Effects of potassium sulfide content in marine diesel fuel oil on emission characteristics of marine furnaces under varying humidity of inlet air

Degraded fuel oils are generally used in marine power plants for economic purposes, so as to reduce operating expenses. These marine fuel oils commonly contain various oxides or sulfide compounds of metallic elements in the fuel ash, and affect the combustion and emission characteristics of marine power plants to different extents. Moreover, marine power plants are more often operated in a highly humid environment. As a result the emission and burning process may also be altered by the various humidity level of the inlet air. The effects of potassium sulfide in marine diesel on the combustion and emission characteristics of marine furnaces under varying levels of relative humidity of inlet air were experimentally investigated in this study. A cylindrical industrial furnace made of AISI 316 stainless steel, and an automatic oil-fired burner were used for the emission characteristics measurements and observation. A mechanically homogenizing machine was used to stir potassium sulfide (K₂SO₄) powder and marine diesel with a preset K₂SO₄ concentration. The relative humidity of the inlet air and temperature were adjusted to their assigned values by a large-size air conditioner before being pumped into the burner. The marine diesel oil mixture was atomized by the inlet air consequently ignited by an electrode and then burned within the horizontal furnace. There were eight rectangular slots cut in the upper portion of the furnace wall so that the probes of a gas analyzer and a thermocouple could be inserted into radial positions in the cylindrical furnace. The concentrations of gas emission and burning gas temperature and the combustion efficiency were analyzed. The experimental results show that the burning gas temperature, carbon dioxide emission and combustion efficiency decreased when the concentrations of excess air and oxygen emission increased with the addition of potassium sulfide in the marine diesel fuel. This is primarily attributed to the fact that the sulfide of an alkali compound such as K₂SO₄ may suppress the oxidation reaction process, leading to inferior combustion characteristics.     

Influences of vanadium compound on burning characteristics of emulsified marine fuel oil C

Vanadium is one of the most significant trace elements in heavy fuel oils. While most previous studies emphasize its effects on the high-temperature corrosion of power-plant materials, the understanding of the basic combustion characteristics influenced by the vanadium content in fuel oils is still rather limited. The influences of the controlling factors, such as water-to-oil ratio, amount of emulsifying agent, and content of vanadium pentoxide on the burning characteristics of marine heavy No.6 fuel oil are thus investigated in this experimental study by using a suspended droplet approach. It is shown that the ignition delay, degree of micro-explosion, burning time, and flame length are affected by those factors to various extents. Increase of the water-to-oil ratio might enhance the micro-explosion phenomenon while the addition of an appropriate amount of the emulsifying agent Span-80 promotes the homogeneity of micro-water-droplets over their oil base, leading to alterations of the heated droplet characteristics of the emulsions. However, the existence of V₂O₅ in a fuel oil would result in deterioration of burning quality.     

Emission characteristics of marine furnaces burned at varying inlet air temperatures and humidity

Marine power plants are frequently operated under varying atmospheric air temperature and humidity conditions. The effects of inlet air temperatures and humidity of marine furnaces such as incinerators and boilers thus attract much research interest. An industrial furnace incorporated with an automatic burner was employed to experimentally investigate the influences of the inlet air temperature and humidity on the emission characteristics. The inlet air humidity and temperature were adjusted using an air-conditioning machine to preset values before being admitted into the burner. ASTM No. 2D diesel oil was atomized, mixed with the inlet air and burned inside the industrial furnace. Eight small rectangular slots were cut on the upper side of the furnace to allow gas analyzer and thermocouple probes to be inserted into the furnace center to measure the axial variations in the gas temperature, burning efficiency and burning gas compositions such as NO_x, SO₂, CO. The experimental results show that the O₂ and NOx emission concentrations decreased while the CO₂ emission concentration and burning efficiency increased with either increasing inlet air humidity or temperature.     

