High quality diesel by hydrotreating of atmospheric gas oil/light cycle oil blends

An improved process for high-quality diesel fuel production by hydrotreating atmospheric gas oil (SRGO) and light cycle oil (LCO) blends is presented in this paper. For this purpose, a set of blends of 5, 10 and 15% by volume of LCO with final boiling points of 300, 325 and 350 °C with a full range gas oil (FBP 350 °C) was hydrotreated in a pilot plant at 340-380 °C, 5.4 MPa, 2.5 h⁻¹ LHSV using a commercial Co-Mo catalyst. A relationship between the concentration of refractory sulfur compounds (those boiling above 316 °C) and aromatics content in the feedstock with the hydrotreating temperature required for meeting a 0.05% sulfur specification was found.The experimental data obtained during the desulfurization was quantitatively represented by a 1.50 to 1.56 order rate equation, with activation energies between 18.9 and 34.1 kcal/mol, depending on the feedstock.     

Hydrotreating of straight run gas oil–light cycle oil blends

A pilot plant study was conducted to evaluate the effect of up to 50 vol% light cycle oil (LCO) on product quality when it is used together with straight run gas oil (SRGO) as a hydrotreating feedstock. Experiments were carried out at reaction pressures of 54, 70 and 90 kg/cm²; reaction temperatures of 350, 360, 370 and 380°C, liquid hourly space velocity (LHSV) of 1.0, 1.5 and 2.0 h⁻¹, and constant hydrogen-to-oil ratio of 2000 ft³/bbl, over a commercial Co–Mo/γ-Al₂O₃ catalyst. The experimental results were used to determine apparent reaction orders and activation energies, which agree with those reported in the literature.     

Storage stability of FCC light cycle oil

This work deals with an evaluating of the storage stability of light cycle oil (LCO) which is produced by a fluid catalytic cracking technology. The LCO was aged according to two methods ASTM D2274 and ASTM D4625. The first test simulates an intensive oxidation stress and the second method is suitable for a long-time storage stability testing. The acid number, the iodine number, the carbon residue and the insolubles amount were chosen as parameters for the evaluation of the stability in both tests. Only the insolubles amount and the carbon residue varied (increased) during both tests. Four types of antioxidants were used as the oxidation inhibitors but no distinct effect on the oxidation stability of the LCO was observed.     

Combustion characteristics of droplets composed of light cycle oil and diesel light oil in a hot-air chamber☆

Development of gas turbines fueled with light cycle oil (LCO) and oil mixture of LCO and diesel light oil (LO) requires an understanding of the droplet burning and vaporization characteristics of those oils. The present study is devoted to comparing the burning characteristics of isolated fuel droplets composed of an LCO and an LO. The tests were conducted in an atmospheric hot-air chamber preset at 1173 K, and the examined LCO had a lower cetane number but higher volatility and aromatics content compared to LO. It was demonstrated that the burning of the LCO droplet was sootier, while that of the LO droplet was more disruptive. At the tested temperature, coke formation was indistinct for both the oils, whereas slightly higher ignition delay time was shown for the LO droplet. The microexplosive burning more or less complicated the time-series droplet size d, an explicit burning rate constant, however, was still definable according to the d²-law to show the overall regression speed of the droplet surface area d² with burning time t. The rate constant exhibited little difference for smaller LCO and LO droplets but was greater for LO when the droplet was larger. The rate constant also gradually increased with increasing the initial droplet diameter d₀, which caused the relative size d/d₀ to be unified (normalized) into a single curve by a burning time t/d₀ⁿ (1.0<n<2.0). Analysis revealed that this unification resulted from the respective overlaps of the unsteady and quasi-steady burning phases for differently sized droplets. Further, it was clarified that the unification and analysis are generally valid to isolated liquid fuel droplet burning in hot ambiences.     

An approach to the deep hydrodesulfurization of light cycle oil

Deep HDS of LCO to be <10 ppm was achieved by fractionating HDS. An LCO fraction having boiling point lower than 340 °C was easily hydrodesulfurized to be <10 ppmS under conventional HDS conditions because the hydrodesulfurization of the reactive sulfur species contained in the fraction was hardly inhibited by the aromatic compounds. In contrast, the heavier fraction was very hard to be hydrodesulfurized since its refractory sulfur species were strongly inhibited by large content of aromatic components. Dilution of the heavier fraction with common solvents showed higher reactivity over NiMo/Al₂O₃ catalyst than itself alone. Decalin, which showed the highest dilution effect, was believed to strip the strongly adsorbed aromatics off from the catalyst surface.     

