RESIDUUM HYDROTREATING/APPLICATION OF LIQUID- SOLID CHROMATOGRAPHY FOR THE STUDY OF HYDROTREATED PRODUCTS.

Iraqi reduced crude (above 350^°C) was hydrotreated in a fixed-bed reactor with commercial Ni-Mo-alumina catalyst. Reaction temperature varied from 320 to 400^°C over liquid hourly space velocity ranging from 0.82 to 2.6 h^-1. Hydrogen pressure was kept constant throughout all the experiment at 6.1 MPa with hydrogen/ oil ratio about 30D NL/L. Asphaltenes were precipitated from the reduced crude and hydrotreated products with 15 parts of n-pentane (by volume) to 1 part of sample. Then, the deasphaltened products were fractionated by liquid- solid chromatography for saturates, aromatics and polar- aromatics separation. The kinetic study of aromatics and polar- aromatics hydrogenation indicates that these reactions are well correlated with a second-order kinetics. The rate constants of aromatics and polar-aromatics hydrogenation were calculated. Finally, the apparent activation energy (Ea), enthalpy of activation (▵H)^* and entropy (▵S)^* were calculated for hydrogenation of aromatics and polar-aromatics of reduced crude during hydrotreating.     

RESIDUUM HYDROTREATING APPLICATION OF IH AND QUANTITATIVE CARBON-13 NMR SPECTROSCOPY FOR THE STUDY OF HYDROTREATED PRODUCTS

ABSTRACT

Bai-Hassan reduced crude (350^°C + ) was hydrotreated in fixed bed reactor with commercial Ni-Mo-alumina catalyst. H and quantitative C NMR are used to derive statistical average structure parameters of feedstock and hydrotreated products. The main aromatic hydrocarbons (of type C_ar,H + C_ar,CH₃ + C_ar,n + C_ar,I) of hydrotreated products decreases by temperature, (at mild conditions) particularly at lower space velocity. The severe operating conditions increases the main aromatic hydrocarbons. An approximate inverse correlation is observed between the behaviour of saturated hydrocarbons and the aromatics of type C_ar,H + C_ar,CH₃ + C_ar,n + C_ar,I during hydrotreating process. Higher temperatures show an increase in the percentage of alkyl aromatics of type C_ar,alkFurthermore, the severe operating conditions promotes the formation of the alkyl aromatics with H_α(ArCH₃) while it decreases the alkyl aromatic having H₈ and H₈ The kinetic study of napthenes formation indicates that this reactin is well correlated with a first-order kinetics. The apparent activation energy lpar;E rpar;, enthalpy lpar;? H rpar;and entropy lpar;? s?lpar; of activation are 23.630 KJ mol 18.390 kJ mol ^-1 and -225.95 J mol^-1 k^-1 respectively.     

CATALYTIC HYDROTREATMENT OF PETROLEUM RESIDUE

ABSTRACT

Iraqi reduced crude (350°C+) with a sulfur content of 4.3 wt% and a total metal content (Ni+V) of 141 WPPM was n-heptane deasphalted at specified conditions. The deasphalted oil (97.2 wt% of original residue) contains 4.1 wt% of sulfur and 103 ppm of metal. The original reduced crude and deasphalted oil were hydrotreated on a commercial Ni-Mo-alumina catalyst presulfided at specified conditions in a laboratory trickle-bed reactor. The reaction temperatures varied from 300 to 420°C with the liquid hourly space velocity (LHSV) ranging from 0.37 to 2.6 h^?1. Hydrogen pressure was kept constant throughout the experiments at 6.1 MPa, with a hydrogen/oil ratio of about 300 NLL^?1 (normal liters of hydrogen per liter of feedstock). Analysis for sulfur, nickel, vanadium and n-pentane asphaltenes were carried out for hydrotreated products from both the original residue and the deasphalted oil. The comparison of the results obtained for the hydrotreatment of deasphalted oil and original reduced crude indicates that the removal of sulfur, nickel and vanadium was higher for the deasphalted oil than those obtained for the non-deasphalted residue over the entire range of conversion. The exclusion of extremely high molecular weight asphaltenes by n-heptane deasphalting seems to improve the access of oil into catalyst pores resulting in higher desulfurization and conversion of the lower molecular weight asphaltenes. The sulfur content of n-pentane precipitated asphaltenes remained unchaneed with LHSV for various temperature for hydrotreated products produced from both deasphalted oil and original reduced crude.     

