Process and Catalyst Needs for Hydrodenitrogenation

During the last decade there has been increased interest in the production of synthetic fuels and chemicals feedstocks from coal and oil shale due to declining petroleum reserves. Table 1 gives the projected gasoline to mid-distillate ratio through the year 2000 and beyond; the shift is away from high-octane fuels requiring a relatively high aromatics content and a relatively low hydrogen content to highly paraffin-based fuels having a high hydrogen content. Figure 1 shows the projected United States energy supply and demand through the year 1990 [2], Current petroleum production in the contiguous United States is about 9 million bbl/day and has declined at a rate of about 0.5 million bbl/day per year for a number of years. Alaskan oil will arrest this decline in production briefly but will not make up for even the loss in the rate of petroleum production incurred in the contiguous 48 states during the last 5 years. In all probability, declining production from current oil fields will not be offset by further new discoveries, and thus the United States will become increasingly dependent on foreign oil. Further, petroleum feedstocks are becoming harder to process as crude quality decreases, and as it becomes more and more necessary to process the bottom of the barrel. Declining oil supply in the face of increasing demand will ultimately require that some of the projected gap be made up with synthetics made from coal and oil shale. Such synthetic feedstocks and heavier petroleum fractions contain higher concentrations of nitrogen than light petroleum stocks, are decidedly more difficult to process, and will place increasing demands on hydroprocessing catalysts and processes.     

Reactor Developments in Hydrotreating and Conversion of Residues

Many industrialized western countries depend on imported foreign crude. In 1977, for example, the United States imported 46% of its oil and petroleum products, chiefly from Saudi Arabia, Iran, and other OPEC nations. By September 1, 1983, the United States imported only 28% of its oil. The chief suppliers were Mexico, with 826,000 barrels per day, Canada, with 479,000, and Venezuela, with 419,000. Saudi Arabia is now seventh on the list of suppliers for the United States. This shift is responsible for the trend toward a heavier crude supply mix on the international market. Transportation fuels and petrochemical feedstocks are in increasing demand; hence many refiners would like to get out of the fuel oil business, More “bottom-of-the-barrel” conversion capability will be required in many refineries to efficiently process these heavier feedstocks and maximize production of light products.     

Reactor Developments in Hydrotreating and Conversion of Residues

Many industrialized western countries depend on imported foreign crude. In 1977, for example, the United States imported 46% of its oil and petroleum products, chiefly from Saudi Arabia, Iran, and other OPEC nations. By September 1, 1983, the United States imported only 28% of its oil. The chief suppliers were Mexico, with 826,000 barrels per day, Canada, with 479,000, and Venezuela, with 419,000. Saudi Arabia is now seventh on the list of suppliers for the United States. This shift is responsible for the trend toward a heavier crude supply mix on the international market. Transportation fuels and petrochemical feedstocks are in increasing demand; hence many refiners would like to get out of the fuel oil business, More “bottom-of-the-barrel” conversion capability will be required in many refineries to efficiently process these heavier feedstocks and maximize production of light products.     

Characteristics of jet fuels produced from hydrogenated shale oils

Shale oils from the United States (Geokinetics, Occidental, Paraho and Tosco II) were hydrotreated, fractionated into jet fuel cuts (boiling range 121–300°C), then characterized to evaluate their suitability as jet fuels. Nitrogen content was considerably higher, though the amount of hydrogen was relatively lower, than in typical petroleum jet fuels. Sulfur content was significantly below the acceptable limit. Trace metal contents in shale oil jet fuels were below the maximum levels for those in petroleum jet fuels. Vanadium, copper, lead and alkali metals were not present. Physical properties, except freezing points, were comparable to those of standard jet fuels.     

Comparison of hydrogenated shale oils with standard jet fuels

The characteristics of jet fuels obtained from typical U.S. shale oils (Geokinetics, Occidental, Paraho and Tosco II) were compared with standard petroleum jet fuels in order to study the possibility of using these shale oils as a substitute. The shale oil fractions distilling below 343°C were catalytically hydroprocessed at low, medium and high severities and fractionated to the jet fuel range (121–300°C). The hydroprocessed products and jet fuels were compared for composition and physical properties. High severity hydroprocessing of shale oils decreased the nitrogen, sulfur, olefin and aromatic content while increasing the hydrogen content. The nitrogen content in shale oil jet fuels was considerably higher even after the high severity treatment. The aromatic content, except in Paraho shale oil, was relatively higher and the hydrogen content was slightly lower. Sulfur and olefin contents were lower at all severities. The physical properties and heat of combustion, except the high freezing point of shale oil jet fuels, were comparable to those of standard petroleum jet fuels.     