Sensitivity of three microalgae to crude oils and fuel oils

Four crude oils and five fuel oils have been tested for toxicity with three microalgae—a blue-green, a green and a diatom. The oils were absorbed on filter paper pads and the pads submerged in the growth medium. The crude oils were less inhibitory than equal amounts of fuel oils. Despite initial growth lags, the crude oils allowed growth at 30 μl/20 ml of culture medium (10⁵ cells/ml) while fuel oils were lethal at 10 μl/20 ml. The toxicity patterns of two of the whole fuel oils were different from that seen with their water soluble fractions (WSF); for example, the Baton Rouge fuel oil sample was very toxic to growth of the three test organisms whereas its WSF was relatively innocuous. Photosynthesis of a sensitive organism Chlorella autotrophica, strain 580 (10⁷ cells/ml), was only temporarily depressed by the crude oils (30 μl/20 ml). Four of the fuel oils inhibited photosynthesis, O₂ output decreasing to zero without recovery. When the fuel oils were heated in a stream of helium they were detoxified. Chemical analyses of two of the toxic fuel oils before and after heating were compared with analyses of the Montana sample, a largely non-toxic fuel oil, in an effort to determine what types of compounds might be involved. Classes of aromatic compounds which were not accountable for the toxicity observed here include naphthalene, methylnaphthalenes, dibenzothiophenes, phenanthrenes and compounds with volatilities greater than methylnaphthalenes. Paraffinic and asphaltic fractions of fuel oil were also non-toxic. The accumulated chemical data suggest that the toxicity of whole fuel oils is due to the less water soluble types of compounds in the higher boiling aromatic fraction.     

柴油的中重度风化鉴别指标研究

以柴油为研究对象,采用溢油风化模拟实验,从分子级水平揭示中长期风化作用对溢油组成的影响。利用相对偏差和重复性限法进行评价和筛选,研究表明,柴油在较短时间(10 d)内,phytane/n-C18和pristine/phytane特征比率可较好地作为油品鉴别的依据;在10~30 d的风化期间,pristine/phytane仍可作为油品鉴别的依据;较长期的风化过程后,上述三个正构烷烃特征比率对于油品鉴别已不再具备意义。所选多环芳烃诊断比值指标中,除MNR、MP/P外,其他参数(MPI-1,MPI-2,Rc,MPDF1,MPDF2,MNR)相对标准偏差在1.10%~5.40%,可较好地用于重度风化溢油源鉴定。     

Reduction of particulate matter and gaseous emission from marine diesel engines using a catalyzed particulate filter

Diesel engines are used widely as the power sources of coastal ships and international vessels primarily due to their high thermal efficiency, high fuel economy and durable performance. However, the gaseous and solid substances exhausted from diesel engines during the combustion process cause air pollution, in particular around harbor regions. In order to effectively reduce particulate matter and gaseous pollution emissions, a catalyzed particulate filter was equipped in the tail pipe of a marine diesel engine. The engine's performance and emission characteristics under various engine speeds and torques were measured using a computerized engine data control and acquisition system accompanied with an engine dynamometer. The effectiveness of installing a catalyzed particulate filter on the reduction of pollutant emissions was examined. The experimental results show that the exhaust gas temperature, carbon monoxide and smoke opacity were reduced significantly upon installation of the particulate filter. In particular, larger conversion of carbon monoxide to carbon dioxide — and thus larger CO₂ and lower CO emissions — were observed for the marine diesel engine equipped with a catalyzed particulate filter and operated at higher engine speeds. This is presumably due to enhancement of the catalytic oxidation reaction that results from an exhaust gas with stronger stirring motion passing through the filter. The absorption of partial heating energy from the exhaust gas by the physical structure of the particulate filter resulted in a reduction in the exhaust gas temperature. The particulate matter could be burnt to a greater extent due to the effect of the catalyst coated on the surface of the particulate filter. Moreover, the fuel consumption rate was increased slightly while the excess oxygen emission was somewhat decreased with the particulate filter.     