THE IMPACT OF ASPHALTENES REMOVAL ON THE KINETICS OF RESIDUUM HYDROTREATING

ABSTRACT

Iraqi reduced crude (above 350°C) prepared in a laboratory distillation unit containing 15 trays was solvent deasphaltened at specified conditions using n-heptane as the precipitant Both the original and deasphaltened reduced crude was hydrotreated on a commercial Ni-Mo- alumina catalyst in a laboratory trickle bed reactor. This investigation was undertaken to understand the role of asphaltenes removal in the kinetics of the desulphurization, demetallization and deasphaltening processes. Kinetic analysis showed that the hydrotreating reactions of the deasphaltened reduced crude followed a first order kinetics. Rate constants calculated for the above reactions are higher than those obtained in the HDS process for the original full residuum.     

CHANGE IN COMPOSITION AND STRUCTURE OF REDUCED CRUDES DURING CONVERSION ON CONTACT MATERIAL

ABSTRACT

Four Chinese 350°C+ reduced crude feedstocks were heated thermally in the presence of a contact material at 480–540°C in a fixed bed reactor. The feed and products were fractionated into eight fractions using normal pentane precipitation and alumina adsorption chromatography and average molecular parameters calculated with a modified Brown-Ladner method. The results obtained show that the conversion of various fractions of the reduced crudes was quite different. The conversion of asphaltic substances was much higher than those of saturates and aromatics. It is shown that the CH₂/CH₃ ratio, aromaticity and the numbers of aromatic, naphthenic and total ring of heavy products were obviously lower than those of reduced crudes. The effect of temperature on metal, sulfur, nitrogen removal has been also investigated. The data indicate that the removal of weak polar non-porphyrin nickel was larger than that of middle and strong polar nickel complex.     

EFFECTS OF HYDROTREATING COKER LIGHT GAS OIL ON FUEL QUALITY

ABSTRACT

Coker light gas oil (LGO) derived from Athabasca bitumen was hydrotreated in a fixed bed reactor using two commercial NiO-MoO₃/Al₂0₃ catalysts. The effect of temperature on product quality was investigated in a pilot plant between 330 and 390 °C at 12.4 MPa, space velocity of 0.5 Ir1 and 700 liter of hydrogen per liter of coker LGO (L/L). The product quality was monitored by ^I3C NMR spectroscopy, elemental analysis, density and distillation techniques.

The data showed that coker LGO can be hydrotreated using nickel-molybdenum catalysts at 350 °C, 0.5 h¹, 12.4 MPa and 700 L/L to meet the diesel product specifications, namely, 0.5 wt % sulfur, 20% aromatics and cetane index of 40. The cetane index improvement and aromatic saturation, which are affected by thermodynamic equilibrium at temperature higher than 370?°C, could reach 29 and 86% respectively. The cetane improvement was attributed to aromatic saturation and hydrocracking with hydrogen consumption ranging from 215-340 L/L. The Ketjenfine KF-840 catalyst was found slightly better performance than Procatalyse HR-348 catalyst.     

Comparison of Different Power-law Kinetic Models for Hydrocracking of Asphaltenes

Abstract

Hydrotreating of Maya crude oil was carried out at a pilot plant scale under the following reaction conditions: pressure of 70–100 kg/cm², hydrogen-to-oil ratio of 5,000 ft³/bbl, temperature of 380°C–420°C, and space-velocity of 0.33–1.5 h^?1. Asphaltenes were precipitated from the feed and from all hydrotreated products using n-heptane as solvent. Hence, variations in asphaltenes concentration were obtained as a function of reaction conditions. Three different kinetic models were studied: a simple power-law model, a modified power-law model which assumes a parallel path reaction for asphaltenes hydrocracking with the same reaction order for more reactive and less reactive asphaltenes, and the same modified power-law model with different orders for both types of asphaltenes. This latter model exhibited the best fit of experimental asphaltenes concentrations.     