Separation of aromatic components from light cycle oil by solvent extraction

To improve the versatility of light cycle oil (LCO), separation of aromatic compounds from LCO by solvent extraction was investigated. LCO was analyzed to identify 35 components: 19 aromatics and 16 alkanes. The batch liquid–liquid equilibrium extraction of LCO was performed using furfural, sulfolane, and methanol as extraction solvents. In each solvent, the aromatics present in LCO were selectively extracted relative to the alkanes. The separation selectivities of aromatics relative to alkanes were larger in sulfolane than in the other solvents. Among the aromatic components, di- and tricyclic compounds were selectively extracted relative to the monocyclic ones.     

Oxidative desulphurization of light cycle oil: Monitoring by FTIR spectroscopy

Oxidative desulphurization received attention as an alternative or an additional technology for deep fuel desulphurization. We studied oxidative desulphurization as an approach to remove sulphur organic compounds in light cycle oil. By FTIR spectroscopy appropriate conditions for oxidation have been experimentally identified as up to 90% of the sulfur compounds in LCO were removed. This spectroscopic technique allowed sulphones quantification by 1302 cm^? 1 band interpretation. Inasmuch sulphones have higher polarity than the parent sulphide molecules they are preferentially extracted from the feedstock. FTIR analysis permits to estimate degree of the sulphur compounds oxidation, degree of desulphurization by extraction method and to register micro quantity of oxidized products.     

劣质催化柴油中多环芳烃选择加氢工艺评价

选取商品柴油加氢精制催化剂和催化柴油选择加氢裂化催化剂,采用N_2吸附-脱附、XRD、TPD、Py-IR等对催化剂进行表征,结果表明,选择加氢裂化催化剂较加氢精制催化剂具有更大的比表面积和孔容,具有更多的中强酸量和较少的弱酸量,并具有更多的B酸中心。以中石化青岛炼化公司生产的高密度、低十六烷值的FCC柴油为原料,对商品加氢精制催化剂和加氢精制/选择加氢裂化组合催化剂进行FCC柴油中多环芳烃选择加氢工艺条件的考察,结果表明,加氢精制催化剂适宜的反应条件为370℃、1.25 h~(-1)、8.0 Mpa,加氢精制/选择加氢裂化催化剂适宜的反应条件为350℃、1.25 h~(-1)、8.0 MPa,组合催化剂的多环芳烃选择加氢效果较好。     

MCM-41-supported Co-Mo catalysts for deep hydrodesulfurization of light cycle oil

Light cycle oil (LCO), a by-product of the fluid catalytic cracking (FCC) process in a petroleum refinery, can be used as a blendstock for the production of diesel and jet fuels. Regulatory and operational issues result in need for new and more active catalysts for the deep hydrodesulfurization (HDS) of diesel feedstocks, such as LCO. This paper reports the activity of a mesoporous molecular sieve MCM-41-supported Co-Mo catalyst in comparison to a commercial γ-alumina (Al₂O₃)-supported Co-Mo catalyst for the desulfurization of a LCO with a sulfur content of 2.19 wt.%. The HDS of dibenzothiophene, 4-methyldibenzothiophene, and 4,6-dimethyldibenzothiophene—polyaromatic sulfur compounds present in LCO—and their relative reactivities in terms of conversion were examined as a function of time on stream in a fixed-bed flow reactor. The MCM-41-supported catalyst demonstrates consistently higher activity for the HDS of the refractory dibenzothiophenic sulfur compounds, particularly 4,6-dimethyldibenzothiophene. The presence of a large concentration of aromatics in LCO appears to inhibit the HDS of the substituted dibenzothiophenes.     

Nitrogen compounds characterization in atmospheric gas oil and light cycle oil from a blend of Mexican crudes

The distribution of basic and non-basic nitrogen compounds along the distillation curves of the middle distillates atmospheric gas oil (AGO) and light cycle oil (LCO), used as feedstocks for diesel fuel production, is presented in this paper. For this purpose, the total and basic nitrogen content of true boiling point distillation fractions of AGO and LCO were obtained, followed by nitrogen compounds identification by a GC-MS technique. The ratio of quinoline, indole and carbazole derivatives was determined as 1/0.75/2.5 in AGO. In LCO, a 1/2.3/12.2 ratio of aniline, indole and carbazole derivatives was found. A complete physical and chemical characterization of both AGO and LCO is also presented.     

