Deasphalted Oil Research Articles

Application Evaluation of Asphalt mixtures using SDAR (Solvent DeAsphaltene Residue)

PURPOSES : The objective of this study is to evaluate the SDAR (solvent deasphaltene residue), which is obtained from the solvent deasphalting (SDA) process, as a pavement material. METHODS : The physical properties of the SDAR were evaluated based on its chemical composition, and asphalt mixtures with the SDAR were fabricated and used for the evaluation of mechanical properties. Firstly, the chemical composition of SARA (saturate, aromatic, resin and asphaltene) was analyzed using the TLC-FID (thin-layer chromatography-flame ionization detector). Moreover, the basic material properties of the asphalt binder with the SDAR were evaluated by the penetration test, softening point test, ductility test, and PG (performance grade) grade test. The rheological properties of the asphalt binder with the SDAR were evaluated by the dynamic shear modulus () obtained using the time-temperature superposition (TTS) principle. Secondly, the mechanical properties of the asphalt mixtures with the SDAR were evaluated. The compactibility was evaluated using the gyratory compacter. Moreover, the tensile strength ratio (TSR) was used for evaluating the moisture susceptibility of the asphalt mixtures (i.e., susceptibility to pothole damage). The dynamic modulus , which is a fundamental property of the asphalt mixture, obtained at different temperatures and loading cycles, was used to evaluate the mechanical properties of the asphalt mixtures. RESULTS AND CONCLUSION : The SDAR shows stiffer and more brittle behavior than the conventional asphalt binder. As the application of the SDAR directly in the field may cause early failures, such as cracks on pavements, it should be applied with modifiers that can favorably modify the brittleness property of the SDAR. Therefore, if appropriate additives are applied on the SDAR, it can be used as a pavement material because of its low cost and strong resistance to rutting.

Current status and prospects of demetallization of heavy petroleum feedstock (Review)

Comparative assessment of the prospects of development of heavy petroleum feedstock (HPF) upgrading technologies in terms of the possibility of removal and recovery of metals contained in the feedstock is presented. It has been shown that HPF demetallization with different efficiencies can be achieved as a result of destructive thermal conversion of the feedstock and nondestructive mass transfer processes. Solvent deasphalting is characterized by simplicity of engineering design and operating flexibility and makes it possible to remove both asphaltenes and metals, whose deposition leads to irreversible deactivation of oil refining catalysts. Promising lines in demetallization by destructive feedstock conversion are associated with processes that provide the highest degree of HPF conversion and the lowest yield of the unconverted residue, in which the feedstock metals are concentrated. In this regard, the development and implementation of petroleum residue upgrading technologies based on the slurry hydrocracking, fluid coking or flexicoking, and supercritical fluid extraction processes creates real prerequisites for the organization of high-conversion comprehensive processing of heavy oils with the isolation of a metal concentrate.

Pyrolysis of asphaltenes in an atmospheric entrained flow reactor: A study on char characterization

Integration of solvent deasphalting and asphaltenes gasification has been reported as a convenient alternative to coker based upgrading of bitumen, derived from oil sands. However, very limited work has been carried out on pyrolysis and gasification of asphaltenes at entrained flow conditions. The present study aims at addressing this gap, and provides a better understanding of the major intermediate in gasification process – char. Chars were prepared at different operating conditions in an atmospheric entrained flow reactor. Extensive characterization techniques were used to identify the changes in morphology, structure and composition of chars. We estimated the global gasification reactivity of chars with steam and CO2. Chars exhibited an internally hollow structure with porous walls. The nominal size of individual char particles and degree of fragmentation were greatly influenced by the operating conditions. H/C ratio, aromaticity and macro-porosity of chars increased with an increase in operating temperature, while content of heteroatoms and global reactivity showed a gradual decrease. Increase in residence time had marginal effect on char composition, morphology and global reactivity. V and Ni tend to accumulate in chars; however, their effect on global reactivity could not be established.

