Petroleum Heavy Oil Research Articles

Atmospheric Residue Desulfurization Process for Residual Oil Upgrading: An Investigation of the Effect of Catalyst Type and Operating Severity on Product Oil Quality

Atmospheric residue desulfurization (ARDS) process is extensively used in upgrading of heavy petroleum oils and residues to more valuable clean environmentally friendly transportation fuels and to partially convert the residues to produce low-sulfur fuel oil and hydrotreated feedstocks. Graded catalyst systems in multiple reactors are used in the process in order to achieve hydrodesulfurization (HDS), hydrodemetallization (HDM), hydrodenitrogenation (HDN), and conversion of residues to distillates at desired levels. The characteristics of the feedstocks processed in different reactors are significantly different. The quality of the feed entering the second reactor is strongly dependent on the operating severity in the first reactor and can have an important impact on the performance of the catalysts in the following reactor with regard to various conversions and deactivation rate. In the present work, a systematic study was conducted on the effect of two industrial catalyst types, namely, MoO3/Al2O3 (HDM)...

03/02156 Hydrocarbon recovery from heavy petroleum reservoirs and oil sand deposits by combined steamflood-solventflood with decreasing steam or water-solvent ratio: Nasr, T. N. U.S. Pat. Appl. Publ. US 2003 62,159 (Cl. 166–272.1; E211343/24), 3 Apr 2003, Appl. 934,963

03/02156 Hydrocarbon recovery from heavy petroleum reservoirs and oil sand deposits by combined steamflood-solventflood with decreasing steam or water-solvent ratio: Nasr, T. N. U.S. Pat. Appl. Publ. US 2003 62,159 (Cl. 166–272.1; E211343/24), 3 Apr 2003, Appl. 934,963

Residual-Oil Hydrotreating Kinetics for Graded Catalyst Systems: Effect of Original and Treated Feedstocks

In the upgrading of heavy petroleum oils and residues by hydrotreatment, multiple-reactor fixed-bed units loaded with different types of catalysts are used extensively. Catalysts for such hydrotreatment processes are chosen on the basis of activity, selectivity, and life. The performance of the overall hydrotreatment process, with regard to various reactions, such as hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM), asphaltenes cracking (HDAsph), and conversion to distillates, as well as catalyst life-on-stream, are clearly linked to the performance of the catalyst in different reactors. Information regarding the activity, selectivity, kinetic parameters, and deactivation of the individual catalysts are, therefore, highly desirable for optimizing reactor loading in the multiple-catalyst system. This paper presents the performance tests for various reactions on two types of industrial hydrotreating catalysts: those used at the midsection and the tail-end of a graded catalyst system designed to hydrotreat atmospheric residual oils. The tests were conducted using straight-run Kuwait atmospheric residue, a demetallized residue, and a demetallized/desulfurized residue. The activity and kinetic parameters for different reactions that are typically occurring during the hydroprocessing of these feedstocks were determined. The results revealed significant changes in activity, depending on the feedstock used for the tests. Furthermore, apparent rate orders and rate constants for some reactions were significantly changed. The study demonstrates the importance of proper selection of the feedstocks used in the performance evaluation and screening of candidate catalysts for graded catalyst systems for residual-oil hydrotreatment.

A Comparative Study of the Effect of Catalyst Type on Hydrotreating Kinetics of Kuwaiti Atmospheric Residue

In the upgrading of heavy petroleum oils and residues by hydrotreating, multiple-reactor fixed-bed units loaded with different types of catalysts are extensively used. Catalysts for such hydrotreating processes are chosen on the basis of activity, selectivity, and life. The performance of the overall hydrotreating process with regard to various reactions, such as hydrodemetallation (HDM), hydrodesulfurization (HDS), hydrodenitrogenation (HDN), asphaltenes cracking (HDAsph), and conversion to distillate and catalyst life-on-stream, is clearly linked to the performance of the catalyst in different reactors. Information regarding the activity, selectivity, kinetics parameters, and deactivation of the individual catalysts are, therefore, highly desirable for optimizing reactor loading in a multiple catalyst system. In the present work, a comparative study was conducted on the kinetics of various reactions such as HDS, HDV, HDNi, HDN, CCR reduction, and asphaltenes conversion in hydrotreating Kuwaiti atmospher...