Kinetic modeling of the hydrotreatment of light cycle oil and heavy gas oil using the structural contributions approach

The kinetics of the hydrodesulfurization of light cycle oil (LCO) and heavy gas oil (HGO) over a CoMo/Al₂O₃ catalyst were investigated in a perfectly mixed flow reactor with stationary basket of the Robinson-Mahoney type at temperatures of 330, 310 and 290 °C, H₂/HC molar ratios of 2.8, 3.6 and 7.2 and a pressure of 65 bar. Hougen-Watson type rate equations were derived for the conversion of dibenzothiophene, substituted (di)benzothiophene and their products. To avoid having to deal with a huge number of model parameters, a methodology based upon structural contributions was applied. In the absence of own kinetic data on key components a number of kinetic and adsorption parameters were taken from published work on a very similar catalyst. For a given value of H₂/HC only a small number of experiments was required to determine the value of the very complex denominators DEN_σ and DEN_τ appearing in the rate equations for the hydrodesulfurization of LCO and of HGO and of their evolution with the conversion of the feedstock. With the rate equations constructed in this way the calculated total conversion of DBT, its conversion into biphenyl and into cyclohexylbenzene were in excellent agreement with the experimental values.     

Inhibition of nitrogen compounds on the hydrodesulfurization of substituted dibenzothiophenes in light cycle oil

The influence of nitrogen compounds on the hydrodesulfurization (HDS) activities of a series of substituted dibenzothiophenes in light cycle oil (LCO) was studied over a NiMo/Al₂O₃ commercial catalyst. Three types of light cycle oil with nitrogen compounds of different concentrations and chemical natures were used as feed—an original fluid catalytic cracking light cycle oil (LCO), LCO with most of its basic nitrogen removed, and an ultra-low nitrogen LCO. Experiments were conducted in a fixed-bed microreactor at a total pressure of 70 atm, temperatures between 330 and 400 °C, and liquid hourly space velocities (LHSV) in the range of 1.0 to 3.5 h⁻¹. The inhibition effects of nitrogen compounds on the HDS reactivity of the three sulfur groups—total sulfur, hard sulfur, easy sulfur—and 14 specific mono-, di- and tri-alkyl substituted dibenzothiophenes were investigated. The results showed that the HDS rate significantly increased using ultra-low nitrogen LCO. Pseudo first-order rate constants were estimated for the 14 mono-, di- and tri-alkyl substituted dibenzothiophenes. The HDS rates could be classified into three groups based on the position of the substituents. It was found that 4 and 6 substituted dibenzothiophenes had the lowest HDS rates. The HDS rate of the 14 substituted dibenzothiophenes were all increased when the ultra-low nitrogen feed was used. The improvement was greater for 4 and 6 substituted dibenzothiophenes than for those with one of the substituents at either the 4 or 6 positions. This finding indicates that the hydrogenation route is more strongly suppressed than hydrogenolysis route by nitrogen compounds since the hydrogenation route is believed to be the predominant reaction pathway for 4 and 6 alkyl-substituted dibenzothiophenes.     

Studies on oil distribution in polymer blends

Oils and resins are widely used in rubber industries to improve or control the mechanical properties, viscoelastic behavior, processability, and tackiness of a rubber compound. Very few fundamental studies have been reported on the function and the mechanism of oils and resins in a rubber mixture. In this article oil or resin distribution to each phase in an immiscible binary elastomer blend was studied by measuring the change of thermodynamical parameters, such as glass transition temperature, melting point of crystallines, and heat at melt of each polymer component. Several independent approaches give consistent results. It was found that aromatic oil was favorably distributed to the polystyrene-butadiene (SBR) phase of an SBR/natural rubber (NR) blend. Similarly, unequal distribution of resin in a blend was observed for a natural resin (rosin) and a petroleum resin. © 1996 John Wiley & Sons, Inc.     

Hydrotreating of light cycle oil using WNi catalysts containing hydrothermally and chemically treated zeolite Y

One W–Ni catalyst supported on hydrothermally treated zeolite Y and two W–Ni catalysts supported on chemically treated zeolite Y were prepared. The catalysts were characterized by NH₃-TPD, pyridine-IR, TEM, BET, and XPS. Their performance of hydrodesulfurization, hydrodenitrogenation, and hydrodearomatization were compared using light cycle oil (LCO) as the feed. The results showed that the hydrothermal treatment promotes HDS activity whereas the chemical approach favours the HDA activity. The HDN activity of the three catalysts was similar. Addition of zeolite Y with high proportion of Brønsted acidity in the catalysts helps to enhance the hydrodearomatization activity.     

Quality characteristics of edible vegetable oil blends

Two edible oil blends, namely groundnut oil:rice-bran oil and mustard oil:rice-bran oil, were prepared in different proportions and stored for a period of three years. Their physicochemical characteristics were determined. The results agreed with expected values except for free fatty acid percents and butyrorefrac-tometer readings, presumably due to rancidity. Fatty acid compositions of the blends were determined and ratios of characteristic fatty acids, like lignoceric to palmitic for groundnut oil:rice-bran oil blends, and erucic to palmitic for mustard oil:rice-bran oil blends, were calculated to identify individual oils in the blend.     