Association Model for Nickel and Vanadium with Asphaltene during Solvent Deasphalting

Solvent deasphalting is a highly efficient process for removing asphaltene and metals from the petroleum residue; however, there are rare modeling studies about the interaction between metals and asphaltene. This work establishes the association models of metals (Ni and V) with asphaltene during solvent deasphalting. The models reveal that the distribution factors of metals are related to the solvent density, association enthalpy, and temperature. The association energy of metal–asphaltene is higher than that of metal–resin. The distribution factor of metals with asphaltene is lower than that without asphaltene. The tuned model could well-predict the distribution factors for both Ni and V. The models provide the thermodynamics and theoretical guide for removing the metals from the heavy oil during solvent deasphalting.

Refining Tahe Heavy Crude Oil to Increase Light Product Yield

Traditional processing technology is not suitable for Tahe crude oil due to its low light distillate yield and poor quality. A new process, atmospheric flash evaporation-solvent deasphalting combined process, was put forward. The appropriate operating conditions of solvent deasphalting process were as follows: iso-pentane solvent, temperature of 175°C, pressure of 3.7MPa, solvent volume ratio of 5.0. Compared with atmospheric distillation-delayed coking process, total liquid product yield by new process could reach 78.77%, increasing by 9.47%. The quality of deasphalting oil met the feed requirements for catalytic cracking and de-oiled asphalt could be used as asphalt mixture additives.

Road Asphalt Prepared by High Softening Point De-oiled Asphalt From Residuum Solvent Deasphalting

Solvent deasphalting process is an effective pretreatment upgrading technology for vacuum residuum. The rational use of the de-oiled asphalt with high softening point needs to be solved when the process was applied to upgrade the residue oil. Preparation of the hard paving asphalt with low penetration by adding a certain proportion of high softening point de-oiled asphalt to the commodity 70# paving asphalt was investigated. The performance and The feasibility of the preparation 50# paving asphalt with high softening point de-oiled asphalt has been also discussed. The experimental results showed that the properties of the blend asphalt were changed in different extent with the different proportion between 70# paving asphalt and high softening point de-oiled asphalt. The rheological behavior tests showed that the anti-rutting performance of blending asphalt could be improved due to the addition of de-oiled asphalt. The qualified 50# paving asphalt could be prepared from the de-oiled asphalt and the commodity 70# paving asphalt with the appropriate blending ratio.

The effect of aromatic interactions on the elasticity of bituminous binders

In this paper, experimental support is provided showing the importance of polyaromaticity on the elastic properties of bituminous binders. Especially the size of the polyaromatic structures seems to play a crucial role. The observations indicate that larger conjugated aromatic structures provide stronger interactions and relate to the elastic behaviour at longer loading times or up to higher temperatures, while smaller aromatic structures determine more the elastic behaviour at short loading times or at low temperatures. In addition to aromatic interactions, natural wax can, upon crystallization, also induce increased elastic effects, especially at low frequencies. A large variety of binders was investigated: bitumen from straight distillation, visbreaking, solvent deasphalting and oxidation were included in the sample set. Average levels of aromaticity were determined by Fourier transform infrared (FT-IR) spectroscopy and by refractive index measurements. Chromatography combined with UV-visible absorption spectroscopy was used as an indicator of the average size of the aromatic structures. Rheological properties were determined using a dynamic shear rheometer, in a temperature range from 0 up to 90 °C. Good relations were observed between the phase angle measurements, at specific test conditions of frequency and temperature, and UV-vis absorption levels at specific wavelengths.

Physical and rheological properties of deasphalted oil produced from solvent deasphalting

Abstract Because of the depletion of conventional oil and its increasing price, technologies that use unconventional oil and low-value crude residues are attracting great attention. Unconventional oil and low-value crude residues contain large amounts of asphaltene, which leads to high viscosity and includes a considerable amount of nitrogen, sulfur, and various metals. Therefore, to utilize such energy resources, asphaltene-removal processes (e.g., solvent deasphalting) are required to obtain deasphalted oil (DAO). DAO is generally used for lube base oils and is converted into transportation fuel and petrochemical raw materials by additional refinement. Herein, the physical and rheological properties of DAO were investigated to develop a better understanding of the DAO characteristics and its efficient utilization. The physical properties of DAO were analyzed by measuring elemental compositions; American Petroleum Institute gravity; saturates, aromatics, resins, and asphaltenes fractions; and boiling-point distributions, and the properties were compared with those of vacuum residues. The DAO viscosity was characterized using a rotational rheometer at various temperatures to analyze the effect of temperature on the DAO fluidity. The DAO viscosity greatly decreased with increasing temperatures and a distinctive transition was observed at ∼70 °C. In the shear viscosity and modulus analyses, DAO exhibited non-Newtonian behavior below 70 °C and Newtonian behavior above 70 °C.