99/03015 The selective oxidation of phenol-formaldehyde resins as a model in the speciation of organic sulfur forms in coals and petroleum heavy oils v

99/03015 The selective oxidation of phenol-formaldehyde resins as a model in the speciation of organic sulfur forms in coals and petroleum heavy oils v

Effect of Solvents on the Liquid-Phase Cracking of Thermosetting Resins

The effect of solvents on the liquid-phase cracking of thermosetting resins was examined in the presence of tetralin (hydrogen-donor solvent), decalin (nondonor solvent), or petroleum heavy oil with a reaction time of 60 min at 430−450 °C in a 200-mL autoclave under 2 MPa of initial nitrogen atmosphere. Epoxy and novolak-type phenol resins, as typical thermosetting resins, showed almost 100 wt % conversion and about an 85 wt % yield of distillable oil when an iron oxide−sulfur catalyst and tetralin solvent were used. With decalin, the oil yield from epoxy resin decreased to 75 wt %; however, the phenol resin gave an extremely low conversion of 30 wt % with an oil yield of 25 wt %. Cracking of a resol-type phenol resin gave only 9 wt % conversion with decalin but increased to 99 wt % with tetralin. ABS and urethane resin also showed high conversions of more than 90 wt % and oil yields of 60−90 wt % with tetralin. In all experimental runs, gas yields were very low at 1−3 wt %, except for the case of urethan...

Hydrocracking of Heavy Petroleum Oils over Transition Metal-loaded Y-Type Zeolites.

Hydrocracking of petroleum heavy oils using transition metal-loaded zeolite catalyst was examined. Deasphalted oil (DAO) derived from vacuum residue of a mixture of Arabian light and medium crudes was successfully converted to gasoline fraction, attaining yield of more than 70%, using palladium and nickel co-loaded Y-type zeolite catalyst, at 350°C for 1h, in H2 pressurized to 4.9MPa. The mechanism of this hydrocracking process is discussed briefly. The authors also tried hydrocracking of fraction heavier than DAO, i.e. maltene, this affording gaseous products (C2-C4) and gasoline fraction, 35% and 52%, respectively, under the following conditions: 400°C, for 3h, in H2 pressurized to 6.9MPa, over the same catalyst.

Free radical behavior in thermal cracking reaction using petroleum heavy oil and model compounds

Thermal cracking mechanism of heavy oil, especially an effect of hydrogen partial pressure was investigated in the thermal cracking reaction using model compounds and Kuwait Vacuum Residue (KW-VR). Free radical recombination was not affected by the change of hydrogen partial pressure.

98/01103 Pyrolysis treatment of hydrocarbon sources such as petroleum heavy oils and naphtha using sensible heat of rough coke oven gas: Ueno, I. Jpn. Kokai Tokkyo Koho JP 09,286,986 [97,286,986] (Cl. C10B27/00), 4 Nov 1997, Appl. 96/102,571, 24 Apr 1996, 4 pp. (in Japanese)

Fischer–Tropsch synthesis seems to develop the following two consecutive paths: a primary process that involves the formation of α-olefin products and a secondary process leading to the production of branched isomers and paraffins and requiring the readsorption of primary α-olefin products. It was already shown by Iglesiaet al.(E. Iglesia, S. C. Reyes, and R. J. Madon,J. Catal.129, 238 (1991)) that such readsorption steps are of fundamental importance for Ru catalysts and that they occur due to the slow diffusive removal of α-olefins when the molecular size increases, this resulting in a long intraparticle residence time. In the present paper α-olefins readsorption was enhanced by changing the metal distribution inside the pores of a titanium silicate (ETS-10), modified by ion exchange with alkali metal ions, used as a support for Ru-based catalysts.

98/00183 Pyrolysis treatment of hydrocarbon sources such as petroleum heavy oils and naphtha using sensible heat of rough coke oven gas

98/00183 Pyrolysis treatment of hydrocarbon sources such as petroleum heavy oils and naphtha using sensible heat of rough coke oven gas

97/01728 Effect of co-hydrogenation of petroleum heavy oil and coal on heavy oil properties

97/01728 Effect of co-hydrogenation of petroleum heavy oil and coal on heavy oil properties

97/00136 Effect of co-hydrogenation of petroleum heavy oil and coal on heavy oil properties

97/00136 Effect of co-hydrogenation of petroleum heavy oil and coal on heavy oil properties

97/00153 Effect of co-hydrogenation of petroleum heavy oil and coal on heavy oil properties

97/00153 Effect of co-hydrogenation of petroleum heavy oil and coal on heavy oil properties

95/05698 Manufacture of needle coke by delayed coking of petroleum heavy oils

95/05698 Manufacture of needle coke by delayed coking of petroleum heavy oils

Toxicities in waterfowl

Waterfowl populations may serve as sentinel species for natural and man-made toxicological problems in the environment. Many toxins cause nonspecific clinical signs, acute mortality, and subtle or no pathological changes, which make toxicological investigations extremely difficult. The purpose of this report is to review the most common toxins causing problems in waterfowl populations, including heavy metals, pesticides, botulism, mycotoxins, algal toxins, and petroleum oil. Where applicable, clinical signs, diagnosis, pathology, and treatment will be discussed. Although most of the information in the literature is based on wild waterfowl populations or experimental toxicological investigations, the information is also applicable to captively managed waterfowl population.

