium, constructed from the oil contaminated soil, mainly consisting of Pseudomonas sp., together with fertilizing, rice husk application, and plowing, was used for the field in situ bioremediation of oil contaminated site in Jianghan Oil field, where the temperature and humidity are very suitable for bioremediation. The variation of total petroleum hydrocarbon, n-alkanes, and polycyclic aromatic hydrocarbons (PAHs) in the bioremediation process showed that more than 95% petroleum hydrocarbons could be efficiently removed. The composition analysis results demonstrated that n-alkanes with long carbon chain and PAHs with 5–6 rings were also degraded in the bioremediation process.     

Biodegradation of petroleum hydrocarbons by soil microflora activated with photoluminescent films

Films on the oxygenase activity of indigenous microflora in oil-polluted soils having an oil concentration of 50 g/kg was studied. The oil utilization in experiments was 30–35 g/kg of soil versus 8–13 g/kg in the control. The IR spectroscopic determination of residual petroleum hydrocarbons showed the appearance of absorption bands at 1710 and 1600 cm^?1, as well as an increase in the spectral coefficients C₁, C₂, A₁, A₂, and A₂ by a factor 1.5–3 and a decrease in C₃ and A₃ by a factor 1.5–2.5, thus indicating intense oil oxidation in the presence of photoluminescent films. Chromatographic analysis data corroborated the occurrence of intense bio-degradation of acyclic saturated hydrocarbons. In experimental samples, light C₉–C₁₄ hydrocarbons completely disappeared and the concentration of higher C₁₅–C₂₈ hydrocarbons decreased by 70–80%. The oil biodegradation factor defined as the ratio of total isoalkanes (pristane + phytane) to total n-alkanes (C₁₇ + C₁₈) increases 5–6-fold when the photoluminescent films are used.     

石油磺酸盐的结构与界面活性的关系及其质量评价

研究了石油磺酸盐的结构与界面活性之间的相互关系并对其进行了质量评价。实验结果表明,当石油磺酸盐溶液与原油的界面张力小于0.050 mN/m、介于0.05～0.150 mN/m或大于0.150 mN/m时,石油磺酸盐的界面活性分别表现为优异、良好和较差;质谱分析结果显示,石油磺酸盐试样中含有烷基苯、烷基萘、烷基茚满、烷基菲、烷基苊、烷基芴和烷基联苯磺酸盐7种类型的磺酸盐,当烷基苯、烷基萘、烷基茚满和烷基苊磺酸盐的质量分数分别为20.0%,5.2%,6.1%,4.6%左右时,试样具有一定的界面活性;待测试样与标准试样(试样9)的相关系数大于0.930时,该试样具有一定的界面活性,相关系数越接近1.000,界面活性越优异。     

Acenaphthene and fluorene hydrogenation on industrial aluminum oxide catalysts in a flow system

Hydrogenation of the tricyclic aromatic hydrocarbons acenaphthene and fluorene on industrial aluminum oxide catalysts in a flow system has been studied. It has been found that total these hydrocarbons are exhaustively hydrogenated in the presence of a nickel-chromium catalyst at 200°C and a pressure of 100 atm to give isomer mixtures of the corresponding perhydroaromatic hydrocarbons decahydroacenaphthene and dodecahydrofluorene. The liquid products obtained can be of interest as components of hydrocarbon fuels with increased density. Certain conformational features of the stereoisomers obtained have been considered. It has been assumed that some spatial isomers of decahydroacenaphthene have six-membered rings in the boat conformation.     

石油降解混合菌群的降解特性研究及群落结构分析

从新疆克拉玛依油田石油污染土壤中分离获得石油降解菌群KO5-2,该菌群在30°C条件下培养7 d对10 g/L总石油烃（TPH）的去除率为56.9%,并且培养3 d ,7 d和9 d后能分别去除100%的芴、98.93%的菲和65.73%的芘。从KO5-2分离得到的来自6个不同菌属的12株可培养单菌,其中只有8株具有降解原油的能力。运用变性梯度凝胶电泳（DGGE）分析不同碳源条件（包括TPH、饱和烃、芴、菲和芘）下KO5-2的群落结构,结果表明,在分别以原油和饱和烃为碳源的培养条件下菌群组成大致相同,在三种不同多环芳烃（PAHs）为碳源的培养条件下,混合菌群的群落结构存在差异。红球菌属（Rhodococcus sp.）和假单胞菌属（Pseudomonas sp.）在五种不同的碳源中均能生存,芽孢杆菌（Bacillus sp.）、鞘氨醇单胞菌属（Sphingomonas sp.）和苍白杆菌（Ochrobactrum sp.）分别是降解饱和烃、PAHs和菲的关键菌。该研究表明,生物修复过程中,混合菌群的群落结构与不同的污染物和单菌株之间的相互作用有关。     

