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.     

Pyrolysis characteristics of a North Korean oil shale

Pyrolysis characteristics of a North Korean oil shale and its pyrolysates were investigated in this paper. The pyrolysis experiments were conducted below 600 °C at a heating rate of 10, 15, 20 and 25 °C/min, respectively. The kinetics data were calculated using both integral and differential methods with the assumption of first order kinetics. The results show that the averaged oil content of the North Korean oil shale is about 12.1 wt% and its heat value is 13,400 kJ/kg. The oil yields at different retorting temperatures show that the higher the retorting temperature the greater the oil and retorting gas yields. The optimal retorting temperature for the North Korean oil shale is about 500 oC. The properties of the North Korean shale oil including density, viscosity, flash point and freezing point are found to be relatively low compared with those of shale oil from FuShun, China. The gasoline fraction, diesel fraction and heavy oil fraction account for 11.5 wt%, 41.5 wt% and 47 wt%, respectively. The major pyrolysis gases are CH4(the most abundant), H2, CO2, H2 S, CO, and C2-C5 hydrocarbons. The heat value of retorting gas is more than 900 kJ/mol, and the retorting gas has high sulfur content.     

Determination of the functional groups and the melting point of iraqi asphaltenes

A qualitative analysis study of n-C5 asphaltene of Iraqi crude oil from (Al-Dura, Kirkuk and Basra) oil fields was done using Fourier transform infrared spectroscopy (FT-IR). The melting points of the three oil derived asphaltenes were determined using Hot stage polarizing microscope at 180?°C for Al-Dura, 125?°C for Kirkuk and 140?°C for Basra asphaltenes. The FTIR spectrum shows an aromatic behavior of the asphaltene samples at a wavelength of 3049?cm^?1 and aliphatic chains were found at wavelengths 2924?cm^?1.     

KINETICS OF HYDRODESULFURIZATION OF HEAVY GAS OIL DERIVED FROM OIL-SANDS BITUMEN

ABSTRACT

With gradual shortage in the supply of crude oil, the importance of producing synthetic crude oil from oil sands and shale oil is increasing day by day. In the present paper, the effects of various process variables such as temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio on the removal of sulfur compounds from oil sands derived heavy gas oil has been studied. The experiments have been carried out in a micro scale trickle bed reactor over a commercial Ni–Mo catalyst. The temperature, liquid hourly space velocity and hydrogen/heavy gas oil volumetric ratio have been varied from 365 to 415°C, 0.5 to 1.9 h^?1 and 400 to 1000 ml, respectively. Under optimum reaction conditions over 96% conversion of sulfur compounds was achieved. The kinetics of the rate of sulfur removal from the oil sands derived heavy gas oil has also been discussed in this article.     

Hydrocracking of Vacuum Gas Oil: Conversion,Product Yields,and Product Quality over an Industrial Hydrocracking Catalyst System

Pilot plant experiments were conducted over an industrial hydrotreating/hydrocracking catalyst system using vacuum gas oil fraction obtained from a refinery crude distillation unit. Extensive pilot plant data were generated on the performance of industrial hydrocracking catalyst system with respect to conversion, product yields, and product quality at various operating conditions. The pilot plant experiments were carried out in a dual-reactor hydrotreating pilot plant system with downflow mode of operation. The temperature varied from 360 to 400°C and liquid hourly space velocity varied from 0.8 to 2.4 hr^?1, keeping a constant pressure of 170 kg/cm² and H₂/HC feed ratio of 845 L/L. The hydrocracked total liquid product was distilled in a true boiling point distillation unit to obtain yields and qualities of different fractions such as naphtha, kerosene, diesel, and unconverted oil. The effect of operating conditions on the performance of the hydrocracking catalyst system was discussed in detail. The kinetics of hydrocracking reaction was studied using a simple first-order reaction and a complex four-lump reaction system and the kinetic parameters were reported.     