Comparative Study on Hydrotreating of Venezuela De-Asphalted Oil: Conversion Behavior of Heteroatom Compounds and HDM Catalyst Deactivation

A 1000 hour hydrotreating experiment was performed to investigate the hydrotreating behavior of heteroatom compounds (first stage) and HDM catalyst deactivation (second stage) using Venezuela De-Asphalted Oil. The effect of reaction severity on impurities removal was the expected one, the deeper the hydrotreating degree, the higher the conversion of impurities. The Characterization of spent HDM catalyst shows that the content of coke deposition on spent HDM catalyst is only 4 wt% while that of metal is more than 30 wt%. Vanadium compounds in DAO with less diffusion resistance can deposit inside of the HDM catalyst grain. Lower coke formation also retard the HDM catalyst by keeping the diffusion pores and active cites. The removal of asphaltenes largely improved the stability of the HDM catalyst.

SDA 방법으로 제조한 오일샌드 역청의 말텐에 대한 유변학적 거동 및 비뉴톤 특성

In this paper, the rheological behaviors and non-Newtonian characteristics of maltenes which is effected by hydrocarbon solvent type, solvent mixing ratio, temperature and shear rate was measured and compared with oil sands bitumen. Maltenes was made by SDA (solvent deasphalting) method from oil sands bitumen. Oil sands bitumen had apparent viscosities of measured at a shear rate of in the range of and showed yield stress of 0.1~0.3 Pa at the temperatures below . All the oil sands bitumen and maltenes exhibited a shear-thinning, i.e. pseudoplastic behavior and apparent viscosity of maltenes decreased with decreasing carbon numbers of hydrocarbon solvent. The change in apparent viscosity with temperature could be described by the simple Guzman-Andrade equation, and maltene viscosities were decreased as the mixing ratio of n-pentane was raised. Also, all maltenes approached to Newtonian fluid as temperature were increased. the degree of pseudoplasticity was enhanced with decreasing carbon number of solvent.

Separation of solvent and deasphalted oil for solvent deasphalting process

Due to the depletion of conventional oil resources and increasing prices, various technologies for utilizing unconventional oil and low-value crude residues, which have not been fully exploited, are currently being explored. The exploitation of unconventional oil and low-value crude residues requires upgrading processes such as carbon rejection and hydrogen addition. Among many existing upgrading processes, solvent deasphalting (SDA), a technology for removing asphaltene-rich pitch and producing higher-value deasphalted oil (DAO) by using paraffinic solvents, is promising because it offers the advantages of low installation cost and flexibility in terms of the control of the quality of pitch and DAO. The SDA process requires a considerable amount of expensive solvent. Thus, solvent recovery, an energy-intensive process, is required for improved efficiency. In this paper, DAO/solvent separation experiments were carried out using two solvents, pentane and hexane, to investigate the effect of operating conditions such as temperature, pressure, and DAO/solvent ratio on the process. The DAO/pentane separation was superior to the DAO/hexane separation under similar conditions. Regardless of the solvent type, solvent recovery was increased as the DAO/solvent ratio in the feed was decreased. Solvent recovery was strongly influenced by variations in temperature but was relatively insensitive to changes in pressure.