Structural Analysis of Petroleum Deasphalted Oils and Their Thermal Cracking Properties.

To provide an insight into the relation between structural characteristics of petroleum heavy oils and their thermal cracking properties, structural analysis of three kinds of deasphalted oils (DAO) by chromatographic separation, followed by 1H and 13C NMR and Curie-point pyrolysis of the oils and their fractions (S: saturates, A: aromatics, and P: polar compounds), was carried out. The oils employed were prepared from the vacuum residues of two Indonesian crudes (Minas and Duri) and an Arabian mixture (AL/AM) using pentane as solvent. The results of structural analysis suggested that aliphatic portion of Minas and Duri-DAO consisted mainly of straight paraffins, whereas a considerable portion of AL/AM-DAO consisted of naphthenic structures. The Curie-point pyrolysis at 670°C indicated that, irrespective of the oils, the amount of coke from their fractions decreased following the order P>A>S. It was also found that the coke formation from each P or A fraction could be suppressed by adding the saturate fraction, AL/AM-DAO-S, whereas in the case of using Minas- or Duri-DAO-S, no effect of the addition was observed. These results suggest a possibility that unique properties of AL/AM-DAO-S observed may be due to the presence of a considerable amount of active hydrogen in the naphthenic components.

石油系重質油を溶媒とする石炭液化反応（Ｉ）

石油系重質油を溶媒とする石炭液化反応（Ｉ）

Hydrocracking catalysts for heavy petroleum oils

The influence of the gel composition on the dimensions of AIPO4-5 crystals formed in the system Al2O3:P2O5:(C2H5)3N:H2O:H2SO4 has been studied systematically. A linear correlation between the water content of the reacting gel and both the maximum length and the aspect ratio of the crystals has been found, whereas amine as well as P2O5 contents are controlling the nucleation process. Crystals with sizes ranging from 20 μm to about 750 μm along the hexagonal c-axis can be synthesized with good yields when these correlations are used.

Inhibiting abilities of hydroaromatics against deterioration of hydrocarbon products. Part 2. Application to rubbers and plastics

The inhibiting abilities of hydroaromatics due to hydrogen donation were applied to the deterioration of rubbers and plastics. Heavy hydroaromatics from petroleum (HHAP) were produced by hydrogenating the highly aromatic oil fractions derived from petroleum heavy oil by thermal treatment and distillation to meet the requirements (especially low volatility) for additives to rubbers and plastics. First, the inhibiting ability of HHAP due to its hydrogen donation was examined, and excellent results were obtained. Tests were then conducted on natural rubber (NR) and styrene-butadiene rubber (SBR) after the addition of 2 wt% and 5 wt% of HHAP. It was found that the addition of HHAP was very effective in inhibiting the deterioration of NR, exceeding the effect of the conventional inhibitor IPPD (phenylisopropyl- p-phenylenediamine). Furthermore, low contamination was observed by adding HHAP, in addition to other effects such as lowering Mooney viscosities and improving bending properties. Next, HHAP was applied to plastics. It was found that the addition of HHAP from 0.1–0.5 wt% was effective for inhibition of the deterioration of polyolefins (polyethylene and polypropylene) at 120°C and 270°C in air. Moreover, excellent inhibiting ability of HHAP against degradation by radiation (γ-ray and electron beam) was found for polyolefin plastics. It was confirmed that the inhibiting abilities of hydroaromatics described in Part 1 could be applied to rubbers and plastics.

Hydrogenation Mechanism of Coal Tar Pitch for Carbon Fiber(Part 3). Effects of Hydrotreatment on Pyrolysis Reactivity of Each Component in Coal Tar Pitch for High Performance Carbon Fiber.

Coal tar pitch for high performance carbon fiber (HPCF) was hydrotreated using tritium labelled tetralin as donor solvent at 450°C for 120min. The hydrogen transfer in this process was determined quantitatively according to results obtained from radioisotope tracer method. The hydrotreatment of pitches can be explained by a general mechanism such as involved in the hydrotreatment of petroleum heavy oil or coal liquefaction. The tritiated pitch was heat-treated in the range of 30 to 1, 000°C under nitrogen atmosphere. It was found that the reaction of carbon-carbon bond cleavage and the evaporation of volatile components were basically completed at about 600°C. The dehydrogenation of polynuclear aromatic rings was sustained up to 1, 000°C. The model based on the first order rate expression was able to analyse TGA data successfully. Activation energies and frequency factors, for the nonisothermal heat treatment of pitches and each component of pitches, were calculated. The pyrolysis activation energies of the pitch and major components (HIS-BS and BIS-THFS fractions) in the pitch decreased when the pitch was hydrotreated.