The Oxidation Stability of Lubricating Oil

Abstract

Lubricating oil is generated throughout the year and collected in central locations in many communities. The studied lube oil has a boiling range of 280°C–400°C, and its physical properties were determined according to standard test methods in ASTM and International Petroleum. Solvent extraction by furfural was carried out using different feed ratios. The best ratio was 1:4 (sample:furfural). The oil was separated into its components using liquid column chromatography. It was found that the aromatic contents decreased. The structure group analysis was determined by infrared spectroscopy and refractive index-density-molecular weight methods. The oxidation stability was carried out according to ASTM method D-48 using an inhibitor. The inhibitor used was a nonionic surfactant, alkanolamide. The results showed that the oxidation stability improved using the inhibitor.     

Visbreaking of Chinese Oil Sand Bitumen

Abstract

Thermal visbreaking of inner Mongolia oil sand bitumen was conducted at several temperatures for different lengths of time in the laboratory. The viscosity of the thermally-treated oil was reduced dramatically with thermal treatment under the condition of adding 0.3 wt% anti-coking agent, the oil sand bitumen reacting at 410°C and 45 min. The kinematic viscosity (100°C) of visbreaking oil is reduced to 138.25 mm²·s^?1 and the qualities of it are conformed to 7# Chinese Standard for Fuel Oil, which can directly be regarded as product.     

Synthesis of temperature-resistant and salt- tolerant surfactant SDB-7 and its performance evaluation for Tahe Oilfield flooding （China）

In order to improve the enhanced oil recovery of high-temperature and high-salt oilfields, a novel temperature-resistant and salt-tolerant surfactant （denoted as SDB-7） was synthesized and evaluated for the Tahe Oilfield （Xinjiang, China）, which is representative of high-temperature and high-salt oilfields. It has a central reservoir temperature of 140 ℃ and salinity of 22.6× 10^4 mg/L. The temperature-resistant and salt-tolerant performance, interfacial activity, oil displacement efficiency, aging properties, and adsorption properties of the synthesized surfactant were evaluated for Tahe Oilfield flooding. The results showed that the SDB-7 was temperature-resistant and salt-tolerant capacity of 140 ℃ and 22.6×10^4 rag/ L, respectively, oil displacement efficiency under static condition of 84%, and adsorption loss of 0.4 mg/ g （less than 1 mg/g-oil sand）. In the heat aging experiment （under the temperature of 140 ℃ for 60 days）, the oil-water interracial tension and oil displacement efficiency of SDB-7 were almost unchanged. The oil displacement experiments showed that, under the temperature of 140 ℃ and the salinity of 22.6× 10^4 mg/L, the surfactant SDB-7 can enhance oil recovery by 14.5% after water flooding,suggesting that SDB-7 has a promising application in high temperature and high salinity （HT/HS） reservoir.     

The Effects of Multi-component Thermal Fluids on the Viscosity of Offshore Heavy Oil

Multi-component thermal fluids stimulation is a feasible way to recover offshore heavy oil reservoir. As a new technology, its mechanism of enhanced oil recovery should be understood through systematic simulation experiments and quantitative analysis. Laboratory experiments were carried out to investigate the effects of temperature, natural gas, and various gases (N₂, CO₂, or N₂+CO₂) on the viscosity of heavy oil from Nanbao block of Bohai offshore oilfield. The results show that in the range of 56°C (reservoir temperature) to 120°C, natural gas saturated and degassed oils are all very sensitive to temperature, and the viscosity is reduced by more than 90% when heated to 120°C; under lower temperature condition, injection of 5MPa N₂, N₂+CO₂, or CO₂ can significantly reduce the viscosity of natural gas saturated heavy oil, with a viscosity reduction ratio of about 20%, 50%, and 80%, respectively, at 56°C. Therefore, heavy oil production by viscosity reduction can be achieved by raising temperature or through gas injection. Taking into account the equipment, heat loss, and cost of steam injection, the technology of moderate heating, auxiliary gas injection is very promising for the recovery of Nanbao heavy oil.     