Geochemistry and charge history of oils from the Yuqi area of Tarim Basin,NW China

The geochemistry, origin and charge history of oils from the Yuqi area of Tarim Basin have been investigated, through GC, GC-MS and fluid inclusion microthermometry analysis. The Yuqi oils accumulated mainly in three intervals: (1) in the Lower-Middle Ordovician Yingshan Formation (O_1-2y) carbonate reservoirs; (2) in the overlying Upper Triassic Halahatang Formation (T₃h); and (3) in the Lower Cretaceous Yageliemu Formation (K₁y) sandstones. Oils from different reservoirs have distinct physical properties, varying from extra-heavy (O_1-2y), heavy (T₃h), to light oils (T₃h and K₁y). However, their geochemical compositions show a high degree of similarity, which indicates that they derive from the same source rock. Abundant tricyclic terpanes, gammacerane, dibenzothiophene and C₂₁C₂₂steranes, together with a low level of diasteranes, indicate an anoxic marine source rock for oils in the Yuqi area. Oil-oil correlation shows that Yuqi oils derive from the same source bed as Tahe oils. The co-occurrence of intact n-alkanes and 25-norhopanes in all the samples supports the proposition that there is a mixture of an early filled severely biodegraded oil and a late filled fresh oil.In this study, charge history is examined on the basis of integration of fluid inclusion homogenization temperature data with 1D burial-thermal history models. Two episodes of oil charging are identified in the O_1-2y reservoir (well YQX1-1) at around 436-420 Ma (Middle-Late Silurian) and 10-3 Ma (Miocene to Pliocene), respectively. For the samples from the T₃h and K₁y intervals, only one episode of oil charge is indicated by the homogenization temperatures of coexisting aqueous inclusions with an inferred timing around 10-3 Ma. The T₃h heavy oil reservoir is assumed to be a secondary hydrocarbon pool, which accumulated by re-migration and re-distribution of hydrocarbons from O_1-2y hydrocarbon pools. The few early biodegraded oils in the K₁y light oils were probably picked up along the migration pathway during the late fresh oil charging.     

Geochemical investigation of oils from Cretaceous to Eocene sedimentary sequences of the Abadan Plain,Southwest Iran

Oil samples from Lower Cretaceous to Eocene reservoirs in southwest Iran were analyzed using gas chromatography–mass spectrometry and gas chromatography–isotope ratio mass spectrometry for genetic classification of oil families and determining their maturity. The Studied oil samples are non-biodegraded and their gravity range from 18.3 to 37° API. The slight even/odd n-alkane predominance, coupled with low Pr/Ph values, suggests their likely source rocks with a predominance of algal organic matter, type IIS kerogen deposited under strongly reducing marine environments. The biomarker distribution of investigated oils is characterized by high concentration of both C₂₉ and C₃₀ hopanes and ratios of C₂₉/C₃₀H are generally greater than unity. There is a marked predominance of C₂₉ regular sterane over C₂₇ and C₂₈ homologs in our studied oils. High sterane/hopane values and cross plot of the δ¹³C sat versus δ¹³C aro show contribution of marine organic matter. Medium value of gammacerane index and other salinity indices show water density stratification and high salinity conditions of the environment of deposition. It can be concluded that the studied reservoirs, due to their variable maturity have different API gravity and contain two oil families (types A and B) with latter being deeper and comprising more mature oils.     

短期风化对混合溢油组成的影响

对两种原油进行混合配比实验,将混合后油样置于人工气候箱进行风化模拟实验,采用气相色谱质谱联用仪(GC-MS)检测风化样品中的生物标志化合物,短期风化作用对混合溢油的油指纹、生物标志化合物诊断指标等的影响。结果表明,混合溢油的正构烷烃总质量变化与单一原油油品的变化规律相近,即前期风化较快,质量减损较多,而后期风化趋缓,不同混合比例的溢油表现差异不明显。常用于短期风化的诊断比值对各混合油样的风化具有指示意义,但难以定性鉴别油品是否发生混合。重复性限法检验只能判定短期风化过程前后的油样为同一油源,而难以反映油样是否为混合油源的特征,各诊断比值的RSD%值较大可能是混合溢油的一个表现。     