Adsorption Kinetics and Thermodynamics of Vanadyl Etioporphyrin on Asphaltene in Pentane

The interaction between vanadyl porphyrins and asphaltene in alkane solvents is important to increase the removal rate of metals during the solvent deasphalting process. Thus, the adsorption kinetics and thermodynamics of vanadyl etioporphyrins on a Canadian oil sands bitumen vacuum tower bottom (VTB) asphaltene in n-pentane were investigated. After adsorption, asphaltene was analyzed via transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). A certain amount of vanadyl porphyrins was adsorbed by the VTB asphaltene. This adsorption process was affected by the asphaltene dosage (0.01 and 0.02 g), the concentration of the n-pentane solution containing vanadyl porphyrins (10 and 15 μg/mL), and the temperature (288, 293, and 298 K). The adsorption rate was initially distinctly high. However, this rate became much slower after around 300 min, until equilibrium was reached after 1800 min. A comparison of four kinetic mod...

Improving the Solvent Deasphalting Process by the Co-treating of Residue and Coal

In view of the harsh conditions of coal liquefaction and the difficulty of residue processing, through medium- and low-temperature heat treatment of vacuum residue with coal, the solvent deasphalting process of residue treated with coal was studied. The results showed that particle size, types, adding amount of coal, and contacting temperature of residue with coal had effects on the solvent deasphalting process. Compared with the solvent deasphalting process of residue directly, coal particle size in 150–830 μm, coal/vacuum residue in 3:10–3:4 at 250°C, the yield of deasphalted oil could increase by 2.6–3.5 wt%, the removal rate of metals, such as nickel and vanadium, were 24.7 and 23.07%, respectively. The content of sulfur and carbon residue in deasphalted oil decreased slightly. Deasphalted oil had a higher yield and better quality when the contacting condition of residue and coal was harsher. The study demonstrated that the solvent deasphalting process could be improved by co-treating of residue and coal under medium and low temperature.

Biodesulfurization of Model Compounds and De-asphalted Bunker Oil by Mixed Culture

In this study, complicated model sulfur compounds in bunker oil and de-asphalted bunker oil were biodesulfurized in a batch process by microbial consortium enriched from oil sludge. Dibenzothiophene (DBT) and benzo[b]naphtho[1,2-d]thiophene (BNT1) were selected as model sulfur compounds. The results show that the mixed culture was able to grow by utilizing DBT and BNT1 as the sole sulfur source, while the cell density was higher using DBT than BNT1 as the sulfur source. GC-MS analysis of their desulfurized metabolites indicates that both DBT and BNT1 could be desulfurized through the sulfur-specific degradation pathway with the selective cleavage of carbon-sulfur bonds. When DBT and BNT1 coexisted, the biodesulfurization efficiency of BNT1 decreased significantly as the DBT concentrations increased (>0.1 mmol/L). BNT1 desulfurization efficiency also decreased along with the increase of 2-hydroxybiphenyl as the end product of DBT desulfurization. For real bunker oil, only 2.8 % of sulfur was removed without de-asphalting after 7 days of biotreatment. After de-asphalting, the biodesulfurization efficiency was significantly improved (26.2-36.5 %), which is mainly attributed to fully mixing of the oil and water due to the decreased viscosity of bunker oil.

Adsorption Kinetics of Nickel Etioporphyrin on VTB-Asphaltene in N-Pentane Solution

It is important to find out how to strengthen the interaction between nickel porphyrins and asphaltene in the alkane solvents of the low molecular weight for raising the removal rate of nickel in the solvent deasphalting process. Therefore, the adsorption kinetics, which describes how the nickel etioporphyrins are adsorbed on asphaltene (the vacuum residue of Canadian oil sands bitumen (VTB)) in the n-pentane solvent, are investigated. The results show that a certain amount of nickel porphyrins is absorbed on the asphaltene of VTB, which means there is a certain adsorption between asphaltene and nickel porphyrins. The adsorption rate is affected by the dosage of asphaltene, the concentration of the n-pentane solution containing nickel porphyrins and the temperature. A comparison in the four kinds of kinetic models on the overall adsorption rate shows that adsorption process can be perfectly described by the pseudo second-order equation.