Features of liquid hydrocarbon and biomarker maturity ratios during HTHP semi-open system pyrolysis of type II and III source rocks

In order to study the liquid hydrocarbon generated by laboratory pyrolysis and the biomarker maturity ratios in expelled oil with the increasing simulation temperature, the Hydrous semi-open system high temperature high pressure (HTHP) pyrolysis experiments was performed on Type II and III source rocks from 350°C to 540°C. The results showed that expelled oil yields in both samples have a trend of increased first and then decreased with the increasing temperature, while an opposite tendency occurred in the residual oil. The biomarker maturity ratios, such as ∑C_21?/∑C₂₂₊ ratio in n-alkanes, Pr/Ph ratio in isoprenoid alkenes, Ts/Tm in terpenes, and C₂₉ββ/(αα + ββ) ratios in steranes are all better indicators in terms of maturity in pyrolysis. However, the maturity biomarkers ratios interpreted by the mechanism of isomerization such as C₃₁-homohopanes 22S/(22S?+?22R) and ααα C₂₉-sterane 20S/(20S + 20R), which had already reached their equilibrium values, indicating that microbiological deterioration is one reason for the failure indicative function of αααC₂₉sterane20S/(20S + 20R) ratio. This research may also play an important role in the studies about the evolution of sedimentary organic matters in geology.     

Shear strengthening viscosity and shear-rate-dependent modulus model for a Shengli crude oil

The steady shear viscosity of a Shengli waxy crude oil at the temperature of 3°C to 4°C, higher than its gel point, was measured by using a parallel-plate rheometer, which shows a shear thickening behavior in the shear rate range of 10^?2–10^?1 s^?1. A spectrum model proposed in our previous work was modified here by considering the modulus change in the spectra, which could be caused by a shear-induced varying internal structure in the crude oil. The shear strengthening viscosity of the Shengli crude oil can be described well by the changing-spectrum viscosity model.     

KINETICS OF HYDROCARBON GAS GENERATION FROM MARINE KEROGEN AND OIL: IMPLICATIONS FOR THE ORIGIN OF NATURAL GASES IN THE HETIANHE GASFIELD, TARIM BASIN, NW CHINA

In this paper we derive kinetic parameters for the generation of gaseous hydrocarbons (C_1‐5) and methane (C₁) from closed‐system laboratory pyrolysis of selected samples of marine kerogen and oil from the SW Tarim Basin. The activation energy distributions for the generation of both C_1‐5 (Ea = 59‐72kcal, A = 1.0×10¹⁴ s^?1) and C₁ (Ea = 61‐78kcal, A = 6.06×10¹⁴ s^?1) hydrocarbons from the marine oil are narrower than those for the generation of these hydrocarbons from marine kerogen (Ea = 50‐74kcal, A = 1.0×10¹⁴ s^?1 for C_1‐5; and Ea = 48‐72kcal, A=3.9×10¹³ s^?1 for C₁, respectively). Using these kinetic parameters, both the yields and timings of C_1‐5 and C₁ hydrocarbons generated from Cambrian source rocks and from in‐reservoir cracking of oil in Ordovician strata were predicted for selected wells along a north‐south profile in the SW of the basin. Thermodynamic conditions for the cracking of oil and kerogen were modelled within the context of the geological framework. It is suggested that marine kerogen began to crack at temperatures of around 120°C (or 0.8 %Ro) and entered the gas window at 138°C (or 1.05 %Ro); whereas the marine oil began to crack at about 140 °C (or 1.1 %Ro) and entered the gas window at 158 °C (or 1.6%Ro). The main geological controls identified for gas accumulations in the Bachu Arch (Southwest Depression, SW Tarim Basin) include the remaining gas potential following Caledonian uplift; oil trapping and preservation in basal Ordovician strata; the extent of breaching of Ordovician reservoirs; and whether reservoir burial depths are sufficiently deep for oil cracking to have occurred. In the Maigaiti Slope and Southwest Depression, the timing of gas generation was later than that in the Bachu Arch, with much higher yields and generation rates, and hence better prospects for gas exploration. It appears from the gas generation kinetics that the primary source for the gases in the Hetianhe gasfield was the Southwest Depression.     