湛江湾柱状沉积物n-alkanes和PAHs组合分子特征及其环境指示作用

本文对湛江湾湾内、湾口和湾外柱状沉积物n-alkanes和PAHs的空间分布、成分谱特征和排放源进行调查分析。结果表明:(1)n-alkanes和PAHs的空间分布一致,浓度水平由高到低依次为:湾内、湾口、湾外,垂直变化不明显;(2)n-alkanes和PAHs的成分谱和L/H、CPI、Ant/(Ant+Phe)、Flu/(Flu+Pyr)、BaA/(BaA+Chry)、IP/(IP+BghiP)等特征参数比值以及主成分分析结果表明C₂₅～C₃₅高碳数n-alkanes的高等植物贡献具有绝对优势,C₁₄～C₂₄中低碳数的n-alkanes和PAHs则有共同的石油、化石燃料燃烧和生物质燃烧等人为源;(3)C₁₄～C₂₄中低碳n-alkanes与PAHs的源解析结果相同,其线性相关系数在0.67以上,表明两者具有较好的相关性,但两者之间的定量关系还需进一步的研究。本研究表明n-alkanes和PAHs对人为源的指示具有一致性,两者具有良好的相关性,能够较好地反映城市的社会经济状况,在进一步的研究中可以建立两者之间的定量关系并形成新的参数,提高人为源解析结果的准确性,深入反映人类活动对海洋环境的影响。     

Chronic sublethal effects of the water soluble fractions of no. 2 fuel oils on the marine isopod, Sphaeroma quadridentatum

Two series of experiments were carried out to assess the long-term effects of the water soluble fractions (WSF) of fuel oils on the marine isopod, Sphaeroma quadridentatum. In one experiment, juvenile isopods (one month old) were exposed to sublethal concentrations (0·1% to 15% WSF) of a fuel oil (Baytown, Exxon) at room temperatures of 24 ± 1–6°C for nine months. These isopods survived to maturity and reproduced. However, growth rate was adversely affected at concentration ≥ 3% WSF and fecundity was depressed at concentrations ≥ 1% WSF. Survival of offspring in clean seawater was dependent to a large extent on the history of the previous generation. Offspring from groups exposed to ≥ 1% WSF experienced high mortality (> 70% within five weeks) even in clean seawater. This may imply that a population of Sphaeroma exposed to WSF as low as 0·2 ppm may eventually disappear, although animals can grow to maturity and reproduce at concentrations < 3 ppm.In another experiment, adult Sphaeroma (three months old) were subjected to the WSFs of four fuel oils (Baton Rouge, Baytown, Montana and New Jersey) for one month. Fecundity was depressed at a concentration > 15% WSF, regardless of the kind of fuel oil. On the other hand, the number of young produced bythe surviving females varied with the type of fuel oil for the same level of WSF. This may be attributed to different relative amounts of toxic components present in the WSF.     

Biodegradation of dispersed marine fuel oil in sediment under engineered pre-spill application strategy

Biodegradation of marine fuel oil was studied by monitoring changes in residual oil and populations of microorganisms in marine sediments. Biodegradation rates for dispersant and soap water were 2.09 and 2.27 g/kg per day, respectively, under pre-application strategy, suggesting that the strategy may promote MFO dispersion and provide with sufficient source of food. The effect of temperature on the effectiveness of pre-application strategy is particularly obvious for the growth of fungi and Pseudomonas maltophilia. The effect of pre-application of soap water on the tolerance of aerobic bacteria, Escherichia coli, and P. maltophilia, was gradually diminished within 25–33 days.     

A mechanistic study of the high-temperature oxidation of organic matter in a carbon analyzer

This study examines the mechanism of oxidation of dissolved organic matter (DOM) in a high-temperature combustion (HTC) carbon analyzer. The HTC analyzer, which is commonly used to measure the concentration of dissolved organic carbon (DOC) in seawater, is still largely empirical in its operation, and little information is yet available on the chemical and physical mechanisms responsible for oxidation of DOM. To examine the role of water, which has been hypothesized to be a source of reactive oxidants in HTC analyzers, several experiments were conducted using gaseous hexane samples and several wet/dry carrier gases. Because the quantity of O₂(g) needed to oxidize an injected sample of DOM is quite small, a substantial effort has been made to exclude O₂(g) from the combustion furnace of the HTC instrument. In this modified, “air-tight” instrument, the efficiency of conversion of hexane into CO₂ was greatest in dry O₂ and slightly lower in moist O₂. Hexane was only slightly oxidized in dry N₂, but it was largely converted into CO₂ when moist N₂ was used as the carrier gas. These experiments confirm that water provides reactive oxidizing species (perhaps hydroxyl radical) that rapidly convert hexane into CO₂ in the combustion tube of a carbon analyzer. Additional experiments with aqueous solutions of potassium hydrogen phthalate and a variety of carrier gases support this basic hypothesis.     