Heavy Crude Oil Upgrading: Jazmin Crude

The Jazmin crude oil is located at the heart of Middle Magdalena in Colombia. It is heavy and sour crude oil with 43 wt.% of vacuum bottoms. It cannot be processed at the conventional refinery without being mixed with other lighter crudes, and should be upgraded to produce synthetic crude with higher concentration of distillates and lower acidity and carbon content. In this paper eight upgrading alternatives are presented. The alternatives include the processing of the crude, reduced crude and vacuum bottoms of the Jazmin crude oil using the following technologies: Distillation, solvent deasphalting, visbreaking, Delayed Coking, and Hydrotreating. The experiments were conducted at pilot scale, and there were used standard analysis techniques such as ASTM. In this study it was found that Jazmine crude oil and its heavy components produce high distillate yields when they were processed with thermal conversion processes. In addition those processes reduce the products acidity. Within the analyzed scheme the one corresponding to the visbreaking of the crude oil and the Delayed Coking of the vacuum bottoms from the visbreaking is perhaps the most attractive, giving 5.9 wt.% of gas, 78.2 wt.% of distillates and 15.9 wt.% of coke.

Crucial technologies supporting future development of petroleum refining industry

The primary tasks of refineries in the future are to improve the yield of light oil and to produce clean fuels and high-quality chemical raw materials. The efficient conversion of heavy oil is necessary to improve the yield of light oil. This conversion requires some crucial technologies, including: (1) residue hydrotreating technology, (2) the research institute of petroleum processing's (RIPP's) integrated combination process for residue hydroprocessing, (3) the integration of selective hydrogenation of fluid catalytic cracking gas oil with selective catalytic cracking process, and (4) the combination of superficial solvent deasphalting, hydrotreatment of deasphalted oil, and fluid catalytic cracking technology. The most important technologies for producing clean fuels such as qualified gasoline and diesel include the RIPP's selective hydrodesulfurization technology, the RIPP's hydrogenation technology for producing ultra-low-sulfur diesel fuel, and catalysts for producing RS-1000 and RS-2000 (grades of ultra-low-sulfur diesel). To produce high quality chemical raw materials, the Sinopec hydroprocessing for maximum propylene of fluid catalytic cracking process is of vital importance. The characteristics and effects of these technologies are summarized in this article. 概述了未来炼油厂主要任务中关键技术的特点和使用效果. (1)提高轻质油收率, 关键在于重油的高效转化, 关键技术包括渣油加氢技术、重油加氢与催化裂化双向组合技术、多产轻质油的催化裂化蜡油选择性加氢工艺与选择性催化裂化工艺集成技术、浅度溶剂脱沥青-脱沥青油加氢处理-催化裂化技术; (2)生产清洁燃料, 主要是生产要求越来越高的清洁汽油和柴油, 关键技术有汽油选择性加氢脱硫技术、柴油超深度加氢脱硫技术、柴油超深度加氢脱硫催化剂; (3)生产优质化工原料, 关键技术主要是催化丙烯技术. The technologies of efficiently processing heavy oil and producing clean transportation fuel and high-quality chemical raw materials are very crucial support to the future petroleum refining industry. Some technologies with good prospects are cited.

Two-Step Adsorption of Endogenous Asphaltenic Surfactants at the Bitumen–Water Interface

We have performed hanging droplet measurements of a straight-run bitumen (SRB) and its corresponding deasphalted oil (DAO) to investigate the adsorption process at the bitumen–water interface (pH 2...

Upgrading of heavy crude oils: Castilla

Oil resources similar to WTI and Brent crude oils are dwindling, so heavy and extra-heavy crude oils, and bitumen must be used to meet the growing demand for fuels. The vast majority of the world's refineries are not suitable for processing these types of feed stock, so upgrading processes are required to make synthetic crude oils from those resources compatible with the equipment installed. By its viscosity Castilla crude oil is not classified as an extra-heavy crude oil, as even on surface it flows. However, it has 45.6wt.% of vacuum bottoms and high concentrations of Conradson Carbon (CCR of 34wt.%) and metals (nickel and vanadium content of 928ppm) within it.This article presents various alternatives for the upgrading of the crude Castilla, using as raw material crude oil free of lights (199°C+), reduced crude (370°C+) and vacuum bottoms. The technologies used in the studied scheme were visbreaking (VBK), delayed coking (DC), solvent deasphalting (DAF), hydrotreating and distillation. The studies were conducted at pilot plant scale and the analysis of the products was done using standard techniques such as ASTM. Among the outstanding results we have the operational scheme of the vacuum bottoms Visbreaking, but this is not a typical Visbreaking process because the coke production was 8.2wt.%. A furnace with some characteristics of a DC furnace, and a pair of soakers that function as coking drums should be used to avoid coke deposition within the internal walls of the coils. This is an innovative technology that sits between visbreaking and delayed coking.

