Liquid Chromatographic determination of phenalenones in middle distillate fuels

The reactions of phenalenones with indoles have previously been shown to result in the formation of sediment during the ambient storage of an unstable catalytically cracked distillate fuel. A liquid Chromatographic method has been developed to directly quantify phenalenone, its methyl homologues and the related benzanthrones in middle distillate fuels, utilizing u.v. absorption at 400 nm for the selective determination of these compounds. These chemical species have been quantified in fuel components which have undergone a variety of refinery processes, including thermal and catalytic cracking.     

Treatment of Synthetic Crudes with Metal Chlorides and Metal Carbonyls

Abstract

The removal of problematic synthetic crude compounds with limited amounts of transition metal chlorides, carbonyls and hydrido carbonyls was investigated. A middle distillate fraction containing pure compounds of nitrogen and sulphur that are typical of this fraction was used. Chlorides of copper, iron, tin and zinc showed significant potential for removal of the nitrogen compounds and ethyl and phenyl mercuric chlorides reacted with these compounds at 200[ddot]C. These chlorides reacted with mercaptans and alkyl sulphides to varying degrees and with the exception of ethyl mercuric chloride had little effect on benzo and dibenzothiophene. However, the carbonyls of cobalt and manganese were quite promising for these thiophenes. Hydrido carbonyls of these metals were more favourable for the nitrogen compounds. There is evidence of competition for sites on the solid metal salts.     

Effect of multistage hydroprocessing on aromatic and nitrogen compositions of shale oil

Geokinetics crude shale oil, a distillate and processing intermediates sampled during four-stage catalytic hydroprocessing of the distillate were analysed for total nitrogen, basic nitrogen and olefinic and aromatic contents. Successive hydroprocessing stages yielded products containing 80, 46, 16 and 2% of the nitrogen content in the feedstock. Total nitrogen, basic nitrogen and aromatic contents were also reduced. Apparent relative reactivities of aromatic hydrocarbons and nitrogen-containing compounds are in agreement with reactivities observed in model compound studies. Hydrodenitrogenation of nitrogen-containing compounds occurred concurrently with hydrogenation of non-nitrogen-containing aromatic hydrocarbons. Hydroprocessing conditions necessary for essentially complete removal of nitrogen yielded a refined oil with low aromatic content.     

石油产品溶剂脱氮研究进展

石油产品中的氮化物对其安定性有较大的影响,在石油加工过程中极微量氮化物就会导致催化剂中毒,含氮燃料燃烧后产生的氮氧化物对大气污染严重。石油脱氮技术主要有酸洗脱氮法、吸附脱氮法和加氢脱氮法。综述了石油产品脱氮研究进展,提出了催化裂化柴油络合萃取脱氮的途径。     

The Use of Clays for the Hydrotreatment of Heavy Crude Oils

The increasing supply of heavy crude oils is a matter of serious concern for the petroleum industry. In order to satisfy the changing pattern of product demand, significant investments in refining conversion processes will be necessary to profitably utilize these heavy crude oils. Although the most efficient and economical solution to this problem will depend to a large extent on individual country and company situations, the most promising technologies will likely involve the conversion of vacuum bottom residual oils, asphalt from deasphalting processes, and superheavy crude oils into useful light and middle distillate products.     

Advanced distillation curve measurement: Application to a bio-derived crude oil prepared from swine manure

We have recently introduced several important improvements in the measurement of distillation curves for complex fluids. This new method is a significant improvement over current approaches, with features including a composition-explicit data channel for each distillate fraction (for both qualitative and quantitative analysis), trace chemical analysis of each distillate fraction, and a corrosivity assessment of each distillate fraction. In the present contribution, we present the application of the advanced distillation curve method to a bio-derived crude oil prepared from swine manure. One motivation behind the work was to precisely measure the distillation curve of the oil derived from swine manure with our advanced distillation apparatus and compare the bio-derived oil to traditional petroleum crude oils. Then, the information content of the bio-derived oil distillation was extended further with the composition-explicit data channel: gas chromatography–mass spectrometry (GC–MS), infrared spectrophotometry (IR), gas chromatography with sulfur chemiluminescence detection (GC-SCD), and the copper strip corrosion test (CSCT) were employed on each distillate volume fraction sampled. Consequently, we can address the composition, quantitate the total sulfur content, and measure the corrosivity. Using these tools, we determined that the bio-derived swine manure oil contained both water and heavy metals.     