硅油粘度对ABS／硅油混合物性能的影响

通过硅油粘度对ABS／硅油混合物性能的影响进行比较深入的研究,从而最终确定了制作门内基板、门立柱等轿车内装件用ABS／硅油混合物专用料所使用的硅油粘度范围。     

Oxidative stability of blends and interesterified blends of soybean oil and palm olein

Improvement of oxidative stability of soybean oil by blending with a more stable oil was investigated. Autoxidation of blends and interesterified blends (9∶1, 8∶2, 7∶3 and 1∶1, w/w) of soybean oil and palm olein was studied with respect to fatty acid composition, fatty acid location and triacylglycerol composition. Rates of formation of triacylglycerol hydroproxides, peroxide value and volatiles were evaluated. The fatty acid composition of soybean oil was changed by blending. Linolenic and linoleic acids decreased and oleic acid increased. The triacylglycerol composition of blends and interesterified blends was different from that of soybean oil. Relative to soybean oil, LnLL, LLL, LLO, LLP, LOO and LLS triacylglycerols were lowered and POO, POP and PLP were higher in blends and interesterified blends (where Ln, L, O, P and S represent linolenic, linoleic, oleic, palmitic and stearic acids, respectively). Interesterification of the blends leads to a decrease in POO and POP and an increase in LOP. Linoleic acid concentration at triacylglycerol carbon-2 was decreased by blending and interesterification. Rates of change for peroxide value and oxidation product formation confirmed the improvement of soybean oil stability by blending and interesterification. But, blends were more stable than interesterified blends. Also, the formation of hexanal, the major volatile of linoleate hydroperoxides of soybean oil, was decreased by blending and interesterification.     

Semiquantitative analysis of thiophenic compounds in light cycle oil (LCO) using C NMR spectroscopy

S-methyltetrafluoroborate salts of the thiophenic compounds (CH₃-S⁺:BF₄⁻) present in LCO petroleum fractions were obtained and analyzed by ¹H and ¹³C NMR spectroscopy. The methylation of the samples was carried out using 99.5% ¹³C enriched methyl iodine, to improve the sensitivity of the technique. The amount of the methylated derivatives was determined by the internal standard method; using dioxane as a reference, 37 sulphur compounds were detected. Among them, benzo[b]thiophene, dibenzo[b,d]thiophene, and several isomers of methyl, dimethyl and trimethyl[b]benzothiophenes were the most abundant. With this research, it was demonstrated that NMR spectroscopy can be used to analyze thiophenic compounds from petroleum medium fractions.     

Physical-chemical properties of waste cooking oil biodiesel and castor oil biodiesel blends

This work presents the physical-chemical properties of fuel blends of waste cooking oil biodiesel or castor oil biodiesel with diesel oil. The properties evaluated were fuel density, kinematic viscosity, cetane index, distillation temperatures, and sulfur content, measured according to standard test methods. The results were analyzed based on present specifications for biodiesel fuel in Brazil, Europe, and USA. Fuel density and viscosity were increased with increasing biodiesel concentration, while fuel sulfur content was reduced. Cetane index is decreased with high biodiesel content in diesel oil. The biodiesel blends distillation temperatures T₁₀ and T₅₀ are higher than those of diesel oil, while the distillation temperature T₉₀ is lower. A brief discussion on the possible effects of fuel property variation with biodiesel concentration on engine performance and exhaust emissions is presented. The maximum biodiesel concentration in diesel oil that meets the required characteristics for internal combustion engine application is evaluated, based on the results obtained.     

Chemical and sensory characteristics of stored menhaden oil/ soybean oil blends

The purpose of this study was to determine the feasibility of increasing the consumption of dietary ω-3 fatty acids by incorporating menhaden oil into a French-type salad dressing. Menhaden/soybean oil blends of 10, 20 and 30% menhaden oil (w/w) were used to prepare an emulsified French salad dressing. The oil blends and salad dressings were stored at 22°C in the dark for 20 wk. The fatty acid profile, peroxide value, and anisidine value were determined. The salad dressings also were evaluated by a sensory panel for flavor, aroma, and aftertaste. The ω-3 fatty acids were stable over time under these storage conditions. Peroxide values rose slowly and consistently over time reaching higher values when more menhaden oil was added. Peroxide values were also higher in the oil blends which were stored with air in the headspace and not flushed with argon. Anisidine values also were higher with each addition of menhaden oil but did not change over time except for the 100% menhaden oil which was stored in air. After eight weeks the sensory panel rated the salad dressing which contained menhaden oil as lower than the ones which did not contain menhaden oil. While a significant amount of ω-3 fatty acids may be incorporated into foods by the addition of menhaden oil, the development over time of off-flavors must be controlled.