Influence of smoking in traditional and industrial conditions on polycyclic aromatic hydrocarbons content in dry fermented sausages (Petrovská klobása) from Serbia

The aim of this study was to determine the content of 13 polycyclic aromatic hydrocarbons (acenaphthylene, fluorene, phenanthrene, anthracene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene and benzo[ghi]perylene) from Environmental Protection Agency list (US-EPA PAHs) in traditional dry fermented sausage Petrovská klobása. Sausages, stuffed in collagen and natural casings, were smoked in traditional (A1, A2, B1 and B2 - direct smoking) and industrial (B3 and B4 - indirect smoking) conditions.The highest total content of 13 US-EPA PAHs was determined in sausages stuffed in natural casings and smoked in traditional conditions at both examined periods, at the end of drying, as well as at the end of storage period (220 μg/kg and 495 μg/kg, respectively). The lowest content of these compounds was determined in sausages stuffed in collagen casings and smoked in industrial conditions, also at both examined periods (31.3 μg/kg; 54.1 μg/kg respectively). Phenanthrene (A1-120; A2-119; B2-37.6 and B4-13.1 μg/kg) and acenaphthylene (B1-45.0 and B3-18.3 μg/kg) were the most abundant PAHs in all examined sausage samples at the end of drying period, while at the end of storage period the most abundant PAHs were phenanthrene (A1-201; A2-107; B2-49.4 and B3-38.7 μg/kg) and anthracene (B1-34.4 and B4-20.1 μg/kg). Benzo[a]pyrene, whose maximum allowed content in smoked meat products is 5 μg/kg (EC No. 1881/2006), was below the limit of detection in all examined samples. Also, PAH4 (sum content of benz[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene) a more suitable indicator for the occurrence of PAHs, with maximum allowed content in smoked meat products of 30 μg/kg (EC No. 835/2011), was below the limit of detection in all examined samples.According to the results obtained in this study, traditional dry fermented sausage Petrovská klobása, smoked in traditional and industrial conditions was safe for its consumers regarding European regulation on PAHs content.     

Prospects for the use of the combined physicochemical and microbiological enhanced oil recovery technique in the White Tiger oil field (Vietnam)

Reservoir fluids of the White Tiger oil field (Vietnam) were studied for the purpose of the development of the combined physicochemical and microbiological technique of enhanced oil recovery. The reservoir conditions of the oil field facilitate the formation of numerous and versatile biocenosis represented by microorganisms of the Pseudomonas, Bacillus, Arthrobacter, Micrococcus, Nocardia, Brevibacterium, Flavobacterium, etc. genera. These microflora positively respond to the introduction of an oil-displacement composition at a concentration of up to 5% as a nitrogen nutrient source. The active multiplication of the microflora is accompanied by the oxidation of saturated White Tiger petroleum hydrocarbons: the proportion of C₁₀–C₁₅ and C₂₁–C₂₆ decreases, the proportion of the isoprenoid hydrocarbons pristane and phytane increases, and the isoprenoid factor increases from 0.54 in the initial oil to 1.65 after its biodegradation. A simulation of the displacement of viscous oil with the use of the detergent composition and hydrocarbon-oxidizing microflora has shown a 12–14% increment in the oil-displacement efficiency, where the contribution of microflora is estimated at 4–6%.     