열중량 분석법을 이용한 Deasphalted Oil의 열분해 특성 분석

기존 경질 원유 자원의 매장량 고갈과 중국, 인도 등 개발도상국에서의 에너지 수요가 급증하면서 원유 자원의 공급이 수요를 감당하지 못하는 상황이 벌어지고 있고, 따라서 상대적으로 활용도가 낮았던 중질유를 효율적으로 이용하는 방안이 대두되고 있다. 중질유를 활용하기 위해서는 경질화 과정을 거쳐야하는데, 특히 공정이 단순하고 경제적인 열분해 기술이 적합하다고 할 수 있겠다. 본 연구에서는 중질유의 열분해 특성 분석의 기초 자료를 얻기 위해 중질유에서 아스팔텐이 제거된 deasphalted oil(DAO)의 열분해 실험을 수행하였다. DAO는 solvent deasphalting 공정을 통하여 얻어지며 주로 탄소수가 20~40인 물질들로 이루어져 있는데, DAO의 열분해 반응 속도론적 분석 결과와 비교 분석하기 위해 DAO의 평균 탄소수를 갖는 탄소수 30의 단일 물질들(<TEX>$C_{30}H_{62}$</TEX>, <TEX>$C_{30}H_{58}O_4S$</TEX>, <TEX>$C_{30}H_{63}O_3P$</TEX>)을 선택하여 추가적인 열분해 실험을 수행하였다. 열분해 실험에서는 열중량 분석기를 이용하여 비등온 열분해 방법(10, 50, <TEX>$100^{\circ}C$</TEX>/min)으로 실험을 진행하였고, 열분해 반응을 분석하는 방법으로는 가장 기초적인 Arrhenius 방법을 비롯하여 Ingraham and Marrier 방법, Coats and Redfern 방법, Ozawa-Flynn-Wall 방법을 이용하였다. Arrhenius, Ingraham and Marrier, Coats and Redfern 방법으로 계산된 DAO의 열분해 반응 평균 활성화에너지 값은 72~99 kJ/mol이었다. 그리고 Ozawa-Flynn-Wall 방법으로 분석된 활성화에너지에서는 전환율의 증가에 따라 DAO의 경우 그 상승 폭이 단일 물질들에 비해 크게 나타났다. The depletion of conventional oil reserves and the increasing energy need in developing countries such as China and India result in exceeding oil demand over supply. As a solution of the problem, the efficient utilization of heavy oil has been receiving more and more interest. In order to utilize heavy oil, upgrading processes are required. Among the upgrading processes, thermal decomposition is thought to be relatively simple and economical. In this study, to understand basic characteristics of thermal decomposition of heavy oil, we conducted pyrolysis experiments of deasphalted oil (DAO) produced by a solvent deasphalting process. DAO is a mixture of many components and consists mainly of materials of carbon number 20~40. For the comparison with results of DAO pyrolysis, additional pyrolysis experiments with single materials of carbon number 30 (<TEX>$C_{30}H_{62}$</TEX>, <TEX>$C_{30}H_{58}O_4S$</TEX>, <TEX>$C_{30}H_{63}O_3P$</TEX>) were conducted. Pyrolysis experiments were carried out non-isothermally with variation of heating rate (10, 50, <TEX>$100^{\circ}C$</TEX>/min) in a thermogravimetric analyzer. Average pyrolysis activation energy determined by using Arrhenius method, Ingraham and Marrier method, and Coats and Redfern method was 72~99 kJ/mol. In the activation energy calculated by Ozawa-Flynn-Wall method, DAO had wider variation than other single materials.