Advanced distillation curve measurements for corrosive fluids: Application to two crude oils

We have recently introduced several important improvements in the measurement of distillation curves for complex fluids. The modifications include a composition-explicit data channel for each distillate fraction (for both qualitative and quantitative analysis) and corrosivity assessment of each distillate fraction. The composition-explicit information is achieved with a new sampling approach that allows precise qualitative as well as quantitative analyses of each fraction, on the fly. We have applied the new method to a variety of fluids, including simple n-alkanes, rocket propellant, gasoline, jet fuels, and a hydrocarbon fluid made corrosive with dissolved hydrogen sulfide. In the current contribution, we present the application of the advanced distillation curve method to two samples of crude oil. A primary motivation behind the work is to precisely measure the distillation curves of these oils using our advanced distillation apparatus; these low uncertainty measurements of true thermodynamic state points can be used for equation of state development and differentiation of crude oil samples. Then, the information content of each distillation was extended much further by use of the composition-explicit data channel: gas chromatography–mass spectrometry (GC–MS), infrared spectrophotometry (IR), gas chromatography with sulfur chemiluminescence detection (GC–SCD), and the copper strip corrosion test (CSCT) were used for each distillate volume fraction sampled. Consequently, for each volume fraction of crude oil distillate sampled, we can address the composition, quantitate the total sulfur content, and measure the corrosivity.     

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.     

煤直接液化粗油提质加工工艺研究现状

分析对比了煤直接液化油的汽油和柴油馏分与石油基汽油和柴油馏分杂原子含量和族组分的差异,指出煤直接液化油中氮和芳烃含量高,需要经过苛刻的加工改质,才能作为车用内燃机燃料使用。介绍了煤液化粗油提质加工的研究现状,讨论了油品加氢催化剂和不同馏分产物的加氢提质工艺,展望了该工艺的发展趋势。     

Ageing of SRC liquids

The ageing characteristics of a 30/70 (wt%) blend of SRC-I and SRC-II and of a SRC-II middle distillate (boiling-point range 450–565K), have been studied. Viscometric, ultimate analysis, solvent separation, gel permeation chromatography, and 600-MHz n.m.r. measurements have been used to monitor the ageing properties of the SRC liquids under various conditions. The viscosity of the blend increases significantly in ten days with oxygen bubbling through at 335K. However, copper, in addition to oxygen, is necessary to change the viscosity of the middle distillate significantly. For the blend, there is a rectilinear increase in log viscosity with increasing wt% of toluene-insolubles formed during oxygenageing. There is also a rectilinear decrease in log viscosity with decreasing content of toluene-insolubles resulting from hydroprocessing of the blend with Ni&z.sbnd;Mo catalyst. These observations indicate that under conditions of oxidative degradation the formation and content of larger molecular-size tolueneinsolubles are mainly responsible for the increased viscosity of the blend. The middle distillate does not contain toluene-insolubles, and oxygen-ageing occurs only in the presence of copper. Oxidative coupling of phenols is proposed as an ageing mechanism for both the blend and the middle distillate.     

Urea, thiourea and guanidine derivatives as multifunctional fuel stabilisers

Different N-substituted derivatives of urea, thiourea and guanidine have been synthesised and characterised for structural information by FT-IR and ¹³C NMR spectroscopy. Accelerated stability tests have been done to evaluate their sediment inhibition and dispersant characteristics on distillate fuels containing high proportions of unstable components and results discussed. It is inferred that urea and guanidine derivatives not only inhibit the reactions responsible for sedimentation in the test fuel but also effectively disperse the gum and sediment formed. It is concluded that the nature of substituents on the central carbon atom and on the amino groups determines the performance behaviour of these compounds.     

Improving the low-temperature properties of alternative diesel fuels: Vegetable oil-derived methyl esters

This work explores near-term approaches for improving the low-temperature properties of triglyceride oil-derived fuels for direct-injection compression-ignition (diesel) engines. Methyl esters from transesterified soybean oil were evaluated as a neat fuel and in blends with petroleum middle distillates. Winterization showed that the cloud point (CP) of methyl soyate may be reduced to −16°C. Twelve cold-flow additives marketed for distillates were tested by standard petroleum methodologies, including CP, pour point (PP), kinematic viscosity, cold filter plugging point (CFPP), and low-temperature flow test (LTFT). Results showed that additive treatment significantly improves the PP of distillate/methyl ester blends; however, additives do not greatly affect CP or viscosity. Both CFPP and LTFT were nearly linear functions of CP, a result that compares well with earlier studies with untreated distillate/methyl ester blends. In particular, additives proved capable of reducing LTFT of neart methyl esters by 5–6°C. This work supports earlier research on the low-temperature properties; that is, approaches for improving the cold flow of methyl ester-based diesel fuels should continue to focus on reducing CP.     

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.     

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.     