Oil hydrocarbon fingerprints of the different marine organisms in some Egyptian Gulf of Suez waters

Oil hydrocarbon fingerprints derived from polycyclic aromatic and aliphatic hydrocarbon were analyzed in marine organisms of various aquatic species muscles collected from 10 different sites along Suez Gulf, Egypt. All samples were analyzed for n-alkanes (C₁₅–C₃₇) and polycyclic aromatic hydrocarbons (EPA list of PAHs). n-Alkanes in ten aquatic species were found to be in the range of 11.391–96.747?ng/g wet weight with a mean value of 60.755?ng/g wet weights. Different indices were calculated for the n-alkanes to assess their sources as carbon preference index (CPI), average chain length (ACL), terrigenous/aquatic ratio (TAR), natural n-alkane ratio (NAR) and proxy ratio (Paq). Most of the various species of n-alkanes were discovered to be from natural sources. Polycyclic aromatic hydrocarbons (PAHs) varied between 81.499 and 5895.608?ng/g wet weight with an average of 2521.126?ng/g wet weight. The contents of ?PAHs were the highest in the tissues. The carcinogenic risks for humans from residual ?PAHs in the various fish tissues higher than10^?5.     

Nickel–molybdenum sulfide naphthalene hydrogenation catalysts synthesized by the in situ decomposition of oil-soluble precursors

Nickel–molybdenum sulfide catalysts for the hydrogenation of aromatic hydrocarbons have been prepared by the in situ decomposition of oil-soluble precursors Mo(CO)₆ and Ni(С₇H₁₅СOO)₂ in a hydrocarbon feedstock and characterized by HRTEM and XPS. The resulting Ni–Mo sulfide material exhibits high catalytic activity in the naphthalene hydrogenation reaction. An optimum Mo/Ni ratio of 1/2 has been selected.     

ORGANIC GEOCHEMISTRY OF BARENTS SEA PETROLEUM: THERMAL MATURITY AND ALTERATION AND MIXING PROCESSES IN OILS AND CONDENSATES

The petroleum system in the Barents Sea is complex with numerous source rocks and multiple uplift events resulting in the remigration and mixing of petroleum. In order to investigate the degree of mixing, 50 oil and condensate samples from 30 wells in the SW Barents Sea were geochemically analysed by GC‐FID and GC‐MS to evaluate their thermal maturity and secondary alteration signatures. Saturated and aromatic compounds from C₁₄–C₁₈ and biomarker range (C₂₀₊) hydrocarbons were compared with light (C₄‐C₈) hydrocarbon alteration and maturity signatures from a previous study. The geochemical data demonstrate that petroleum generation occurred from the early‐ to late‐oil/condensate window, correlating to calculated vitrinite reflection values of between 0.7%R_c and 1.9%R_c. Two maturation traits are in general present in the oil samples analysed and indicate mixing of petroleum phases: a C₂₀₊ fraction which represents a possible “black‐oil ‐related” signature; and a C_20‐ fraction, which is probably a more recent oil charge. However, maturity variations are less pronounced in condensates, which in general exhibit higher generation temperatures than oils but are influenced by severe phase fractionation effects. The samples are characterised by diverse biodegradation signatures including depletion of C_15‐ saturated compounds, almost complete removal of n‐alkanes, elevated Pr/n‐C₁₇ values, high 17α(H), 25‐norhopane content, and a reverse trend in methylated naphthalene distribution. However, the presence of the more recent, unaltered light hydrocarbon charge together with the oil with a palaeo‐biodegraded signature is clear evidence that mixing has occurred. A cross‐plot of C₂₄‐tetracyclic terpane/C₃₀αβ‐hopane versus C₂₃‐C₂₉‐tricyclic terpane/C₃₀αβ‐hopane can be used to discriminate between Palaeozoic/Triassic and Jurassic‐generated petroleums in the Barents Sea region, since it appears to be maturity independent.     

Application of Hydrogen Peroxide and Fenton as Pre- and Post-treatment Steps for Composting of Bottom Sludge from Crude Oil Storage Tanks

In this research the feasibility of chemical oxidation with H₂O₂ and Fenton's reagent for degradation of petroleum hydrocarbons before and after composting of bottom sludge from crude oil storage tanks was investigated. Results showed that total petroleum hydrocarbons removal in composting reactor was 80.2%. In chemical oxidation steps, petroleum hydrocarbons removal enhanced with increasing oxidant concentrations. Increasing oxidation time from 24 to 48 h had a little effect on petroleum hydrocarbons removal. The study showed that chemical oxidation as a pre-treatment step was more effective than post-treatment. It was also deduced that petroleum hydrocarbons in the sludge and composted mixture can be oxidized by hydrogen peroxide without adding supplementary iron.     