Effect of Sulfur on the Fischer-Tropsch Synthesis

One of the principalcauses of present concern is the current unavailability of alternative sources of fuels for transporation. Other fuel imensive sectors, such as electric power generation, can depend on coal or nuclear fuel to provide the energy if petroleum-based fuels become scare. The transporation sector, on the other hand, is projected to need liquid fuels. Due to the relevant abundance of coal in the United States, it isimperative to find ways of converting coal to liquid fuels. Products from coal liquefaction processes contain a high aromatic content. Though this is a desirable comporent isgasoline, it is a very undersirable one in jet and diesel fuels (Table 1). In even higher boiling materials such as gas oils, the high aromatic content makes it quite difficult to produce gasoline by normal rednery processess. Fischer-Tropsch (FT)synthesis, in which carbon produces mainly straight chain aliphatic hydrogen obtained from coal gastfication are reacted over a caralyst, is the only develped coal-derived process which produces mainly straight chain aliphatic hydrocarbons. Although such aliphatic hydrocarbons are not very desirable on motor gasolines due to their low octare number, diesel and jet fuels containing such aliphatic, hydrocarbons are considered high quality materials. In addition, the higher boiling gas oil traction from the FT process is easily converted to gasoline and diesel fuel by conventional refining technology     

SHALE OIL HYDROPROCESSING TO PRODUCE SYNTHETIC JET FUELS

The crude shale oil fractions below 343°C available in the United States, (a) Geokinetics, (b) Occidental, (c) Paraho, and (d) Tosco II, were catalytically hydroprocessed at low, medium and high severities. The hydroprocessed oils were fractionated to the jet fuel cuts range of 121-300°C. Shale-oil jet fuels were characterized and compared with petroleum jet fuels to evaluate their suitability as future jet fuel oil substitutes. Nitrogen content in shale-oil jet cuts was in the range of 0.03 to 1.15 wt%. The lowest nitrogen content, 0.03 wt% in high severity Occidental jet fuel, was considerably higher than that of the petroleum jet fuel cuts (1-5 ppm). The sulfur content and mercaptan sulfur content in shale-oil jet fuel was significantly lower than in petroleum jet fuel (total sulfur = 0.3 wt% maximum, mercaptan sulfur = 0.003 wt% maximum), the hydrogen content (13-14wt%) in the shale-oil jet fuel cut was lower than that of petroleum jet fuel (15-16 wt%). The jet fuel distillates, volume percent of the shale-oil and petroleum, that were operated at the same temperatures were comparable; with the exception of the freezing points of the shale-oil fuel cut which were much higher than those of the petroleum jet fuel.     

Characterization of heavy petroleum feedstocks

Characterization of key heavy petroleum feedstock properties is important for optimizing the production of clean transportation fuels. A correlation-based method has been developed to accurately estimate the aromatic carbon and total hydrogen content of heavy petroleum feedstocks. The new characterization methodology is significantly superior to existing methods in that it is applicable to all types of heavy petroleum feedstocks, uses only two (most) commonly measured bulk petroleum properties and is more accurate. The new method has been validated via analysis of an unprecedented number (three hundred and fifty four) of heavy petroleum feedstocks with an extremely broad range of properties.     

我国页岩油的加工

页岩油性质和天然石油相似,因此,天然石油加工制取轻质油品工艺,一般也适用于页岩油。但和天然石油不同的是,页岩油含氮、硫、氧等非烃化合物量高,不饱和烃多,轻馏分少,所以必须采用深度加工与精制的工艺流程,才能得到合格的轻质液体燃料。由于石油资源日趋紧张,页岩油的开发利用得到了关注。介绍了我国对页岩油加氢精制、加氢裂化与非加氢精制研究的进展。     