DELAYED COKING OF HYDROTREATED REDUCED CRUDE

ABSTRACT

A laboratory coking unit was designed and constructed for an experimental study of the delayed coking process of hydrotreated Kirkuk reduced crude. The yield and analysis of coke, gases and liquid products were obtained for each experiment. The gas < C₄. and gasoline yield decrease by increasing Liquid hourly space velocity (LHSV) while the yields of kerosene and gas oil increase and no effect of LHSV on petroleum coke yield was observed, The specific gravity of gasoline, kerosene and gas oil decreases by increasing LHSV. The increase in LHSV (decrease in residence time) decreases the olefinic hydrocarbons of produced gas oil and fraction 350-450^°C. Sulfur content of produced coke and coking residue increases by increasing residence time while it changes slightly for kerosene and gas oil. By increasing the recycle ratio (RR), the yield of gas decreases while the coke yield increases. Sulfur content of gas oil and coking residue increases with an increase in the recycle ratio while it decreases for coke. Metals content of coke decreases with an increase in the recycle ratio and coke with accepted properties for aluminum anode manufacture could be produced when a recycle ratio of 1.4 was used.     

The Improvement of the Quality of Raffinate Obtained from Solvent Extraction of Lubricating Oils

Abstract

Vacuum distillates of an Egyptian crude oil were subjected to solvent extraction process applying N-methyl-2-pyrrolidone (NMP) and furfural as dearomatization solvents. The study shows that the extraction solvent together with the temperature and solvent-to-oil ratio have a significant effect on the yield and quality of produced lubricating oils. The optimum temperature for extracting light waxy distillates with NMP is 55°C at the solvent-to-feed ratio 2:1. These conditions are appropriate to remove the major portion of aromatics from the raffinate. The apparent activation energy (Ea), enthalpy (ΔH*), entropy (ΔS*), and free energy of activation (ΔG*) were calculated for the solvent dearomatization process.     

Production of High-Grade Asphalt from Liaoshu Crude Oil

Abstract

The high viscous crude oil for Shuguang No. 1 zone of Liaohe oilfield has the characteristics of high density (ρ₂₀ = 0.9977 g.cm^?3), high viscidity (ν₁₀₀ = 1,223.9 mm².s^?1), and high solidifying point (SP = 48°C), which belongs to low sulfur naphthene-base crude oil. The comprehensive evaluations indicate that this oil has no gasoline fraction and the diesel oil is only 7.19%. In addition, the lubricating oil distillate is not suited to produce lubricating oil and heavy oil is not good feedstock for catalytic cracking. However, the low wax and high resin, as well as asphaltene content, make it an ideal raw material for producing paving asphalt. The vacuum residue of this crude acted as base oil and three kinds of waste oil with high aromatics and low wax content were selected as blenders. Various brands of high-grade paving asphalts meeting GB/T15180-94 (China) specification were produced by blending method. The blending effects were investigated and corresponding mathematics models were set up.     

Hydrogenation of aromatic compounds in the presence of dibenzothiophene over bimetallic catalysts containing mesoporous aluminosilicates

The hydrogenation of a mixture of naphthalene, tetralin, and toluene (a solution in n-heptane) in the presence of dibenzothiophene (150 and 400 ppm on a sulfur basis) over Pt-Pd catalysts containing Al-HMS mesoporous aluminosilicates has been studied. The catalyst supports contained 35 wt % Al-HMS and 65 wt % γ-Al₂O₃. The Pt and Pd loadings in the catalysts were 0.2 and 0.8 wt %, respectively. The process was carried out at 200–240°C, a pressure of 30 atm, and a weight hourly space velocity of 1.7 h^?1. It has been found that the catalyst based on Al-HMS with Si/Al = 10 exhibits the highest activity. Thus, in the hydrogenation of a model mixture containing 150 and 400 ppm of sulfur, the conversion of toluene at 240°C was 22.2 and 10.9 wt %, respectively. In the presence of this catalyst, the concentration of aromatic hydrocarbons in the hydrotreated diesel fraction decreased from 28.4 to 6.8 wt %, and the sulfur content decreased from 45 to 5 ppm.     

CONTRIBUTION TO THE SEPARATION OF ACIDIC COMPONENTS FROM COAL LIQUEFACTION OIL

ABSTRACT

The naphtha fractions of coal hydrogenation products (IBP-130^°C) were separated by successive extraction with potassium hydroxide solution. Basic oil was also separated from the residue. The extracted fractions were analyzed by H-NMR and FI mass spectroscopy. It is concluded that the consecutive extraction with dilute potassium hydroxide solution should be capable of fractional separation of acidic oil from coal oil and further separation of individual component may be done by increasing the consecutive extraction steps.     