The Biodegradation Kinetics of Refining Wastewater by Microorganism UBD

Abstract

In order to develop the wastewater treatment technology for the refineries, the authors studied the biodegradation kinetics of the total petroleum hydrocarbon (TPH) in the refining wastewater based on the experiment data through simplifying the Monod equation properly. The biodegradation kinetics equation can be expressed as v = v_max = 0.25 . The microorganism UBD has strong ability for the biodegradation of the refining wastewater. It can be seen from the parameters of the kinetics equation that the TPH in the refining wastewater is not the nondegradation compound for the microorganism UBD.     

ELECTROCHEMICAL CONVERSION OF NAPHTHALENE IN C2H5OH-H2-LiCl SYSTEM

ABSTRACT

This paper studies the electrical conversion of naphthalene in C₂H₅OH-H₂-LiCl system and the effect of various parameters on conversion and product selectivity. It shows that the main products in this system are from anodic oxidation of naphthalene rather than cathodic reduction of naphthalene and solvent and support electrolyte take part in electrochemical reaction.     

Catalytic pyrolysis of light hydrocarbons in the presence of ultrafine particles formed by electrically induced explosive dispersion of metal wires

The catalytic pyrolysis of C₁–C₄ light hydrocarbons in a continuous tubular reactor in the presence of ultrafine metal particles formed by electrical exploding of monometallic (Ag, Al, Cu, Fe, Ni, Ti, Pt, W, Mo) and bimetallic (Mo, Cu; Fe, Al; W, Ni; W, Pt) wires has been studied. The study has been performed in the temperature range of 500–850°C, a gas mixture flow rate of 50–100 mL/min, and a contact time of 5–10 s. The catalytic activities of ultrafine particles have been matched under comparable conditions, the influence of the metal nature on the yield of ethylene and propylene has been examined, and sooting has been evaluated. The best results for the basic parameters of the catalytic pyrolysis of C₁–C₄ hydrocarbons (yield of ethylene and propylene, ethylene selectivity, and coking) have been shown by W, Fe, and Mo ultrafine particles obtained by electrical explosion of respective wires.     

Treatment of Petroleum Effluent Using a Tubular Electrochemical Reactor

The electrooxidation as a new treatment technology for the purification of petroleum refinery wastewater was used. About 85% COD reduction and complete removal of total petroleum hydrocarbon was achieved for the optimal conditions of current density 30 mA/cm², pH 8, supporting electrolyte 4 g/L, flow rate 120 LPH, and treatment time 24 min using tubular electrochemical reactor. The result shows the applicability of electrochemical technology as an alternative for recycle and reuse of petroleum refinery wastewater. This technology decreases the time required for treating the petroleum effluent, the volume of consumed water, and discharged wastewater.     

炼油厂恶臭污染源综合监测与评价 Ⅰ.污染源监测

 建立了炼油厂各类贮罐呼吸气、污水处理场逸散气及氧化脱硫醇尾气等恶臭无组织排放源的采样与分析成套技术,监测项目基本涵盖石油炼制特征恶臭污染物和油气组分。废气样品用双连球和聚四氟乙烯采样袋采集。废气中特征恶臭污染物的组成及烃类碳数分布用气相色谱/质谱法定性和半定量分析,挥发性硫化物含量用新型的硫化学发光检测/宽口径毛细管气相色谱法分析,总烃含量用总烃分析仪法分析,C1~C3烃类含量用火焰离子化检测/气相色谱法分析,苯系物和氨气含量参照国家标准方法分析。监测了多家炼油厂的典型恶臭污染源,较为全面和系统地获取了炼油厂恶臭污染源排放特征。     

Epoxidation and oxidative dihydroxylation of C<Subscript>10</Subscript>–C<Subscript>13</Subscript> unsaturated bridged hydrocarbons involving hydrogen peroxide and modified forms of heteromolybdic compounds

Induced oxidation of C₁₀–C₁₃ tricyclic bridged olefins synthesized from C₅–C₈ cyclodiene hydrocarbons using hydrogen peroxide has been studied. It has been shown that phosphomolybdic heteropoly compounds supported on a finely divided carbon material and additionally modified with HBr and CoCO₃ or Gd₂O₃ exhibit high activity in this reaction. Depending on the conditions of the experiments, the main reaction products are the corresponding oxiranes and diols that retain the structure of the reactant hydrocarbons.