RECOVERY OF ORGANIC MATTER FROM GREEN RIVER OIL SHALE AT TEMPERATURES OF 400°C AND BELOW

ABSTRACT

Experiments to recover organic matter from Green River oil shale in high yields at temperatures of 400^°C and below are described. Three different recovery procedures are discussed: 1) experiments wherein liquid organic materials were extracted at atmospheric pressure and temperatures below 75^°C by solvents of different strengths, 2) autoclave experiments where liquid organics were recovered by heating the shale with a variety of solvents at temperatures between 300 and 400^°C and pressures between 5 and 32 MPa, and 3) an autoclave experiment where liquid organics were recovered by heating shale in an argon atmosphere for 1 hour at 400^°C. The liquid organic materials recovered in these experiments represent from four to 90 weight percent of the total organic material in the shale. The liquid organic materials have an average molecular weight of between 500 and 600 amu as compared to a typical shale oil that has an average molecular weight of 300 to 350 amu. Elemental analyses show that the liquid organic materials contain high percentages of hydrogen and nitrogen, as does shale oil. Moreover, the liquid organic materials also contain much larger concentrations of oxygen-containing compounds than shale oil. The experimental results suggest the possibility of developing a new process for recovering both organic and inorganic material from Green River shale.     

Heating oil sand and effects on the interlayers

The condition of oil sand may change and produce new fractures at high temperature. However, the changing process of oil sand and its characteristics is not clear enough and still lacks certain experiments. Therefore, a new experiment is operated to study oil sand and its interlayers at high temperature. It is found that when the temperature reaches 180°C at first, fractures can be seen obviously along oil sand interlayers. After the oil sand is cooled and heated again, more cracks are produced vertical to the original fracture at 160°C. Different thicknesses and different lithologies are tested to produce cracks at different temperatures (100°C, 200°C, and 300°C). Cracks are produced suddenly when certain temperature thresholds are reached. These data are useful to study the heating process of oil sand in heavy oil reservoirs.     

Synthesis and characterization of Ni-Mo catalyst using pea pod (Pisum sativum L) as carbon support and its hydrotreating potential for gas oil,Jatropha oil,and their blends

Ni-Mo catalyst was prepared directly on pea pod using boric acid as a surface modifying agent. The BET surface area of the pea pod derived carbon based catalyst was found to be 380 m²/g. The activity of the inventive catalyst was tested in micro down flow reactor for hydrotreating of gas oil, 20% Jatropha oil in gas oil at the temperature range of 330–370°C, 90 bar H₂ pressure and space velocity of 1 h^?1 followed by Jatropha oil at 370°C, and keeping the other process parameters constant. The gas oil hydrotreating activity of the catalyst studied at temperatures below 370°C was found to be lower than that of the commercial alumina- and carbon-supported Ni-Mo catalysts; however, the activity was found to be comparable at 370°C.     

Catalytic co-cracking of waste polypropylene and residual fuel oil

Abstract

Industrial waste polypropylene (PP) homopolymer and residual fuel oil (RFO) were pyrolyzed together in presence of catalyst ZSM-5 under the atmospheric pressure with different mixing ratios of the feedstocks. The experiments were carried out in a batch reactor at two different temperatures of 500?°C and 600?°C with the blended mixture (PP/RFO) to catalyst (ZSM-5) ratio of 4:1. The effects of blending ratios between the two feedstocks and temperature with respect to the yield of the products oil, gas, and residual coke were determined. The optimum blending ratio of PP and RFO with respect the higher quantity yield of liquid product was found to be 1:1 at 500?°C. The percentages of liquid fuel, gas, and coke were observed to be 74.8%, 10.2%, and 15% at 500?°C.     