2003年上半年原油价格走势分析及预测

2003年上半年委内瑞拉供应量剧减，以及美伊战争等因素影响，上半年布伦特油价为28．17美元/桶，同比上涨19．7％，其中一季度为30．62美元/桶，二季度为25．80美元/桶。三、四季度世界石油需求增长有所回升，但欧佩克履约情况、伊拉克产量恢复情况及美国石油库存等是影响未来石油市场的不确定因素。预计三季度油价仍将起伏不定，布伦特油平均价格可能维持在28美元／桶左右，四季度为25．5美元/桶。     

煤、油页岩和石油焦混烧特性及其动力学

为了充分利用劣质燃料油页岩和难以利用的高硫石油焦,以煤、劣质燃料油页岩及高硫燃料石油焦的混合燃料为研究对象,采用热重-差热的试验方法和差减微分法,对其混烧特性曲线和混烧特性机理进行分析,计算出试样各种燃烧特性参数及燃烧动力学参数。结果表明:煤、油页岩、石油焦的质量比为1∶6∶3的混烧试样S7的DTG曲线先后出现挥发分的析出着火燃烧峰和剩余固定碳的着火燃烧峰;煤、油页岩、石油焦的质量比为6∶3∶1的混烧试样S4的可燃特性指数及着火特性指数均大于油页岩及石油焦的值,而且混合试样的燃尽指数均大于煤及石油焦的值,同时,混合样品的综合燃烧特性指数均大于油页岩的值;试样S4的活化能最小,该混合试样的燃烧反应最容易进行。只要煤、油页岩及石油焦混合比例适当,其混合燃烧特性将优于油页岩及石油焦单独的燃烧特性。     

Relation between fuel properties and chemical composition. 1. Jet fuels from coal,oil shale and tar sands

Jet fuels derived from coal, oil shale and tar sands were subjected to extensive chemical and physical property analysis. The straight-chain alkane content of each fractionated fuel was determined by gas chromatography and combined GC-mass spectrometry. Average parameters of the aromatic fractions of these fuels were obtained by p.m.r. spectroscopy. These analytical data were used to help explain differences in several important properties of the alternative fuels compared with jet fuel derived from petroleum. While suitable fuels can be produced from these alternative fossil-fuel sources, the processing requirements will be much different. The alternative fossil-fuel crude oils used in this work are similar to the lower-API-gravity petroleum crudes and therefore hydrocracking and delayed coking will be extensively used to produce military fuels.     

Geometrical Theory of Heterogeneous Catalysis and the Role of Tunneling Therein

The utilization of petroleum is managed primarily by heterogeneous catalysis. This technology at least quadruples the usefulness of a given amount of crude oil as compared to thermal processing. It seems clear that a similar increase in the usefulness of other fossil fuels such as coal and oil shale should be possible, In view of the energy shortage which we have all come to realize in the last year or so, the important central role of heterogeneous catalysis seems to be obvious.     

炼厂制氢技术路线选择和成本分析

初步讨论炼厂制氢的必要性,对规模化的制氢技术进行了简要介绍。通过有代表性的天然气、渣油、水煤浆、干粉煤为制氢原料,分析讨论各原料制氢流程的最佳技术路线配置和典型物料平衡,并对4类原料选定的技术路线制氢成本进行技术经济分析,从成本角度初步探讨适宜炼厂制氢的原料和技术路线选择,结果表明,煤作为原料制氢不仅在技术上具有可行性,在经济性上也表现出越来越强的优势,以煤为原料的制氢装置在炼厂特别是重质油炼厂中将会得到广泛应用。     

煤基燃料的制备与应用

随着国内能源消费的增长,特别是车用燃料的迅速增长,石油消费总量越来越大,但国内石油资源有限,专家预计2010年和2020年石油的对外依存度将达到50%和60%,威胁国家能源的安全供应.但我国煤炭资源相对丰富,大力发展以煤为原料的合成液体替代燃料,提供部分车用燃料,将是解决能源安全供应问题的重要途径之一.论述和比较了合成煤基燃料的3种不同工艺路线：煤直接液化合成油,煤间接液化合成油和煤基含氧燃料合成.前两种工艺的主要目标是提高燃料的H/C比,以合成粗油或碳氢化合物为目标产物.新一代煤直接液化合成油技术还没有工业化装置投入运行,但间接F-T合成碳氢燃料已有成功的工业经验.和石油基燃料相比,虽然煤基碳氢燃料还不具有明显的经济优势,但对于石油资源有限的中国具有重要的战略意义.煤间接液化也可合成煤基含氧燃料,即甲醇燃料和二甲醚燃料等.和碳氢燃料相比,合成煤基含氧燃料不仅具有明显的技术和经济优势,而且充分利用了煤中C、H和O 3种主要元素,可以实现资源、能源、环境和经济可持续发展.     