An oxygenating additive for improving the performance and emission characteristics of marine diesel engines

Diesel engines provide the major power sources for marine transportation and contribute to the prosperity of the worldwide economy. However, the emissions from diesel engines also seriously threaten the environment and are considered one of the major sources of air pollution. The pollutants emitted from marine vessels are confirmed to cause the ecological environmental problems such as the ozone layer destruction, enhancement of the greenhouse effect, and acid rain, etc. Marine diesel engine emissions such as particulate matter and black smoke carry carcinogen components that significantly impact the health of human beings. Investigations on reducing pollutants, in particular particulate matter and nitrogen oxides are critical to human health, welfare and continued prosperity. The addition of an oxygenating agent into fuel oil is one of the possible approaches for reducing this problem because of the obvious fuel oil constituent influences on engine emission characteristics. Ethylene glycol monoacetate was found to be a promising candidate primarily due to its low poison and oxygen-rich composition properties. In this experimental study ethylene glycol monoacetate was mixed with diesel fuel in various proportions to prepare oxygenated diesel fuel. A four-cylinder diesel engine was used to test the engine performance and emission characteristics. The influences of ethylene glycol monoacetate ration to diesel oil, inlet air temperature and humidity parameters on the engine’s speed and torque were considered. The experimental results show that an increase in the inlet air temperature caused an increase in brake specific fuel consumption (BSFC), carbon monoxide, carbon dioxide emission, and exhaust gas temperature, while decreasing the excess air, oxygen and nitrogen oxide emission concentrations. Increasing the inlet air humidity increased the carbon monoxide concentration while the decreased excess air, oxygen and nitrogen oxide emission concentrations. In addition, increasing ethylene glycol monoacetate ratio in the diesel fuel caused an increase in the BSFC while the excess air and oxygen emission concentrations decreased.     

柴油分散液对马粪海胆细胞色素P450 活性的影响

试验研究了不同质量浓度下(5、20、50 mg/L)三组柴油分散液,对马粪海胆的肠体、性腺、体液三个部位的抗氧化还原系统细胞色素P450活性变化的影响。结果表明,随着污染暴露时间的增加,三个部位的细胞色素P450活性均呈现出先被诱导、后被抑制的规律,并且油浓度越高,出现诱导和抑制效应的时间越早,活性变化的幅度也越大。海胆P450活性变化在一定程度上能够反映油污染的强度及其对海洋生物的毒性效应,可作为海洋石油烃污染监测的毒理学指标。     

Effects of CO<Subscript>2</Subscript> on Marine Fish: Larvae and Adults

CO₂-enriched seawater was far more toxic to eggs and larvae of a marine fish, silver seabream, Pagrus major, than HCl-acidified seawater when tested at the same seawater pH. Data on the effects of acidified seawater can therefore not be used to estimate the toxicity of CO₂, as has been done in earlier studies. Ontogenetic changes in CO₂ tolerance of two marine bony fishes (Pag. major and Japanese sillago, Sillago japonica) showed a similar, characteristic pattern: the cleavage and juvenile stages were most susceptible, whereas the preflexion and flexion stages were much more tolerant to CO₂. Adult Japanese amberjack, Seriola quinqueradiata, and bastard halibut, Paralichthys olivaceus, died within 8 and 48 h, respectively, during exposure to seawater equilibrated with 5% CO₂. Only 20% of a cartilaginous fish, starspotted smooth-hound, Mustelus manazo, died at 7% CO₂ within 72 h. Arterial pH initially decreased but completely recovered within 1-24 h for Ser. quinqueradiata and Par. olivaceus at 1 and 3% CO₂, but the recovery was slower and complete only at 1% for M. manazo. During exposure to 5% CO₂, Par. olivaceus died after arterial pH had been completely restored. Exposure to 5% CO₂ rapidly depressed the cardiac output of Ser. quinqueradiata, while 1% CO₂ had no effect. Both levels of ambient CO₂ had no effect on blood O₂ levels. We tentatively conclude that cardiac failure is important in the mechanisms by which CO₂ kills fish. High CO₂ levels near injection points during CO₂ ocean sequestration are likely to have acute deleterious effects on both larvae and adults of marine fishes. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effects of MV Rena heavy fuel oil and dispersed oil on yellowtail kingfish early life stages