Hydrothermal transformation of heavy oil and organic matter from carbonate rocks of oil fields of Tatarstan

In laboratory model experiments were identified features of hydrothermal transformation of heavy oil and organic matter productivity of carbonate rocks from Bashkirian stage of deposits of the Middle-Carboniferous of Tatarstan territories. Experiments were conducted at temperature of 360?°C in hydrogen environment in presence of aqueous phase. The impact of hydrothermal factors on rocks leads to decrease in content of insoluble OM - kerogen and increase content of free hydrocarbons. With increase in content of saturated and aromatic hydrocarbons, content of resin-asphaltene components decreases. Changes in composition lead to significant reduction in density of heavy oil from 0.9254 to 0.8273?g/cm³.     

Rheological behavior of Algerian crude oil: effect of temperature and refined product

Abstract

The rheological behavior and its variation with temperature and refined product concentration of a crude oil sample coming from a quagmire of the separation station of Tin Fouye Tabankort oilfield/southern Algeria were investigated experimentally. The experiments were carried out at various temperatures (20, 30 and 50?°C) over the shear rate range of 0 to 700?s^?1 by using a controlled stress rheometer (AR 2000, TA Instrument). The results showed that the crude oil exhibit non-Newtonian of shear thinning behavior at low shear rate and Newtonian behavior at high shear rate and was adequately described by Casson and Herschel–Bulkley models. The rheological measurements through the steady flow test and viscoelastic behavior, including the storage modulus (G′), loss modulus (G″), and complex modulus (G*), has indicated that the rheological properties of the crude oil were greatly influenced by the temperature and the additive concentration.     

Hydrocracking of Polyolefin Thermal Cracking Waxes Over Ni-loaded Molecular Sieve Catalysts

The hydrocracking of thermal cracking waxes obtained from pyrolysis of polyolefin at 360°C for 120 min has been studied using Ni-loaded molecular sieves catalysts. According to XRD, TPR, and BET data, the presence of nickel oxide did not seem to damage the crystalline framework of the catalytic supports. Hydrocracking experiments were carried out in a stirred autoclave reactor at 300°C for 120 min under 2.0 MPa of hydrogen. The results suggested the existence of a balance between the acid and metal function over bifunctional catalysts, which affects hydrogenation and hydroisomerization of thermal cracking waxes. Hydrocracking reactions took place extensively over mixture of Ni/HBeta and ZSM-5, leading toward higher fractions of gases (30.2%) and diesel (23.5%). The higher fractions of gasoline (33.5%) and lube base oil (19.0%) were obtained over mixture of Ni/HSAPO-11 and ZSM-5. In contrast, hydrocracking reaction occurred in a lower extent over mixture of Ni/NMCM-41 and ZSM-5, which produces lube base oil with lower pour point (–10°C), gasoline and diesel with lower bromine numbers (1.1 and 0.8 g Br₂/100 g sample). The viscosity index of lube base oil was in the range of 131–171 over all three mixed catalysts.     

The Variation of the Gel Point of Daqing Crude Oil with Pipelining History

Abstract

Daqing crude oil is a typical waxy crude oil with a wax content of 26.6 wt% and a gel point of 32°C. In order to conduct the safety analysis of pipeline operation, the variation of gel point of Daqing crude oil with thermal and shear history was studied through pipelining simulation experiments. The experiments were performed under different annual throughputs and shear rates of pipeline flow. The results suggest that the change of shear action has little effect on the gel point of crude oil. As the final dynamic cooling temperature is increased, the change of gel point experiences two stages, staying constant at first and then decreasing. Through 13 groups of pipelining simulation experiments, the effects of heating temperature ranging from 45°C to 65°C on gel point of Daqing crude oil were studied. It has been indicated that the gel point increases as the heating temperature is increased under the same final dynamic cooling temperature. The relation equation was constructed to be used to predict the gel point under certain heating temperatures and final dynamic cooling temperature. The average absolute deviation of 52 predicted values of gel point is 0.58°C.