两条煤制油与石油路线的技术环境和经济分析

中国液体燃料的生产严重依赖石油,为了缓解石油高度对外依存带来的风险,中国正在积极探索石油的替代路线。在中国“富煤贫油”的情况下,煤制油有望成为缓解石油供应安全风险的重要替代途径。利用生命周期评价的方法(from cradle to gate)从能耗、碳排放和经济性三个角度对煤直接液化(direct coal liquefaction,DCL)和煤间接液化(indirect coal liquefaction,ICL)进行分析,并与传统炼油(oil refining,OR)路线进行对比。结果表明:DCL和ICL路线的生命周期能耗分别是OR路线生命周期能耗的2.4倍和2.8倍,碳排放分别是OR路线碳排放的8倍和10倍。当油价低于45美元/桶时,无论是DCL还是ICL均难以与OR路线竞争;当油价在35美元/桶~65美元/桶,煤价在低于400元/t时,ICL有较好的竞争力;而当油价高于75美元/桶时,即使煤价高达700元/t,DCL仍具较好的竞争力。     

石脑油、煤、天然气路线制烯烃的经济性分析

通过模型测算了不同原料价格对应的烯烃生产成本，以及相同烯烃生产成本下，烯烃生产企业能承受的石油、石脑油、煤和天然气的价格对应关系。对石脑油、煤、天然气为原料生产烯烃的经济性进行了分析。初步分析了融资方案对成本测算和项目决策的影响。指出在考虑融资方案影响的情况下，原油价格35美元／bbl为煤、天然气制烯烃项目与石脑油制烯烃项目相竞争的节点。     

A review of recent advances on process technologies for upgrading of heavy oils and residua

The term hydroconversion is used to signify processes by which molecules in petroleum feedstocks are split or saturated with hydrogen gas while tumbling boiling ranges and impurities content from petroleum fractions. Hydroprocessing is a broad term that includes hydrocracking, hydrotreating, and hydrorefining. To meet the gradual changes in petroleum stipulate, in particular a reduced demand for heavy fuel oil, advanced technologies for residue hydroprocessing are now extremely necessary. A refining process is needed for treating heavy petroleum fractions (atmospheric or vacuum oil residue) in the presence of catalysts and hydrogen at high pressure. In this article the different technologies for residua processing: thermal, catalytic fixed and ebullated types of hydroconversion are reviewed and discussed. A possibility of combining the advantages of these technologies together with suitable catalyst with enhanced and controlled cracking activity is also analyzed.     

Synthesis and Characterization of Mesostructured Materials

Catalysis and heterogeneous catalysts are essential to our present technology for the production and consumption of fuels, the manufacture and processing of chemical feedstocks and plastics [1,2]. It had been estimated that the introduction of this technology has permitted savings of more than 400 million barrels of oil each year [l]. Today, worldwide catalysts sales exceed $5.9 billion per year, and it has been estimated that catalysts generate fuels and chemicals worth $2.4 trillion annually, equivalent to half the U.S. Gross National Product [1,2].     

A Technological Perspective for Catalytic Processes Based on Synthesis Gas

Continuously increasing oil prices, a dwindling supply of indigenous petroleum, and the existence of extensive coal reserves has made the conversion of coal to chemicals and clean-burning fuels an increasingly important part of the national energy programs for a number of industrial nations. In particular, there is a growing interest in the production and use of synthesis gas as a feedstock for the manufacture of fuels and chemicals. Most of the proposed routes are catalytic in nature, and are directed at overcoming the limitations of Fischer-Tropsch chemistry, especially selectivity. Over the past several years, research efforts have led to new selective routes to various fuel fractions; to petrochemical feedstocks including light olefins and various aromatics; to commodity chemicals such as ethylene glycol, ethanol, and acetic acid; and to a number of other fuels and chemicals.