Accelerated oxidation of diesel distillate: Infrared spectra of soluble and insoluble gums

An infrared spectroscopic study of some products associated with petroleum diesel distillate instability is described. Spectra of soluble and insoluble gums which formed in the fuels during accelerated and ambient ageing are compared. The results indicate that gums derived from accelerated ageing are not the same as those which form during ambient storage. Spectral features relating to the chemical structures of gum components are discussed.     

Upgrading of middle distillate fractions of a syncrude from Athabasca oil sands

Current processes for upgrading bitumen from Athabasca oil sands produce synthetic crudes which are high in aromatics and deficient in hydrogen. As a consequence, middle distillate fractions derived from these syncrudes produce diesel fuels of low cetane number and jet fuels which are hydrogen deficient. Results obtained from bench-scale hydrotreating experiments indicate that quality fuels may be produced from Athabasca syncrudes. Middle distillate fractions from this source were subjected to high-severity hydroprocessing in a continuous-flow reactor unit using conventional hydrotreating catalysts which were pre-sulphided by a mixture of $\text{H}{}_2\text{H}{}_2\text{S}$. Aromatic hydrogenation at high temperatures and pressures was affected by the approach to thermodynamic equilibrium, however, at lower temperatures, in some cases virtually 100% saturation was achieved and treated fractions were found to meet cetane number and jet fuel smoke point requirements. Data treatment in the present study includes a model for the hydrogenation kinetics and correlations between aromatic carbon and fuel combustion properties.     

Sulphides and thiophenes of sulphur petroleum distillates

• 1.1. The structural group composition of sulphides and thiophenes of middle distillates of mercaptan (Orenburg), sulphide (Samotlor) and thiophene (Usinsk) type sulphurous petroleums are compared.
• 2.2. Sulphides in Usink distillate are wholly represented by thiaindanes. Thiamono- and thiabicycloparaffins (their total being 54·8 and 72·2% of sulphides, respectively) dominate the sulphides of Orenburg and Samotlor distillates. Thiaparaffins figure significantly in the Orenburg distillate where they form 13·7% of the sulphides.
• 3.3. Maximum aromaticity of thiophene compounds of Orenburg petroleum distillate and maximum cyclic recurrence in Usink petroleum distillate was established. 63·5% of the thiophenes of the Samotlor distillate is represented by polyalkylthiophenes and alkylbenzothiophenes.

     

大豆植物甾醇精制工艺的研究

植物甾醇是功能性食品添加剂,大豆植物油脱臭馏出物,有大量的粗植物甾醇的副产物。采用石油醚洗涤乙醇重结晶精制的生产工艺,使用EDTA作为金属络合剂去除金属离子,用高性能的活性炭和活性白土去除苯并芘,从而精制高品质植物甾醇。     

The evaluation of crude glycerine

Summary A number of tests applicable to crude glycerine have been studied to find a means of detecting crude glycerines which will cause more difficulty in the refinery or yield a poorer product than would be expected from the results of analyses customarily made. Five tests have been found which are believed to be useful in this way. They are determination of pH, determination of nitrogen, distillation, measurement of the color of the distillate, and measurement of distillate color of stability when heated. It has not been possible to set limits of acceptability for these tests, but a glycerine refiner using one or more of them and correlating laboratory results with experience in the refinery should be able to establish his own standards of quality. Now a division of Arthur D. Little Inc.     

Methodology for inferring kinetic parameters of diesel oil HDS reactions based on scarce experimental data

Nowadays environmental regulations of fossil fuels emissions impose stricter limits for contaminants such as sulfur, nitrogen and aromatics from middle distillate petroleum fractions. The most important process used in oil refineries to reach the required specifications is catalytic hydrogenation. A key issue to optimize these units is the availability of reliable kinetic models for this complex, tri-phase reaction. A detailed, phenomenological model of the reactor would demand an exceeding experimental effort for consistently estimating all the necessary kinetic and transport parameters. Thus, a simplified approach is generally used for routine assessment of new catalysts and/or new streams to be processed. Due to the difficulty of characterization of these streams, which are very complex mixtures of numerous species, most models are based on pseudo-components. This approach, however, does not allow for model generalization with respect to feed composition. This paper presents and discusses a new methodology for dealing with this problem. Conventional neural network (NN) training algorithms are used for inducing NNs to predict kinetic parameters of simplified models for the catalytic hydrodesulfurization (HDS) reaction, using macro properties of the feed as input. As in practice there are rarely enough experimental data to subsidize empirical learning algorithms, the paper proposes and describes an ad hoc methodology for artificially enlarging the initial scarce experimental data. Results from inferring kinetic parameters of the catalytic removal of sulfur using NNs, based on macro-properties of oil middle distillates, are presented and discussed.