An Orthogonal Method for Aromatization Reactions of Shenghua FCC Gasoline

Abstract

Using a confined fluidized bed reactor and aromatization catalysts (LBO-A and LBO-16), the aromatization performance of Shenghua fluid catalytic cracking (FCC) gasoline has been studied in an orthogonal method. The experimental results reveal that the optimum reaction condition for the light oil yield was reaction temperature 420°C, WHSV 40 h^?1, mass ratio catalyst to oil 4 and 75% LBO-A and 25% LBO-16; the optimum reaction condition for aromatics amount in the light oil was reaction temperature 420°C, WHSV 30 h^?1, mass ratio catalyst to oil 5 and 65% LBO-A and 35% LBO-16, the olefin content is remarkably reduced from about 54.7% to 12.8% and 8.7% (by mass), respectively, at the same time the reaction mechanism of aromatization reaction is put forward based on the experimental result.     

Effect of Severity on Hydrotreating of Demetallized Oil Monitored by 1H-NMR Spectroscopy

Abstract

A study on aromatic hydrogenation of demetallized oil has been carried out using a commercial catalyst under pilot plant reaction conditions similar to those found in industrial processes. The feedstock was contacted with the catalysts in a trickled bed reactor unit at 330°C, 350°C, and 370°C. A combination of physicochemical characterization of feed and products and ¹H-NMR spectra was used to monitor changes in the aromatic fractions caused by variation in reaction temperature. Analysis of the ¹H-NMR spectra, along with the quantitative variation in the areas of the resonance lines, showed that the diaromatics with relatively long alkyl changes present in the lightest distillation cuts of the products were highly hydrogenated. In contrast, smaller changes in aromaticity in the heaviest fractions were observed under the same conditions. A limit of about 2 wt% of the integrals corresponding to the diaromatic+ species suggests a thermodynamical limitation of hydrogenation under the studied reaction conditions.     

THE PROPERTIES OF WATER LAYERS ON COAL SURFACES

ABSTRACT

The results of programmed thermodesorption investigations of water from coal surfaces are presented and correlated with the measurements of water adsorption and desorption from the gaseous phase at a temperature of 20^°C. From the data obtained, the activation energies of water molecules were calculated and possible structures of water adsorbed layers on the coal surfaces were suggested. On the basis of the DTA curve, the water adsorption heat on the coal surfaces 20^°C was calculated and presented in the form of dependence on water adsorption value from the gaseous phase.     

FREE RADICALS FORMED IN HYDROTREATED COAL LIQUID AND INFLUENCE OF OXYGEN

ABSTRACT

The behavior of radicals formed in hydrotreated coal liquid with heat treatment and the influence of oxygen have been investigated by electron spin resonance (e.s.r.) spectroscopy. A set of e.s.r. spectral lines identified as phenalenyl radical appears from 50^°C as the oil is heated in argon atmosphere. The radical concentration is enhanced with temperature, reaches a maximum between 130 and 150^°C and then decreases at higher temperatures. The radical is very stable even at 200^°C for the sample hydrotreated under mild condition, whereas the radical in the sample treated under severe conditions disappears drastically from 150^°C. When oxygen is introduced in the oil, the radical is converted into semiquinone and/or aryloxy radicals and stable molecules. The treatment in the presence of oxygen at higher temperatures is considered to accompany the formation of other aryloxy radicals by the reaction of aromatic hydrocarbons and oxygen.     

EFFECT OF PREHYDROGENATION ON HYDROCONVERSION OF MAYA RESIDUUM,PART II: HYDROGEN INCORPORATION

ABSTRACT

Maya 650° F residuum (Maya AR) was prehydrogenated over a standard hydroprocessing catalyst. The 650°F residuum of this product lpar;HMaya ARrpar; and Maya AR were then separately hydroprocessed further at selected conditions. The products were examined by elemental, ¹H, and ¹³C NMR analyses to determine the how hydrogen was incorporated during processing.