ABSTRACT

The grounding of the MV Rena has highlighted the lack of information concerning the effects of oil-related compounds on New Zealand marine life. Yellowtail kingfish (YTK), Seriola lalandi, embryos were exposed in static incubations to the water-accommodated fraction (WAF) of Rena heavy fuel oil as well as a similar preparation treated with the commercial dispersant Corexit 9500. Mortality in WAF treatments generally increased in association with total polycyclic aromatic hydrocarbon (tPAH) concentration over a 24-h period. Physical abnormalities were observed in some of the larvae exposed to WAF for 48 h. There was no survival in dispersed oil treatments after 24 h of exposure. These treatments had greater tPAH concentrations (2–53?µgL^?1) than equivalent WAF dilutions (0.2–1.5?µgL^?1?tPAH). Indications are that significant morbidity is induced in YTK at ecologically relevant tPAH concentrations. This highlights the need for further research into oil and dispersant toxicity in New Zealand marine species.     

Cu2+/SnO2复合纳米光催化剂的制备及其对海洋柴油污染物的降解

采用化学沉淀法成功制备了Cu2+/SnO2复合纳米光催化剂,采用XRD、SEM等测试手段对复合纳米光催化剂的粒径、形态等进行表征。在紫外光条件下,分别改变催化剂掺杂比、催化剂煅烧温度、催化剂投加量、柴油初始含量和光照时间等单因素,探究不同条件对Cu2+/SnO2复合纳米光催化剂降解海洋柴油污染物的影响。结果表明,自制复合纳米光催化剂可以有效降解海水中的柴油污染物,在紫外光作用下,于400℃下煅烧Cu/Sn掺杂比为0. 03的Cu2+/SnO2复合纳米光催化剂、投加量为0. 2 g/dm3、柴油初始含量为0. 15 g/dm3、H2O2溶液含量为0. 2 g/dm3、溶液的p H为7、光照时间3 h时效果最好,海水中柴油的去除率最高,达到86. 98%。Cu2+/SnO2复合纳米光催化剂用聚丙烯纳米球负载后可以实际应用于海洋中,便于回收。     

Origin of crude oils from oilfields in the Zagros Fold Belt,southern Iraq: Relation to organic matter input and paleoenvironmental conditions

Crude oil samples from Cretaceous and Tertiary reservoir sections in the Zagros Fold Belt oil fields, southern Iraq were investigated using non-biomarker and biomarker parameters. The results of this study have been used to assess source of organic matter, and the genetic link between oils and their potential source rocks in the basin. The oils are characterized by high sulphur and trace metal (Ni, V) contents and relatively low API gravity values (17.4–22.7° API). This indicates that these oils are heavy and generated from a marine source rock containing Type II-S kerogen. This is supported by their biomarker distributions of normal alkanes, regular isoprenoids, terpanes and steranes and the bulk carbon isotope compositions of their saturated and aromatic hydrocarbons. The oils are characterized by low Pr/Ph ratios (<1), high values of the C₃₅ homohopane index and C₃₁-22R/C₃₀ hopane ratios, relatively high C₂₇ sterane concentrations, and the predominance of C₂₉-norhopane. These biomarkers suggest that the oils were generated predominantly from a marine carbonate source rock, deposited under reducing conditions and containing plankton/algal and microorganisms source input. The presence of gammacerane also suggests water column stratification during source rock deposition.The biomarker characteristics of the oils are consistent with those of the Middle Jurassic Sargelu carbonate as the effective source rock in the basin. Biomarker maturity data indicate that the oils were generated from early maturity source rocks.