For all processing steps, hydrogen was incorporated in capping fragments formed during cracking reactions, as well as in hydrogenation reactions, heteroatom removal, and hydrocarbon gas formation, but the distribution of the hydrogen was dependent upon the type and severity of the process: For the direct hydroconversion of Maya AR, 25 to 30% of the total hydrogen was incorporated for heteroatom removal and hydrocarbon gas formation. The remaining hydrogen was incorporated in hydrogenation and cracking reactions.

For the two-step hydroconversion process, 30 to 40% of the total hydrogen was incorporated for heteroatom removal and hydrocarbon gas formation. The remaining was primarily incorporated in hydrogenation reactions. Some was incorporated into cracking reactions in the moderate severity case, but almost none was seen in the low severity case.

The hydrogen incorporation during each specific processing step is discussed, along with an evaluation of the prehydrogenation step a residuum conversion process option. These results will be also compared to previously reported hydrogen incorporation measurements on other feeds and processing methods.     

THERMAL EFFECT ON THE PERMANENT VISCOSITY OF A SASKATCHEWAN HEAVY OIL

ABSTRACT

Future energy demands will likely cause increased activity towards the recovery of heavy oil using non-conventional means. Most non-conventional attempts to recover Saskatchewan's heavy oil resources have utilized thermal techniques.

This report discusses the permanent viscosity changes which occur when heavy oil.is subjected to thermal processes from 220 to 425°C. It was observed that under closed operating conditions, the oil viscosity drops in a manner which can be modeled by a first order, kinetic reaction model. The rate constant for this reaction varied from 0.3 × 10^?3 to 6.0 × 10^?3 h^?1 depending on temperature and the assumed molecular weights of the model components. These findings closely parallel earlier results.

Experimental observations on thermal effects during opened operating conditions indicate a dramatic and rapid rise In the remaining crude oil viscosity. The oil was observed to increase its permanent absolute viscosity by a factor as high as 21 times its original absolute viscosity. The single product, first order kinetic model was not capable of predicting this rise in oil viscosity. A simple, two product, first order kinetic model was developed and found to fit the data satisfactorily with a rate constant of 0.6 h^?1 for heavy product formation and a rate constant of 0.03?h^?1 for light product formation at 275°C.     

Hydrogenation of aromatic hydrocarbons in the presence of dibenzothiophene over platinum-palladium catalysts based on Al-SBA-15 aluminosilicates

The hydrogenation of a 2-methylnaphthalene solution in n-heptane in the presence of dibenzothiophene (400 ppm in terms of sulfur) over Pt-Pd catalysts containing Al-SBA-15 mesoporous aluminosilicates has been studied. Supports for the catalysts contained 35 wt % Al-SBA-15 and 65 wt % γ-Al₂O₃. The Pt and Pd contents of the catalysts was 0.25 and 1.0 wt %, respectively. Experiments with the model feedstock were conducted in an autoclave at 240–260°C, an initial hydrogen pressure of 30 atm, and a substrate/metal weight ratio of 30. It has been found that a catalyst based on Al-SBA-15 with Si/Al = 5 exhibits the highest activity under poisoning with 400 ppm sulfur. Thus, the conversion of 2-methylnaphthalene at 260°C after 3 h was 85% with the selectivity for methyltetralins of 97%. The dearomatization of a hydrotreated diesel fraction with 45 ppm sulfur at 260°C at a pressure of 30 atm and a space velocity of 2.4 h^?1 has made it possible to decrease the total aromatic content, in particular reduce the concentration of polycyclic aromatic compounds to a level of less than 1 wt %.     

RAPID PYROLYSIS OF EASTERN CANADIAN COALS BY FREE FALL REACTORS

Abstract

The effect of temperature was investigated on the rapid pyrolysis of Prince, Lingan and No. 26 coals in the temperature range of 525^° to 750^°C using a 600 cm high stainless-steel free fall reactor at atmospheric pressure.

The yields of char, condensibles and gaseous products were determined at 25^°C intervals. Gaseous products were analysed for H₂, CO, CO₂, CH₄ and C₂+.

Volatile product (condensible and gas) yields exceeded the volatile product in the A.S.T.M. methods at and above 700^°C.

Some experiments using Prince coal were repeated at reduced pressure (50 mm mercury) in both the 600 cm height stainless-steel and a 140 cm height quartz reactor in order to find out the effect of pressure and retention time.

The experimental results indicated that the condensable yield was higher at the lower pressure and at the shorter retention time. The effect of retention time was far more pronounced.